CN104559888A - Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate - Google Patents
Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate Download PDFInfo
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- CN104559888A CN104559888A CN201410836835.0A CN201410836835A CN104559888A CN 104559888 A CN104559888 A CN 104559888A CN 201410836835 A CN201410836835 A CN 201410836835A CN 104559888 A CN104559888 A CN 104559888A
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Abstract
The invention discloses a copper-clad plate applicable to a high multi-layer PCB (printed circuit board). The copper-clad plate is prepared from an adhesive, glass fiber cloth and copper foil, wherein a solid in the adhesive comprises components in percentage by weight as follows: 5%-40% of phenolic epoxy resin, 4%-20% of isocyanate-modified brominated epoxy resin, 6%-25% of high-bromine epoxy resin, 3%-20% of a toughening agent, 10%-45% of a phenolic resin curing agent, 3%-15% of tetrabromobisphenol A, 2%-16% of a styrene-maleic anhydride copolymer, 0.007%-0.030% of a phenolic resin curing accelerator, 1%-5% of a heat stabilizer and 10%-50% of inorganic filler. The invention further discloses a preparation method of the copper-clad plate applicable to the high multi-layer PCB. The prepared copper-clad plate has the high glass-transition temperature (Tg is higher than or equal to 190 DEG C), the excellent heat resistance, the low coefficient of thermal expansion (CTE is smaller than or equal to 2.3%) and the medium dielectric constant/dielectric loss (Dk is smaller than or equal to 4.3, and Df is smaller than or equal to 0.0135) and can be applicable to production of the high multi-layer PCB.
Description
Technical field
The present invention relates to copper-clad plate preparing technical field, specifically, relate to and be a kind ofly suitable for copper-clad plate of high multilayer printed wiring board and preparation method thereof.
Background technology
Along with high-density and the high performance of PCB, HDI/BUM plate, embedded components multi-ply wood and high multi-ply wood etc. obtain fast development, and the increasing and the increase of area of the PCB number of plies, thickness, when high-temperature soldering, particularly pb-free solder, in order to ensure the reliability of welding, higher welding temperature or longer weld interval need be born, thus, its baseplate material is had higher requirement, compared with conventional material, this kind of sheet material should have higher second-order transition temperature and thermotolerance.On July 1st, 2006 starts, and the formal enforcement of European Union's two instructions (about restriction use Hazardous Substances Directive in electronic and electrical equipment with about scrapping electronic and electrical equipment instruction), indicates that global electronic industry will enter the pb-free solder epoch.Because welding temperature is high, to the corresponding raising of copper-clad plate thermal reliability, traditional plumber's solder can not re-use, and the welding temperature needed for the alternative solders such as SAC now all increases substantially.And traditional F R-4 copper-clad plate, because thermotolerance is low, second-order transition temperature only has 130-140 DEG C, heat decomposition temperature generally only has 300-310 DEG C, although widespread use in general electronic products, can not apply in high density interconnect and integrated circuit fields, existing electronic product development rapidly, and along with lightening, the multiple stratification of printed electronic circuit and the development of semiconductor mount technologies, require that substrate must have the performance such as high Tg, high heat-resisting and low-expansion coefficient, to improve reliability that is interconnected and that install.
In recent years, various electronics is along with the increase of information processing capacity, and the encapsulation technology such as densification and multiple stratification that is highly integrated, distribution of the semiconducter device carried develops hastily.For the insulating material of printed-wiring board (PWB) used in electronic equipment of various etc., loss during in order to improve the transmission speed of signal and lower Signal transmissions, require specific inductivity and tangent of the dielectric loss angle low, and in order to reach the high multiple stratification brought by distribution increase, also require that glass transition temp is high, therefore develop the resin combination matched therewith also particularly important.
Summary of the invention
Jian is to provide a kind of copper-clad plate being applicable to high multilayer printed wiring board in the Shang Wen of stating Ti ﹐ an object of the present invention.This copper-clad plate has high second-order transition temperature (Tg≤190 DEG C), excellent thermotolerance and low thermal expansivity (CTE≤2.3%), medium specific inductivity/dielectric loss (Dk≤4.3, Df≤0.0135), the making of high multilayer printed wiring board (PCB) can be applicable to.
Two of object of the present invention is to provide the above-mentioned preparation method being applicable to the copper-clad plate of high multilayer printed wiring board.
For realizing object of the present invention, technical scheme of the present invention is:
Be applicable to a copper-clad plate for high multilayer printed wiring board, this copper-clad plate is by tackiness agent, and glasscloth and Copper Foil are prepared from, described tackiness agent is made up of solid substance and organic solvent, wherein, the weight percentage of solid substance is 50-90%, and organic solvent is surplus;
Described solid substance is made up of the component of following weight percentage:
In the preferred embodiment of the present invention, the weight percentage of solid substance is 55-75%.
In the preferred embodiment of the present invention, described novolac epoxy can be bisphenol A-type novolac epoxy, bisphenol-f type novolac epoxy or o-cresol formaldehyde epoxy resin, or above-mentioned resin can be used alone or can combine more than two kinds persons simultaneously jointly uses.
In the present invention, this kind of resin can select the KEB-3180 resin that the BNE200 resin of Changchun, Taiwan Chemical Manufacture or Korea S can be grand, but is not limited only to this.
In the preferred embodiment of the present invention, the brominated epoxy resin physical property of described isocyanic acid modification requires as shown in table 1:
Table 1
This isocyanate-modified epoxy resin is one or both the mixture in the epoxy resin of the epoxy resin of aromatic series diphenylmethanediisocyanate (MDI) modification, tolylene diisocyanate (TDI) modification, it gives basic machinery required for tackiness agent of the present invention and thermal characteristics, and has good toughness and excellent copper-stripping intensity.
In the preferred embodiment of the present invention, described isocyanate-modified epoxy resin preferably with the XU-19074 epoxy resin of DOW Chemical production or the SEB-350 resin of Korea S SHIN-A chemical industry, but is not limited only to this.
In the preferred embodiment of the present invention, described High Bromine epoxy Resin physical property requires as shown in table 2:
Table 2
In the preferred embodiment of the present invention, in described High Bromine epoxy Resin the present invention, this kind of resin can select the BEB400 resin of Changchun, Taiwan Chemical Manufacture.
In the preferred embodiment of the present invention, described phenolic resin curative is the resol of phenol and formaldehyde crosslinking, and described phenol is one or more the mixture in phenol, xylenol, ethylphenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl-phenol, tert.-butyl phenol or dihydroxyphenyl propane.As the phenol novolacs that preferred described resol is phenol and formaldehyde crosslinking, or the bisphenol A phenolic resin of dihydroxyphenyl propane and formaldehyde crosslinking, or the mixture of phenol novolacs and bisphenol A phenolic resin.In the preferred embodiment of the present invention, the toughner used is core shell rubbers (CSR) used for epoxy resin, play the effect increasing toughness of material in the material, the FORTEGRA that in described the present invention, this kind of toughner can preferably use Dow Chemical to produce
tM351 resins.But be not limited only to this.
In the preferred embodiment of the present invention, described phenolic resin curative can preferably use Korea S can the KPH-2003 resin of grand Chemical Manufacture, but is not limited only to this.
In an optimization example of the present invention, as described in styrene - maleic acid Yu copolymer has good thermal reliability and very low dielectric properties, the invention of this Yu styrene - maleic acid copolymer with Sartomer company SMA EF - 30 or EF - 40.
In the preferred embodiment of the present invention, the thermo-stabilizer used is a kind of epoxy resin of liquid state, play heat stabilization in the material, promote the unfailing performances such as the thermotolerance of material. the XQ82969 resin that in the present invention, this kind of resin can select Dow Chemical to produce, but be not limited only to this.
In the preferred embodiment of the present invention, described epoxy resin curing accelerator is imidazolium compounds, is preferably the mixture of 2-ethyl-4-methylimidazole or glyoxal ethyline or 2-ethyl-4-methylimidazole and glyoxal ethyline.
In the preferred embodiment of the present invention, suitable filler is added in described resin combination, to reduce the coefficient of expansion of the making copper-clad plate material of resin combination, also can play the effect of the specific inductivity reducing material, this filler can be the mixing of one or more in silicon-dioxide (comprising crystal type, fusion, hollow type and spherical silicon dioxide), aluminum oxide, mica, talcum powder, boron nitride etc.The preferred silicon of the present invention than 525 fused silica fillers of section, but is not limited only to this.
In the preferred embodiment of the present invention, described organic solvent be dimethyl formamide, acetone, methyl ethyl ketone, one or more mixture in methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether.
The above-mentioned preparation method being applicable to the copper-clad plate of high multilayer printed wiring board, comprises the following steps:
(1) tackiness agent is prepared:
1). According to the formula ratio in A stirred tank add some organic solvents and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, rotating speed of 500 ~ 1500 RPM, keep stirring and control tank temperature in the 20 to 45 ℃, solutions until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;After adding inorganic filler, adding stirring 20 to 50 minutes;
2). in steel basin, add (bromination ring oxygen tree fat ﹔ (C) toughness reinforcing dose of ﹔ (D) high brominated eopxy tree fat ﹔ (E) phenolic resin curing agent ﹔ (F) thermo-stabilizer of (A) phenol formaldehyde epoxy resin ﹔ (B) isocyanic acid modification successively by formula ratio.Keep in reinforced process stirring with 1000-1500 rev/min of rotating speed, after interpolation, open efficient shearing and emulsification 0.5-4 hour, carry out simultaneously cooling water circulation with retentive control cell body temperature at 20-45 DEG C;
3). take epoxy resin curing accelerator by formula ratio, joined in remaining organic solvent, after dissolving completely, this solution is added in steel basin, and continue to keep 1000-1500 rev/min to stir 3-15 hour, be i.e. obtained tackiness agent;
(2) prepreg is prepared:
1) tackiness agent prepared by step (1) is recycled to adhesive applicator, through preimpregnation, main leaching, tackiness agent is evenly coated on glasscloth,
2) glasscloth of application of adhesive toasts through 110 DEG C of-250 DEG C of drying bakers, makes solvent evaporates, and tackiness agent initial reaction solidifies, obtained prepreg; Wherein, gluing linear speed controls as 7-28m/min,
Prepreg physical parameter controls: gelation time 90-175 second, and the mass percent of tackiness agent in prepreg is 36%-75%, and adhesive flow degree is 15%-40%, volatile matter <0.75%;
(3) typesetting, compacting:
1) prepreg prepared by step (2) is cut into same size size, 1-18 opens one group, more superimposed with Copper Foil, then suppresses;
2) pressing parameter controls as follows:
A. pressure: 100-550psi;
B. temperature of heat plate: 80-200 DEG C;
C. vacuum tightness: 0.030-0.080Mpa;
D. the press time: 130-180 minute;
E. set time: >180 DEG C keeps 30-90 minute.
In a preferred embodiment of the invention, in step (2), glasscloth used can select E level, and specification can be selected from 101,104,106,1078,1080,1086,2113,2313,2116,1506 or 7628.
In a preferred embodiment of the invention, in step (3), Copper Foil used can select 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
The specification that the present invention prepares the copper-clad laminate of gained can be 36 × 48 inches, 36.5 × 48.5 inches, 37 × 49 inches, 40 × 48 inches, 40.5 × 48.5 inches, 41 × 49 inches, 42 × 48 inches, 42.5 × 48.5 inches or 43 × 49 inches, and its thickness is 0.05-3.2mm.
The copper-clad plate preparing gained due to the present invention has high glass-transition temperature (Tg >=190 DEG C), excellent thermotolerance and low thermal expansivity (CTE≤2.3%), medium specific inductivity/dielectric loss (Dk≤4.3, Df≤0.0135), the making of high multi-layer PCB printed circuit board can be applicable to.
Embodiment
The present invention is further illustrated below by comparative example and embodiment.
The characteristic being applicable to the copper-clad plate of high multilayer printed wiring board preparing gained is in the following Examples and Comparative Examples measured by following methods (with reference to IPC-TM-650).
(1) second-order transition temperature (Tg)
Second-order transition temperature refers to sheet material in the situation of being heated by the temperature (DEG C) of glassy transition corresponding to elastomeric state (rubbery state).
Detection method: adopt differential scanning calorimetry (DSC).
(2) the thermally stratified layer time (T-260)
The T-260 thermally stratified layer time refers to that sheet material is under the design temperature of 260 DEG C, because demixing phenomenon appears in the effect of heat, and duration before this.
Detection method: adopt thermo-mechanical analysis method (TMA).
(3) scolding tin thermotolerance
Scolding tin thermotolerance, refers to that sheet material immerses in the melting scolding tin of 288 DEG C, without occurring layering and bubbling duration.
Detection method: the substrate after etching is cut into 5.0cm × 5.0cm size, and edges of boards use 120 orders and 800 order sand paperings successively, pressure-cook certain hour, put into 288 DEG C of tin melting furnaces, observe with or without phenomenons such as layerings.
(4) stripping strength
According to the test of IPC-TM-650-2.4.8C method.
Describe the present invention in detail below in conjunction with specific embodiment, following examples unless expressly stated otherwise.
Mentioned phenolic epoxy resin for South Korea can be long chemical production of KEB - 3165 resin, isocyanate modification of brominated epoxy resin for dow chemical production of XU - 19074 epoxy resin, toughening agent for dow production FORTEGRA < sup TranNum = "133" > TM < / sup > 351 resin, epoxy resin high bromine is Taiwan changchun chemical production BEB400 resin, phenolic resin curing agent for South Korea to lung chemical production KPH - 2003 resin, styrene - maleic acid Yu copolymer SMA EF - 30 for Sartomer company, heat stabilizer for dow XQ82969 resin production.Glasscloth can select E level, and specification can be selected from 101,104,106,1078,1080,1086,2113,2313,2116,1506 or 7628.Copper Foil used can select 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
Embodiment 1
1. the mass percentage of the solid substance in tackiness agent is 66.5%, and all the other are organic solvent (such as methyl ethyl ketone), and wherein, the formula of solid substance saw the following form for 1 (by weight)
Table 1
< tables TranNum = "138" num = "0001" > < table TranNum = "139" > < tgroup TranNum = "140" cols = "2" > < colspec TranNum = "141" colname = "c001 colwidth" = "57%" / > < colspec TranNum = "142" colname = "c002 colwidth" = "43%" / > < tbody TranNum = "143" > < row TranNum = "144" > < entry TranNum = "145" morerows = "1" > raw materials < / entry > < entry TranNum = "146" morerows = "1" > solid weight (g) < entry > < / row > < row TranNum = "147" > < entry TranNum = "148" morerows = "1" > type phenolic epoxy resin< entry > < entry TranNum = "149" morerows = "1" > 22 < / entry > < / row > < row TranNum = "150" > < entry TranNum = "151" morerows = "1" > isocyanate modification of brominated epoxy resin < entry > < entry TranNum = "152" morerows = "1" > 7 < / entry > < / row > < row TranNum = "153" > < entry TranNum = "154" morerows = "1" > flexibilizer < entry > < entry TranNum = "155" morerows = "1" > 5 < / entry > < / row > < row TranNum = "156" > < entry TranNum = "157" morerows = "1" > high bromine epoxy resin < entry >< entry TranNum = "158" morerows = "1" > 8 < entry > < / row > < row TranNum = "159" > < entry TranNum = "160" morerows = "1" > tetrabromobisphenol A < entry > < entry TranNum = "161" morerows = "1" > 4.5 < / entry > < / row > < row TranNum = "162" > < entry TranNum = "163" morerows = "1" > phenolic resin curing agent < entry > < entry TranNum = "164" morerows = "1" > 16 < / entry > < / row > < row TranNum = "165" > < entry TranNum = "166" morerows = "1" > yu styrene - maleic acid copolymer < entry > < entry TranNum = "167" morerows = "1" > 3 < / entry > < / row > < row TranNum = "168" > < entry TranNum = "169" morerows = "1" > 2 - ethyl - 4 - methyl imidazole (2 e4mz) < entry > < entry TranNum = "170" morerows = "1" > 0.05 < / entry > < / row > < row TranNum = "171" > < entry TranNum = "172" morerows = "1" > heat stabilizer < entry > < entry TranNum = "173" morerows = "1" > 0.9 < / entry > < / row > < row TranNum = "174" > < entry TranNum = "175" morerows = "1" > silica < entry > < entry TranNum = "176" morerows = "1" > 31 < / entry > < / row > < / tbody > < / tgroup > < / table > < / name >
2. the preparation method of tackiness agent:
(1) according to the above weight within the mixing tank add organic solvent methyl ethyl ketone 49 g and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, speed 800 r/min, and continue to stir 120 minutes until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, toughner, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take 2-ethyl-4-methylimidazole by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The tackiness agent continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 2 below for the present embodiment:
Table 2
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 195 |
| Peel strength of copper foil (1oz), lb/in | 7.5 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.20 |
| Dk(5GHZ) | 4.21 |
| Df(5GHZ) | 0.0125 |
Embodiment 2
1. the mass percentage of the solid substance in tackiness agent is 65%, and all the other are organic solvent (such as methyl ethyl ketone),
Wherein, the formula of solid substance saw the following form for 3 (by weight)
Table 3
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 17 |
| The brominated epoxy resin of isocyanic acid modification | 10 |
| Flexibilizer | 4 |
| High Bromine epoxy Resin | 10 |
| Tetrabromobisphenol A | 4 |
| Phenolic resin curative | 18 |
| Styrene-Ma carrys out sour Yu copolymer | 3.5 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.04 |
| Heat stabilizer | 0.9 |
| Silica | 33 |
2. the preparation method of tackiness agent:
(1) according to the above weight in A stirred tank in organic solvent methyl ethyl ketone 66 grams and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, speed 800 r/min, and continue to stir 120 minutes until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, toughner, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take 2-ethyl-4-methylimidazole by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The tackiness agent continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 4 below for the present embodiment:
Table 4
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 193 |
| Peel strength of copper foil (1oz), lb/in | 7.1 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.22 |
| Dk(5GHZ) | 4.25 |
| Df(5GHZ) | 0.013 |
Embodiment 3
1. the mass percentage of the solid substance in tackiness agent is 62.3%, and all the other are organic solvent (such as methyl ethyl ketone), and wherein, the formula of solid substance saw the following form for 5 (by weight)
Table 5
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 25 |
| The brominated epoxy resin of isocyanic acid modification | 7 |
| Flexibilizer | 6 |
| High Bromine epoxy Resin | 12 |
| Tetrabromobisphenol A | 3 |
| Phenolic resin curative | 22 |
| Styrene-Ma carrys out sour Yu copolymer | 3 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.04 |
| Heat stabilizer | 0.9 |
| Silica | 35 |
2. the preparation method of tackiness agent:
(1) according to the above weight in A stirred tank in organic solvent methyl ethyl ketone 66 grams and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, speed 800 r/min, and continue to stir 120 minutes until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, toughner, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take 2-ethyl-4-methylimidazole by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The tackiness agent continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 6 below for the present embodiment:
Table 6
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 196 |
| Peel strength of copper foil (1oz), lb/in | 7.6 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.25 |
| Dk(5GHZ) | 4.28 |
| Df(5GHZ) | 0.0127 |
Embodiment 4
1. the mass percentage of the solid substance in tackiness agent is 69%, and all the other are organic solvent (such as methyl ethyl ketone), and wherein, the formula of solid substance saw the following form for 7 (by weight)
Table 7
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 29 |
| The brominated epoxy resin of isocyanic acid modification | 6 |
| Flexibilizer | 10 |
| High Bromine epoxy Resin | 10 |
| Tetrabromobisphenol A | 4 |
| Phenolic resin curative | 25 |
| Styrene-Ma carrys out sour Yu copolymer | 5 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.04 |
| Heat stabilizer | 0.9 |
| Silica | 27 |
2. the preparation method of tackiness agent:
(1) according to the above weight in A stirred tank in organic solvent methyl ethyl ketone 66 grams and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, speed 800 r/min, and continue to stir 120 minutes until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, toughner, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take 2-ethyl-4-methylimidazole by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The resin glue continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 8 below for the present embodiment:
Table 8
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 198 |
| Peel strength of copper foil (1oz), lb/in | 7.7 |
| T288(TMA),min | >60 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.19 |
| Dk(5GHZ) | 4.21 |
| Df(5GHZ) | 0.0127 |
Comparative example 1
1. the mass percentage of the solid substance in tackiness agent is 62.5%, and all the other are organic solvent (such as propylene glycol monomethyl ether),
Wherein, the formula of solid substance saw the following form for 9 (by weight)
Table 9
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 30 |
| The brominated epoxy resin of isocyanic acid modification | 12 |
| High Bromine epoxy Resin | 10 |
| Phenolic resin curative | 27 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.07 |
| Thermo-stabilizer | 1.3 |
| Aluminium hydroxide | 13 |
| Silicon-dioxide | 17 |
2. the preparation method of tackiness agent:
(1) in steel basin, organic solvent propylene glycol monomethyl ether 66 grams is added by above weight, turn on agitator, rotating speed 600 revs/min, and Keep agitation 30 minutes;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take 2-ethyl-4-methylimidazole by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The resin glue continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 10 below for the present embodiment:
Table 10
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 181 |
| Peel strength of copper foil (1oz), lb/in | 8.3 |
| T288(TMA),min | 45 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.51 |
| Dk(5GHZ) | 4.65 |
| Df(5GHZ) | 0.0157 |
Comparative example 2
1. the mass percentage of the solid substance in tackiness agent is 70%, and all the other are organic solvent (such as propylene glycol monomethyl ether),
Wherein, the formula of solid substance saw the following form for 11 (by weight)
Table 11
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 35 |
| The brominated epoxy resin of isocyanic acid modification | 10 |
| High Bromine epoxy Resin | 4 |
| Phenolic resin curative | 30 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.08 |
| Thermo-stabilizer | 1 |
| Aluminium hydroxide | 6 |
| Silicon-dioxide | 25 |
2. the preparation method of tackiness agent:
(1) in steel basin, organic solvent propylene glycol monomethyl ether 50 grams is added by above weight, turn on agitator, rotating speed 600 revs/min, and Keep agitation 30 minutes;
(2) in steel basin, add novolac epoxy, the brominated epoxy resin of isocyanic acid modification, High Bromine epoxy Resin, resol and thermo-stabilizer successively by formula ratio, keep in reinforced process stirring with 1000 revs/min of rotating speeds;
(3) take propylene glycol monomethyl ether by formula ratio, after it is dissolved completely with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether, this solution is added in steel basin, and continue maintenance 1200 revs/min stirring 2 hours, obtained tackiness agent.
3. prepare copper-clad laminate
The resin glue continuously coating obtained in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions, drying obtains prepreg, by superimposed for 8 prepregs, the high temperature extension Copper Foil of its upper and lower each placement 1 35um, through 190 DEG C, the heating under pressure of 350PSI, pressurization 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. to prepare the performance perameter of the copper-clad laminate of gained as shown in table 12 below for the present embodiment:
Table 12
| Project | Test result |
| Second-order transition temperature (DSC), DEG C | 185 |
| Peel strength of copper foil (1oz), lb/in | 8.2 |
| T288(TMA),min | 50 |
| Scolding tin thermotolerance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.58 |
| Dk(5GHZ) | 4.68 |
| Df(5GHZ) | 0.0153 |
The copper-clad plate that to sum up the present invention obtains has high second-order transition temperature (Tg≤190 DEG C), excellent thermotolerance and low thermal expansivity (CTE≤2.3%), medium specific inductivity/dielectric loss (Dk≤4.3, Df≤0.0135), the making of multilayer and high multi-layer PCB printed circuit board can be applicable to.
Claims (23)
1. be applicable to a copper-clad plate for high multilayer printed wiring board, this copper-clad plate is by tackiness agent, and glasscloth and Copper Foil are prepared from, described tackiness agent is made up of solid substance and organic solvent, wherein, the weight percentage of solid substance is 50-90%, and organic solvent is surplus;
Described solid substance is made up of the component of following weight percentage:
2. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, the weight percentage of described solid substance is 55-75%.
3. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described novolac epoxy is a kind of or two or more arbitrarily mixing in bisphenol A-type novolac epoxy, bisphenol-f type novolac epoxy or o-cresol formaldehyde epoxy resin.
4. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described novolac epoxy is the KEB-3180 resin that the BNE200 resin of Changchun, Taiwan Chemical Manufacture or Korea S can be grand.
5. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, the brominated epoxy resin physical property of described isocyanic acid modification requires as epoxy equivalent (weight) 300-380EEW, hydrolyzable chlorine 300MAX, bromine content 16-23wt%.
6. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described isocyanate-modified epoxy resin is one or both the mixture in the epoxy resin of the epoxy resin of aromatic series diphenylmethanediisocyanate (MDI) modification, tolylene diisocyanate (TDI) modification.
7. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described isocyanate-modified epoxy resin is preferably with the XU-19074 epoxy resin of DOW Chemical production or the SEB-350 resin of Korea S SHIN-A chemical industry.
8. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described High Bromine epoxy Resin physical property requires as epoxy equivalent (weight) 380-420EEW, hydrolyzable chlorine 300MAX, bromine content 46-50wt%.
9. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described High Bromine epoxy Resin selects the BEB400 resin of Changchun, Taiwan Chemical Manufacture.
10. a kind of copper-clad plate being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described phenolic resin curative is the resol of phenol and formaldehyde crosslinking, and described phenol is one or more the mixture in phenol, xylenol, ethylphenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl-phenol, tert.-butyl phenol or dihydroxyphenyl propane.
11. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described resol is the phenol novolacs of phenol and formaldehyde crosslinking, or the bisphenol A phenolic resin of dihydroxyphenyl propane and formaldehyde crosslinking, or the mixture of phenol novolacs and bisphenol A phenolic resin.
12. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, the FORTEGRA that described toughner uses Dow Chemical to produce
tM351 resins.
13. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described phenolic resin curative uses Korea S can the KPH-2003 resin of grand Chemical Manufacture.
14. As a kind of claim 1 is suitable for high multilayer printed circuit board copper clad, its characteristics is described Yu styrene - maleic acid copolymer with Sartomer company SMA EF - 30 or EF - 40.
15. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described thermo-stabilizer is the XQ82969 resin that Dow Chemical is produced.
16. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described epoxy resin curing accelerator is the mixture of 2-ethyl-4-methylimidazole or glyoxal ethyline or 2-ethyl-4-methylimidazole and glyoxal ethyline.
17. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described filler is the mixing of one or more in silicon-dioxide, aluminum oxide, mica, talcum powder, boron nitride etc.
18. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, is characterized in that, described filler is the 525 fused silica fillers of silicon than section.
19. a kind of copper-clad plates being applicable to high multilayer printed wiring board as claimed in claim 1, it is characterized in that, described organic solvent be dimethyl formamide, acetone, methyl ethyl ketone, one or more mixture in methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether.
20. any one of claim 1 to 19 claims are applicable to the preparation method of the copper-clad plate of high multilayer printed wiring board, it is characterized in that, comprise the following steps:
(1) tackiness agent is prepared:
1). According to the formula ratio in A stirred tank add some organic solvents and tetrabromobisphenol A Yu, styrene - maleic acid copolymer, open the blender, speed of 500-500 r/min, keep stirring and control tank temperature in the 20 to 45 ℃, solutions until tetrabromobisphenol A Yu and styrene - maleic acid copolymer dissolved completely;After adding inorganic filler, adding stirring 20 to 50 minutes;
2). in steel basin, add (bromination ring oxygen tree fat ﹔ (C) toughness reinforcing dose of ﹔ (D) high brominated eopxy tree fat ﹔ (E) phenolic resin curing agent ﹔ (F) thermo-stabilizer of (A) phenol formaldehyde epoxy resin ﹔ (B) isocyanic acid modification successively by formula ratio.Keep in reinforced process stirring with 1000-1500 rev/min of rotating speed, after interpolation, open efficient shearing and emulsification 0.5-4 hour, carry out simultaneously cooling water circulation with retentive control cell body temperature at 20-45 DEG C;
3). take epoxy resin curing accelerator by formula ratio, joined in remaining organic solvent, after dissolving completely, this solution is added in steel basin, and continue to keep 1000-1500 rev/min to stir 3-15 hour, be i.e. obtained tackiness agent;
(2) prepreg is prepared:
1) tackiness agent prepared by step (1) is recycled to adhesive applicator, through preimpregnation, main leaching, tackiness agent is evenly coated on glasscloth,
2) glasscloth of application of adhesive toasts through 110 DEG C of-250 DEG C of drying bakers, makes solvent evaporates, and tackiness agent initial reaction solidifies, obtained prepreg; Wherein, gluing linear speed controls as 7-28m/min,
Prepreg physical parameter controls: gelation time 90-175 second, and the mass percent of tackiness agent in prepreg is 36%-75%, and adhesive flow degree is 15%-40%, volatile matter <0.75%;
(3) typesetting, compacting:
1) prepreg prepared by step (2) is cut into same size size, 1-18 opens one group, more superimposed with Copper Foil, then suppresses;
2) pressing parameter controls as follows:
A. pressure: 100-550psi;
B. temperature of heat plate: 80-200 DEG C;
C. vacuum tightness: 0.030-0.080Mpa;
D. the press time: 130-180 minute;
E. set time: >180 DEG C keeps 30-90 minute.
The preparation method of the copper-clad plate of high multilayer printed wiring board is applicable to described in 21. claims 20, it is characterized in that, in step (2), E level selected by glasscloth used, and specification is selected from 101,104,106,1078,1080,1086,2113,2313,2116,1506 or 7628.
Be applicable to the preparation method of the copper-clad plate of high multilayer printed wiring board described in 22. claims 20, it is characterized in that, in step (3), Copper Foil used can select 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
The preparation method of the copper-clad plate of high multilayer printed wiring board is applicable to described in 23. claims 20, it is characterized in that, the specification of the copper-clad plate of gained can be 36 × 48 inches, 36.5 × 48.5 inches, 37 × 49 inches, 40 × 48 inches, 40.5 × 48.5 inches, 41 × 49 inches, 42 × 48 inches, 42.5 × 48.5 inches or 43 × 49 inches, and its thickness is 0.05-3.2mm.
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| CN108299789A (en) * | 2017-01-11 | 2018-07-20 | 江门建滔积层板有限公司 | A kind of preparation method of high heat resistance copper-clad laminate glue |
| CN107266858A (en) * | 2017-06-13 | 2017-10-20 | 南亚新材料科技股份有限公司 | A kind of middle Tg compositions of thermosetting resin and preparation method thereof |
| CN107298831A (en) * | 2017-07-20 | 2017-10-27 | 南亚新材料科技股份有限公司 | Improve proof tracking index and Drilling operation performance prepreg and its application |
| CN109535651A (en) * | 2018-11-01 | 2019-03-29 | 吉安市宏瑞兴科技有限公司 | A kind of resin combination and preparation method thereof |
| CN109719967A (en) * | 2018-12-29 | 2019-05-07 | 江苏联鑫电子工业有限公司 | High Tg lead-free copper-clad plate of high tenacity and preparation method thereof |
| CN109719967B (en) * | 2018-12-29 | 2021-05-04 | 江苏联鑫电子工业有限公司 | High-toughness high-Tg lead-free copper-clad plate and preparation method thereof |
| CN112063111A (en) * | 2020-09-15 | 2020-12-11 | 广德龙泰电子科技有限公司 | Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof |
| CN114889265A (en) * | 2022-04-12 | 2022-08-12 | 江西省宏瑞兴科技股份有限公司 | High-reliability copper-clad plate suitable for high-speed field and preparation method thereof |
| CN115339195A (en) * | 2022-07-26 | 2022-11-15 | 江西省宏瑞兴科技股份有限公司 | Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof |
| CN115339195B (en) * | 2022-07-26 | 2024-02-13 | 江西省宏瑞兴科技股份有限公司 | Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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Application publication date: 20150429 |