CN104559054A - Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate - Google Patents
Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate Download PDFInfo
- Publication number
- CN104559054A CN104559054A CN201310514542.6A CN201310514542A CN104559054A CN 104559054 A CN104559054 A CN 104559054A CN 201310514542 A CN201310514542 A CN 201310514542A CN 104559054 A CN104559054 A CN 104559054A
- Authority
- CN
- China
- Prior art keywords
- resin
- cyanate ester
- preparation
- prepreg
- parts
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a resin composition and preparation methods of a prepreg, a composite substrate and a PCB (printed circuit board) substrate. The resin composition comprises the following components in parts by weight: 20-30 parts of multifunctional epoxy resin, 50-78 parts of a modified acid anhydride, 10-22 parts of cyanate resin, 11-72 parts of a filler and 0.01-0.05 part of an accelerant. The preparation method of the prepreg comprises the following steps: mixing the resin composition with an organic solvent to obtain a resin solution, wherein the solid content by mass fraction in the resin solution is 50-65%; and immersing glass fiber cloth into the resin solution to obtain a preimpregnated material and then drying the preimpregnated material for manufacturing. The composite substrate is formed by stacking the prepregs according to a perdetermined number and pressing. The PCB substrate is formed by stacking the prepregs according to the perdetermined number, applying metal foils on double sides or single sides of the prepregs and pressing. The resin composition disclosed by the invention has the advantages of high heat resistance, low dielectric loss and significant cost advantage.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to the preparation method of a kind of resin combination and prepreg, composite base material and PCB substrate.
Background technology
Cyanate ester resin because of have excellent high temperature resistance, dielectric properties by vast be engaged in novel material development person favor.Be that matrix has been widely used in composite base material and high-frequency circuit board with cyanate ester resin; cyanate is complicated because producing synthesis technique; condition harshness causes its cost of manufacture high; commercially available bisphenol A cyanate ester resin more than 600.0RMB/ kilogram; this price is produced dealer to the composite base material of mass-producing volume production or circuit substrate and is caused heavy cost pressure; and because large ratio employs cyanate ester resin in resin combination, composite base material also can be caused really up to the mark or excessively crisp.For this reason, the exploitation composite base material that not only met thermotolerance, rigidity, dielectricity but also had a cost advantage is become by market.
Summary of the invention
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, propose the preparation method of a kind of resin combination and prepreg, composite base material and PCB substrate, this resin combination has high heat-resisting, low-dielectric loss and the advantage of remarkable cost advantage.
Technical problem of the present invention is solved by following technical scheme:
A kind of resin combination, is made up of the component of following weight part: polyfunctional epoxy resin 20-30 part, modified anhydride 50-78 part, cyanate ester resin 10-22 part, filler 11-72 part and promotor 0.01-0.05 part.
A kind of preparation method of prepreg, described resin combination and organic solvent are mixed to get resin solution, the massfraction of the solid content of described resin solution is 50 ~ 65%, glass-fiber-fabric is immersed in described resin solution and obtains prepreg, then dry described prepreg and make described prepreg.
A preparation method for composite base material, by described prepreg by the folded material of predetermined number, is pressed into described composite base material.
A preparation method for PCB substrate, by described prepreg by the folded material of predetermined number, two-sided or one side mixes tinsel, is pressed into described PCB substrate.
The beneficial effect that the present invention is compared with the prior art is: the present invention adopts the polyfunctional epoxy resin of excellent heat resistance to be matrix, curing cross-linked density is high, ensure that product has high thermotolerance, with modified anhydride and a small amount of (with modified anhydride than) cyanate ester resin jointly coordinate and make solidifying agent, both ensure that product had excellent dielectric properties, the thermotolerance of product can be improved again, if be used alone wherein a kind of solidifying agent, thermotolerance can be caused to be deteriorated, the slickness (levelling property) of product is bad, mix in resin combination filler and other component proportions collaborative after that product is had is high heat-resisting, low-dielectric loss and the advantage of remarkable cost advantage.
Embodiment
Below in conjunction with preferred embodiment the invention will be further described.
The invention provides a kind of resin combination, in one embodiment, resin combination is made up of the component of following weight part: polyfunctional epoxy resin 20-30 part, modified anhydride 50-78 part, cyanate ester resin 10-22 part, filler 11-72 part and promotor 0.01-0.05 part.
In some preferred embodiments, at least one in following scheme can also be adopted:
Described polyfunctional epoxy resin is 25-28 part; Described modified anhydride is 60-75 part; Described cyanate ester resin is 15-20 part; Described filler is 50-65 part; Described epoxy resin is one or more the mixture in dicyclopentadiene phenolic polyfunctional epoxy resin, naphthalene nucleus type tetrafunctional epoxy resin and biphenyl type epoxy resin, dicyclopentadiene phenolic polyfunctional epoxy resin can make resin combination have good specific inductivity, naphthalene nucleus type tetrafunctional epoxy resin can make resin combination have excellent thermotolerance, and biphenyl type epoxy resin can make composition have desirable tangent of the dielectric loss angle value; Described modified anhydride is phenylethene modified maleic anhydride (i.e. styrene-maleic anhydride copolymer); Described cyanate ester resin is a kind of in bisphenol A cyanate ester prepolymer and multifunctional cyanate ester resin or their combination; Described multifunctional cyanate ester resin is one or more the combination in line style multifunctional cyanate ester resin, ortho-cresol type multifunctional cyanate ester resin (i.e. poly-ortho-cresol cyanate ester resin) and dicyclopentadiene phenolic cyanate ester resin, when using two or more cyanate ester resin mixing to mix with modified anhydride again, resin combination has better wetting property and levelling property, and obtained prepreg surface is more smooth, smooth; Described promotor is imidazoles promotor; Described imidazoles promotor is a kind of in glyoxal ethyline, 2-ethyl-4-methylimidazole and 2-phenylimidazole or their combination; Described filler is one or more the mixing in silica powder, silicon powder, polyhedral oligomeric silsesquioxane and cenosphere; Described filler is silica powder, and its particle diameter is 1 ~ 15 micron, purity (massfraction) >=98%.
Multifunctional described in the present invention refers to that functionality is at least 3.
Resin combination of the present invention can be applied in adhesive sheet (or being called prepreg), composite base material, PCB substrate.
During preparation adhesive sheet, specific practice is as follows:
Polyfunctional epoxy resin, modified anhydride, cyanate ester resin, filler and promotor are mixed according to the above ratio, join in organic solvent and be made into above-mentioned resin solution, the consumption of organic solvent is determined according to the solid content of resin combination in resin solution, the massfraction of the solid content of resin solution is 50 ~ 65%, glass-fiber-fabric is immersed in above-mentioned resin solution and obtains prepreg, then dry the adhesive sheet that prepreg makes semi-cured state.The adhesive sheet of preparation has good resistance to thermal reliability and significant cost advantage, has desirable bonding and dielectric properties simultaneously, and the paving being applicable to composite base material is covered and shaping, is especially applicable to high-frequency circuit board and uses.
Preferably, the condition of drying prepreg is: dry 2 minutes at 80 DEG C in an oven, dries 3 minutes at 130 DEG C, then dries 5 minutes at 175 DEG C.
Preferably, organic solvent can be butanone or acetone or both mixing; When the mixing that solvent is butanone and acetone, the volume ratio of butanone and acetone is 1:2 ~ 2:3, uses the mixed solvent of such ratio can increase the slickness of product.
When preparing composite base material, specific practice is as follows: by above-mentioned obtained adhesive sheet by the folded material of the number of setting, be pressed into composite base material.Preferably, be compressed on that temperature is 210 ± 5 DEG C, pressure is 30 ± 5kgf/cm
2under carry out.
During preparation PCB substrate, specific practice is as follows: by the adhesive sheet of above-mentioned system by the folded material of the number of setting, two-sided or one side mixes tinsel, is pressed into PCB substrate.Preferably, be compressed on that temperature is 210 ± 5 DEG C, pressure is 30 ± 5kgf/cm
2under carry out; Metal in tinsel can be copper, silver, gold, nickel etc., and preferably use Copper Foil, then the PCB substrate prepared is called copper-clad plate.
Below by way of preferred specific embodiment, the present invention is further elaborated.
Embodiment one
Take the dicyclopentadiene phenolic polyfunctional epoxy resin of 26 weight parts, the phenylethene modified maleic anhydride of 50 weight parts, 10 weight parts bisphenol A cyanate ester resin, the silica powder of purity >=98% of 11 weight parts, the glyoxal ethyline (2-MI) of 0.01 weight part, join in the butanone of 65 weight parts and be made into the resin solution that solid content is 60%, namely in resin solution, the mass ratio of each component is: dicyclopentadiene phenolic polyfunctional epoxy resin: phenylethene modified maleic anhydride: bisphenol A cyanate ester resin: silica powder: glyoxal ethyline: butanone=26:50:10:11:0.01:65.With 8 (250mm*250mm) 7628 quartz fabric immerse in above-mentioned resin solution, carry out impregnation.Cured in an oven by 80 DEG C/2 minutes+130 DEG C/3 minutes+175 DEG C/5 minutes, make the adhesive sheet of semi-cured state, the gel time (G-T) of adhesive sheet is 105 ± 15 seconds (171 DEG C), and degree of mobilization is 25 ± 5%.By above-mentioned 8 adhesive sheets superposition alignment, respectively join the Copper Foil of 1 35 μm up and down, in vacuum press, by temperature 210 DEG C, pressure 30kgf/cm
2condition, suppress 180 minutes, make the double face copper that thickness is 1.6mm.
Embodiment two
Take the biphenyl type epoxy resin of 26 weight parts, 78 weight parts phenylethene modified maleic anhydride, the ortho-cresol type multifunctional cyanate ester resin of 22 weight parts, the silica powder of purity >=98% of 72 weight parts, the 2-ethyl-4-methylimidazole of 0.03 weight part, join in the acetone of 132 weight parts and be made into the resin solution that solid content is 60%, namely in resin solution, the mass ratio of each component is: biphenyl type epoxy resin: phenylethene modified maleic anhydride: ortho-cresol type multifunctional cyanate ester resin: silica powder: 2-ethyl-4-methylimidazole: acetone=26:78:22:72:0.03:132.With 8 (250mm*250mm) 7628 quartz fabric immerse in above-mentioned resin solution, carry out impregnation, cured in an oven by 80 DEG C/2 minutes+130 DEG C/3 minutes+175 DEG C/5 minutes, make the adhesive sheet of semi-cured state, the gel time (G-T) of adhesive sheet is 105 ± 15 seconds (171 DEG C), and degree of mobilization is 25 ± 5%.By above-mentioned 8 adhesive sheets superposition alignment, respectively join the Copper Foil of 1 35 μm up and down, in vacuum press, by temperature 210 DEG C, the condition of pressure 30kgf/cm2, suppresses 180 minutes, makes the double face copper that thickness is 1.6mm.
In other embodiments, the weight part of polyfunctional epoxy resin can also be 20 parts, 22 parts, 25 parts, 28 parts, 30 parts etc.; Modified anhydride can also be 52 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts etc.; The weight part of cyanate ester resin can also be 12 parts, 15 parts, 18 parts, 20 parts etc.; The weight part of filler can also be 15 parts, 20 parts, 30 parts, 40 parts, 50 parts, 55 parts, 60 parts, 65 parts etc.; The weight part of promotor can also be 0.02 part, 0.04 part, 0.05 part etc.
Comparative example
Take 400 grams of bisphenol A cyanate ester prepolymers separately as solidifying agent, 200 grams of bisphenol A-type novolac epoxys and 0.06 gram of glyoxal ethyline, with acetone/butanone mixed solvent, be made into the resin solution that solid content is 60%.With 8 (250mm*250mm) 7628 quartz fabric immerse in above-mentioned resin solution, carry out impregnation.Make the adhesive sheet of semi-cured state.The gel time (G-T) of adhesive sheet is 105 seconds (171 DEG C), and degree of mobilization is 22%.Other conditions are identical with embodiment one, make the double face copper that thickness is 1.6mm.
Comparative example and embodiment are compared, result is as shown in the table:
As can be seen here, resin combination in embodiment adopts the polyfunctional epoxy resin being different from the excellent heat resistance of bisphenol A-type novolac epoxy, curing cross-linked density is high, ensure that product has high thermotolerance, solidifying agent adopts symmetrical configuration, the phenylethene modified maleic anhydride that polarity is low and a small amount of cyanate ensure that product has excellent dielectric properties, because high-purity quartz powder has the heat-resisting of excellence, low-dielectric loss and low cost (silica powder city price 28.0RMB/ kilogram), the adding of silica powder product is had heat-resisting, the net effect of low-dielectric loss and low cost.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some equivalent to substitute or obvious modification can also be made, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (17)
1. a resin combination, is characterized in that, is made up of the component of following weight part: polyfunctional epoxy resin 20-30 part, modified anhydride 50-78 part, cyanate ester resin 10-22 part, filler 11-72 part and promotor 0.01-0.05 part.
2. the resin combination according to claims 1, is characterized in that: described polyfunctional epoxy resin is 25-28 part, and/or described modified anhydride is 60-75 part, and/or described cyanate ester resin is 15-20 part, and/or described filler is 50-65 part.
3. resin combination according to claim 1 and 2, is characterized in that: described epoxy resin is one or more the mixture in dicyclopentadiene phenolic polyfunctional epoxy resin, naphthalene nucleus type tetrafunctional epoxy resin and biphenyl type epoxy resin.
4. resin combination according to claim 1 and 2, is characterized in that: described modified anhydride is phenylethene modified maleic anhydride.
5. resin combination according to claim 1 and 2, is characterized in that: described cyanate ester resin is a kind of in bisphenol A cyanate ester prepolymer and multifunctional cyanate ester resin or their combination.
6. resin combination according to claim 5, is characterized in that: described multifunctional cyanate ester resin is one or more the combination in line style multifunctional cyanate ester resin, ortho-cresol type multifunctional cyanate ester resin and dicyclopentadiene phenolic cyanate ester resin.
7. resin combination according to claim 1 and 2, is characterized in that: described promotor is imidazoles promotor.
8. resin combination according to claim 7, is characterized in that: described imidazoles promotor is one or more the combination in glyoxal ethyline, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
9. resin combination according to claim 1 and 2, is characterized in that: described filler is one or more the mixing in silica powder, silicon powder, polyhedral oligomeric silsesquioxane and cenosphere.
10. resin combination according to claim 9, is characterized in that: described filler is silica powder, and particle diameter is 1 ~ 15 micron, purity >=98%.
The preparation method of 11. 1 kinds of prepregs, it is characterized in that: the resin combination described in claim 1-10 any one and organic solvent are mixed to get resin solution, the massfraction of the solid content of described resin solution is 50 ~ 65%, glass-fiber-fabric is immersed in described resin solution and obtains prepreg, then dry described prepreg and make described prepreg.
The preparation method of 12. prepregs as claimed in claim 11, is characterized in that: described organic solvent is butanone or acetone or both mixing.
The preparation method of 13. prepregs as claimed in claim 12, is characterized in that: described solvent is the mixing of butanone and acetone, the volume ratio of described butanone and acetone is 1:2 ~ 2:3.
The preparation method of 14. 1 kinds of composite base materials, is characterized in that: the prepreg preparation method described in claim 11-13 any one prepared, by the folded material of predetermined number, is pressed into described composite base material.
The preparation method of 15. composite base materials as claimed in claim 14, is characterized in that: described in be compressed on that temperature is 210 ± 5 DEG C, pressure is 30 ± 5kgf/cm
2under carry out.
The preparation method of 16. 1 kinds of PCB substrate, is characterized in that: the prepreg preparation method described in claim 11-13 any one prepared is by the folded material of predetermined number, and two-sided or one side mixes tinsel, is pressed into described PCB substrate.
The preparation method of 17. PCB substrate as claimed in claim 16, is characterized in that: described in be compressed on that temperature is 210 ± 5 DEG C, pressure is 30 ± 5kgf/cm
2under carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310514542.6A CN104559054A (en) | 2013-10-25 | 2013-10-25 | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310514542.6A CN104559054A (en) | 2013-10-25 | 2013-10-25 | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104559054A true CN104559054A (en) | 2015-04-29 |
Family
ID=53076174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310514542.6A Pending CN104559054A (en) | 2013-10-25 | 2013-10-25 | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104559054A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199103A (en) * | 2015-11-06 | 2015-12-30 | 苏州太湖电工新材料股份有限公司 | Siliceous modified high-temperature-resistant cyanate resin, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702677A (en) * | 2012-02-29 | 2012-10-03 | 深圳光启创新技术有限公司 | Composition with low dielectric constant and low loss |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
-
2013
- 2013-10-25 CN CN201310514542.6A patent/CN104559054A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702677A (en) * | 2012-02-29 | 2012-10-03 | 深圳光启创新技术有限公司 | Composition with low dielectric constant and low loss |
| CN103265810A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Resin composition for high-frequency high-speed substrate as well as prepreg and laminated board made of resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199103A (en) * | 2015-11-06 | 2015-12-30 | 苏州太湖电工新材料股份有限公司 | Siliceous modified high-temperature-resistant cyanate resin, and preparation method and application thereof |
| CN105199103B (en) * | 2015-11-06 | 2017-08-22 | 苏州太湖电工新材料股份有限公司 | A kind of siliceous modified, high temperature resistant cyanate ester resin, its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107964203B (en) | Low-dielectric prepreg composition, copper-clad plate and manufacturing method thereof | |
| CN101538397B (en) | Epoxy resin composition, glue film made of same and preparation method | |
| EP3162561A1 (en) | Thermoset resin sandwiched pre-preg body, manufacturing method and copper clad plate | |
| CN103129042B (en) | A kind of carbon fiber base fabric composite material and Synthesis and applications thereof | |
| CN102558858A (en) | Resin compound for copper-coated laminated boards and prepreg | |
| CN1966572A (en) | Resin composition and its uses in adhesive sheet and copper-cladded plate | |
| TW201217446A (en) | Polymer resin composition, insulating film manufactured using the polymer resin composition, and method of manufacturing the insulating film | |
| CN109112364B (en) | Silicon carbide reinforced aluminum-based composite material for electronic packaging and preparation method thereof | |
| CN101885900A (en) | Resin composition, bonding sheet and copper-clad plate made using same, manufacturing method thereof | |
| CN101767481A (en) | Method for preparing highly heat-conductive copper-clad plate | |
| CN115139589A (en) | High-thermal-conductivity copper-clad plate and preparation method thereof | |
| CN104589667A (en) | Preparation method and application of bonding sheet for copper clad laminate | |
| CN112175354A (en) | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof | |
| CN106751711B (en) | Fluorine-substituted vinyl polymer resin composition, prepreg and laminate | |
| CN104559054A (en) | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate | |
| CN112063111A (en) | Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof | |
| CN112250997A (en) | Heat-resistant epoxy resin composition, lead-free middle-Tg copper-clad plate and preparation method thereof | |
| CN103129090B (en) | The preparation method of a kind of glass-film base copper-clad plate and prepared copper-clad plate thereof | |
| CN104559177A (en) | Resin composition and preparation methods of prepreg, composite substrate and PCB (printed circuit board) substrate | |
| CN102529222B (en) | High-insulation metal-based copper-clad plate with low thermal resistance and preparation method thereof | |
| JPH0197633A (en) | Manufacture of laminated plate for printed circuit | |
| CN103192577A (en) | High-thermal-conductivity copper-clad plate manufacturing method | |
| JP2894496B2 (en) | Manufacturing method of printed circuit board | |
| CN112250999A (en) | Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof | |
| CN102888088B (en) | Composite material and method for preparing base material from the composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |