CN102311614A - Resin composition and prepreg prepared by using same - Google Patents
Resin composition and prepreg prepared by using same Download PDFInfo
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- CN102311614A CN102311614A CN 201110085557 CN201110085557A CN102311614A CN 102311614 A CN102311614 A CN 102311614A CN 201110085557 CN201110085557 CN 201110085557 CN 201110085557 A CN201110085557 A CN 201110085557A CN 102311614 A CN102311614 A CN 102311614A
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- epoxy resin
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- 0 CC(C)(c(cc1*)cc(*)c1OCC(CC(*)(*)C1OC1)O)c(cc1*)cc(*)c1OC(*)(*)C1OC1 Chemical compound CC(C)(c(cc1*)cc(*)c1OCC(CC(*)(*)C1OC1)O)c(cc1*)cc(*)c1OC(*)(*)C1OC1 0.000 description 3
- YTIOTECNALVSFJ-UHFFFAOYSA-N CCC(C)(C)Cc(cc1)ccc1-c1ccc(CC)cc1 Chemical compound CCC(C)(C)Cc(cc1)ccc1-c1ccc(CC)cc1 YTIOTECNALVSFJ-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N O=Cc1ccccc1 Chemical compound O=Cc1ccccc1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
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- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
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Abstract
The invention relates to a resin composition and a prepreg prepared by using the same. The resin composition comprises the following components in parts by weight: 100 parts of base resin, 20-60 parts of phenoxy resin, 10-50 parts of biphenyl epoxy resin and 5-25 parts of core-shell rubber. The prepreg prepared by using the resin composition comprises a reinforcing material and the resin composition which is adhered onto the reinforcing material by impregnation and drying. In the invention, common epoxy resin is modified by virtue of the phenoxy resin, the core-shell rubber and the biphenyl epoxy resin, so that no-flow resin composition and the prepreg thereof are developed; the prepared prepreg has higher flexibility and bonding strength as well as no flow and can be stored for a long time, thereby solving the problem that bonding performance between the no-flow prepreg and a PI (poly imide) material is relatively low so that the reliability of a rigid-flexible combined printed circuit board prepared by using the no-flow prepreg is reduced; and glass transition temperature of the no-flow prepreg after being cured can reach up to more than 165 DEG C, thus the heat resistance, reliability and the like as well as quality percent of pass of the prepared rigid-flexible combined printed circuit board are improved.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of resin combination and use the prepreg of its making.
Background technology
Along with electronics microminiaturization, multifunction, require PCB densification, high performance, install for the 3 D stereo of realizing electronic product simultaneously, consider more and more to use rigid-flexible combination technology, thereby rigid-flexible combination PCB development is more and more faster.
Gummosis prepreg (No flow prepreg) not; With respect to common FR-4 bonding sheet (prepreg); Its B b stage resin b is not gummosis or seldom gummosis under HTHP; While bonding forces etc. are functional, are applicable to that conduct connects material between rigidity pcb board and the flexible PCB plate, therefore are widely used in rigid-flexible combination (rigid-flexible) printed circuit board (PCB) and make.Up to now great majority not the gummosis prepregs be that the resin combination of main ingredient constitutes all with modified epoxies such as rubber.Yet existing not gummosis prepreg subject matter: poor with PI (polyimide) face bonding force; Generally all require to carry out plasma treatment to improve bonding force to the PI face before the PCB processing; Even also limited to bonding increase rate like this, be difficult to satisfy more power PC B request for utilization.
Summary of the invention
The object of the present invention is to provide a kind of resin combination, adopt phenoxy resin, biphenyl epoxy resin and core shell rubbers that epoxy-resin systems is carried out toughening modifying, reduce Resin Flow, be beneficial to and make not gummosis prepreg.
Another object of the present invention is to provide a kind of prepreg that uses above-mentioned resin combination to make; Have higher snappiness and bonding strength; High glass-transition temperature is applicable to that multilayered rigidity and flexibility combination PCB and hierarchic structure PCB are bonding, and has higher reliability.
Be to realize above-mentioned purpose, the present invention provides a kind of resin combination, and it comprises that component and weight part thereof are following: 100 parts of matrix resins, phenoxy resin 20-60 part, biphenyl epoxy resin 10-50 part, core shell rubbers 5-25 part.
Said matrix resin is an epoxy resin; It comprises multifunctional phenol-2-glycidyl ether compound, polyfunctional alcohol-2-glycidyl ether compound, cresol-novolak epoxy resin, has the halogenide or the phosphide of the above-mentioned epoxy resin of high flame retardant, and epoxy resin is for wherein one or more mix use separately.
The structural formula of said phenoxy resin is as follows:
N=50-150 wherein, radicals R
1, R
2, R
3, R
4Represent H atom, Br atom or contain the group of P element, R
1, R
2, R
3, R
4Between identical or different atom or the group of representative.
The structural formula of said biphenyl epoxy resin is as follows:
The material of said core shell rubbers center part is selected from a kind of in silicone resin, vinyl resin, divinyl rubber and the synthetic polyisoprene, the material of shell part be selected from contain can with the resin of the functional group of epoxy resin reaction.
Also comprise solidifying agent and curing catalyst, said solidifying agent is amine or resol, or both are shared, and solidifying agent and epoxy resin equivalence ratio are 0.95-1.05; Curing catalyst is imidazoles and verivate thereof, and consumption is the 0.15-1.5% of weight epoxy part.
Further, the present invention provides a kind of prepreg that uses above-mentioned resin combination to make, and it comprises strongthener, reaches through the dry postadhesion of impregnation resin combination above that.
Said strongthener adopts natural fiber, organic synthetic fibers, organic fabric or inorganic fibre.
During making; Through solvent each component of said resin combination is dissolved into glue together, strongthener is fully soaked in the glue, will evenly contain the strongthener that is soaked with glue then and in 150-170 ℃ of baking oven, toast; Make the resin combination semicure, promptly make prepreg.
Beneficial effect of the present invention: the present invention is through the modification to ordinary epoxy resin of phenoxy resin, core shell rubbers and biphenyl epoxy resin; Develop not gummosis resin combination and prepreg thereof; Prepared prepreg has higher snappiness and bonding strength; Gummosis not, but prolonged preservation have simultaneously solved current this series products and the PI material adhesive power hard and soft weakness that combines the printed substrate reliability decrease that causes with its making on the low side; And solidifying the back second-order transition temperature can be up to more than 165 ℃, thereby has improved the thermotolerance of making hard and soft combination (rigid-flexible) printed circuit board (PCB), safety etc. and up-to-standard rate.
Embodiment
Resin combination of the present invention, it comprises that component has: matrix resin (epoxy resin), phenoxy resin, biphenyl epoxy resin, core shell rubbers, solidifying agent, curing catalyst etc.Wherein, calculating with weight part, is in the matrix resin at 100 parts of epoxy resin, and adding phenoxy resin is 20-60 part, preferred 30-50 part; Biphenyl epoxy resin is 10-50 part; Core shell rubbers is 5-25 part.
Said epoxy resin is as matrix resin; Adopt common epoxy resin; Can be multifunctional phenol-2-glycidyl ether compound, polyfunctional alcohol-2-glycidyl ether compound, cresol-novolak epoxy resin, have the halogenide or the phosphide of the above-mentioned epoxy resin of high flame retardant, epoxy resin can be in the above-mentioned resin a kind of separately or make up multiple mixing and use.
The structural formula of said phenoxy resin is as follows:
N=50-150 wherein, radicals R
1, R
2, R
3, R
4Represent H atom, Br atom or contain the group of P element, R
1, R
2, R
3, R
4Between identical or different atom or the group of representative.Phenoxy resin (or brominated phenols epoxy resins) is a kind of good flexible resin that has, and is used as toughner to epoxy resin roughening with CSR, adopts biphenyl epoxy resin simultaneously, improves the bonding force of resin combination and PI film.
The structural formula of said biphenyl epoxy resin is as follows:
In not gummosis or low gummosis resin system, introduce biphenyl epoxy resin and can improve the resin bonding force surperficial with the PI film.
The material of said core shell rubbers (CSR) center part is selected from a kind of in silicone resin, vinyl resin, divinyl rubber and the synthetic polyisoprene etc., the material of shell part be selected from contain can with the resin of the functional group of epoxy resin reaction.
In the resin combination of the present invention; Use through phenoxy resin, biphenyl epoxy resin and CSR; Ordinary epoxy resin is carried out modification, develop not gummosis resin combination and prepreg thereof, significantly improve its flexility; And use CSR can reduce the resin dust releasing, the second-order transition temperature (Tg) to the resin solidification system does not obviously influence simultaneously.Wherein, after phenoxy resin and CSR reached certain proportion, it can rely on self bigger molecular weight to form certain external phase, dissolves a part of biphenyl epoxy resin, and itself and biphenyl epoxy resin can well be mixed, and can not produce microphase-separated.Putting before this, the snappiness of phenol oxygen epoxy resin and CSR itself can clearly show, thereby improves the snappiness of product; And when HTHP, be difficult for producing molecular chain movement, realize the not purpose of gummosis of pressing plate; CSR plays toughness reinforcing the time, can guarantee that second-order transition temperature does not obviously reduce, and overcomes the common common fault of using common toughner to cause Tg to reduce.When phenoxy resin and CSR consumption do not reach enough ratios; Because its amount can not form certain external phase less, can not form certain solvency action to biphenyl epoxy resin, produced and be separated; Make the inner stress of resin system strengthen, cause the folding quality of sheet material to be affected
Said solidifying agent can be amine or resol.Solidifying agent is an amount of among the present invention, make it with the epoxy resin equivalence ratio be 0.95-1.05; And curing catalyst can use imidazoles (like glyoxal ethyline, 1-Methylimidazole etc.) and verivate thereof, and consumption is that epoxy resin is the 0.15-1.5% of matrix resin, mainly plays adjustment resin combination glue gelation index, and is stable to guarantee controlling of production process.
In addition, under the prerequisite that does not influence resin system subjectivity property of the present invention, can suitably increase organic filler, or mineral filler (like silicon-dioxide, white lake etc.), to reach the purpose that reduces cost.
The prepreg that uses resin combination of the present invention to make comprises strongthener, reaches through the dry postadhesion of impregnation resin combination above that.Said strongthener adopts natural fiber, organic synthetic fibers, organic fabric or inorganic fibre etc., like glasscloth.In this prepreg, because the adding of phenoxy resin and CSR, its flexility significantly improves; Resin Flow reduces; Do not fall resin-oatmeal, and be greatly improved, and the second-order transition temperature after the curing can reach more than 165 ℃ with the bonding force of Copper Foil and PI film; Be applicable to that multilayered rigidity and flexibility combines PCB and hierarchic structure PCB, and have higher safety.
It comprises the steps: when making
1, with solvent each component (epoxy resin, solidifying agent, toughner etc.) of resin combination is dissolved into glue together, and the solids content of adjusting glue is 40-60%;
2, fully soak into glasscloth in the glue;
3, in adhesive applicator, use the folder shaft device that unnecessary glue on the glasscloth is struck off, the control resin content, and make the resin thickness on the glasscloth even;
4, the glasscloth that has soaked into glue in the 3rd step was toasted several minutes in high temperature oven, make epoxy resin cure, can obtain not gummosis prepreg to the B stage.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
1, with an amount of N (DMF) and butanone (MEK) mixed solvent (1: 1) 30 weight part resol and 1.5 weight part promotor (2-MI) are dissolved earlier, stir more than 60 minutes;
2, epoxy resin (100 weight part), biphenyl epoxy resin (10 weight part), phenoxy resin (20 weight part), core shell rubbers (25 weight part) are added successively again, stir more than 4 hours, thorough mixing is even, and the formation resin content is 50% solution;
3, with above-mentioned solution impregnation on 1080 glasscloths, put in the 150-170 ℃ of baking oven baking 6-8 minute into, can obtain containing the prepreg of B scalariform attitude resin layer.
Embodiment 2:
1, with an amount of N (DMF) and butanone (MEK) mixed solvent (1: 1) 3 weight part solidifying agent (amine) and 1 weight part promotor (2-MI) are dissolved earlier, stir more than 60 minutes;
2, epoxy resin (100 weight part), biphenyl epoxy resin (50 weight part), phenoxy resin (60 weight part), core shell rubbers (15 weight part) are added successively again, stir more than 4 hours, thorough mixing is even, and the formation resin content is 50% solution;
3, with above-mentioned solution impregnation on 1080 glasscloths, put in the 150-170 ℃ of baking oven baking 6-8 minute into, can obtain containing the prepreg of B scalariform attitude resin layer.
Embodiment 3:
1, with an amount of N (DMF) and butanone (MEK) mixed solvent (1: 1) 3 weight part solidifying agent (amine) and 1 weight part promotor (2-MI) are dissolved earlier, stir more than 60 minutes;
2, epoxy resin (100 weight part), biphenyl epoxy resin (50 weight part), phenoxy resin (30 weight part), core shell rubbers (25 weight part) are added successively again, stir more than 4 hours, thorough mixing is even, and the formation resin content is 50% solution;
3, with above-mentioned solution impregnation on 1080 glasscloths, put in the 150-170 ℃ of baking oven baking 6-8 minute into, can obtain containing the prepreg of B scalariform attitude resin layer.
Comparative example 1:
1, with an amount of N (DMF) and butanone (MEK) mixed solvent (1: 1) 3 weight part solidifying agent (amine) and 2 weight part promotor (2-MI) are dissolved earlier, stir more than 60 minutes;
2, epoxy resin (100 weight part), phenoxy resin (60 weight part), core shell rubbers (15 weight part) are added successively again, stir more than 4 hours, thorough mixing is even, and the formation resin content is 50% solution;
3, with above-mentioned solution impregnation on 1080 glasscloths, put in the 150-170 ℃ of baking oven baking 6-8 minute into, can obtain containing the prepreg of B scalariform attitude resin layer.
Comparative example 2:
1, with an amount of N (DMF) and butanone (MEK) mixed solvent (1: 1) 3 weight part solidifying agent (amine) and 2 weight part promotor (2-MI) are dissolved earlier, stir more than 60 minutes;
2, again with epoxy resin (100 weight part), phenoxy resin (80 weight part), adding successively, stir more than 4 hours, thorough mixing is even, and the formation resin content is 50% solution;
3, with above-mentioned solution impregnation on 1080 glasscloths, put in the 150-170 ℃ of baking oven baking 6-8 minute into, can obtain containing the prepreg of B scalariform attitude resin layer.
Each embodiment and comparative example result specifically see table 1.
The The performance test results contrast of the prepreg of each embodiment of table 1. and comparative example
, then lower from the result of table 1 with PI face bonding force if do not add biphenyl epoxy resin to recently seeing, if only carry out toughness reinforcingly, then can cause the second-order transition temperature reduction with a large amount of phenoxy resins.
In sum; The present invention is through the modification to ordinary epoxy resin of phenoxy resin, core shell rubbers and biphenyl epoxy resin; Develop not gummosis resin combination and prepreg thereof, prepared prepreg has higher snappiness and bonding strength, not gummosis; But while prolonged preservation; Solved current this series products and the PI material adhesive power hard and soft weakness that combines the printed substrate reliability decrease that causes with its making on the low side, and solidify the back second-order transition temperature can be up to more than 165 ℃, thereby improved the thermotolerance of making hard and soft combination (rigid-flexible) printed circuit board (PCB), safety etc. and up-to-standard rate.
Above embodiment; Be not that the content of compsn of the present invention is done any restriction; Every foundation technical spirit of the present invention or compsn composition or content all still belong in the scope of technical scheme of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (9)
1. a resin combination is characterized in that, it comprises that component and weight part thereof are following: 100 parts of matrix resins, phenoxy resin 20-60 part, biphenyl epoxy resin 10-50 part, core shell rubbers 5-25 part.
2. resin combination as claimed in claim 1; It is characterized in that; Said matrix resin is an epoxy resin; It comprises multifunctional phenol-2-glycidyl ether compound, polyfunctional alcohol-2-glycidyl ether compound, cresol-novolak epoxy resin, has the halogenide or the phosphide of the above-mentioned epoxy resin of high flame retardant, and epoxy resin is for wherein one or more mix use separately.
3. resin combination as claimed in claim 1 is characterized in that, the structural formula of said phenoxy resin is as follows:
N=50-150 wherein, radicals R
1, R
2, R
3, R
4Represent H atom, Br atom or contain the group of P element, R
1, R
2, R
3, R
4Between identical or different atom or the group of representative.
4. resin combination as claimed in claim 1 is characterized in that, the structural formula of said biphenyl epoxy resin is as follows:
5. resin combination as claimed in claim 1; It is characterized in that; The material of said core shell rubbers center part is selected from a kind of in silicone resin, vinyl resin, divinyl rubber and the synthetic polyisoprene, the material of shell part be selected from contain can with the resin of the functional group of epoxy resin reaction.
6. resin combination as claimed in claim 1 is characterized in that, also comprises solidifying agent and curing catalyst, and said solidifying agent is amine or resol, and solidifying agent and epoxy resin equivalence ratio are 0.95-1.05; Curing catalyst is imidazoles and verivate thereof, and consumption is the 0.15-1.5% of weight epoxy part.
7. a prepreg that uses resin combination as claimed in claim 1 to make is characterized in that, comprises strongthener, reaches through the dry postadhesion of impregnation resin combination above that.
8. prepreg as claimed in claim 7 is characterized in that, said strongthener adopts natural fiber, organic synthetic fibers, organic fabric or inorganic fibre.
9. prepreg as claimed in claim 7; It is characterized in that, during making, each component of said resin combination is dissolved into glue together through solvent; Fully soak into strongthener in the glue; To evenly contain the strongthener that is soaked with glue then and in 150-170 ℃ of baking oven, toast, make the resin combination semicure, promptly make prepreg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110085557 CN102311614B (en) | 2011-04-03 | 2011-04-03 | Resin composition and prepreg prepared by using same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110085557 CN102311614B (en) | 2011-04-03 | 2011-04-03 | Resin composition and prepreg prepared by using same |
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|---|---|
| CN102311614A true CN102311614A (en) | 2012-01-11 |
| CN102311614B CN102311614B (en) | 2013-09-18 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775734A (en) * | 2012-08-15 | 2012-11-14 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg prepared by using same |
| GB2510835A (en) * | 2013-02-13 | 2014-08-20 | Hexcel Composites Ltd | Fire retardant epoxy resin formulations and their use |
| WO2014202593A1 (en) * | 2013-06-19 | 2014-12-24 | Hexcel Composites Limited | Improvements in or relating to epoxy resin formulations |
| CN104302126A (en) * | 2014-10-11 | 2015-01-21 | 无锡长辉机电科技有限公司 | Manufacturing technique of rigid and flexible combined printed board |
| CN105255115A (en) * | 2015-11-09 | 2016-01-20 | 浙江华正新材料股份有限公司 | Thermosetting resin system composite material capable of being re-molded by being heated and preparation method thereof |
| CN105602195A (en) * | 2015-12-30 | 2016-05-25 | 广东生益科技股份有限公司 | Resin composition, prepreg and copper-clad plate |
| WO2017092471A1 (en) * | 2015-12-02 | 2017-06-08 | 广东生益科技股份有限公司 | Thermosetting alkyl polyol glycidyl ether resin composition and application thereof |
| CN109749360A (en) * | 2017-11-08 | 2019-05-14 | 广东生益科技股份有限公司 | Compositions of thermosetting resin and with its preparation can the copper-clad plate of static bending, printed wiring board |
| CN110121532A (en) * | 2017-04-07 | 2019-08-13 | 松下知识产权经营株式会社 | Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board |
| CN110734626A (en) * | 2019-11-13 | 2020-01-31 | 河北岳如信息科技有限公司 | epoxy resin material for circuit board |
| CN112759958A (en) * | 2020-12-30 | 2021-05-07 | 深圳市杰昌实业有限公司 | Protective coating for metal material surface |
| CN117124666A (en) * | 2023-09-20 | 2023-11-28 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
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| CN101240109A (en) * | 2007-09-30 | 2008-08-13 | 广东生益科技股份有限公司 | Resin composition and semi-solidifying sheet for printed board prepared from the same |
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| JP2008088280A (en) * | 2006-10-02 | 2008-04-17 | Sumitomo Bakelite Co Ltd | Prepreg, circuit board and semiconductor device |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775734A (en) * | 2012-08-15 | 2012-11-14 | 广东生益科技股份有限公司 | Halogen-free resin composition and prepreg prepared by using same |
| GB2512992B (en) * | 2013-02-13 | 2015-10-07 | Hexcel Composites Ltd | Fire retardant epoxy resin formulations and their use |
| GB2510835A (en) * | 2013-02-13 | 2014-08-20 | Hexcel Composites Ltd | Fire retardant epoxy resin formulations and their use |
| GB2512992A (en) * | 2013-02-13 | 2014-10-15 | Hexcel Composites Ltd | Fire retardant epoxy resin formulations and their use |
| US9969852B2 (en) | 2013-06-19 | 2018-05-15 | Hexcel Composites Limited | Epoxy resin formulations |
| CN105324417A (en) * | 2013-06-19 | 2016-02-10 | 赫克塞尔合成有限公司 | Improvements in or relating to epoxy resin formulations |
| WO2014202593A1 (en) * | 2013-06-19 | 2014-12-24 | Hexcel Composites Limited | Improvements in or relating to epoxy resin formulations |
| CN105324417B (en) * | 2013-06-19 | 2019-05-17 | 赫克塞尔合成有限公司 | The improvement of epoxy resin formulations or improvement in relation to epoxy resin formulations |
| CN104302126A (en) * | 2014-10-11 | 2015-01-21 | 无锡长辉机电科技有限公司 | Manufacturing technique of rigid and flexible combined printed board |
| CN105255115A (en) * | 2015-11-09 | 2016-01-20 | 浙江华正新材料股份有限公司 | Thermosetting resin system composite material capable of being re-molded by being heated and preparation method thereof |
| WO2017092471A1 (en) * | 2015-12-02 | 2017-06-08 | 广东生益科技股份有限公司 | Thermosetting alkyl polyol glycidyl ether resin composition and application thereof |
| CN105602195A (en) * | 2015-12-30 | 2016-05-25 | 广东生益科技股份有限公司 | Resin composition, prepreg and copper-clad plate |
| TWI829631B (en) * | 2017-04-07 | 2024-01-21 | 日商松下知識產權經營股份有限公司 | Resin compositions, prepregs, metallized laminated boards, printed wiring boards, and flexible rigid printed wiring boards |
| CN110121532A (en) * | 2017-04-07 | 2019-08-13 | 松下知识产权经营株式会社 | Resin combination, prepreg, metal-clad, printed circuit board and flexible rigid print circuit board |
| CN109749360A (en) * | 2017-11-08 | 2019-05-14 | 广东生益科技股份有限公司 | Compositions of thermosetting resin and with its preparation can the copper-clad plate of static bending, printed wiring board |
| CN109749360B (en) * | 2017-11-08 | 2021-11-30 | 广东生益科技股份有限公司 | Thermosetting resin composition, copper-clad plate capable of being bent statically and printed circuit board prepared from thermosetting resin composition |
| CN110734626A (en) * | 2019-11-13 | 2020-01-31 | 河北岳如信息科技有限公司 | epoxy resin material for circuit board |
| CN112759958A (en) * | 2020-12-30 | 2021-05-07 | 深圳市杰昌实业有限公司 | Protective coating for metal material surface |
| CN117124666A (en) * | 2023-09-20 | 2023-11-28 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
| CN117124666B (en) * | 2023-09-20 | 2024-02-02 | 江苏耀鸿电子有限公司 | Ageing-resistant flame-retardant epoxy resin-based copper-clad plate and preparation method thereof |
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|---|---|
| CN102311614B (en) | 2013-09-18 |
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