CN101845200A - Halogen-free thermosetting resin composite, prepreg and laminate made of same - Google Patents
Halogen-free thermosetting resin composite, prepreg and laminate made of same Download PDFInfo
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- CN101845200A CN101845200A CN201010174607A CN201010174607A CN101845200A CN 101845200 A CN101845200 A CN 101845200A CN 201010174607 A CN201010174607 A CN 201010174607A CN 201010174607 A CN201010174607 A CN 201010174607A CN 101845200 A CN101845200 A CN 101845200A
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Abstract
The invention provides a halogen-free thermosetting resin composite, which comprises 15-75 weight parts of benzoxazine resin (A), 25-85 weight parts of silicon modified phosphorus-containing epoxy resin (B) and 0.1-80 weight parts of hardener (C) by regarding the overall weight of organic solids in components of the benzoxazine resin (A) and the silicon modified phosphorus-containing epoxy resin (B) as 100 weight parts. The prepreg and the laminate for a printed circuit, which are made of the halogen-free thermosetting resin composite, have good heat resistance, excellent heat and humidity resistance, low expansion ratio requirement, low dielectric loss factor, low water absorption and favorable processability.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin and reach by its prepreg that makes and printed electronic circuit laminated plate material the halogen-free thermosetting resin composite that particularly relates to the multilayer printed circuit veneer sheet of outstanding resistance toheat, excellent wet-hot aging performance, low thermal expansion requirement, low-dielectric loss factor, low water absorbable and good workability and effectively utilize low dielectric loss factor printed electronic circuit veneer sheet to use.
Background technology
The implementing in full along with European RoHS and WEEE instruction (using some objectionable impurities to instruct and instruct) on July 1st, 2006 about scrapping electrical and electronic product about restriction in electrical and electronic product, the halogen-free and lead-freeization of electronic product has been trend of the times, then stands in the breach as the copper-clad plate of baseplate material.Traditional copper-clad plate material generally adopts brominated flame retardant (as brominated epoxy resin, tetrabromo-bisphenol etc.) to guarantee that flame retardant resistance reaches UL94 V-0 grade.But correlative study shows, can generate carcinogenic De dioxin, serious harm HUMAN HEALTH, and contaminate environment during the bromide burning.Therefore, in order to satisfy non-halogen requirement, need seek a kind of brand-new and effective fire-retardant approach.At present the method that generally adopts in the industry is to use phosphorous epoxy resin to substitute in the past bromide fire retardant, phosphorous epoxy resin commonly used is generally the luxuriant and rich with fragrance type compound of phosphorus (DOPO) and bisphenol A type epoxy resin or multifunctional novolac epoxy, generates as o-cresol formaldehyde epoxy (CNE), bisphenol A-type phenolic aldehyde epoxy (BNE), phenol type phenolic aldehyde epoxy (PNE) reaction.The veneer sheet part of using these phosphorous epoxy resins to make can satisfy the requirement of halogen-free flameproof, guarantee that the goods combustionproperty reaches the ratio that the UL94V-0 rank need guarantee phosphorus content, but goods exist wicking thermotolerance deficiency, the moisture absorption, humidity are handled the insufficient problem of back wicking thermotolerance easily.For the easy moisture absorption of phosphorous epoxy resin commonly used, the moist relatively poor shortcoming of back wicking thermotolerance of handling, general method is to add benzoxazine colophony at present.Can generate the structure of similar resol after the benzoxazine colophony open loop, can effectively reduce the water-intake rate of curing system, and raising chemical resistant properties, there are toughness, the insufficient problem of wicking thermotolerance but solidify metacoxa, are difficult to reach the balance of wicking thermotolerance, humidity resistance, flame retardant resistance and processibility.
Summary of the invention
The objective of the invention is to solve above-mentioned technical problem, the prepreg, the printed electronic circuit veneer sheet that a kind of halogen-free thermosetting resin composite and use said composition are provided and make, this printed electronic circuit veneer sheet has good processibility, outstanding wicking thermotolerance and excellent wet-hot aging performance, low thermal expansion, low-dielectric loss factor, and flame retardant resistance satisfies UL94 V-0.
Purpose of the present invention is achieved through the following technical solutions:
A kind of halogen-free thermosetting resin composite, said composition comprises benzoxazine colophony (A), silicon modification phosphorous epoxy resin (B) and stiffening agent (C),, contain in the said composition as 100 weight parts in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition:
The benzoxazine colophony with following general formula (1) (A) of (I) 15～75 weight parts, described benzoxazine colophony (A) are that a class has phenyl ring with the nitrogenous ring-opening polymerization resol of oxazine ring heterocycle structure;
The silicon modification phosphorous epoxy resin (B) with following general formula (2) of 25～85 weight parts;
R
x, R
yFor
OCH
3, CH
3N=0,1,2,3,4......
(2)
The stiffening agent (C) of (II) 0.1～80 weight part, wherein said stiffening agent (C) are selected from amine, phenols, acid anhydrides at least or have a kind of in the compound of triazine ring.
Further, as 100 weight parts, being preferably benzoxazine colophony (A) is that 25～70 weight parts, silicon modification phosphorous epoxy resin (B) are 30～75 weight parts in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition.
Further, the weight percent of the phosphorus content of described silicon modification phosphorous epoxy resin (B) is 1.0～3.5, and the weight percent of silicone content is 0.2～4.0.
Further, described stiffening agent (C) is selected from a kind of of diaminodiphenylmethane, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, the nitrogenous resol of triazine modification, styrene-maleic anhydride at least, organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition is 100 weight part meters, and stiffening agent (C) is 0.1 to 60 weight part.
Further, in the described halogen-free thermosetting resin composite, in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition as 100 weight parts, the phosphorus modified phenolic compounds that also comprises 1～30 weight part, the weight percent of phosphorus content is 2.5～14.4 in the described phosphorus modified phenolic compounds.
Further, in the described halogen-free thermosetting resin composite, in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition as 100 weight parts, the imidazoles promotor that also comprises 0.01～2.0 weight part, described promotor are one of them of glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
Further, in the described halogen-free thermosetting resin composite, as 100 weight parts, also comprise the mineral filler of 7 to 300 weight parts in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition, be preferably 15 to 90 weight parts.
Further, described mineral filler is the material that is selected from aluminium hydroxide, magnesium hydroxide, wollastonite, silicon dioxide powder, magnesium oxide, Calucium Silicate powder, silica microballoon, lime carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide, zinc borate, zinc molybdate at least, preferred aluminium hydroxide, silicon dioxide powder, zinc borate, zinc molybdate.
The present invention has also disclosed a kind of manufacture method of the prepreg that is made by described halogen-free thermosetting resin composite, comprises the steps:
The first, will weave material or non-weaving material are immersed in the described halogen-free thermosetting resin composite solution, and described fabric composition can be inorganic or organic composition;
The second, weaving material or non-weaving material behind the dipping are formed through heat drying, described heating condition is to toast 4～7 minutes under 170 ℃ of environment.
The present invention has also disclosed a kind of manufacture method of the veneer sheet that is made by described prepreg, comprises the steps:
The first, with some many described prepreg stacks,
The second, be covered with tinsel at the single or double of described prepreg,
The 3rd, hot compacting.
Beneficial effect of the present invention is mainly reflected in: the prepreg, the printed electronic circuit veneer sheet that a kind of halogen-free thermosetting resin composite are provided and use said composition to make, this halogen-free thermosetting resin composite has cohesiveness and wicking thermotolerance preferably, and excellent wet-hot aging performance, low thermal expansion, low-dielectric loss factor, utilization has prepreg, the printed electronic circuit veneer sheet that excellent in performance makes, and has good processibility and flame retardant resistance and satisfies UL94-V0.
Embodiment
The present invention is described in detail below in conjunction with embodiment:
The invention provides a kind of halogen-free thermosetting resin composite, said composition comprises benzoxazine colophony A, silicon modification phosphorous epoxy resin B and stiffening agent C,, contain in the described composition as 100 weight parts in organic total solid of described benzoxazine colophony A and silicon modification phosphorous epoxy resin B composition:
The benzoxazine colophony A with following general formula (1) of (I) 15～75 weight parts, described benzoxazine colophony are that a class has phenyl ring with the nitrogenous ring-opening polymerization resol of oxazine ring heterocycle structure;
The silicon modification phosphorous epoxy resin B with following general formula (2) of 25～85 weight parts;
R
x, R
yFor
OCH
3, CH
3N=0,1,2,3,4......
(2)
The stiffening agent C of (II) 0.1～80 weight part, wherein said stiffening agent are selected from amine, phenols, acid anhydrides at least or have a kind of in the compound of triazine ring.
Be preferably further, described benzoxazine colophony A is 25～70 weight parts, and silicon modification phosphorous epoxy resin B is 30～75 weight parts.
Wherein can generate the structure of similar resol after the benzoxazine colophony A open loop, can effectively reduce the water-intake rate of curing system, have excellent wet-hot aging performance, low-dielectric loss factor, high glass-transition temperature, and contain the nitrogen element in the benzoxazine colophony molecular structure fire-retardant factor is provided.Benzoxazine colophony ratio in halogen-free thermosetting resin composite of the present invention is higher than the wicking thermotolerance that 75 weight parts will reduce veneer sheet, and its ratio is lower than 15 weight part veneer sheet wet-hot aging performances can be not enough.
Among the present invention, the weight percent of the phosphorus content of described silicon modification phosphorous epoxy resin B is 1.0～3.5, and the weight percent of silicone content is 0.2～4.0; Introduced the soft segment that contains siloxane bond (Si-O) in the described silicon modification phosphorous epoxy resin B molecular chain, the bond distance is big, and internal rotation is more easy, and the macromolecular chain kindliness is good, good toughness.Siloxane bond (Si-O) among the silicon modification phosphorous epoxy resin B in the phosphorous thermosetting epoxy resin component of the present invention has very high thermostability, and silicon modification phosphorous epoxy resin B has excellent wicking thermotolerance.
Stiffening agent C is that amine, phenols, acid anhydrides or one of them kind of the compound with triazine ring are formed preferred diaminodiphenylmethane, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, the nitrogenous resol of triazine modification, styrene-maleic anhydride.Stiffening agent C weight part is preferably 0.1～60.
In the halogen-free thermosetting resin composite provided by the invention, in organic total solid of benzoxazine colophony A and silicon modification phosphorous epoxy resin B composition as 100 weight parts, the phosphorus modified phenolic compounds that also contains 1 to 30 weight part, the weight percent of phosphorus content is 2.5～14.4 in this phosphorus modified phenolic compounds.
In the halogen-free thermosetting resin composite provided by the invention, in organic total solid of benzoxazine colophony A and silicon modification phosphorous epoxy resin B composition as 100 weight parts, the imidazoles promotor of also containing 0.01 to 2.0 weight part, this promotor can be selected from glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
In the halogen-free thermosetting resin composite of the present invention, as 100 weight parts, also contain the mineral filler of 7 to 300 weight parts, be preferably 15 to 90 weight parts in organic total solid of benzoxazine colophony A and silicon modification phosphorous epoxy resin B composition.Wherein mineral filler is the material that is selected from aluminium hydroxide, magnesium hydroxide, wollastonite, silicon dioxide powder, magnesium oxide, Calucium Silicate powder, silica microballoon, lime carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide, zinc borate, zinc molybdate at least, preferred aluminium hydroxide, silicon dioxide powder, zinc borate, zinc molybdate.
The present invention has also disclosed a kind of manufacture method of the prepreg that is made by described halogen-free thermosetting resin composite, in brief, be to use halogen-free thermosetting resin composite provided by the invention and weaving material or non-weaving material, the fabric composition can be inorganic or organic composition, forms through the dipping heat drying.
Halogen-free thermosetting resin composite provided by the invention obtains for conventional preparation method, benzoxazine colophony, phosphorous epoxy resin, solidifying agent, promotor, filler and proper amount of solvent are joined in the mixed glue still, solids content is 62～75%, stir, and slaking 4-8 hour, promptly make compositions of thermosetting resin solution of the present invention.Then will weave the material or non-weaving material be immersed in the described halogen-free thermosetting resin composite solution; Weaving material after will flooding then or non-weaving material form through heat drying and promptly form prepreg provided by the invention, and described heating condition is to toast 4～7 minutes under 170 ℃ of environment.
The present invention has also disclosed a kind of manufacture method of the veneer sheet that is made by described prepreg, comprises the steps:
The first, with many described prepreg stacks,
The second, be covered with tinsel at the single or double of described prepreg,
The 3rd, hot compacting.
Now the present invention is described in detail as follows according to embodiment, can more easily explain the present invention by embodiment and comparative example, yet they can not be used for limiting the scope of claim of the present invention.Hereinafter there is not special instruction, its part representative " weight part ", its % representative " weight % ".
Embodiment 1～8 and comparative example 1～6
Weight fraction by each component in the table prepares resin compound according to the method for front.
Table 1: composite formula (weight part)
Table 2: Comparative Examples prescription (weight part)
Annotate: in the table, the benchmark of weight part system in organic total solid of benzoxazine colophony (A) and the multifunctional phosphorous epoxy resin of phosphonitrile modification (B) composition as 100 weight parts.
The implication of each letter representative in the table is:
A. benzoxazine colophony: D125, Sichuan Dongcai Technology Group Co., Ltd produces;
B. silicon modification phosphorous epoxy resin: KDP-550MC65, Guktoh Chemical Co., Ltd. produces;
C. stiffening agent:
C1: diaminodiphenylsulfone(DDS), Japanese Wakayama Chemical Manufacture;
C2: the nitrogenous resol of triazine modification, PS6313, nitrogen content 20%, the Japan group holds chemical industry Co., Ltd. and produces;
D. promotor: 2-PZ, Japanese four countries change into production;
E. phosphorus modified phenolic compounds: XZ92741, Dow Chemical production;
F. mineral filler:
F1: aluminium hydroxide, median size are 1 to 5 μ m, and purity is more than 99%;
F2: silicon-dioxide, median size are 1 to 3 μ m, and purity is more than 99%;
H: luxuriant and rich with fragrance type compound of phosphorus and bisphenol type epoxy response type Resins, epoxy;
I: luxuriant and rich with fragrance type compound of phosphorus and multifunctional phenolic aldehyde epoxy reaction type Resins, epoxy.
Table 3, table 4 are respectively the performance tests that embodiment and comparative example are carried out.
Table 3
Table 4
The testing method of characteristic is as follows in the table:
(1) second-order transition temperature (Tg ℃):
According to dsc, measure according to the DSC method of IPC-TM-650 2.4.25 defined.
(2) stripping strength (PS):
According to " after the thermal stresses " experiment condition in the IPC-TM-650 2.4.8 method, the stripping strength of test metal cap rock.
(3) internal layer stripping strength:
Use the 1.6mm veneer sheet, peeled off the batten that test layer is seen cohesive strength, recording materials tensiometer pull-up batten masterpiece is a veneer sheet internal layer stripping strength (N/mm)
(4) resistance to flame (flame retardancy):
Measure according to the UV94 method.
(5) wicking thermotolerance:
Use the two sides band copper sample of 50 * 50mm, immerses in 288 ℃ the scolding tin time of writing down sample layering bubble.
(6) the moist back wicking thermotolerance of handling:
(base material of 100 * 100mm) sample kept 3 hours in 121 ℃, the pressure cooking treatment unit of 105Kpa after, record is immersed in sample layering in 288 ℃ the solder bath, bubble or corrugated time.
(7) water-absorbent:
Measure according to IPC-TM-650 2.6.2.1 method.
(8) specific inductivity:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the specific inductivity under the 1MHz.
(9) dielectric loss angle tangent:
Use flat band method according to IPC-TM-650 2.5.5.9, measure the dielectric loss factor under the 1MHz.
(10) drop impact toughness (veneer sheet fragility):
Use Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.
Good toughness and poor judge: cross bar is clear, illustrates that the toughness of product is good more, and ☆ represents with character; Cross bar is fuzzy, illustrates that the poor toughness of product, fragility are big, and ◎ represents with character; The clear readability of cross bar illustrates that toughness of products is general between clear and fuzzy, ◇ represents with character.
(11) thermally stratified layer time T-300:
Measure according to IPC-TM-650 2.4.24 method.
(12) thermal expansivity Z axle CTE (TMA):
Measure according to IPC-TM-650 2.4.24 method.
(13) heat decomposition temperature Td:
Measure according to IPC-TM-650 2.4.26 method.
To sum up the result is as can be known:
Prepreg that halogen-free thermosetting resin composite of the present invention is made and laminate for printed circuits, have outstanding resistance toheat, excellent wet-hot aging performance, low thermal expansion requirement, low-dielectric loss factor, low water absorbable and excellent machinability, incendivity satisfies UV94 V-0 rank.
Above embodiment is not the restriction to the present composition, so the equivalence that all principles according to the present invention, technical spirit, structure, shape are made changes, trickle modification and modification, all still belongs in protection scope of the present invention.
Claims (10)
1. halogen-free thermosetting resin composite, said composition comprises benzoxazine colophony (A), silicon modification phosphorous epoxy resin (B) and stiffening agent (C), it is characterized in that: as 100 weight parts, contain in the described composition in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition:
(I) benzoxazine colophony with following general formula (1) (A) of 15～75 weight parts, described benzoxazine colophony (A) are that a class has phenyl ring with the nitrogenous ring-opening polymerization resol of oxazine ring heterocycle structure;
The silicon modification phosphorous epoxy resin (B) with following general formula (2) of 25～85 weight parts;
(II) stiffening agent of 0.1～80 weight part (C), wherein said stiffening agent (C) are selected from amine, phenols, acid anhydrides at least or have a kind of in the compound of triazine ring.
2. halogen-free thermosetting resin composite according to claim 1, it is characterized in that: the organic total solid in described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition is 25～70 weight parts as 100 weight part benzoxazine colophonies (A), and silicon modification phosphorous epoxy resin (B) is 30～75 weight parts.
3. any one halogen-free thermosetting resin composite according to claim 1 and 2 is characterized in that: the weight percent of the phosphorus content of described silicon modification phosphorous epoxy resin (B) is 1.0～3.5, and the weight percent of silicone content is 0.2～4.0.
4. halogen-free thermosetting resin composite according to claim 1 is characterized in that: described stiffening agent (C) is selected from a kind of of diaminodiphenylmethane, diaminodiphenylsulfone(DDS), diaminodiphenyl oxide, the nitrogenous resol of triazine modification, styrene-maleic anhydride at least.
5. halogen-free thermosetting resin composite according to claim 1, it is characterized in that: in the described halogen-free thermosetting resin composite, in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition as 100 weight parts, the phosphorus modified phenolic compounds that also comprises 1～30 weight part, the weight percent of phosphorus content is 2.5～14.4 in the described phosphorus modified phenolic compounds.
6. halogen-free thermosetting resin composite according to claim 1, it is characterized in that: in the described halogen-free thermosetting resin composite, in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition as 100 weight parts, the imidazoles promotor that also comprises 0.01～2.0 weight part, described promotor are one of them of glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
7. halogen-free thermosetting resin composite according to claim 1, it is characterized in that: in the described halogen-free thermosetting resin composite, in organic total solid of described benzoxazine colophony (A) and silicon modification phosphorous epoxy resin (B) composition as 100 weight parts, also comprise the mineral filler of 7 to 300 weight parts, be preferably 15 to 90 weight parts.
8. halogen-free thermosetting resin composite according to claim 7, it is characterized in that: described mineral filler is the material that is selected from aluminium hydroxide, magnesium hydroxide, wollastonite, silicon dioxide powder, magnesium oxide, Calucium Silicate powder, silica microballoon, lime carbonate, clay, kaolin, glass powder, mica powder, titanium dioxide, zinc borate, zinc molybdate at least, preferred aluminium hydroxide, silicon dioxide powder, zinc borate, zinc molybdate.
9. the manufacture method of a prepreg that is made by the described halogen-free thermosetting resin composite of claim 1 is characterized in that: comprises the steps,
The first, will weave material or non-weaving material are immersed in the described halogen-free thermosetting resin composite solution, and described fabric composition can be inorganic or organic composition;
The second, weaving material or non-weaving material behind the dipping are formed through heat drying, described heating condition is to toast 4～7 minutes under 170 ℃ of environment.
10. the manufacture method of a veneer sheet that is made by the described prepreg of claim 9 is characterized in that: comprises the steps,
The first, with several described prepreg stacks;
The second, be covered with tinsel at the single or double of described prepreg;
The 3rd, hot compacting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010174607A CN101845200A (en) | 2010-05-18 | 2010-05-18 | Halogen-free thermosetting resin composite, prepreg and laminate made of same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010174607A CN101845200A (en) | 2010-05-18 | 2010-05-18 | Halogen-free thermosetting resin composite, prepreg and laminate made of same |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131131A (en) * | 2011-11-23 | 2013-06-05 | 台光电子材料股份有限公司 | Halogen-free resin composition and copper clad laminate and printed circuit board applying the same |
| CN103509329A (en) * | 2012-06-28 | 2014-01-15 | 中山台光电子材料有限公司 | Low dielectric resin composite and copper foil base plate applying composite as well as printed circuit board |
| WO2015051541A1 (en) * | 2013-10-11 | 2015-04-16 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
| CN105824192A (en) * | 2016-04-05 | 2016-08-03 | 浙江康尔达新材料股份有限公司 | Infrared sensitive composition and printing plate precursors prepared by composition |
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2010
- 2010-05-18 CN CN201010174607A patent/CN101845200A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131131A (en) * | 2011-11-23 | 2013-06-05 | 台光电子材料股份有限公司 | Halogen-free resin composition and copper clad laminate and printed circuit board applying the same |
| CN103131131B (en) * | 2011-11-23 | 2015-07-15 | 台光电子材料股份有限公司 | Halogen-free resin composition and copper clad laminate and printed circuit board applying the same |
| CN103509329A (en) * | 2012-06-28 | 2014-01-15 | 中山台光电子材料有限公司 | Low dielectric resin composite and copper foil base plate applying composite as well as printed circuit board |
| CN103509329B (en) * | 2012-06-28 | 2016-01-20 | 中山台光电子材料有限公司 | Low dielectric resin constituent and apply its copper clad laminate and printed circuit board (PCB) |
| WO2015051541A1 (en) * | 2013-10-11 | 2015-04-16 | 广东生益科技股份有限公司 | Thermosetting resin composition and use thereof |
| US10208188B2 (en) | 2013-10-11 | 2019-02-19 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and uses thereof |
| CN105482452A (en) * | 2015-12-25 | 2016-04-13 | 广东生益科技股份有限公司 | Halogen-free resin composition as well as prepreg, laminated board and printed circuit board containing halogen-free resin composition |
| CN105824192A (en) * | 2016-04-05 | 2016-08-03 | 浙江康尔达新材料股份有限公司 | Infrared sensitive composition and printing plate precursors prepared by composition |
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Application publication date: 20100929 |