CN102181143A - High-frequency thermosetting resin composition, prepreg and laminated sheet - Google Patents
High-frequency thermosetting resin composition, prepreg and laminated sheet Download PDFInfo
- Publication number
- CN102181143A CN102181143A CN 201110088157 CN201110088157A CN102181143A CN 102181143 A CN102181143 A CN 102181143A CN 201110088157 CN201110088157 CN 201110088157 CN 201110088157 A CN201110088157 A CN 201110088157A CN 102181143 A CN102181143 A CN 102181143A
- Authority
- CN
- China
- Prior art keywords
- resin
- cyanate ester
- parts
- ester resin
- high frequency
- 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.)
- Granted
Links
Abstract
The invention discloses a high-frequency thermosetting resin composition. The high-frequency thermosetting resin composition comprises the following components in part by weight: 10 to 60 parts of halogen-free epoxy resin, 15 to 70 parts of polyphenyl ether resin, and 5 to 60 parts of composite cyanate resin; an accelerator is 0.01 to 2 parts; and the composite cyanate resin comprises thiocyanate resin. The composition can realize halogen-free flame resistance, and does not influence the heat resistance and dielectric performance of a product; and a laminated sheet prepared from the composition has high peel strength and heat resistance of a copper foil and a low dielectric constant and low dielectric loss under the high-frequency condition.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin, relate in particular to and a kind ofly be used for the compositions of thermosetting resin of high frequency veneer sheet and by its prepreg that makes and used for printed circuit veneer sheet.
Background technology
For a long time, Resins, epoxy has obtained using in a large number and widely in the FR-4 veneer sheet owing to have comprehensive advantages such as starting material wide material sources, processibility is good, cost is lower.Yet,, the used for printed circuit veneer sheet is had higher requirement aspect the dielectric properties along with the high-speed high frequencyization of information processing in recent years and information transmission.In simple terms, promptly laminate sheet material need possess low specific inductivity and dielectric loss, delay, distortion and the loss of signal during with the minimizing high-speed transfer, and interference between signals.But common Resins, epoxy specific inductivity and dielectric loss are higher, are difficult to satisfy the application of high frequency aspect.Polyphenylene oxide is a kind of high performance resin, because the symmetry that its molecular chain is good, less Intermolecular Forces and higher aryl ratio, make it have excellent dielectric characteristics, promptly low specific inductivity and dielectric loss can satisfy frequency applications well to the dielectric material performance demands.Simultaneously, polyphenylene oxide also has high glass transition, low water absorption and excellent impact toughness etc., has broad application prospects in the high frequency laminate sheet material.But, problems such as that the polyphenylene oxide resin of macromolecule (＞10000) exists is poorly soluble,, melt viscosity height not good with epoxy resin compatibility, cause the veneer sheet of making phenomenons such as thermotolerance deficiency, cohesiveness are low, poor dimensional stability to occur, have a strong impact on its work reliability.
Traditional laminate sheet material mainly adopts brominated resins such as brominated epoxy resin, tetrabromo-bisphenol to guarantee flame retardant resistance.But, can generate objectionable impuritiess such as hydrogen bromide, furans, dioxin during the bromide burning, the serious harm HUMAN HEALTH is polluted living environment.Therefore, non-halogen has been trend of the times.As the substitute of brominated resin, mainly contain metallic compound and phosphorous resin/compound.Metallic compound such as zinc borate, aluminium hydroxide etc. have certain improvement to flame retardant resistance, but flame retardant effect is limited, and meeting severe exacerbation dielectric properties; And phosphorous resin, flame retardant resistance is better comparatively speaking for P contained compound, generally can be divided into addition type and response type two big classes.Addition type P contained compound commonly used mainly contains phosphoric acid ester, phosphonitrile etc., and it plays the effect of softening agent in resin system, can reduce the thermotolerance and the mechanical property of finished product, and exists the problem of oozing out under the high temperature, influences the reliability of finished product; And the phosphorous resin of response type at present commonly used mainly is phosphorous epoxy or phosphorus-containing phenolic aldehyde, but these are the dielectric properties that the resin of structure can reduce curing system equally with Resins, epoxy or resol.
Summary of the invention
Goal of the invention of the present invention provides a kind of high frequency veneer sheet compositions of thermosetting resin, and the prepreg and the veneer sheet that use the above-mentioned composition preparation are provided simultaneously.Said composition should realize halogen-free flameproof, and has excellent Copper Foil stripping strength and thermotolerance, has low-k and low dielectric loss under the high frequency condition simultaneously.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of high frequency compositions of thermosetting resin with solid weight meter, comprising:
(A) halogen-free epoxy resin is 10～60 parts;
(B) polyphenylene oxide resin is 15～70 parts;
(C) compound cyanate ester resin is 5～60 parts;
(D) promotor is 0.01～2 part;
Above-mentioned Resin A, B, the total amount of C component is 100 parts;
Wherein, described compound cyanate ester resin is the mixture of the phosphorous cyanate ester resin and second component, and described second component is selected from a kind of in the performed polymer of bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenol aldehyde type cyanate ester resin, tetramethyl-Bisphenol F type cyanate ester resin, bis-phenol M type cyanate ester resin, bisphenol E-type cyanate resin and above-mentioned cyanate ester resin or their arbitrary combination.
In the technique scheme, described halogen-free epoxy resin is the Racemic glycidol ether type epoxy, as bisphenol A epoxide resin, bisphenol F epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic Resins, epoxy, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane Resins, epoxy, biphenyl type epoxy resin, naphthalene nucleus type Resins, epoxy, dicyclopentadiene type Resins, epoxy, aralkyl line style phenolic aldehyde epoxy tree, a kind of in glycidyl amine type epoxy resin, the glycidyl ester type epoxy resin or their arbitrary combination.
In the technique scheme, the molecular weight of described polyphenylene oxide resin is 500～5000 g/mol, and hydroxyl equivalent is 250～2500 g/eq, and its structure is suc as formula (1):
In the formula, m, n should adjust to make polyphenylene oxide resin molecular weight in the scope of 500～5000g/mol;
X is
, R=S1:
, S2:
, S3:
, S4:
, S5:
, S6:
In the technique scheme, described phosphorous cyanate ester resin is the P contained compound modified cyanic acid ester resin, and in 100 parts of weight resins, phosphorous cyanate ester resin is 5～25 parts, and phosphorus content is 2～10%.Wherein, P contained compound in the described phosphorous cyanate ester resin is phosphoric acid salt, phosphoric acid ester, phosphonitrile, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO), 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-HQ), 10-(2,5-dihydroxyl naphthyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO-NQ) or other DOPO derivatives a kind of or their arbitrary combination.Its structure respectively as following various shown in:
(2)
Wherein ,-R-is selected from:
(3)
Wherein, R
1, R
2And R
3Be selected from respectively:
Annotate: have Ge Wei – OCN among the R1 at least
Wherein ,-R-is selected from:
(5)
In the technique scheme, described promotor is glyoxaline compound or organic metal salt or its two kinds of mixtures.Described imidazolium compounds is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4-methylimidazole, and described organic metal salt is selected from sad, methyl ethyl diketone, naphthenic acid, Whitfield's ointment, the stearate of zinc, copper, iron, tin, cobalt, aluminium.
A kind of prepreg that uses the above-mentioned composition preparation, in 100 parts of the weight of described composition, the mineral filler that adds 0～70 part, and adding organic solvent, make solids content and be 50～70% mixed glue solution, flood this glue by glass cloth, baking prepared and got in 2～10 minutes under 100～170 ℃ then.
In the technique scheme, described mineral filler is selected from a kind of of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, lime carbonate, magnesium hydroxide, zinc borate or their arbitrary combination; Described solvent is selected from a kind of of acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether or their arbitrary combination.
A kind of veneer sheet is covered with tinsel by the one or both sides of above-mentioned prepreg, forms in 2～4 hours at 2～5MPa pressure and 180～250 ℃ of temperatures systems.
Wherein tinsel can be a Copper Foil, also can be aluminium foil, and their thickness is not particularly limited.Be used for making the Copper Foil of copper-clad plate, be particularly suitable for using electrolytic copper foil.According to needed veneer sheet thickness, can adopt a prepreg, also can adopt the stack of several prepregs after, be prepared at its one or both sides clad with metal foil.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. the present invention has added phosphorous cyanate, and the composition of acquisition can be realized halogen-free flameproof and not influence the thermotolerance and the dielectric properties of product.
2. adopt the printed wiring veneer sheet of present composition preparation, have excellent Copper Foil stripping strength and thermotolerance, have low-k and low dielectric loss under the high frequency condition simultaneously.
Embodiment
Below in conjunction with embodiment the present invention is further described,, does not hereinafter have special instruction so that more easily explain the present invention, " part " representative " weight part ", " % " representative " weight % ":
Embodiment 1:
(structure is suc as formula 1, and R=S1) resin joins in the 40g butanone, stirs it is dissolved fully with the 40g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 30g biphenyl type epoxy resin (NC-3000 respectively, Japan's chemical drug), (structure is suc as formula 2 for the phosphorous cyanate ester resin of 15g, R=A1), 15g bisphenol A cyanate ester (CY-10, the Wuqiao chemical industry), 0.4g2-ethyl-4-methylimidazole and 0.4g aluminium acetylacetonate, mix and obtain glue.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment 2:
(structure is suc as formula 1, and R=S2) resin joins in the 45g butanone, stirs it is dissolved fully with the 45g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 25g biphenyl type epoxy resin (NC-3000 respectively, Japan's chemical drug), (structure is suc as formula 4 for the phosphorous cyanate ester resin of 15g, R=A1), 15g bisphenol A cyanate ester (CY-10, the Wuqiao chemical industry), 0.4g 2-ethyl-4-methylimidazole and 0.4g aluminium acetylacetonate, mix and obtain glue.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment 3:
(structure is suc as formula 1, and R=S1) resin joins in the 30g butanone, stirs it is dissolved fully with the 35g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 30g trifunctional phenol-type epoxy resin (TFE1250 respectively, the Changchun artificial resin), (structure is suc as formula 5 for the phosphorous cyanate ester resin of 25g, R1=D4, R2=D5, R3=D7), 10g dicyclopentadiene type ethylene rhodanate (CY-3, Wuqiao chemical industry), 0.4g2-ethyl-4-methylimidazole and 0.4g zinc acetylacetonate, mix and obtain glue.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment 4:
(structure is suc as formula 1, and R=S1) resin joins in the 50g butanone, stirs it is dissolved fully with the 50g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 30g naphthalene nucleus type Resins, epoxy (NC-7300 respectively, Japan's chemical drug), (structure is suc as formula 2, R=A1), 10g phenol aldehyde type cyanate, 0.5g2-Methylimidazole and 0.5g zinc acetylacetonate, mixes and obtains glue for the phosphorous cyanate ester resin of 10g.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Embodiment 5:
(structure is suc as formula 1, and R=S1) resin joins in the 40g butanone, stirs it is dissolved fully with the 40g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 30g biphenyl type epoxy resin (NC-3000 respectively, Japan's chemical drug), (structure is suc as formula 2 for the phosphorous cyanate ester resin of 15g, R=A1), 15g bisphenol A cyanate ester (CY-10, the Wuqiao chemical industry), 15g fused silica, 0.5g2-Methylimidazole and 0.5g acetylacetone cobalt, mix and obtain glue.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Comparative Examples 1:
(structure is suc as formula 1, and R=S1) resin joins in the 40g butanone, stirs it is dissolved fully with the 40g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, (XZ92530 DOW), 0.4g2-Methylimidazole and 0.3g aluminium acetylacetonate, mixes and obtains glue to add 15g bisphenol A cyanate ester (CY-10, Wuqiao chemical industry), 45g phosphorous epoxy resin respectively.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Comparative Examples 2:
(structure is suc as formula 1, and R=S1) resin joins in the 40g butanone, stirs it is dissolved fully with the 40g polyphenylene oxide resin.After treating that polyphenylene oxide resin dissolves fully, add 30g biphenyl type epoxy resin (NC-3000 respectively, Japan's chemical drug), 15g bisphenol A cyanate ester (CY-10, Wuqiao chemical industry), 15g zinc borate, 0.4g2-ethyl-4-methylimidazole and 0.2g aluminium acetylacetonate, mix and obtain glue.Choose smooth bright and clean, E-glass cloth that thickness is 0.1mm, evenly apply above-mentioned glue, in baking oven 150 ℃ down baking made prepreg in 5 minutes.With 8 above-mentioned prepreg stacks, enclose the Copper Foil of 35 μ m up and down, place the vacuum hotpressing machine to obtain veneer sheet in 3 hours at 3MPa pressure and 220 ℃ of temperatures systems.The copper clad laminate performance that obtains is as shown in table 1.
Table 1 adopts the copper clad laminate performance of different embodiment gained
Annotate: relevant test data is based on the veneer sheet sample of RC=40 ~ 50% in the table.
The testing method of characteristic is as follows in the table:
(1) resistance to flame (flame retardancy): measure according to the UV94 method.
(2) the wicking time (minute): wicking to layering is bubbled the time in 288 ℃ tin stove.
(3) specific inductivity: use flat band method according to IPC-TM-650 2.5.5.9, measure the specific inductivity under the 1GHz.
(4) dielectric loss angle tangent: use flat band method according to IPC-TM-650 2.5.5.9, measure the dielectric loss factor under the 1GHz.
(5) second-order transition temperature (Tg, ℃):
According to differential scanning calorimetric (DSC) method, measure according to the DSC method of IPC-TM-650 2.4.25 defined.
(6) stripping strength (PS, N/MM):
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.
(7) wicking thermotolerance after the wet heat treatment:
Getting 3 10cm * 10cm, thickness is the sample that tinsel is removed on 0.80mm, two sides, 100 ℃ of dryings 2 hours, pressure-cook test (Pressure Cooker test) machine then, after handling 1 hour under 121 ℃, 2 normal atmosphere, wicking 20s in 288 ℃ tin stove, whether visual observations has demixing phenomenon.If any 0,1,2,3 demixing phenomenons are designated as 0/3,1/3,2/3,3/3 respectively in 3.
From Comparative Examples 1 and Comparative Examples 2 as can be seen, compare with the embodiment 1 that adds phosphorous cyanate ester resin, add phosphorous epoxy resin or add the flame retardant resistance mineral filler no matter be, it is limited that the incendivity of composition is improved degree, and specific inductivity, second-order transition temperature and the humidity resistance of composition all have decline in various degree simultaneously.
Claims (9)
1. high frequency compositions of thermosetting resin is characterized in that: with solid weight meter, comprising:
(A) halogen-free epoxy resin is 10～60 parts;
(B) polyphenylene oxide resin is 15～70 parts;
(C) compound cyanate ester resin is 5～60 parts;
(D) promotor is 0.01～2 part;
Above-mentioned Resin A, B, the total amount of C component is 100 parts;
Wherein, described compound cyanate ester resin is the mixture of the phosphorous cyanate ester resin and second component, and described second component is selected from a kind of in the performed polymer of bisphenol A cyanate ester resin, Bisphenol F type cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenol aldehyde type cyanate ester resin, tetramethyl-Bisphenol F type cyanate ester resin, bis-phenol M type cyanate ester resin, bisphenol E-type cyanate resin and above-mentioned cyanate ester resin or their arbitrary combination.
2. high frequency compositions of thermosetting resin according to claim 1 is characterized in that: described halogen-free epoxy resin is a kind of in Racemic glycidol ether type epoxy, glycidyl amine type epoxy resin, the glycidyl ester type epoxy resin or their arbitrary combination.
3. high frequency compositions of thermosetting resin according to claim 1 is characterized in that: the molecular weight of described polyphenylene oxide resin is 500～5000g/mol, and hydroxyl equivalent is 250～2500 g/eq.
4. high frequency compositions of thermosetting resin according to claim 1, it is characterized in that: in 100 parts of weight resins, phosphorous cyanate ester resin is 5～25 parts, and described phosphorous cyanate ester resin is the P contained compound modified cyanic acid ester resin, and phosphorus content is 2～10% weight parts.
5. high frequency compositions of thermosetting resin according to claim 1 is characterized in that: described promotor is glyoxaline compound, organometalate compound or its two kinds of mixtures.
6. high frequency compositions of thermosetting resin according to claim 5 is characterized in that: described imidazolium compounds is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4-methylimidazole; Described organic metal salt is selected from sad, methyl ethyl diketone, naphthenic acid, Whitfield's ointment, the stearate of zinc, copper, iron, tin, cobalt, aluminium.
7. prepreg that uses high frequency as claimed in claim 1 with the compositions of thermosetting resin preparation, it is characterized in that: in 100 parts of the weight of described composition, the mineral filler that adds 0～70 part, and adding organic solvent, to make solids content be 50～70%(weight ratio) glue, flood this glue by glass cloth, baking prepared and got in 2～10 minutes under 100～170 ℃ then.
8. prepreg according to claim 7 is characterized in that: described mineral filler is selected from a kind of of silicon-dioxide, boron nitride, aluminium hydroxide, boehmite, talcum, clay, mica, kaolin, barium sulfate, lime carbonate, magnesium hydroxide, zinc borate or their arbitrary combination; Described organic solvent is selected from a kind of of acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether or their arbitrary combination.
9. high frequency veneer sheet is characterized in that: described veneer sheet is that the prepreg one or both sides by claim 7 are covered with tinsel, forms in 2～4 hours at 2～5MPa pressure and 180～250 ℃ of temperatures systems.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100881570A CN102181143B (en) | 2011-04-08 | 2011-04-08 | High-frequency thermosetting resin composition, prepreg and laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100881570A CN102181143B (en) | 2011-04-08 | 2011-04-08 | High-frequency thermosetting resin composition, prepreg and laminated sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102181143A true CN102181143A (en) | 2011-09-14 |
| CN102181143B CN102181143B (en) | 2012-10-31 |
Family
ID=44567448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100881570A Active CN102181143B (en) | 2011-04-08 | 2011-04-08 | High-frequency thermosetting resin composition, prepreg and laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102181143B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516530A (en) * | 2011-12-08 | 2012-06-27 | 中山台光电子材料有限公司 | Epoxy modified polyphenylene ether resin, resin composition and its application |
| CN102585480A (en) * | 2011-12-29 | 2012-07-18 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg prepared from composition, and laminated board prepared from composition and used for printed circuit board |
| CN102604075A (en) * | 2012-03-02 | 2012-07-25 | 浙江大学 | Method for preparing dihydroxy-terminated polyphenylene oxide in aqueous medium and product as well as application thereof |
| CN103013110A (en) * | 2011-09-27 | 2013-04-03 | 台光电子材料股份有限公司 | Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same |
| WO2013097133A1 (en) * | 2011-12-29 | 2013-07-04 | 广东生益科技股份有限公司 | Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom |
| CN103304809A (en) * | 2013-06-20 | 2013-09-18 | 苏州生益科技有限公司 | Halogen-free flame-retardant prepolymer and prepreg and laminated board made from same |
| CN103554811A (en) * | 2013-11-05 | 2014-02-05 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made from thermosetting resin composition |
| CN104140517A (en) * | 2014-08-13 | 2014-11-12 | 厦门誉匠复合材料有限公司 | High transparency non-yellowing TPU (thermoplastic polyurethane) material and preparation method thereof |
| CN104271671A (en) * | 2012-03-29 | 2015-01-07 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| TWI491671B (en) * | 2013-05-21 | 2015-07-11 | Elite Material Co Ltd | Low dielectric halogen-free resin compositions and circuit boards for which they are used |
| CN105062066A (en) * | 2015-09-02 | 2015-11-18 | 苏州益可泰电子材料有限公司 | High-frequency electronic medium material |
| CN105440586A (en) * | 2015-12-18 | 2016-03-30 | 宏昌电子材料股份有限公司 | Modified epoxy resin composition with excellent dielectric properties, and applications thereof |
| WO2016074289A1 (en) * | 2014-11-11 | 2016-05-19 | 广东生益科技股份有限公司 | Thermoset resin composition, and prepreg and laminated board made of same |
| CN106279704A (en) * | 2015-05-27 | 2017-01-04 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde polyfunctional epoxy resin and purposes |
| CN104140517B (en) * | 2014-08-13 | 2017-01-04 | 厦门誉匠复合材料有限公司 | A kind of high transparency non yellowing TPU material and preparation method thereof |
| CN106867025A (en) * | 2017-03-02 | 2017-06-20 | 张家港市五湖新材料技术开发有限公司 | A kind of efficient flame-retarding agent and preparation method thereof |
| WO2017152602A1 (en) * | 2016-03-10 | 2017-09-14 | 广东生益科技股份有限公司 | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same |
| CN108219367A (en) * | 2016-12-22 | 2018-06-29 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it |
| CN110804308A (en) * | 2019-12-02 | 2020-02-18 | 珠海宏昌电子材料有限公司 | Polyphenyl ether epoxy resin composition, preparation method and application |
| US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
| CN111825955A (en) * | 2020-07-23 | 2020-10-27 | 海南大学 | High-frequency prepreg, preparation method thereof, copper-clad plate and preparation method thereof |
| CN115044186A (en) * | 2022-07-15 | 2022-09-13 | 山东金宝电子股份有限公司 | Black resin glue solution, preparation method of prepreg, copper-clad plate and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488672A (en) * | 2003-08-01 | 2004-04-14 | 广州宏昌电子材料工业有限公司 | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same |
| CN101796132A (en) * | 2007-09-27 | 2010-08-04 | 松下电工株式会社 | Epoxy resin composition, prepreg using the epoxy resin composition, metal-clad laminate, and printed wiring board |
-
2011
- 2011-04-08 CN CN2011100881570A patent/CN102181143B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488672A (en) * | 2003-08-01 | 2004-04-14 | 广州宏昌电子材料工业有限公司 | Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same |
| CN101796132A (en) * | 2007-09-27 | 2010-08-04 | 松下电工株式会社 | Epoxy resin composition, prepreg using the epoxy resin composition, metal-clad laminate, and printed wiring board |
Cited By (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013110B (en) * | 2011-09-27 | 2014-12-17 | 台光电子材料股份有限公司 | Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same |
| CN103013110A (en) * | 2011-09-27 | 2013-04-03 | 台光电子材料股份有限公司 | Halogen-free resin composition as well as copper foil substrate and printed circuit board applying same |
| CN102516530B (en) * | 2011-12-08 | 2014-03-12 | 中山台光电子材料有限公司 | Epoxy modified polyphenylene ether resin, resin composition and its application |
| TWI494370B (en) * | 2011-12-08 | 2015-08-01 | Elite Electronic Material Zhongshan Co Ltd | Epoxy group-modified polyphenylene ether resin, resin composition and application thereof |
| WO2013083062A1 (en) * | 2011-12-08 | 2013-06-13 | 中山台光电子材料有限公司 | Epoxy-modified polyphenylene oxide resin, resin composition and applications thereof |
| CN102516530A (en) * | 2011-12-08 | 2012-06-27 | 中山台光电子材料有限公司 | Epoxy modified polyphenylene ether resin, resin composition and its application |
| WO2013097133A1 (en) * | 2011-12-29 | 2013-07-04 | 广东生益科技股份有限公司 | Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom |
| EP2799493A4 (en) * | 2011-12-29 | 2015-12-23 | Shengyi Technology Co Ltd | Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom |
| EP2799493A1 (en) * | 2011-12-29 | 2014-11-05 | Shengyi Technology Co., Ltd | Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom |
| CN102585480A (en) * | 2011-12-29 | 2012-07-18 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg prepared from composition, and laminated board prepared from composition and used for printed circuit board |
| US9670362B2 (en) | 2011-12-29 | 2017-06-06 | Shengyi Technology Co., Ltd. | Thermoset resin composition, and prepreg and laminate for printed circuit board manufactured therefrom |
| CN102604075A (en) * | 2012-03-02 | 2012-07-25 | 浙江大学 | Method for preparing dihydroxy-terminated polyphenylene oxide in aqueous medium and product as well as application thereof |
| US9394439B2 (en) | 2012-03-29 | 2016-07-19 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| CN104271671A (en) * | 2012-03-29 | 2015-01-07 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| TWI491671B (en) * | 2013-05-21 | 2015-07-11 | Elite Material Co Ltd | Low dielectric halogen-free resin compositions and circuit boards for which they are used |
| CN103304809A (en) * | 2013-06-20 | 2013-09-18 | 苏州生益科技有限公司 | Halogen-free flame-retardant prepolymer and prepreg and laminated board made from same |
| CN103304809B (en) * | 2013-06-20 | 2015-09-23 | 苏州生益科技有限公司 | A kind of Halogen-free flame-retardant prepolymer and the prepreg using it to make and veneer sheet |
| CN103554811B (en) * | 2013-11-05 | 2016-06-15 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use prepreg and the laminate of its making |
| CN103554811A (en) * | 2013-11-05 | 2014-02-05 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made from thermosetting resin composition |
| US10662304B2 (en) | 2013-12-31 | 2020-05-26 | Saint-Gobain Performance Plastics Corporation | Composites for protecting signal transmitters/receivers |
| CN104140517A (en) * | 2014-08-13 | 2014-11-12 | 厦门誉匠复合材料有限公司 | High transparency non-yellowing TPU (thermoplastic polyurethane) material and preparation method thereof |
| CN104140517B (en) * | 2014-08-13 | 2017-01-04 | 厦门誉匠复合材料有限公司 | A kind of high transparency non yellowing TPU material and preparation method thereof |
| WO2016074289A1 (en) * | 2014-11-11 | 2016-05-19 | 广东生益科技股份有限公司 | Thermoset resin composition, and prepreg and laminated board made of same |
| CN106279704A (en) * | 2015-05-27 | 2017-01-04 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde polyfunctional epoxy resin and purposes |
| CN106279704B (en) * | 2015-05-27 | 2020-10-27 | 南亚塑胶工业股份有限公司 | Polyphenyl ether modified phenol-benzaldehyde multifunctional epoxy resin and application |
| CN105062066A (en) * | 2015-09-02 | 2015-11-18 | 苏州益可泰电子材料有限公司 | High-frequency electronic medium material |
| CN105062066B (en) * | 2015-09-02 | 2018-07-06 | 南京安尔泰通信科技有限公司 | High-frequency electronic dielectric material |
| CN105440586A (en) * | 2015-12-18 | 2016-03-30 | 宏昌电子材料股份有限公司 | Modified epoxy resin composition with excellent dielectric properties, and applications thereof |
| CN107177030A (en) * | 2016-03-10 | 2017-09-19 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits |
| CN107177030B (en) * | 2016-03-10 | 2019-06-14 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and prepreg and laminate for printed circuits using it |
| WO2017152602A1 (en) * | 2016-03-10 | 2017-09-14 | 广东生益科技股份有限公司 | Halogen-free thermosetting resin composition, and prepreg and laminate for printed circuits using same |
| CN108219367A (en) * | 2016-12-22 | 2018-06-29 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite, prepreg, laminate and printed wiring board containing it |
| CN108219367B (en) * | 2016-12-22 | 2022-05-13 | 广东生益科技股份有限公司 | Halogen-free thermosetting resin composition, prepreg containing same, laminated board and printed circuit board |
| CN106867025B (en) * | 2017-03-02 | 2019-05-03 | 张家港市五湖新材料技术开发有限公司 | A kind of efficient flame-retarding agent and preparation method thereof |
| CN106867025A (en) * | 2017-03-02 | 2017-06-20 | 张家港市五湖新材料技术开发有限公司 | A kind of efficient flame-retarding agent and preparation method thereof |
| CN110804308A (en) * | 2019-12-02 | 2020-02-18 | 珠海宏昌电子材料有限公司 | Polyphenyl ether epoxy resin composition, preparation method and application |
| CN110804308B (en) * | 2019-12-02 | 2022-05-13 | 珠海宏昌电子材料有限公司 | Polyphenyl ether epoxy resin composition, preparation method and application |
| CN111825955A (en) * | 2020-07-23 | 2020-10-27 | 海南大学 | High-frequency prepreg, preparation method thereof, copper-clad plate and preparation method thereof |
| CN111825955B (en) * | 2020-07-23 | 2023-07-21 | 海南大学 | Prepreg for high frequency, preparation method thereof and copper-clad plate and preparation method thereof |
| CN115044186A (en) * | 2022-07-15 | 2022-09-13 | 山东金宝电子股份有限公司 | Black resin glue solution, preparation method of prepreg, copper-clad plate and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102181143B (en) | 2012-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181143B (en) | High-frequency thermosetting resin composition, prepreg and laminated sheet | |
| CN102199351B (en) | Thermosetting resin composition, prepreg and laminated board | |
| EP3219757B1 (en) | Halogen-free resin composition and prepreg and laminate prepared therefrom | |
| KR101508083B1 (en) | Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same | |
| JP6470400B2 (en) | High CTI halogen-free epoxy resin composition for copper clad plate and method of using the same | |
| CN101418204B (en) | Halogen-free flameproof adhesive and application thereof in bonding sheet and copper clad laminate | |
| CN102174242B (en) | Halogen-free resin composition and prepreg and laminated board made of same | |
| EP2706091B1 (en) | Epoxy resin composition, and prepreg and copper clad laminate made therefrom | |
| EP2896653B1 (en) | Epoxy resin composition, and, prepreg and copper clad laminate manufactured using the composition | |
| CN105348743B (en) | halogen-free resin composition, prepreg and laminate | |
| TW201617380A (en) | Low dielectric polyester composite having phosphorous and method of manufacturing the same | |
| EP2896654B1 (en) | Epoxy resin compound, and, prepreg and copper-clad laminate manufactured using the compound | |
| CN110951216B (en) | Thermosetting resin composition, and prepreg and laminated board using same | |
| AU2014411037A1 (en) | Thermosetting resin composition and prepreg and laminated board prepared therefrom | |
| CN102276961A (en) | Halogen-free phosphorus-free epoxy resin composition, and semi-curing sheet and laminated sheet manufactured thereby | |
| CN103435973A (en) | Halogen-free epoxy resin composition as well as prepreg and laminate made from same | |
| CN101906239A (en) | Halogen-free flame-retardant resin composition and application thereof in manufacturing copper-clad plate | |
| CN102051024A (en) | Halogen-free flame-retardant epoxy resin composition and application thereof | |
| JP5756922B2 (en) | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board | |
| CN101845200A (en) | Halogen-free thermosetting resin composite, prepreg and laminate made of same | |
| TWI596155B (en) | Halogen-free thermosetting resin composition and prepreg and printed circuit laminate using the same | |
| TWI388622B (en) | And a thermosetting resin composition having an acid anhydride hardening | |
| KR101476895B1 (en) | Resin compositions and metal foil laminate comprising the resin composition | |
| EP2374828B1 (en) | Preparation of a low dielectric brominated resin with a symmetric or saturated heterocyclic aliphatic molecular structure and composition comprising said resin | |
| US8039560B1 (en) | Low dielectric brominated resin with a symmetric or saturated heterocyclic alphatic molecular structure and the preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |