CN102181143B - High-frequency thermosetting resin composition, prepreg and laminated sheet - Google Patents
High-frequency thermosetting resin composition, prepreg and laminated sheet Download PDFInfo
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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, epoxy resin 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 of signals, distortion and loss during with the minimizing high-speed transfer, and interference between signals.But common epoxy resin specific inductivity and dielectric loss are higher, are difficult to satisfy the application of high frequency aspect.Ppe 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, ppe also has high glass transition, low water absorption and excellent impact toughness etc., in the high frequency laminate sheet material, has broad application prospects.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 property; 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, white lake 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 two big types of addition type and response types.Addition type P contained compound commonly used mainly contains SULPHOSUCCINIC 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 safety 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 epoxy resin or resol.
Summary of the invention
Goal of the invention of the present invention provides a kind of high frequency veneer sheet and uses compositions of thermosetting resin, and the prepreg and the veneer sheet that use the above-mentioned compsn 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.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts is: a kind of high frequency is used 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, Said compound cyanate ester resin is the mixture of the phosphorous cyanate ester resin and second component, and said 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, phenolic 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; Said halogen-free epoxy resin is the Racemic glycidol ether type epoxy; Like bisphenol A epoxide resin, bisphenol F epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, 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 said polyphenylene oxide resin is 500～5000 g/mol, and hydroxyl equivalent is 250～2500 g/eq, and its structure is suc as formula (1):
(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, said 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 said phosphorous cyanate ester resin is phosphoric acid salt, SULPHOSUCCINIC 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 verivates 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, said promotor is glyoxaline compound or organic metal salt or its two kinds of mixtures.Said imidazolium compounds is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4-methylimidazole, and said 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 compsn preparation; In 100 parts of the weight of said compsn; 50～70% mixed glue solution is processed solids content and is in the mineral filler that adds 0～70 part, and add organic solvent; By this glue of glass cloth dipping, baking prepared and got in 2～10 minutes under 100～170 ℃ then.
In the technique scheme, said mineral filler is selected from a kind of of silicon-dioxide, SP 1, white lake, boehmite, talcum, clay, mica, kaolin, permanent white, lime carbonate, Marinco H, zinc borate or their arbitrary combination; Said solvent is selected from a kind of of acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, EGME, 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, the not special restriction of their thickness.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, prepare at its one or both sides clad with metal foil.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention has added phosphorous cyanate, and the compsn 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,, hereinafter do not 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, 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, 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; (structure is suc as formula 5, R1=D4 to add 30g trifunctional phenol-type epoxy resin (TFE1250, Changchun artificial resin), the phosphorous cyanate ester resin of 25g respectively; 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 epoxy resin (NC-7300 respectively; Japan's chemical drug), (structure is suc as formula 2, R=A1), 10g phenolic 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, 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 following 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.
Can find out from Comparative Examples 1 and Comparative Examples 2; 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 compsn is improved degree, and specific inductivity, second-order transition temperature and the humidity resistance of compsn all have decline in various degree simultaneously.
Claims (8)
1. a high frequency is used compositions of thermosetting resin, it 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, the structure of said polyphenylene oxide resin is suc as formula (1):
In the formula, m, n adjust to make polyphenylene oxide resin molecular weight in the scope of 500～5000g/mol;
X is
; R=S1:
; S2:
; S3:
; S4:
; S5:
, S6:
;
Wherein, Said compound cyanate ester resin is the mixture of the phosphorous cyanate ester resin and second component, and said 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, phenolic 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 100 parts of weight resins; Phosphorous cyanate ester resin is 5～25 parts; Said phosphorous cyanate ester resin is the P contained compound modified cyanic acid ester resin; Phosphorus content is 2～10% weight parts, and said P contained compound is phosphoric acid salt, SULPHOSUCCINIC ACID ESTER, phosphonitrile, 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound, 10-(2; The 5-dihydroxy phenyl)-a kind of in the 10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, 10-(2,5-dihydroxyl naphthyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound or their arbitrary combination.
2. high frequency according to claim 1 is used compositions of thermosetting resin, it is characterized in that: said 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 according to claim 1 is used compositions of thermosetting resin, it is characterized in that: the hydroxyl equivalent of said polyphenylene oxide resin is 250～2500 g/eq.
4. high frequency according to claim 1 is used compositions of thermosetting resin, it is characterized in that: said promotor is glyoxaline compound, organometalate compound or its two kinds of mixtures.
5. high frequency according to claim 4 is used compositions of thermosetting resin, it is characterized in that: said imidazolium compounds is selected from glyoxal ethyline, 2-phenylimidazole or 2-ethyl-4-methylimidazole; Said organic metal salt is selected from sad, methyl ethyl diketone, naphthenic acid, Whitfield's ointment, the stearate of zinc, copper, iron, tin, cobalt, aluminium.
6. 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 said compsn; The mineral filler that adds 0～70 part; And add organic solvent and process the glue that solids content is 50～70% (weight ratios), by this glue of glass cloth dipping, then 100～170 ℃ of baking preparations in 2～10 minutes and getting down.
7. prepreg according to claim 6 is characterized in that: said mineral filler is selected from a kind of of silicon-dioxide, SP 1, white lake, boehmite, talcum, clay, mica, kaolin, permanent white, lime carbonate, Marinco H, zinc borate or their arbitrary combination; Said organic solvent is selected from a kind of of acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, EGME, propylene glycol monomethyl ether or their arbitrary combination.
8. a high frequency is used veneer sheet, it is characterized in that: said 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.
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| CN102181143A (en) | 2011-09-14 |
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