CN102443138A - Epoxy resin composition as well as prepreg and copper-foil-clad laminated board prepared by using same - Google Patents
Epoxy resin composition as well as prepreg and copper-foil-clad laminated board prepared by using same Download PDFInfo
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- CN102443138A CN102443138A CN2011103170617A CN201110317061A CN102443138A CN 102443138 A CN102443138 A CN 102443138A CN 2011103170617 A CN2011103170617 A CN 2011103170617A CN 201110317061 A CN201110317061 A CN 201110317061A CN 102443138 A CN102443138 A CN 102443138A
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Abstract
The invention relates to an epoxy resin composition as well as a prepreg and a copper-foil-clad laminated board prepared by using the same. The epoxy resin composition comprises the following essential components: (A) epoxy resin containing a naphthol structure, (B) an active ester serving as a curing agent, and (C) a curing accelerant. Because epoxy resin at least contains the naphthol structure in the molecular structure, the epoxy resin composition provided by the invention has higher functionality degree and high glass transition temperature; at the same time, the naphthol group structure is introduced to the molecular structure, thus the cured product has low water absorptivity and low expansion coefficient; due to the active ester serving as the curing agent, the advantages that the a polar group is not generated during the reaction between the active ester and epoxy, thus the dielectric properties are excellent and moisture and heat resistance are good are fully exerted; and in addition, because of the epoxy resin containing the special naphthol structure, the hydroscopicity of the resin cured product is further reduced and the dielectric loss value of the cured product is lowered. The prepreg and the copper-foil-clad laminated board provided by the invention have excellent dielectric properties, moisture and heat resistance and high glass transition temperature.
Description
Technical field
The present invention relates to a kind of resin combination, the prepreg and the copper-clad laminate that relate in particular to a kind of composition epoxy resin and use its making.
Background technology
Along with high speed and multifunction that electronic product information is handled, applying frequency improves constantly, and 3-6GHz will become main flow, except keeping that the thermotolerance of laminate sheet material is had the higher requirement, requires meeting more and more lower to its specific inductivity and dielectric loss value.Existing traditional F R-4 is difficult to satisfy the user demand of the high frequency and the high speed development of electronic product; Simultaneously baseplate material no longer is the mechanical support role who plays the part of under the traditional sense, and will become the important channel that PCB and manufacturer terminal planner promote product performance with electronic package.Because high DK can make the signal transfer rate slack-off, high Df can make signal section be converted into heat energy loss in baseplate material, thereby reduces the focus of chasing that DK/Df has become the substrate dealer.Traditional FR-4 material adopts Dyhard RU 100 as solidifying agent more; This solidifying agent is owing to have third order reaction amine; Have the good process operability, but since its carbon-nitrogen bond a little less than, easily cracking at high temperature; Cause the heat-resisting decomposition temperature of cured article lower, heat-resisting requirement that can't adapted to leadless technology.Under this background; Enforcement on a large scale along with lead-free process in 2006; Begin to adopt the solidifying agent of resol in the industry as epoxy; Resol has highdensity phenyl ring heat resistant structure, thus with curable epoxide after the thermotolerance of system very excellent, but the trend that the dielectric properties of cured product are worsened appears simultaneously.
Japanese Patent Laid is opened 2002-012650; 2003-082063 has proposed synthetic a series of active ester solidifying agent that contain phenyl ring, naphthalene nucleus or biphenyl structural as curing agent for epoxy resin such as IAAN; IABN, TriABN, TAAN; The cured product that obtains is compared with traditional phenolic aldehyde, can significantly reduce its specific inductivity and dielectric loss value.
Japanese Patent Laid is opened 2003-252958 and has been proposed employing biphenyl type epoxy resin and active ester as solidifying agent; Specific inductivity and dielectric loss value cured product can be reduced; But, the epoxy resin that adopts hand over density low because being the curing of difunctionality and active ester; The thermotolerance of cured article is lower, and the sparkling temperature is low.
Japanese Patent Laid is opened 2004-155990; Adopt the reaction of aromatic carboxylic acid and aromatic series phenol to obtain a kind of polyfunctionality active ester solidifying agent, use this active ester solidifying agent cured phenolic type epoxy can obtain the cured product of superior heat resistance, better specific inductivity and dielectric loss value.
Japanese Patent Laid is opened 2009-235165 and has been proposed a kind of new polyfunctionality active ester solidifying agent, solidifies a kind of epoxy that contains aliphatic structure, can be had higher sparkling transition temperature simultaneously and than the cured product of low-k and dielectric loss.
Japanese Patent Laid is opened 2009-040919, and to have proposed a kind of specific inductivity stable, the compositions of thermosetting resin that the conductive layer property followed is excellent, and main ingredient comprises epoxy resin, active ester stiffening agent, hardening accelerator, organic solvent.The cured product that obtains has good being knotted property of Copper Foil, and specific inductivity and dielectric loss are studied the consumption of epoxy resin and active ester, does not make a search for the relation of epoxy resin and active ester structure and performance.
In addition; Japanese Patent Laid is opened 2009-242559; The spy opens 2009-242560, and the spy opens 2010-077344, and the spy opens 2010-077343 and proposed employing alkylated phenol or alkylated naphthalene phenol-type epoxy phenolic resin, biphenyl type novolac epoxy respectively; As solidifying agent, can obtain the cured product of agent of low hygroscopicity, low-k and dielectric loss tangent with active ester.
In the more than existing patented technology; Though all proposed to use active ester can improve the wet fastness of cured product as epoxy resin, reduce water-intake rate, reduce specific inductivity and the dielectric loss value of cured product; But its shortcoming is to be difficult in to obtain a good balance between thermotolerance and the dielectric properties; Make cured product have high second-order transition temperature and low dielectric loss tangent value simultaneously, and make its dielectric properties more stable with the variation of frequency, water-intake rate is lower.
Summary of the invention
The object of the present invention is to provide a kind of composition epoxy resin, the required superior dielectric properties of copper-clad laminate, wet-hot aging performance and high second-order transition temperature can be provided.
Another object of the present invention is to, a kind of prepreg and copper-clad laminate that uses above-mentioned composition epoxy resin to make is provided, have excellent dielectric properties, wet-hot aging performance, also have high second-order transition temperature simultaneously, lower water-intake rate.
For realizing above-mentioned purpose, the present invention provides a kind of composition epoxy resin, comprises following necessary component:
(A) contain the epoxy resin of naphthol component;
(B) active ester solidifying agent;
(C) curing catalyst.
The epoxy resin that said component (A) contains naphthol component comprises at least a epoxy resin with following structural formula:
Formula one:
Wherein m, n are respectively 1 or 2, and q is 1～10 integer, and R is that H or carbonatoms are 1～5 alkyl.
Said component (B) active ester solidifying agent is to be got by a kind of phenolic cpd, two functionality carboxylic acid aromatics or acid halide and reaction of a kind of monohydroxy compound that connects through the aliphatic acyclic hydrocarbon structure.
Said two functionality carboxylic acid aromatics or acid halide consumption are 1mol, and the phenolic cpd consumption that connects through the aliphatic acyclic hydrocarbon structure is 0.05～0.75mol, and the monohydroxy compound consumption is 0.25～0.95mol.
Said component (B) active ester comprises the active ester of following structural formula:
Formula two:
X is phenyl ring or naphthalene nucleus in the formula, and j is 0 or 1, and k is 0 or 1, and n representes that average repeating unit is 0.25-1.25.
Said curing catalyst is one or more mixtures in glyoxaline compound, the piperidines.
Also comprise fire retardant, the combined amount of fire retardant is preferably the 5-100 weight part with respect to total 100 weight parts of component (A), component (B) and component (C); This fire retardant is brominated or halogen-free flame retardants, and said brominated flame-retardant is decabromodiphynly oxide, TDE, brominated styrene, the two tetrabromo phthalimides of ethylene or brominated polycarbonate; Said halogen-free flame retardants is three (2; The 6-3,5-dimethylphenyl) phosphine, 10-(2; The 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2, and 6-two (2; The 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is assorted-10-phosphine phenanthrene-10-oxide compound, phenoxy phosphine cyanogen compound, zinc borate, SULPHOSUCCINIC ACID ESTER, poly phosphate, phosphonium flame retardant, siliceous fire retardant or contain nitrogen combustion inhibitor.
Further comprise the organic or inorganic filler, the combined amount of filler is the 5-500 weight part with respect to total 100 weight parts of component (A), component (B) and component (C), is preferably the 5-300 weight part; Mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride AlN, SP 1, silit, white lake, titanium oxide, strontium titanate, barium titanate, aluminum oxide, permanent white, talcum powder, Calucium Silicate powder, lime carbonate, the mica; Organic filler is selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide, the polyethersulfone powder.
Simultaneously, the present invention provides a kind of prepreg that uses above-mentioned composition epoxy resin to make, and comprises strongthener and through the composition epoxy resin of impregnation drying postadhesion on it.
Further; The present invention also provides a kind of copper-clad laminate that uses above-mentioned composition epoxy resin to make; Comprise several superimposed prepregs and cover the Copper Foil in superimposed prepreg one or both sides, said prepreg adopts said composition epoxy resin to process.
Beneficial effect of the present invention: composition epoxy resin 1. of the present invention adopts the epoxy resin that contains a kind of naphthol component in the molecular structure at least, and it has higher functionality, has high second-order transition temperature; Introduce the naphthols unit structure in the molecular structure simultaneously, cured article has low water-intake rate, the ground coefficient of expansion; 2. composition epoxy resin of the present invention with active ester as solidifying agent; Given full play to active ester and do not generated the polar group group with epoxy reaction; Thereby the good advantage of the excellent wet-hot aging performance of dielectric properties; The epoxy resin that contains specific naphthol component has in addition further reduced the water-absorbent of resin cured matter, reduces the dielectric loss value of cured article; 3. prepreg and copper-clad laminate thereof that the above-mentioned composition epoxy resin of use of the present invention is made have excellent dielectric properties, wet-hot aging performance, also have high second-order transition temperature simultaneously.
Embodiment
Composition epoxy resin of the present invention comprises following necessary component:
(A) contain the epoxy resin of naphthol component;
(B) active ester solidifying agent;
(C) curing catalyst.
By the solid ingredient listed as parts by weight, component (A) contains the epoxy resin of naphthol component and the consumption of component (B) active ester solidifying agent gets for calculating according to the molar equivalent ratio, and its equivalence ratio is 0.9～1.2.
The epoxy resin that said component (A) contains naphthol component comprises at least a epoxy resin with following structural formula:
Formula one:
Wherein m, n are respectively 1 or 2, and q is 1～10 integer, and R is that H or carbonatoms are 1～5 alkyl.
The above-mentioned epoxy resin that contains naphthol component more specifically can be following structural formula:
Formula three:
Q is 1～10 integer in the formula;
Formula four:
Q is 1～10 integer in the formula;
Formula five:
Q is 1～10 integer in the formula.
Said component (B) active ester solidifying agent is to be got by a kind of phenolic cpd, two functionality carboxylic acid aromatics or acid halide and reaction of a kind of monohydroxy compound that connects through the aliphatic acyclic hydrocarbon structure.Said two functionality carboxylic acid aromatics or acid halide consumption are 1mol, and the phenolic cpd consumption that connects through the aliphatic acyclic hydrocarbon structure is 0.05～0.75mol, and the monohydroxy compound consumption is 0.25～0.95mol.
Said component (B) active ester comprises the active ester of following structural formula:
Formula two:
X is phenyl ring or naphthalene nucleus in the formula, and j is 0 or 1, and k is 0 or 1, and n representes that average repeating unit is 0.25-1.25.
Said curing catalyst is one or more mixtures in glyoxaline compound, the piperidines.Accelerator level is epoxy resin and the 100 parts of calculating of component (B) active ester solidifying agent gross weight that contain a kind of naphthol component in relative component (A) molecular structure at least, and its weight part is 0.05～1.0 part.
If needed, can also contain fire retardant among the present invention, provide resin cured matter to have flame-retarding characteristic, meet UL 94V-0 requirement.Fire retardant to optionally adding does not have special qualification, can be for brominated or halogen-free flame retardants, halogen flame, phosphonium flame retardant, siliceous fire retardant, contain nitrogen combustion inhibitor etc., and be good not influence dielectric properties.Said brominated flame-retardant can be decabromodiphynly oxide, TDE, brominated styrene, the two tetrabromo phthalimides of ethylene or brominated polycarbonate; Said halogen-free flame retardants is three (2; The 6-3,5-dimethylphenyl) phosphine, 10-(2; The 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2, and 6-two (2; The 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is assorted-10-phosphine phenanthrene-10-oxide compound, phenoxy phosphine cyanogen compound, zinc borate, SULPHOSUCCINIC ACID ESTER, poly phosphate, phosphonium flame retardant, siliceous fire retardant or contain nitrogen combustion inhibitor.The optional commercialization material such as the BT-93 of bromide fire retardant Albemarle Corporation, BT-93W, HP-8010, HP-3010; Halogen-free flame retardants has SP-100, PX-200, PX-202, FR-700, OP-930, OP-935 but be not limited to above material.The consumption of fire retardant reaches UL 94V-0 grade requirement according to cured product to be decided, and does not have special restriction, and total 100 weight parts with respect to component (A), component (B) and component (C) are preferably the 5-100 weight part, more preferably 10～50 weight parts.
If needed, can also further contain the organic or inorganic filler among the present invention.Filler to optionally adding does not have special qualification, and mineral filler can be selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride AlN, SP 1, silit, white lake, titanium oxide, strontium titanate, barium titanate, aluminum oxide, permanent white, talcum powder, Calucium Silicate powder, lime carbonate, the mica etc.; Organic filler can be selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide, the polyethersulfone powder etc.In addition, the shape of mineral filler, particle diameter etc. do not have special the qualification yet, and particle diameter is 0.01-50 μ m usually, is preferably 0.01-20 μ m, and the spy is preferably 0.1-10 μ m, and the mineral filler of this particle size range more is prone to disperse in resin liquid.Moreover the combined amount of filler does not have special qualification yet, and total 100 weight parts with respect to component (A), component (B) and component (C) are the 5-1000 weight part, are preferably the 5-300 weight part, 5-200 weight part more preferably, and the spy is preferably the 5-150 weight part.
The prepreg that uses above-mentioned composition epoxy resin to make comprises strongthener and through the composition epoxy resin of the dry postadhesion of impregnation on it, and the strongthener of strongthener use prior art is like glass cloth etc.The copper-clad laminate that uses above-mentioned composition epoxy resin to make comprises several superimposed prepregs and covers the Copper Foil in superimposed prepreg one or both sides, and said prepreg adopts said composition epoxy resin to make.
Composition epoxy resin of the present invention is processed certain density glue, and through lay-up, oven dry is at a certain temperature driven solvent away and is made resin combination carry out semicure then, obtains prepreg.Then above-mentioned described prepreg one or more is lumped together according to certain order stack; Copper Foil is covered the prepreg both sides that are being superimposed with each other respectively; Curing makes copper-clad laminate in thermocompressor, and its solidification value is 150-250 ℃, and solidifying pressure is 25-60Kg/cm
2
To the above-mentioned copper-clad laminate of processing, survey its specific inductivity and dielectric loss factor, second-order transition temperature and wet-hot aging performance, further give to explain in detail and describe like following embodiment.
Embodiment 1:
Get a container, add the naphthol type novolac epoxy NC-7300L of 100 weight parts, add equivalent weight part active ester solidifying agent HPC-8000-65T then, stir, add an amount of DMAP, and solvent toluene, continue to stir glue.Flood above-mentioned glue with glasscloth (model is 2116, and thickness is 0.08mm), and be controlled to suitable thickness, oven dry removes to desolvate and makes prepreg then.Use several prepared prepregs to be superimposed with each other, on its both sides, respectively cover a Copper Foil, put into to solidify in the thermocompressor and process said copper-clad laminate.Physical data is as shown in table 1.
Embodiment 2～3:
Manufacture craft is identical with embodiment 1, and prescription composition and physical data thereof are as shown in table 1.
Comparative example 1-3:
Manufacture craft is identical with embodiment 1, and prescription composition and physical data thereof are as shown in table 1.
The prescription of each embodiment of table 1. and comparative example is formed and physical data
The material of enumerating in the table is specific as follows:
NC-7300L: naphthol type novolac epoxy, epoxy equivalent (weight): 214g/eq;
NC-7000L: naphthol type novolac epoxy, epoxy equivalent (weight): 232g/eq;
NC-7700L: naphthol type novolac epoxy, epoxy equivalent (weight): 233g/eq;
HP-7200-H: dicyclopentadiene type novolac epoxy, epoxy equivalent (weight): 280g/eq;
N-690: face cresol novolak epoxy, epoxy equivalent (weight): 215g/eq;
HPC-8000-65T: active ester solidifying agent, active ester equivalent: 223g/eq;
TD-2090: linear phenolic curing agent, hydroxyl equivalent: 105g/eq;
The DMAP:4-Dimethylamino pyridine;
2E4MZ:2-ethyl-4-methylimidazole.
The testing method of above characteristic is following:
(1) second-order transition temperature (Tg): use the DMA test, measure according to the DMA testing method of IPC-TM-6502.4.24 defined.
(2) specific inductivity and dielectric loss factor: test according to the SPDR method.
(3) humidity resistance evaluation: after the Copper Foil etching with the copper-clad plate surface, estimate substrate; In substrate placement force pot, under 120 ℃, 105KPa condition, handle 2h; After be immersed in 288 ℃ the tin stove, when substrate layering plate bursting, write down the corresponding time; When surpassing in the tin stove, substrate can finish to estimate when 5min also bubble or layering do not occur.
Physical Property Analysis
Can know the comparative example 1-2 that from the physical data of table 1 when using existing novolac epoxy to solidify with active ester, second-order transition temperature is general, dielectric properties and water-intake rate generally epoxy have improvement, and the while wet-hot aging performance is good; In the comparative example 3 with the epoxy resin of spline structure with the phenolic aldehyde solidified time, though can obtain high glass transition, dielectric properties; Wet-hot aging performance is all relatively poor; Embodiment 1-3 uses naphthol type novolac epoxy active ester co-cured, because the existence of naphthol component, the water-intake rate of the laminate sheet material that obtains is low; Dielectric properties and wet-hot aging performance are excellent, and second-order transition temperature is high.
As stated, compare with general copper clad laminate, copper-clad laminate of the present invention has excellent more dielectric properties, high second-order transition temperature, and wet-hot aging performance is good simultaneously, is suitable for the high frequency field.
The above; Be merely preferred embodiment of the present invention; For the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (10)
1. a composition epoxy resin is characterized in that, comprises following necessary component:
(A) contain the epoxy resin of naphthol component;
(B) active ester solidifying agent;
(C) curing catalyst.
2. composition epoxy resin as claimed in claim 1 is characterized in that, the epoxy resin that said component (A) contains naphthol component comprises at least a epoxy resin with following structural formula:
Formula one:
Wherein m, n are respectively 1 or 2, and q is 1～10 integer, and R is that H or carbonatoms are 1～5 alkyl.
3. composition epoxy resin as claimed in claim 1; It is characterized in that said component (B) active ester solidifying agent is to be got by a kind of phenolic cpd, two functionality carboxylic acid aromatics or acid halide and reaction of a kind of monohydroxy compound that connects through the aliphatic acyclic hydrocarbon structure.
4. composition epoxy resin as claimed in claim 3; It is characterized in that; Said two functionality carboxylic acid aromatics or acid halide consumption are 1mol; The phenolic cpd consumption that connects through the aliphatic acyclic hydrocarbon structure is 0.05～0.75mol, and the monohydroxy compound consumption is 0.25～0.95mol.
5. composition epoxy resin as claimed in claim 1 is characterized in that, said component (B) active ester comprises the active ester of following structural formula:
Formula two:
X is phenyl ring or naphthalene nucleus in the formula, and j is 0 or 1, and k is 0 or 1, and n representes that average repeating unit is 0.25-1.25.
6. composition epoxy resin as claimed in claim 1 is characterized in that, said curing catalyst is one or more mixtures in glyoxaline compound, the piperidines.
7. composition epoxy resin as claimed in claim 1 is characterized in that, also comprises fire retardant, and the combined amount of fire retardant is preferably the 5-100 weight part with respect to total 100 weight parts of component (A), component (B) and component (C); This fire retardant is brominated or halogen-free flame retardants, and said brominated flame-retardant is decabromodiphynly oxide, TDE, brominated styrene, the two tetrabromo phthalimides of ethylene or brominated polycarbonate; Said halogen-free flame retardants is three (2; The 6-3,5-dimethylphenyl) phosphine, 10-(2; The 5-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phosphine phenanthrene-10-oxide compound, 2, and 6-two (2; The 6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9, the 10-dihydro-9-oxy is assorted-10-phosphine phenanthrene-10-oxide compound, phenoxy phosphine cyanogen compound, zinc borate, SULPHOSUCCINIC ACID ESTER, poly phosphate, phosphonium flame retardant, siliceous fire retardant or contain nitrogen combustion inhibitor.
8. composition epoxy resin as claimed in claim 1 is characterized in that, further comprises the organic or inorganic filler, and the combined amount of filler is preferably the 5-500 weight part with respect to total 100 weight parts of component (A), component (B) and component (C); Mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride AlN, SP 1, silit, white lake, titanium oxide, strontium titanate, barium titanate, aluminum oxide, permanent white, talcum powder, Calucium Silicate powder, lime carbonate, the mica; Organic filler is selected from one or more in polytetrafluorethylepowder powder, polyphenylene sulfide, the polyethersulfone powder.
9. a prepreg that uses composition epoxy resin as claimed in claim 1 to make is characterized in that, comprises strongthener and through the composition epoxy resin of impregnation drying postadhesion on it.
10. one kind is used the copper-clad laminate of composition epoxy resin making according to claim 1; It is characterized in that; Comprise several superimposed prepregs and cover the Copper Foil in superimposed prepreg one or both sides, said prepreg adopts said composition epoxy resin to process.
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