CN101328301A - Liquid thermosetting resin composition and method for manufacturing printed circuit board using the same - Google Patents
Liquid thermosetting resin composition and method for manufacturing printed circuit board using the same Download PDFInfo
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- CN101328301A CN101328301A CNA2008100295587A CN200810029558A CN101328301A CN 101328301 A CN101328301 A CN 101328301A CN A2008100295587 A CNA2008100295587 A CN A2008100295587A CN 200810029558 A CN200810029558 A CN 200810029558A CN 101328301 A CN101328301 A CN 101328301A
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Abstract
The invention provides a liquid thermosetting resin composition. The composition comprises the components in weight percentage: 30 to 80 percent of epoxide resin, 2 to 25 percent of firming agent, 20 to 80 percent of filling material, 0.001 to 5 percent of thixotropic agent, 0.001 to 5 percent of visbreaking dispersant, 0 to 5 percent of foam suppressor and a catalyst the weight of which is no more than 0.5 percent of the total weight of the epoxide resin and the firming agent; the components are mixed and evenly stirred; the liquid thermosetting resin composition has the advantages of good fluidity and metallic wettability, higher Tg, lower CTE and good self deaeration performance, and can overcome the defects of shrinkage in a hole, cracking in the hole, bubble in the hole and the connection of resins between holes. The invention also provides a method for manufacturing a printed circuit board by using the liquid thermosetting resin composition, which aims to improve the defects of the insufficient rubber filling after plate pressing and the cracking or the layering of resins after thermal shock and improve the credibility such as the heat reliability, etc. of the thick copper printed circuit board.
Description
Technical field
The present invention relates to a kind of liquid thermosetting resin composition that is applied to dual platen or multi-ply wood (containing the high-density multi-layered plate of HDI) through hole, blind hole or micropore consent, and be applied to the manufacture method of thick copper printed circuit board.
Background technology
Along with the terminal electronic product towards gently, thin, short, little direction develops, driven the develop rapidly of printed circuit board (being called for short PCB) design or processing technology, for example live width/line-spacing of PCB is more and more littler, the thickness of PCB is more and more thinner, BGA (encapsulation internal memory) arranges the variation of more and more closeer and components and parts weldprocedure etc., thereby accelerated the application of jack process and resin, while is under the pressure of the appearance of the RoHS of European Union instruction and each national environmental legislation of the whole world, the corresponding importing of leadless process, the characteristic of plug socket resin requires for the reliability of the PCB that adopts jack process particularly important.
Because the coefficient of expansion of plug socket resin (being called for short CTE) is higher at present, and the CTE of the resin of substrate and prepreg is relatively low, both CTE do not match, when adopting the consent flow process of Fig. 1 or Fig. 2, the plug socket resin that Fig. 3 easily takes place after through high temperature operation such as reflow shrinks and Kong Wei fills up phenomenon, or the resin seminess of Fig. 4 takes place.Even owing to the consent of bad Fig. 5 of appearance of thixotropic property of plug socket resin is linked to be the sheet phenomenon, perhaps because the viscosity of plug socket resin is too high and self deaeration poor performance, bubble phenomenon in the hole of Fig. 6 can appear behind consent.More than these phenomenons the reliability of PCB is had bigger negative impact.Present in addition plug socket resin on the market is very expensive, is unfavorable for the popularization that PCB is in enormous quantities and multi-usage is used.
Demand along with power supply increases rapidly in addition, the demand of thick copper PCB is also in sustainable growth, but the technology before the thick copper coin pressing still adopts traditional technology (the staggered stack of central layer and prepreg pressing), as Fig. 7, after the multi-ply wood pressing, space because thick copper between (particularly thick copper thickness more than the 5oz) circuit is darker, the resin that need fill out is more, be prone to not foot phenomenon of filler, or because woven fiber glass filler after strain produces bigger stress, after thermal shocking, be prone to crackle (crack) even layering (Delamination) phenomenon then, run into the pressing bottleneck at present.
Summary of the invention
The present invention is directed to the existing disappearance of above-mentioned known techniques, purpose is to provide that a kind of thixotropic property is good, strong, the moistening metallicity of deaeration performance reach well CTE lower and with a kind of liquid thermosetting resin composition of the CTE coupling of existing substrate/prepreg resin, consent is discontented to improve, in the hole resin crackle, consent in flakes with the hole in shortcoming such as bubble.
Another object of the present invention provides the method that the above-mentioned liquid thermosetting resin composition of a kind of usefulness is made printed circuit board, improves filler deficiency and shortcomings such as resin crackle after the thermal shocking or layering behind the pressing plate.
For achieving the above object, solution of the present invention is:
A kind of liquid thermosetting resin composition, the material that comprises following weight percent: 30～80% Resins, epoxy, 2～25% solidifying agent, 20～80% fillers, 0.001～5% thixotropic agent, 0.001～5% viscosity reduction dispersion agent, 0～5% defoamer and be no more than Resins, epoxy and 0.5% catalyzer of solidifying agent gross weight, mixed and stir.
Described liquid thermosetting resin composition is when 25 ℃ of temperature, and viscosity is 10～55Pa.s.
Described Resins, epoxy is meant bisphenol f type epoxy resin, bisphenol A-type ring resin, bisphenol-s epoxy resin, novolac epoxy (comprises linear phenolic epoxy resin, the o-Hydroxytoluene formaldehyde epoxy resin, the bisphenol A-type novolac epoxy, how phenol novolak epoxy, phosphorated novolac epoxy etc.), 1,1,2,2-four (p-hydroxybenzene) ethane four tetraglycidel ether epoxy resins, triphenol methylmethane triglycidyl ether Resins, epoxy, 4, the 4-diamino diphenyl methane tetraglycidyl ether, the mixture of one or more in glycolylurea (hydantion) Resins, epoxy or the cycloaliphatic epoxy resin.
Described solidifying agent is one or more the mixture in amine, resol or the acid anhydride type curing agent.
Described catalyzer is one or more the mixture in imidazoles, quaternary amine, quaternary amine or the quaternary alkylphosphonium salt.
Described filler is one or more the mixture in silicon-dioxide, aluminum oxide, mica, talcum powder, lime carbonate, boron nitride, aluminium nitride, silicon carbide, diamond, calcined clay, aluminum oxide, aluminium nitride fibres or the glass fibre, the particle maximum particle diameter of filler is 25 μ m, and median size is no more than 10 μ m.
Described thixotropic agent is one or more the mixing in hydrophilic aerosil or the hydrophobic type aerosil.
Described thixotropic agent also comprises one or more the mixing in thixotroping auxiliary agent wilkinite, multi-hydroxy carboxy acid's amides solution, the polycarboxylic alkylammonium salt solution.
Described viscosity reduction dispersion agent is one or more mixing of solvent-borne type or no-solvent type wetting dispersing agent (for example polyether-modified polydimethylsiloxane, boric acid ester, vinylformic acid etc. have the multipolymer of acidic-group etc.).
Described defoamer is one or more the mixing in the polysiloxane of organosilicon, inorganic silicon, no silicon froth breaking polyacrylic ester and polymers soln or the polyethers.
Adopt above-mentioned liquid thermosetting resin composition to make the method for printed circuit board, may further comprise the steps: the first step evenly is coated to resin Wu Tong district or circuit upper surface between the circuit of printed electronic circuit thickness of slab copper central layer; In second step, the central layer and the upper and lower Copper Foil stack pressing that have applied resin are solidified.
In above-mentioned second step, central layer and the prepreg and the upper and lower Copper Foil stack pressing curing of resin will have been applied.
Earlier with the Copper Foil brown or the melanism of thick copper central layer, carry out removing after the Procuring resin on the copper foil circuit after the perhaps above-mentioned the first step earlier before the above-mentioned the first step, will apply the Copper Foil brown or the melanism of the thick copper central layer of resin again.
Above-mentioned Procuring condition is 60～130 ℃, 20～60 minutes; The pressing condition of cure is 130～200 ℃, 20～180 minutes.
Being described as follows of each component in the composition:
Resins, epoxy is bisphenol f type epoxy resin, bisphenol A-type ring resin, bisphenol-s epoxy resin, novolac epoxy (comprises linear phenolic epoxy resin, the o-Hydroxytoluene formaldehyde epoxy resin, the bisphenol A-type novolac epoxy, how phenol novolak epoxy, phosphorated novolac epoxy etc.), 1,1,2,2-four (p-hydroxybenzene) ethane four tetraglycidel ether epoxy resins, triphenol methylmethane triglycidyl ether Resins, epoxy, 4, the 4-diamino diphenyl methane tetraglycidyl ether, glycolylurea (hydantion) Resins, epoxy, or one or more the mixture in the cycloaliphatic epoxy resin, particularly low-molecular-weight liquid bisphenol F type or bisphenol A type epoxy resin can be used as first-selection.The main effect of Resins, epoxy provides good insulation performance performance and resistance toheat in the constituent, its weight percent 30～80%, and optimized percentage is 45～65%.
Solidifying agent is one or more the mixture in amine, resol or the acid anhydride type curing agent.Described amine is as Dicy (Dyhard RU 100), 2MZ-A (2,4-diamino-6-[2 '-Methylimidazole-(1 ')]-ethyl-S-two azines), DDS (4,4 '-diaminodiphenylsulfone(DDS)) etc.The effect of solidifying agent in constituent is cured epoxy resin, forms cross-linked network, realizes good insulation performance performance and resistance toheat, and its weight percent is 2～25%, and optimized percentage is 3～10%.
Catalyzer is an imidazoles, the especially imidazoles of alkyl replacement, such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethyl-4-phenylimidazole etc.Other appropriate catalyst comprises various quaternary amines or doped quaternary ammonium salt and quaternary alkylphosphonium salt, as benzyldimethylamine, triphenyl phosphorus.The catalyzer that suggestion is used is a 2-ethyl-4-methylimidazole.Catalyst consumption depends on following factor: the type of the type of used Resins, epoxy, the type of solidifying agent and catalyzer etc.Generally speaking, catalyst consumption is no more than 0.5% of Resins, epoxy and solidifying agent gross weight, and first-selected numerical range is 0.01%-0.05%.
Filler is one or more the mixing in silicon-dioxide (comprising crystal type, fusion and ball Like silicon-dioxide), aluminum oxide, mica, talcum powder, lime carbonate, boron nitride, aluminium nitride, silicon carbide, diamond, calcined clay, aluminum oxide, aluminium nitride fibres or the glass fibre.The size of particles of filler is variant slightly according to the difference of its application, general maximum particle diameter is below 25 μ m (containing), median size is 10 μ m following (containing), but median size (containing) below 3 μ m is the best, the percentage of filler is 20～80% in the constituent, and the suggestion percentage is 30～60%.
Thixotropic agent is an aerosil, i.e. the mixing of one or more of hydrophilic and hydrophobic type aerosil also can be added other thixotroping auxiliary agent, as wilkinite, multi-hydroxy carboxy acid's amides solution, polycarboxylic alkylammonium salt solution or the like.Its percentage in constituent is 0.001～5%, and the optimized percentage example is 0.5～2%.
The viscosity reduction dispersion agent is one or more mixing of solvent-borne type or no-solvent type wetting dispersing agent, has the interpolymer (as BYK-W9010) of acidic-group etc. as polyether-modified polydimethylsiloxane, boric acid ester, vinylformic acid etc., play a part to reduce the viscosity of resin combination and improve the dispersing property of filler in constituent, its percentage in constituent is 0.001～5%, and the optimized percentage example is 0.01～1%.
Defoamer, as the polysiloxane of organosilicon or inorganic silicon, no silicon froth breaking polyacrylic ester and polymers soln (as BYK-A560), polyethers etc., also can add other other dispersion agent, as polyacrylic acid, triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol etc., purpose is that the bubble in the resin combination can be taken off fast from the inside to surface, improves bubble shortcoming in the constituent consent.Its percentage in constituent is 0～5%, and the optimized percentage example is 0.01～1%.
In addition, also can add materials such as coupling agent, pigment and dyestuff as required in the liquid thermosetting resin composition.
Above-mentioned liquid thermosetting resin composition is when 25 ℃ of temperature, and its viscosity to guarantee Resin Flow and metal wetting property preferably, does not occur resin shortcoming in flakes between the hole at 10～55Pa.s simultaneously again.
After adopting such scheme, liquid thermosetting resin composition thixotropic property provided by the invention is good, strong, the moistening metallicity of deaeration performance reach well CTE lower and with the CTE of existing substrate/prepreg resin coupling, can improve that consent is discontented, in the hole resin crackle, consent in flakes with the hole in shortcoming such as bubble, the while can be reduced the cost of resin combination effectively.The above-mentioned liquid thermosetting resin composition of the employing that provides of the present invention is made the method for printed circuit board, can improve filler deficiency and shortcomings such as resin crackle after the thermal shocking or layering behind the pressing plate, to improve the reliabilities such as thermal reliability of thick copper printed circuit board.
Description of drawings
Fig. 1 is the consent schematic flow sheet of dual platen;
Fig. 2 is multiple-plate consent schematic flow sheet;
Fig. 3 is the discontented synoptic diagram of resin shrinkage and consent;
Fig. 4 is resin crackle (crack) synoptic diagram behind the consent and after the thermal shocking;
Fig. 5 be consent behind the consent and consent between resin phenomenon synoptic diagram in flakes;
Fig. 6 is a bubble synoptic diagram in the hole behind the consent;
Fig. 7 is the preceding schematic flow sheet of the pressing of known thick copper multilayer plate;
Fig. 8 is the schematic flow sheet (schematic flow sheet before the pressing of thick copper multilayer plate) of the manufacturing approach craft one of printed circuit board;
Fig. 9 is the another kind of schematic flow sheet (schematic flow sheet before the pressing of thick copper multilayer plate) of the manufacturing approach craft one of printed circuit board;
Figure 10 is the schematic flow sheet (schematic flow sheet before the pressing of thick copper multilayer plate) of the manufacturing approach craft two of printed circuit board;
The drawing reference numeral explanation:
1. dual platen is holed and is electroplated 1. boring of a multi-ply wood and plating
2. 3. consent and Procuring and curing grind (removing the outer resin of overfolw hole)
4. electroplate and 5. paste the dry film image
6. the 7. multiple-plate making of blind hole of outer-layer circuit moulding
8. print heavy gold and silver of green oil and chemistry or tin 9. scolding tin and Reflow Soldering (assembling) excessively
(a) thick copper central layer (b) central layer circuit moulding
(c) central layer Copper Foil oxide treatment (brown or melanism)
(d1) resin printing central layer Wu Tong district (initial oxidation processing)
(d2) resin-coating central layer surface (initial oxidation processing)
(e) resin printing central layer Wu Tong district (elder generation is oxide treatment not) and Procuring
(f) the outer resin of overfolw hole is removed in grinding
(g) the central layer Copper Foil oxide treatment (brown or melanism) after the resin printing
(h) multi-ply wood lamination (before the pressing)
Embodiment
Following embodiment is a detailed description to liquid thermosetting resin composition of the present invention, but is not scope of the present invention to be made define.Each composition all calculates with parts by weight in following examples and the comparative example.
The embodiment 1～8 of liquid thermosetting resin composition and each set of dispense of comparative example 1～3 are than as shown in table 1.
Table 1
More than each constituent concocting method among each embodiment, be to adopt high-shear impeller uniform filling to be distributed in the mixture of other each component, heated and stirred is disperseed in case of necessity, forms liquid thermosetting resin composition.
Elaborate with embodiment 1 and 6 pairs of liquid thermosetting resin compositions of the present invention of embodiment: adopt low viscous bisphenol f type epoxy resin can realize the good fluidity and the wetting property of resin among the embodiment 1; Adopt 2MZ-A and 4, the 4-DDS curing of arrange in pairs or groups, can realize improving Tg (second-order transition temperature), or reduction low temperature is to the purpose (relatively example 1～3) of pyritous CTE (for example 50～260 ℃), thereby improve the resin crackle; Other adds the surface tension that the thixotropic agent aerosil improves resin, prevents resin joined together in the PTH hole at PTH aperture levelling (be between the hole resin phenomenon) in flakes; BYK in the component
The viscosity reduction dispersion agent of-W 9010 and so on reduces the tackify effect of filler effectively, and filler is uniformly dispersed in resin, makes resin combination can improve the adding proportion of filler, reduces CTE effectively, to prevent the generation of pitch shake line and resin shrinkage; In component, add a small amount of BYK
The froth breaking auxiliary agent of-A 560 and so on makes automatically deaeration of resin combination, prevents bubble generation in the hole behind the filling holes with resin.
Embodiment 6 with the difference part of embodiment 1 is: adopt the novolac epoxy of multiple functional radical partly to replace bisphenol f type epoxy resin, simultaneously do not adopt 4, the 4-DDS solidifying agent, reach the purpose that improves Tg and reduce cost, promptly on the good fluidity basis that guarantees resin, reduce cost and the CTE of low temperature, prevent the generation of resin crackle in the hole to high temperature (for example 50～260 ℃).The function of all the other components is identical with embodiment 1.
Table 2 is depicted as the characteristic of liquid thermosetting resin composition of above each embodiment and comparative example and the characteristic test result who is applied to make printed circuit board thereof.Viscosity adopts Brookfield Viscometer (Brookfield viscometer) to test, Tg (second-order transition temperature) adopts DSC (differential scanning calorimetry) test, CTE (thermal expansivity) adopts TMA (thermo-mechanical analysis method) test, these methods are all the common method of this area, and therefore concrete testing method and step no longer are described in detail in detail herein.And in the hole of consent characteristic between resin shrinkage and hole resin be to adopt visual inspection to distinguish in flakes, bubble and hole internal fissure are to adopt little dicing method to examine under a microscope to obtain in the hole, abrasive property is the complexity that scraper or brushing are removed the outer resin of overfolw hole, can observe the brushing number of times and can learn.
Table 2
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Resin properties | |||||||||||
| Viscosity (Pa.s) | 24 | 16 | 28 | 26 | 30 | 32 | 32 | 32 | 11 | 30 | 32 |
| Gel time (sec) (171 ℃ of hot plates) | 228 | 203 | 226 | 225 | 198 | 196 | 190 | 195 | 174 | 195 | 197 |
| Tg(DSC)(℃) | 139 | 139 | 137 | 137 | 146 | 144 | 147 | 144 | 121 | 119 | 120 |
| CTE (ppm/ ℃) before the Tg | 43 | 54 | 45 | 43 | 39 | 41 | 40 | 42 | 66 | 47 | 49 |
| CTE behind the Tg (ppm/ ℃) | 162 | 283 | 164 | 162 | 157 | 159 | 157 | 159 | 324 | 183 | 186 |
| CTE(％)(50- 260℃) | 3.3 | 4.2 | 3.4 | 3.3 | 3.1 | 3.2 | 3.1 | 3.2 | 5.1 | 3.9 | 4.0 |
| The consent characteristic | |||||||||||
| Resin shrinkage in the hole | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Do not have |
| Bubble in the hole | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have | Have |
| Resin in flakes between the hole | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Have | Have |
| The hole internal fissure | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Especially | Have | Have | Have |
| Abrasive property | Good | Good | Good | Good | Good | Good | Good | Good | Difference | Difference | Difference |
From embodiment 1～8 and comparative example 1～3 to recently, the Tg of embodiment is apparently higher than comparative example; CTE before and after the Tg is lower than comparative example, and particularly 50～260 ℃ CTE is starkly lower than about 20% of comparative example Schwellenwert; Add the aerosil thixotropic agent in addition and can prevent between the hole resin phenomenon in flakes; The interpolation of viscosity reduction dispersion agent can reduce viscosity effectively and improve the dispersiveness of filler in resin, can improve the adding proportion of filler, further reduces the CTE of resin combination, and it is obviously more a lot of than the effect of coupling agent; The interpolation of defoamer is indispensable, can carry out deaeration voluntarily, reduces or prevent the generation of bubble in the hole.
CTE (50～260 ℃) after liquid thermosetting resin composition among the above embodiment 1～8 solidifies is about 3.1～3.4%, with present Mid-Tg﹠amp; The baseplate material CTE that contains filler (filler) and High Tg compares approaching, thereby can be widely used in the complete processing of general PCB and high-end PCB for example micropore consent of the consent of high laminate, HDI plate and high aperture ratio blind hole consent and thick copper coin processing etc.
Below be detailed description, but be not scope of the present invention to be made define the method that adopts above-mentioned liquid thermosetting resin composition manufacturing printed circuit board.
Technical process such as Fig. 7 before the pressing of known thick copper multilayer plate, thick copper central layer (a) is through the pad pasting image and be etched into internal layer circuit (b), internal layer circuit on the central layer carries out Copper Foil oxide treatment (for example brown or melanism are handled) then, form the central layer (c) that oxide treatment is crossed, then these central layers and prepreg is interlaced is superimposed as (h), the multi-ply wood of folding is at last sent into thermocompressor, adopts certain pressing formula to carry out pressing.But adopt the preceding synergetic multi-ply wood of technical process of known pressing, fashionable in high-temperature high-pressure, because the thickness of thick copper is too thick, particularly 3～5oz and above thick copper, space between the central layer thick copper circuit is darker, and large-area thick copper Wu Tong district, need more resin to go to fill, and the resin on the prepreg is often not enough, usually cause circuit between the space, particularly the dead angle can't be filled up and not foot phenomenon of filler occur, and the multi-ply wood that presses is easy to plate bursting layering (delamination) when carrying out thermal shocking or process PCB high-temperature process, even perhaps filler OK, but since the resin major part on the prepreg be used to fill circuit between Wu Tong district, cause between the central layer amount of resin on the prepreg few, in thermal shocking or when passing through the PCB high-temperature process, can't bear bigger thermal stresses owing to amount of resin on the prepreg is few, also be easy to occur resin crackle (crack), even plate bursting layering (delamination), thereby the inefficacy that causes whole thick copper multilayer plate is scrapped.
And two kinds of novel procesies that the present invention mentions: one, the Copper Foil elder generation's brown or the melanism of thick copper central layer, then print or apply liquid thermosetting resin, will apply the central layer of resin and the upper and lower interlaced stack of prepreg then and solidify this technology such as Fig. 8 and Fig. 9 with upper and lower Copper Foil pressing; They are two years old, the Copper Foil elder generation of thick copper central layer is brown or melanism not, but after internal layer circuit finishes, directly print or apply liquid thermosetting resin, and remove resin on the copper foil circuit after the first Procuring, carry out brown or melanism afterwards again, solidify this technology such as Figure 10 with prepreg and Copper Foil stack pressing then.Fig. 8 and new technological flow shown in Figure 9 have been Duoed the operation (d1) of printing or coated with resins or (d2) than known flow process, purpose is with the close or lower resin combination of the CTE of CTE and central layer and prepreg the deep space crack between the thick copper circuit to be completed earlier, and then with the interlaced multi-ply wood (h) that is superimposed as of prepreg, can guarantee that like this amount of resin on the prepreg is more, can bear bigger thermal stresses and defectives such as resin crackle (crack) or plate bursting layering can not occur.The difference of Fig. 8 and Fig. 9 is the difference of resin printing and coating processes, common ground be the resin printing or apply after can not need Procuring and directly build up the multi-ply wood pressing, shorten the flow process time, certainly Fig. 9 also can be through passing through brushing just pressing afterwards again after Procuring/curing or the Procuring/curing, just the flow process time increases, and increases cost.
The difference of the technical process of Figure 10 and Fig. 8 or Fig. 9 exists in addition: Fig. 8 or Fig. 9 are printing or coated with resins after the first Copper Foil oxide treatment, Figure 10 is a not Copper Foil oxide treatment of elder generation, but behind the resin on first resin printing or coating (e) and Procuring/curing back grinding (f) Copper Foil, carry out Copper Foil oxide treatment (g) again, be pressed into multi-ply wood after last central layer and the interlaced stack of prepreg (h), this technical process can allow the resin on the prepreg need to fill deep space crack and other Wu Tong district between the thick copper circuit hardly equally, guarantee that the resin on the prepreg is enough, bear bigger thermal stresses with activation, and self can not produce bigger stress because of woven fiber glass filler after strain yet, so resin crackle (crack) or plate bursting layering (delamination) defective can not appear in the multi-ply wood after the pressing through thermal shocking or PCB high-temperature process the time.
In sum, have good flowability and metal wetting property, higher Tg, low CTE and good self deaeration performance with a kind of liquid thermosetting resin composition provided by the invention, can overcome in the hole in contraction, hole internal fissure, the hole that resin waits defective in flakes between bubble and hole, and can cut market with low cost, be beneficial to and promote of the widespread use of this class thermosetting resin composition in PCB processing; The manufacture method of printed circuit board provided by the invention in addition can be optimized the technology before the thick copper coin pressing, improves the reliability after thick copper (containing more than the thick copper 2oz) the plate pressing, and the direction that is beneficial to the past thicker copper coin (for example 12oz and above PCB) of promotion develops.
Claims (15)
1, a kind of liquid thermosetting resin composition, it is characterized in that comprising the material of following weight percent: 30～80% Resins, epoxy, 2～25% solidifying agent, 20～80% fillers, 0.001～5% thixotropic agent, 0.001～5% viscosity reduction dispersion agent, 0～5% defoamer and be no more than Resins, epoxy and 0.5% catalyzer of solidifying agent gross weight, mixed and stir.
2, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described liquid thermosetting resin composition is when 25 ℃ of temperature, and viscosity is 10～55Pa.s.
3, a kind of liquid thermosetting resin composition as claimed in claim 1, it is characterized in that: described Resins, epoxy is meant bisphenol f type epoxy resin, bisphenol A-type ring resin, bisphenol-s epoxy resin, novolac epoxy, 1,1,2,2-four (p-hydroxybenzene) ethane four tetraglycidel ether epoxy resins, triphenol methylmethane triglycidyl ether Resins, epoxy, 4, the mixture of one or more in 4-diamino diphenyl methane tetraglycidyl ether, glycolylurea epoxide resin or the cycloaliphatic epoxy resin.
4, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described solidifying agent is one or more the mixture in amine, resol or the acid anhydride type curing agent.
5, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described catalyzer is one or more the mixture in imidazoles, quaternary amine, quaternary amine or the quaternary alkylphosphonium salt.
6, a kind of liquid thermosetting resin composition as claimed in claim 1, it is characterized in that: described filler is one or more the mixture in silicon-dioxide, aluminum oxide, mica, talcum powder, lime carbonate, boron nitride, aluminium nitride, silicon carbide, diamond, calcined clay, aluminum oxide, aluminium nitride fibres or the glass fibre, the particle maximum particle diameter of filler is 25 μ m, and median size is no more than 10 μ m.
7, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described thixotropic agent is one or more the mixing in hydrophilic aerosil or the hydrophobic type aerosil.
8, a kind of liquid thermosetting resin composition as claimed in claim 7 is characterized in that: described thixotropic agent also comprises one or more the mixing in thixotroping auxiliary agent wilkinite, multi-hydroxy carboxy acid's amides solution, the polycarboxylic alkylammonium salt solution.
9, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described viscosity reduction dispersion agent is one or more the mixing in solvent-borne type or the no-solvent type wetting dispersing agent.
10, a kind of liquid thermosetting resin composition as claimed in claim 1 is characterized in that: described defoamer is one or more the mixing in the polysiloxane of organosilicon, inorganic silicon, no silicon froth breaking polyacrylic ester and polymers soln or the polyethers.
11, adopt the method for liquid thermosetting resin composition manufacturing printed circuit board according to claim 1, it is characterized in that may further comprise the steps: the first step evenly is coated to described liquid thermosetting resin composition Wu Tong district or circuit upper surface between the circuit of printed electronic circuit thickness of slab copper central layer; In second step, the central layer and the upper and lower Copper Foil stack pressing that have applied resin are solidified.
12, the method for manufacturing printed circuit board as claimed in claim 11 is characterized in that: in described second step, will apply central layer and the prepreg and the upper and lower Copper Foil stack pressing curing of resin.
13, the method for manufacturing printed circuit board as claimed in claim 11 is characterized in that: elder generation is with the Copper Foil brown or the melanism of thick copper central layer before the described the first step.
14, the method for manufacturing printed circuit board as claimed in claim 11 is characterized in that: carry out removing after the Procuring resin on the copper foil circuit after the described the first step earlier, will apply the Copper Foil brown or the melanism of the thick copper central layer of resin again.
15, as the method for claim 11,12,13 or 14 described manufacturing printed circuit boards, it is characterized in that: described Procuring condition is 60～130 ℃, 20～60 minutes; The pressing condition of cure is 130～200 ℃, 20～180 minutes.
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| CNA2008100295587A CN101328301A (en) | 2008-07-18 | 2008-07-18 | Liquid thermosetting resin composition and method for manufacturing printed circuit board using the same |
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| CNA2008100295587A CN101328301A (en) | 2008-07-18 | 2008-07-18 | Liquid thermosetting resin composition and method for manufacturing printed circuit board using the same |
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| CNA2008100295587A Pending CN101328301A (en) | 2008-07-18 | 2008-07-18 | Liquid thermosetting resin composition and method for manufacturing printed circuit board using the same |
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| CN110573581A (en) * | 2017-12-11 | 2019-12-13 | 株式会社Lg化学 | thermosetting resin composition for coating metal thin film and metal laminate using the same |
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| CN109385241A (en) * | 2018-10-11 | 2019-02-26 | 中国科学院长春应用化学研究所 | A kind of silicon Graft Epoxy Resin adhesive |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
| CN115612246A (en) * | 2022-12-15 | 2023-01-17 | 成都科宜高分子科技有限公司 | Composition for forming PCB (printed Circuit Board) hole plugging resin, preparation method, application and filling process |
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Open date: 20081224 |