CN103030931B - Thermosetting resin packing material and printed circuit board (PCB) - Google Patents
Thermosetting resin packing material and printed circuit board (PCB) Download PDFInfo
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- CN103030931B CN103030931B CN201210369532.3A CN201210369532A CN103030931B CN 103030931 B CN103030931 B CN 103030931B CN 201210369532 A CN201210369532 A CN 201210369532A CN 103030931 B CN103030931 B CN 103030931B
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Abstract
The present invention relates to thermosetting resin packing material and printed circuit board (PCB), the thermosetting resin packing material of the storage-stable excellence that provides a liquid type and can at room temperature preserve for a long time, and provide by using this thermosetting resin packing material, be formed with the high printed circuit board (PCB)s of reliability such as the hole such as through hole, the via portion of conductive layer, resistance to sweating heat performance, electrical characteristics thereby can operability fill well on recess between surperficial conductor circuit, internal face. Contain at least one thermosetting resin packing material epoxy resin, epoxy curing agent and inorganic filler, for the recess of printed circuit board (PCB) and the hole portion of dual platen or multilager base plate, contain at least one in the group that is selected from modified aliphatic polyamines and modification ester ring type polyamines composition as described epoxy curing agent. In suitable mode, also contain dicyandiamide as described epoxy curing agent.
Description
Technical field
The present invention relates to for example leading to for the recess between the conductor circuit of printed circuit board (PCB), dual platen or multilager base plateAt least thermosetting resin packing material and the printed circuit board (PCB) of filling perforation in any one etc. of the hole such as hole, via portion.
Background technology
In recent years,, along with the miniaturization multifunction of e-machine, require miniaturization, the encapsulation of the pattern of printed circuit board (PCB)The downsizing of area, the densification of component packages. Therefore, use at the two sides base that is provided with through hole (throughhole)On plate, core, form successively insulating barrier, conductor circuit, and carry out interlayer connection and multiple stratification with via (viahole) etc.The multilager base plates such as laminated circuit board. Then, carry out BGA(BGA Package, ballgridarray), LGA(grid arrayEncapsulation, landgridarray) etc. face battle array (Areaarray) encapsulation.
In this printed circuit board (PCB), on the recess between surperficial conductor circuit, internal face, be formed with conductive layer through hole,The hole portions such as via are by filled thermoset resin filling materials such as print processes. Now, due to thermosetting resin packing material withOverflow some modes from hole portion and fill, the part of overflowing is waited and (is for example carried out planarization removal by grinding after solidifyingWith reference to patent documentation 1 etc.).
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-75027 communique
Summary of the invention
The problem that invention will solve
As aforesaid thermosetting resin packing material, as recorded in aforementioned patent document 1, use contains conventionallyAs the epoxy resin of thermosetting resin composition, as the imidazole curing agent of curing agent and the thermosetting resin of inorganic fillerPacking material.
But, in the situation of epoxy resin and imidazole curing agent combination, aforementioned composition after mixing storage at room temperature steadyQualitative poor, as a liquid type resin combination at room temperature storage meeting gelation (solidifying) for a long time, become and cannot use. Therefore,Need in freezer or freezer, preserve (for example, at 10 DEG C, can preserve 3 months ~ 5 months) by low temperature, when product is preserved,More bothersome while dispatching from the factory, existing problems aspect operability, cost.
In light of this situation, its main purpose is, a liquid type is provided and can at room temperature preserves for a long time in the present inventionThe thermosetting resin packing material of storage-stable excellence.
And then the object of the invention is to, by using this thermosetting resin packing material, thus the operability of providingFill well and on recess between surperficial conductor circuit, internal face, be formed with the hole such as through hole, the via portion of conductive layer and resistance toThe printed circuit board (PCB) of sweating heat excellent performance.
For the scheme of dealing with problems
In order to reach aforementioned object, according to the present invention, can provide a kind of thermosetting resin packing material, it is characterized in that,It is contain epoxy resin, epoxy curing agent and inorganic filler, for recess and the dual platen or many of printed circuit board (PCB)At least resin filling materials in any one of the hole portion of laminar substrate, it contains and selects free modified aliphatic polyamines and modification fatAt least one in the group of ring type polyamines composition is as aforementioned epoxy resins curing agent.
In suitable embodiment, also contain dicyandiamide as aforementioned epoxy resins curing agent.
And then according to the present invention, provide a kind of printed circuit board (PCB), it is characterized in that having by aforementioned hot thermosetting resin and fillThe hole portion that the solidfied material of material has been filled. Wherein, " the hole portion " mentioning in this description comprise following both: printed circuit board (PCB)The through hole such as non-through hole and through hole such as via.
The effect of invention
Thermosetting resin packing material of the present invention, as aforementioned, contain and selects free modified aliphatic polyamines and modification ester ring typeAt least one in the group of polyamines composition be as epoxy curing agent, is therefore a liquid type and at room temperature can protects for a long timeDeposit, for example, can at 25 DEG C, preserve more than 180 days gel-free, storage-stable excellence, therefore its operation judicial convenience. ItsIn, " room temperature " is herein identical with the temperature range meaning under operating environment, for example, be conventionally set as approximately 15 DEG C above and 30 DEG CFollowing temperature range.
In addition, as epoxy curing agent, combining with above-mentioned polyamines and then containing other amine is curing agent, particularly twoIn the suitable embodiment of cyanamide, the thickening efficiency when suppressing to preserve under room temperature, therefore can further preserve for a long time, anotherCan reduce the consumption of above-mentioned polyamines outward.
And then, the thermosetting resin packing material of the application of the invention, can provide can operability ST Stuffing Table wellThe hole such as through hole, the via portion and the resistance to sweating heat performance that on recess between the conductor circuit of face, internal face, are formed with conductive layer are excellentDifferent printed circuit board (PCB).
Brief description of the drawings
Fig. 1 is hole portion insulating barrier periphery, the outer insulation (solder mask) that represents the evaluation substrate of embodiment, comparative exampleThe schematic cross-section of state.
Description of reference numerals
1 substrate
2 through holes
3 conductor layers
4 hole portion insulating barriers (solidfied material of thermosetting resin packing material)
5 solder masks
X leafing
Y crackle
Detailed description of the invention
As previously mentioned, thermosetting resin packing material of the present invention is characterised in that, it is for containing epoxy resin, epoxy treeFat curing agent and inorganic filler, at least any one of the recess of printed circuit board (PCB) and the hole portion of dual platen or multilager base plateResin filling materials in person, it contains in the group of selecting free modified aliphatic polyamines and modification ester ring type polyamines composition at leastA kind of as aforementioned epoxy resins curing agent.
Find according to the inventor's etc. research, these modified aliphatic polyamines and modification ester ring type polyamines are set as epoxyWhen the curing agent of fat plays a role, mixes with epoxy resin, after mixing, can be used as a liquid type resin combination and use, and, forOne liquid type also can at room temperature be preserved (working life is long) for a long time, for example can at 25 DEG C, preserve more than 180 days gel-free,Storage-stable excellence under room temperature. In addition, with other amine be for example dicyandiamide of curing agent and derivative thereof, boron trifluoride-The amines such as amine complex are compared, can cause at a lower temperature curing reaction, and can manufacture high-fire resistance, resistance to waterSolidfied material.
And then find according to the inventor's etc. research, as epoxy curing agent, with freely above-mentioned modified fat of choosingAt least one in the group of family's polyamines and modification ester ring type polyamines composition combines, and then is used in combination other amines, spyNot in the situation of thermosetting resin packing material of dicyandiamide, the thickening efficiency when suppressing preservation at room temperature, thereforeCan further preserve for a long time, in addition, even if use a small amount of polyamines also to solidify, thereby can reduce above-mentioned modified aliphatic polyaminesConsumption with modification ester ring type polyamines.
The present invention forms based on aforesaid opinion. Fill out by using thermosetting resin of the present invention as described aboveFill material, can manufacture on the recess of can operability filling well between surperficial conductor circuit, internal face and be formed with conductive layerThe hole such as through hole, via portion and the high printed circuit board (PCB) of reliability of resistance to sweating heat performance, electrical characteristics etc. Below, to thisEach constituent of bright thermosetting resin packing material describes.
As the epoxy resin for thermosetting resin packing material of the present invention, as long as have more than two in a partEpoxy radicals, can use known epoxy resin. For example can list bisphenol A type epoxy resin, bisphenol S type epoxy treeFat, dinaphthyl phenol-type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic varnish type epoxyThe diglycidyl ether of resin, alicyclic epoxy resin, polyethylene glycol or the diglycidyl ether of polypropylene glycol, polytetramethyleneGlycol diglycidyl ether, glycerine polyglycidyl ether, trimethylolpropane polyglycidyl ether, phenyl-1,3-bis-shrinks sweetOil ether, biphenyl-4,4 '-diglycidyl ether, 1, the diglycidyl ether of 6-hexanediol diglycidyl ether, ethylene glycol or the third twoThe diglycidyl ether of alcohol, D-sorbite polyglycidyl ether, sorbitan polyglycidyl ether, three (2,3-epoxy thirdBase) there is more than two epoxy radicals in a part such as isocyanuric acid ester, three (2-ethoxy) triglycidyl isocyanurateCompound, four glycidyl group ADP methylmethane, four glycidyl group m-xylene diamine, triglycidyl group p-aminophenylThe amine type epoxy resin such as phenol, diglycidylaniline, diglycidyl ortho-aminotoluene etc., preferably at normal temperature for example at 20 DEG CFor liquid epoxy resin.
About their commercially available product, as bisphenol A-type liquid-state epoxy resin, can list Mitsubishi Chemical Ind manufactureJER828, as Bisphenol F type liquid-state epoxy resin, can list Mitsubishi Chemical Ind manufacture jER807, as amine type liquid stateEpoxy resin (para-aminophenol type liquid-state epoxy resin), can list jER-630, Sumitomo Chemical that Mitsubishi Chemical Ind manufacturesThe ELM-100 that company manufactures etc.
Among these, preferably, viscosity is low, can in the time make paste, increase the compounding amount of inorganic filler and compriseHeat-resisting skeleton is the liquid-state epoxy resin of phenyl ring etc.
Aforesaid epoxy resin can be used alone or combines two or more uses.
Epoxy curing agent is used for making epoxy resin cure, in the present invention, uses and selects free modified aliphatic polyamines and changeProperty ester ring type polyamines composition group at least one. These modified aliphatic polyamines and modification ester ring type polyamines can be used aloneOr combine two or more uses. In these modified aliphatic polyamines and modification ester ring type polyamines, conventionally contain a small amount of unmodified amine,But still can use completely no problemly.
As epoxy curing agent, using modified aliphatic polyamines is that curing agent or modification ester ring type polyamines are curing agentTime, as described above, working life (epoxy resin mixes the rear spendable general time with curing agent) is elongated, in addition, toxicity,Skin irritation reduces, operability improves.
Above-mentioned polyamines be curing agent preferably taking following material as principal component: the alkylidene two of carbon number more than 2 and below 6Many containing aromatic rings aliphatic more than 8 and below 15 of polyalkylenepolyamines more than 2 and below 6 of amine, carbon number, carbon numberThe addition compound of the aliphatic polyamines such as amine or IPD, 1, the ester ring type polyamines such as two (amino methyl) cyclohexanes of 3-Addition compound or the mixing of the addition compound of above-mentioned aliphatic polyamine and the addition compound of above-mentioned ester ring type polyaminesThing. The particularly preferably curing agent taking the addition compound of benzene dimethylamine or IPD as principal component.
As the addition compound of above-mentioned aliphatic polyamine, preferably make this aliphatic polyamine and arylolycidyl ethers (spyPhenyl glycidyl ether or cresyl glycidyl ether) or alkyl glycidyl ether carry out the chemical combination of addition reaction gainedThing. In addition, as the addition compound of above-mentioned ester ring type polyamines, preferably make this ester ring type polyamines and n-butyl glycidyl ether,Bisphenol A diglycidyl ethers etc. carry out the compound of addition reaction gained.
As aliphatic polyamine, can list the alkylidene two of the carbon number such as ethylenediamine, propane diamine more than 2 and below 6The carbon such as polyalkylenepolyamines, benzene dimethylamine of carbon number more than 2 and below 6 such as amine, diethylenetriamines, diethylenetriamineAtomicity more than 8 and below 15 containing aromatic rings aliphatic polyamine etc. As the example of the commercially available product of aliphatic polyamine, for example canList FXE-1000 or FXR-1020, FujicureFXR-1030, FujicureFXR-1080, FXR-1090M2(FujiChanging into industrial group manufactures), Ancamine(registration mark) 2089K, Sunmide(registration mark) P-117, SunmideX-4150、Ancamine2422、SurwetR、SunmideTX-3000、SunmideA-100（AirProductJapan,Inc. manufacture) etc.
As ester ring type polyamines, can exemplify IPD, 1, two (amino methyl) cyclohexanes of 3-, two (4-aminoCyclohexyl) methane, ENB diamines, 1,2-DACH, Laromin etc. As the commercially available product of ester ring type polyamines, exampleAs listed Ancamine1618, Ancamine2074, Ancamine2596, Ancamine2199, SunmideIM-544、SunmideI-544、Ancamine2075、Ancamine2280、Ancamine1934、Ancamine2228（AirProductJapan, Inc. manufacture), Daitocurar(registration mark) mostly industry of F-5197, DaitocurarB-1616(Company manufactures), FujicureFXD-821, Fujicure4233(Fuji change into industrial group and manufacture), jERCURE(registrationTrade mark) 113(Mitsubishi Chemical Ind manufacture), Laromin(registration mark) C-260(BASF company manufacture) etc.
About modified aliphatic polyamines as described above or the compounding ratio of modification ester ring type polyamines, suitable is relativeBe more than 0.1 mass parts, below 30 mass parts in 100 mass parts epoxy resin, be preferably that 1 mass parts is above, 20 mass parts withUnder. The compounding ratio of modified aliphatic polyamines or modification ester ring type polyamines with respect to 100 mass parts epoxy resin lower than 0.1 qualityPart time, conventionally the precuring speed of composition epoxy resin is slack-off, in solidfied material, easily occur space residual and crackleRaw, therefore not preferred. On the other hand, compounding ratio exceedes 30 mass parts and when the compounding of volume ground, is difficult to obtain the storage under room temperatureStability improves the effect of such expectation.
In addition, thermosetting resin packing material of the present invention preferably, as epoxy curing agent, in choosing freelyState at least one combination in the group of modified aliphatic polyamines and modification ester ring type polyamines composition, and then be used in combination other aminationsCompound, particularly dicyandiamide. Thus, the thickening efficiency when preservation at room temperature of thermosetting resin packing material is inhibited, because ofThis can further preserve for a long time, and in addition, even if use a small amount of polyamines also to solidify, thereby it is many to reduce above-mentioned modified aliphaticThe consumption of amine and modification ester ring type polyamines. In addition, known dicyandiamide, melamine, methyl guanamines, benzoguanamine, 3,9-Two ［ 2-(3,5-diaminourea-2,4,6-triazine base) ethyl ］-2,4,8, the guanamines such as 10-tetra-oxaspiros ［ 5,5 ］ hendecane andIts derivative and their acylate, epoxy adduct etc. have adaptation, the rust-preventing characteristic with copper, can be used as epoxy treeThe curing agent of fat plays a role and contributes to the variable color of the copper that prevents printed circuit board (PCB), therefore can use aptly.
This amine is that the compounding ratio of curing agent is that common ratio is enough, for example, with respect to 100 mass parts epoxy treesFat is that 0.1 mass parts is above, 10 mass parts are suitable below.
In thermosetting resin packing material of the present invention, inorganic filler is for relaxing stress, the adjustment that cure shrinkage causesLinear expansion coefficient. As this inorganic filler, can use the known inorganic filler using in common resin combination. ToolBody, for example can list silica, barium sulfate, calcium carbonate, silicon nitride, aluminium nitride, boron nitride, aluminium oxide, magnesia,The gold such as the non-metallic fillers such as aluminium hydroxide, magnesium hydroxide, titanium oxide, mica, talcum, organobentonite, copper, gold, silver, palladium, siliconBelong to filler. These can be used alone or combine two or more uses.
In these inorganic fillers, can suitable use agent of low hygroscopicity, the silica of low volumetric expansion excellence, calcium carbonate.As silica, amorphous silica, crystalline silica all can, can be also their mixture. Particularly preferably withoutSetting (melting) silica. In addition, as calcium carbonate, natural powdered whiting, synthetic precipitated calcium carbonate all can.
About the shape of this inorganic filler, can list spherical, needle-like, sheet, flakey, hollow shape, indefinite shape,Hexagonal shape, cubic, laminar etc., preferably spherical from the viewpoint of the high compounding of inorganic filler.
In addition, the average grain diameter of these inorganic fillers is that 0.1 μ m is above and 25 μ m are following, is preferably 0.1 μ m above and 15 μScope below m is suitable. When average grain diameter less than 0.1 μ m, because specific area is large, the shadow of filler agglutination each otherRing, dispersion easily occurs bad, and be difficult to increase the loading of filler. On the other hand, while exceeding 25 μ m, there is pair printed circuitThe fillibility of the hole portion of plate worsens, and the problem that flatness worsens in the time that the part of filling perforation forms conductor layer. More preferably 1 μ mAbove and below 10 μ m.
About the compounding ratio of this inorganic filler, suitable is is 40 with respect to the total amount of thermosetting resin packing materialQuality % is above and 90 quality % following, it is above and below 80 quality % to be preferably 40 quality %. When less than 40 quality %, the consolidating of gainedThe thermal expansion of compound becomes excessive, and then is difficult to obtain sufficient abrasiveness, adaptation. On the other hand, while exceeding 90 quality %,Be difficult to paste, be difficult to obtain good printing, hole fillibility. More preferably more than 50 quality % and below 75 quality %.
In thermosetting resin packing material of the present invention, in order to give thixotropy, can add filling out of crossing by fatty acid treatmentMaterial or the unsetting filler such as organobentonite, talcum.
As above-mentioned aliphatic acid, can use as general formula: (R1COO)n-R2(substituent R1For more than 5 hydrocarbon of carbon number, getFor base R2For hydrogen or metal alkoxide, metal, n is more than 1 and is 4 following) shown in compound. About this aliphatic acid, substituent R1'sCarbon number is 5 when above, can show and give thixotropic effect. More preferably n is more than 7.
As aliphatic acid, can be the unrighted acid in carbochain with two keys or triple bond, can be also not comprise thisA little saturated fatty acids. (numeral is followed successively by quantity and the parantheses of carbon number, unsaturated bond for example can to list stearic acidIn be to show based on the numerical value of its position. 18:0), caproic acid (6:0), oleic acid (18:1(9)), arachic acid (20:0), behenic acid(22:0), melissic acid (30:0) etc. The substituent R of these aliphatic acid1Carbon number be preferably more than 5 and below 30. More excellentElect carbon number as more than 5 and below 20. In addition, can be also for example to make substituent R2For sealing (capping) with alkoxylTitanate esters (titanate) the substituent metal alkoxide that is etc., in the structure of coupling agent system, have that long (carbon number is 5Above) material of the skeleton of aliphatic chain. For example can commodity in use name KR-TTS(AjinomotoFine-TechnoCo.,Inc. manufacture) etc. In addition also can use the metal such as aluminum stearate, barium stearate (be respectively Chuan Cun and change into industrial group's manufacture)Soap. As the element of other metallic soaps, also have Ca, Zn, Li, Mg, Na etc.
About the compounding ratio of this aliphatic acid, be that 0.1 mass parts is above, 2 quality with respect to 100 mass parts inorganic fillersRatio below part is suitable. When less than 0.1 mass parts, cannot give sufficient thixotropy, on the other hand, exceed 2 qualityWhen part, the apparent viscosity of thermosetting resin packing material becomes too high, and the landfill of the hole portion to printed circuit board (PCB) reduces. Separately, after filling and solidifying, have bubble remaining etc. in the portion of hole in the portion of hole outward, defoaming worsens, and easily produces space, crackle. More excellentMore than electing 0.1 mass parts as and below 1 mass parts.
Aliphatic acid can, by carrying out compounding with having carried out surface-treated inorganic filler with aliphatic acid in advance, can more haveGive to effect thermosetting resin packing material thixotropy. Now, fall when the untreated filler of the comparable use of compounding ratio of aliphatic acidLow, inorganic filler be all fatty acid treatment cross filler time, the compounding ratio of aliphatic acid is filled out with respect to 100 mass parts are inorganicMaterial, more than being preferably 0.1 mass parts and below 1 mass parts.
In addition, in thermosetting resin packing material of the present invention, can further use silane series coupling agent. By compounding siliconMethane series coupling agent, can make the adaptation of inorganic filler and epoxy resin improve, and suppresses the generation of crackle in its solidfied material.
As silane series coupling agent, for example, can list epoxy silane, vinyl silanes, imidazoles silane, hydrosulphonyl silane, firstBase acryloyl-oxy base silane, amino silane, styryl silane, isocynate silane, thioether silane, ureido silane etc. In addition,Silane series coupling agent also can be by carrying out compounding with having carried out surface-treated inorganic filler with silane series coupling agent in advance.
About the compounding ratio of this silane series coupling agent, be preferably 0.05 with respect to 100 mass parts inorganic fillersMore than mass parts, below 2.5 mass parts. When less than 0.05 mass parts, cannot obtain sufficient adaptation, easily cause crackleOccur. On the other hand, while exceeding 2.5 mass parts, thermosetting resin packing material is filled solid in the hole of printed circuit board (PCB) portionAfter change, have bubble remaining etc. in the portion of hole, defoaming worsens, easily produces space, crackle.
Thermosetting resin packing material of the present invention uses while being at room temperature liquid epoxy resin, might not useRetarder thinner, but in order to regulate the viscosity of composition, also can add a small amount of retarder thinner. As retarder thinner, for example canList the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Methyl cellosolve, the molten fibre of butylAgent, methyl carbitol, ethyl carbitol, BC, propylene glycol monomethyl ether, DPE, triethylene glycol list secondThe glycol ethers such as ether; The ester classes such as the acetic acid esters compound of ethyl acetate, butyl acetate and above-mentioned glycol ethers; Ethanol, propyl alcohol, secondThe alcohols such as glycol, propane diols; The aliphatic hydrocarbon such as octane, decane; The stones such as benzinum, naphtha, hydrogenated naphtha, solvent naphthaThe organic solvents such as oil series solvent. They can be used alone or combine two or more uses.
About the compounding ratio of retarder thinner, it is desirable to into 10 quality % of the total amount of thermosetting resin packing material withUnder, be preferably 5 quality % following, more preferably below 3 quality %. When the compounding ratio of retarder thinner exceedes 10 quality %, while solidifyingDue to the impact of the evaporation of volatile ingredient, in the hole portion insulating barrier after solidifying, easily produce bubble, crackle. Therefore, desirable especiallyIt is solvent-free thermosetting resin packing material.
In thermosetting resin packing material of the present invention, can need compounding to make phenolic compounds, formaldehyde and primary according to otherAmine reaction and Ju You oxazine Huan oxazine compounds. By Han You oxazine compounds, be filled in the hole portion of printed circuit board (PCB)Thermosetting resin packing material solidify after, on the solidfied material forming, while carrying out chemical plating, can easily utilize Gao MengThe alligatoring of the solidfied material of acid aqueous solutions of potassium etc., improves plating and peel strength.
In addition, also can add phthalocyanine blue, phthalocyanine green, dual-azo yellow, the oxygen for common serigraphy China ink against corrosionChange the known colouring agents such as titanium, carbon black, naphthalene be black.
In addition, the storage stability while preservation in order to give, can add quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, companyThe known hot polymerization inhibitor such as benzenetriol, phenthazine, for adjusting viscosity etc., can add clay, kaolin, organobentonite, illiteracyKnown thickener, the thixotropic agent such as de-soil. In addition, can compounding silicon system, defoamer, levelling agent, the imidazoles such as fluorine system, macromolecularThe known additive kind of adaptation imparting agents such as system, thiazole system, triazole system, silane coupler and so on.
About the thermosetting resin packing material of gained, 25 DEG C of the viscosity of measuring with rotary viscosimeter agent, 5rpm30Sec value is for 200dPaSec is above and 1000dPaSec is preferred below. When not enough 200dPaSec, be difficult to keepShape, can produce sagging. On the other hand, while exceeding 1000dPaSec, the landfill of the hole portion to printed circuit board (PCB) reduces. MoreMore than being preferably 200dPaSec and below 800dPaSec.
Viscosity by the cone rotor (circular cone rotor) recorded in JISZ8803 and the dull and stereotyped cone-plate type viscosimeter forming,For example measure by TV-30 type (eastern machine industry is manufactured, 3 ° × R9.7 of rotor).
Thermosetting resin packing material of the present invention uses the known patternings such as silk screen print method, rolling method, mould Tu FaMethod, is for example filled in the hole portion that is formed with the printed circuit board (PCB) of the conductive layers such as copper on the wall of surface and hole portion. Now, to omitMicro-mode of overflowing from hole portion is filled completely. Then, hole portion has been filled to the printed circuit board (PCB) example of thermosetting resin packing materialThereby as by heating at 150 DEG C about 60 minutes, thermosetting resin packing material solidified, form solidfied material. Preferably exampleAs more than approximately 90 DEG C and 130 DEG C heat below more than approximately 30 minutes and below 90 minutes left and right and make its precuring. Carry out like thisThe hardness ratio of the solidfied material of precuring is lower, and the part that do not need of therefore overflowing from substrate surface can be by physical grinding easilyRemove, can form tabular surface. Then, again more than approximately 140 DEG C and 180 DEG C heat below more than approximately 30 minutes and 90 minutes withLower left and right makes it solidify (finally solidifying) completely. Now, due to low expansion, solidfied material expands and does not also shrink hardly, becomesThe excellent final solidfied materials such as dimensional stability is good, agent of low hygroscopicity, adaptation, electrical insulating property. In addition above-mentioned precuring thing,Hardness can be controlled by the heat time, the heating-up temperature that change precuring.
Then, the part that do not need of the solidfied material overflowing from the surface of printed circuit board (PCB) is passed through to known physical grinding sideAfter method removal, planarization, surperficial conductive layer pattern is changed into predetermined pattern, form the circuit pattern of regulation. In addition, according toNeed, also can utilize potassium permanganate solution etc. to be cured after the surface coarsening of thing, by chemical plating etc. at solidfied materialUpper formation conductive layer.
Embodiment
Below illustrate that embodiment and comparative example are specifically described the present invention, but the present invention is not subject to the limit of following embodimentSystem. Wherein, following " part " and " % " unless otherwise specified, are quality criteria.
The preparation of paste
Composition shown in table 1 is carried out, after premixed, using triple-roller mill with mixer with compounding ratio (mass parts) separatelyDisperse, prepare the embodiment 1 to 8 of thermosetting resin packing material and the paste of comparative example 1,2.
[table 1]
Performance evaluation
To the performance evaluation of enumerating as follows as each paste of aforementioned operation gained, it the results are shown in table 2.
Viscosity:
Take the sample of the each paste of 0.2ml, with cone-plate type viscosimeter (TV-30 that Dong Ji industry company manufactures) 25 DEG C,Under the condition of rotating speed 5rpm/min, measure.
Printing (fillibility):
As shown in Figure 1, be formed with on the glass epoxy substrate 1 of through hole 2 of conductor layer 3 having by plate face plating, utilizeSilk screen print method is filled in each paste in through hole by following printing condition. After filling, put into heated air circulation type drying oven,At 130 DEG C, carry out the precuring of 45 minutes, obtain evaluating substrate. According to the solidfied material 4 being filled in the through hole of this evaluation substrateFilling extent, evaluate fillibility. Metewand as below.
Zero: be filled completely.
×: the bottom (lack of fill) that is not filled to through hole.
Printing condition
Scraper plate: scrape thickness of slab 20mm, 70 ° of hardness, oblique grinding: 23 °,
Version: PET100 order twill version,
Coining: 60kgf/cm2, scraper velocity 5cm/Sec,
Blade angle: 80 °
Gelation time:
According to the hot plate method of JISC2105, measure by gelation testing machine, remaining on mensuration temperature (150DEG C) 0.5ml sample in be gelation time so that the moment of torsion in rotating rod when rotation reaches time of 30% of peak torque. WillMinute is made as 30 minutes, more than this, is judged as not gelation.
Cross section state after solidifying:
On the substrate of thickness 1.6mm/ through hole footpath 0.25mm/ spacing 1mm, use Semi-automatic printer in through hole, to fill respectivelyPaste, by heated air circulation type drying oven heating 130 DEG C × 45 minutes+150 DEG C × 60 minutes, solidifies it. By commenting of gainedAfter valency substrate grinds to form cross-section use, with observation by light microscope, confirm whether the cross section of the solidfied material in through-hole section producesRaw crackle (underbead crack Y), space as shown in Figure 1. Determinating reference is as follows.
Zero: without abnormal.
×: there are crackle, space to produce.
Resistance to sweating heat performance:
As shown in Figure 1, on the substrate of thickness 1.6mm/ through hole footpath 0.25mm/ spacing 1mm, use Semi-automatic printer logicalThe each paste of the interior filling in hole 2, by heated air circulation type drying oven heating 130 DEG C × 45 minutes+150 DEG C × 60 minutes, solidifies it.And then at upper strata coating solder resist, under standard conditions, expose, develop, solidify, form solder mask 5, make and evaluate substrate.
This evaluation substrate is carried out in the scolder liquid of 260 DEG C, after 5 dippings in each 10 seconds, naturally cool to chamberTemperature. With visual and evaluation substrate observation by light microscope gained, confirm the solidfied material in the insulating barrier 4(of hole portion through-hole section) weekEnclose the phenomenon that the periphery of through hole while whether producing leafing (delamination) X(scolder levelling floats, be designated hereinafter simply as " layerFrom "). Determinating reference is as follows.
Zero: delamination occurs.
△: the surrounding of hole portion insulating barrier observes the state of slight leafing.
×: the surrounding of hole portion insulating barrier produces the leafing of larger width with ring-type.
[table 2]
As shown in table 2, in embodiment 1 to 8, even if preserve at 25 DEG C after 180 days, also can not there is not gelation and protectDeposit, storage-stable excellence under room temperature, shown good fillibility. In addition, resistance to sweating heat performance is also no problem. EspeciallyBe in embodiment 5,6, as epoxy curing agent, also further contain dicyandiamide with the combination of modified aliphatic polyamines, suppressAt 25 DEG C, preserve the thickening efficiency after 180 days.
On the other hand, only use in the comparative example 1 of dicyandiamide as epoxy curing agent, do not solidify when preheatingAnd cannot evaluate. In addition, use in the situation of imdazole derivatives as the comparative example 2 of epoxy curing agent the storage under room temperatureTibetan stability worsens, and preserves after 180 days at 25 DEG C gelation occurs, and cannot in through-hole section, fill, and therefore cannot evaluate.
Claims (2)
1. a thermosetting resin packing material, is characterized in that, it is for containing epoxy resin, epoxy curing agent and inorganicFiller, at least resin filling of any one of the recess of printed circuit board (PCB) and the hole portion of dual platen or multilager base plateMaterial, it contains in the group of selecting free modified aliphatic polyamines and modification ester ring type polyamines composition at least a kind as described ringEpoxy resins curing agent,
As described epoxy curing agent, also contain dicyandiamide,
With respect to the total amount of described thermosetting resin packing material, the compounding ratio of described inorganic filler be 40 quality % above andBelow 90 quality %.
2. a printed circuit board (PCB), is characterized in that, has solidifying by thermosetting resin packing material claimed in claim 1The hole portion that thing has been filled.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011217114A JP5901923B2 (en) | 2011-09-30 | 2011-09-30 | Thermosetting resin filler and printed wiring board |
| JP2011-217114 | 2011-09-30 |
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| CN103030931A CN103030931A (en) | 2013-04-10 |
| CN103030931B true CN103030931B (en) | 2016-05-04 |
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| CN104072946B (en) * | 2013-03-28 | 2017-03-22 | 太阳油墨（苏州）有限公司 | Thermosetting resin composition and printed circuit board filled with the resin composition |
| KR102438315B1 (en) * | 2013-09-04 | 2022-08-30 | 크레도 다이어그노스틱스 바이오메디컬 피티이. 엘티디. | Assay test device, kit and method of using |
| CA2935321A1 (en) * | 2014-02-07 | 2015-08-13 | Sika Technology Ag | Amine for low-emission epoxy resin products |
| JP6443688B2 (en) * | 2015-12-16 | 2018-12-26 | 株式会社オートネットワーク技術研究所 | Circuit structure and electrical junction box |
| TWI656172B (en) | 2017-09-18 | 2019-04-11 | 台燿科技股份有限公司 | Solvent-free resin composition and uses of the same |
| TWI698484B (en) | 2018-10-12 | 2020-07-11 | 台燿科技股份有限公司 | Solvent-free resin composition and uses of the same |
| CN111432549A (en) * | 2019-01-09 | 2020-07-17 | 鸿富锦精密工业(武汉)有限公司 | Circuit board |
| WO2023167267A1 (en) * | 2022-03-02 | 2023-09-07 | 太陽ホールディングス株式会社 | Curable resin composition, cured product, and printed wiring board |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1477918A (en) * | 2002-07-10 | 2004-02-25 | 日本特殊陶业株式会社 | Filling material, multilayer circuit board and its manufacturing method |
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| JP3548691B2 (en) * | 1998-01-07 | 2004-07-28 | 太陽インキ製造株式会社 | Liquid thermosetting filling composition and method for filling permanent holes in printed wiring boards using the same |
| ATE316560T1 (en) * | 1999-06-18 | 2006-02-15 | Hitachi Chemical Co Ltd | ADHESIVE, ADHESIVE ARTICLE, CIRCUIT SUBSTRATE FOR SEMICONDUCTOR MOUNTING HAVING AN ADHESIVE AND A SEMICONDUCTOR ASSEMBLY CONTAINING THE SAME |
| JP3906634B2 (en) * | 1999-11-30 | 2007-04-18 | オムロン株式会社 | One-part epoxy resin composition |
| JP2006124698A (en) * | 2001-05-16 | 2006-05-18 | Sekisui Chem Co Ltd | Curing resin composition, and sealant and end-sealing material for display element |
| JP2003105061A (en) * | 2001-09-27 | 2003-04-09 | Sanei Kagaku Kk | Photo-thermally curable resin composition, production method for hole-filled printed circuit board, and hole- filled printed circuit board |
| JP2003286333A (en) * | 2002-03-28 | 2003-10-10 | Mitsubishi Gas Chem Co Inc | Epoxy composition for filling through-hole and method for filling hole of printed wiring board |
| JP4706709B2 (en) * | 2008-03-07 | 2011-06-22 | オムロン株式会社 | One-part epoxy resin composition and use thereof |
| JP5419514B2 (en) * | 2009-03-30 | 2014-02-19 | 太陽ホールディングス株式会社 | Hole filling resin composition and printed wiring board filled with this resin composition |
| JP4893836B2 (en) * | 2010-01-29 | 2012-03-07 | オムロン株式会社 | One-part epoxy resin composition and use thereof |
| CN101985549A (en) * | 2010-11-03 | 2011-03-16 | 烟台德邦电子材料有限公司 | SMT (surface mounted technology) surface mount adhesive and preparation method thereof |
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| CN1477918A (en) * | 2002-07-10 | 2004-02-25 | 日本特殊陶业株式会社 | Filling material, multilayer circuit board and its manufacturing method |
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| CN103030931A (en) | 2013-04-10 |
| JP5901923B2 (en) | 2016-04-13 |
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