CN105802129A - Hole-filling thermocuring resin composition for printed circuit board, cured substance and printed circuit board - Google Patents

Abstract

The invention provides a hole-filling thermocuring resin composition for a printed circuit board, a cured substance and the printed circuit board; the hole-filling thermocuring resin composition for the printed circuit board is characterized by containing (A) epoxy resin having one molecule with two or more epoxy groups, (B) a filler, (C) a thermocuring catalyst, and (D) an organic solvent, wherein the (A) epoxy resin having one molecule with two or more epoxy groups contains (A-1) bisphenol type epoxy resin which is liquid at room temperature, and (A-2) epoxy resin which has one molecule with two or more epoxy groups and is solid at room temperature.

Description

The Porefilling heat curing resin composition of printed circuit board (PCB), solidfied material and printed circuit board (PCB)

Technical field

The present invention relates to the Porefilling heat curing resin composition of printed circuit board (PCB), particularly relate to as with In the hole portions such as the through hole in the printed circuit board (PCB) such as multilager base plate, double-sided substrate, via are forever filled out The compositions in hole and useful hot curing resin composition.And then, the present invention relates to use said composition The hole such as through hole, via portion has been carried out the printed circuit board (PCB) that permanent filling perforation processes.Need explanation Be, in this specification, " hole portion " refer to be referred to as in the manufacture process of printed circuit board (PCB) formed through hole, The term of via etc..

Background technology

Printed circuit board (PCB) is formed with conductor circuit pattern on base material, utilizes in the connection dish portion of conductor circuit Welding and be equipped with electronic unit, in order to protect conductor and circuit part beyond connection dish is coated with resistance Weldering film.So, soldering-resistance layer has following function: prevent weldering when carrying electronic unit to printed circuit board (PCB) Material is attached to unnecessary portion, prevents circuit oxidation or corrosion.

In recent years, the downsizing of the graph thinning of the conductor circuit pattern of printed circuit board (PCB) and erection space is Advance, in order to tackle the miniaturization/multifunction of the equipment possessing printed circuit board (PCB) further, it is desirable to printing Further compactization of circuit board.Therefore, following multilayer board is developed: setting It is placed in potting resin filler in the through hole of tellite so that it is be solidified to form even surface, then By alternately laminated to interlayer resin insulating layers and conductor circuit layers on this circuit substrate, thus the multilamellar formed Printed circuit board (PCB)；Or it is filled with on the substrate of resin filler in through hole etc. and directly forms soldering-resistance layer Multilayer board.In such circumstances it is desirable to be developed for being filled into the hole such as through hole, via portion In printing, the permanent filling perforation compositions of the solidfied material excellent such as resistance to soldering heat performance (sees WO2002/044274 publication).

Summary of the invention

The problem that invention is to be solved

And then, electronic equipment is according to using environment to be heated cooled, the most concomitantly, and printed circuit Plate also repeats to expand/shrink.Its result, when remaining volatile composition in filler, it occurs Volatilization (aerofluxus), makes filler crack, the fault of leafing etc.Produce this crackle, leafing Time, hot and humid under PCT patience (pressure cooker patience) reduce, and cause the exhausted of printed circuit board (PCB) The deterioration of edge reliability.

The present invention makes in view of foregoing problem of the prior art, and its basic object is to carry The generation of aerofluxus is suppressed not have hole under the hot conditions of cured, solder leveling etc. for being obtained in that Portion's insulating barrier cracks the solidfied material of the problem of (underbead crack) and for being filled into hole portion The Porefilling heat curing resin composition of printed circuit board (PCB) of printing excellence, solidfied material, printed circuit Plate.

For solving the scheme of problem

In order to solve the problems referred to above, present inventor has performed further investigation.First, in order to reduce as splitting Stricture of vagina, the capacity of key factor of leafing, it is contemplated that do not use reactive diluted material.Reactive dilution Material refers to, and at room temperature for low viscous liquid, can by heating or ultraviolet irradiate occur consolidate Change the material of reaction, sometimes can substitute for organic solvent and use.But, this reactive diluted material Owing to boiling point is higher than organic solvent, the therefore meeting remained unreacted thing when not being fully cured, sometimes because of it After heating process and volatilize.On the other hand, when using reactive diluted material, gluing of resin combination Degree becomes too high, and printing reduces.

On the other hand, when using organic solvent in a large number to reduce the viscosity of resin combination, in solidification Thing produces bubble, the unfavorable condition such as cracks.

So, present inventor has performed research further, result is by using specific resin, successfully It also is able to prevent self-curing when need not reactive diluted material compounded with organic solvent even if obtaining The generation of the aerofluxus of thing, the solidfied material that resistance to anti-thread breakage excellence can be obtained and printing in the portion of hole is excellent Different thermally curable resin composition, thus complete the present invention.

The present invention is the Porefilling heat curing resin composition of a kind of printed circuit board (PCB), it is characterised in that Contain: (A) 1 molecule has the epoxy resin of more than 2 epoxy radicals, (B) filler, (C) heat Curing catalysts and (D) organic solvent, have more than 2 epoxy radicals in aforementioned (A) 1 molecule Epoxy resin contain under (A-1) room temperature for the bisphenol-type epoxy resin of liquid and (A-2) room temperature Down for 1 molecule of solid has the epoxy resin of more than 2 epoxy radicals.

As the preferred present invention, according to the Porefilling heat curing resin combination of above-mentioned printed circuit board (PCB) Thing, aforementioned (C) thermal curing catalyst is imidazoles.

And then, the present invention is a kind of solidfied material, it is characterised in that it is filling out aforementioned printed circuit board (PCB) Hole hot curing resin composition carries out heat cure and obtains.

Additionally, the present invention is a kind of printed circuit board (PCB), it is characterised in that have said curing thing.And then, The present invention is a kind of printed circuit board (PCB), it is characterised in that the hole portion of printed circuit board (PCB) is by aforementioned Thermocurable The solidfied material of resin combination is filled.

The effect of invention

In accordance with the invention it is possible to provide the aerofluxus suppressed from solidfied material, resistance to anti-thread breakage excellence can be obtained Solidfied material and the excellent hot curing resin composition of printing in the portion of hole.It addition, the present invention Hot curing resin composition be best suitable in the hole portions such as the through hole of printed circuit board (PCB), via fill, Therefore, it is possible to be used as permanent insulating properties via-fill applications.

Additionally, in accordance with the invention it is possible to provide and do not damage consolidating of resistance to soldering heat performance and resistance to anti-thread breakage excellence Compound and there is the printed circuit board (PCB) of this solidfied material.

Detailed description of the invention

The Porefilling heat curing resin composition of the printed circuit board (PCB) of the present invention is characterised by, contains: (A) have the epoxy resin of more than 2 epoxy radicals in 1 molecule, (B) filler, (C) heat cure are urged Agent and (D) organic solvent, have the epoxy of more than 2 epoxy radicals in aforementioned (A) 1 molecule Resin contains under (A-1) room temperature for being solid under the bisphenol-type epoxy resin of liquid and (A-2) room temperature 1 molecule of body has the epoxy resin of more than 2 epoxy radicals.

The hot curing resin composition of the present invention is due to combination above-mentioned (A)～(D) composition, and then (A) 1 molecule has the epoxy resin of more than 2 epoxy radicals and contains under (A-1) room temperature the bisphenol type for liquid For 1 molecule of solid has the epoxy of more than 2 epoxy radicals under epoxy resin and (A-2) room temperature Resin, therefore, it is possible to formed such as lower opening portion insulating barrier: under the conditions of the high temperature such as cured, solder leveling The generation of aerofluxus is suppressed not have in hole portion insulating barrier to crack (underbead crack) or at hole portion insulating barrier Periphery produce and outer insulation (solder mask layer, insulating resin layer) between stripping (leafing) Etc problem, and excellences such as resistance to soldering heat performance, moisture-proof, PCT patience, insulating reliability. It addition, the hot curing resin composition of the present invention is excellent due to printing, therefore it is best suitable for printing electricity The hole portions such as the through hole of road plate, via fill.

Hereinafter, " Porefilling heat curing resin composition of printed circuit board (PCB) " is write a Chinese character in simplified form into " Thermocurable Resin combination ".

(A) 1 molecule in the hot curing resin composition of the present invention have more than 2 epoxy radicals Epoxy resin contains under (A-1) room temperature under the bisphenol-type epoxy resin of liquid and (A-2) room temperature For 1 molecule of solid has the epoxy resin of more than 2 epoxy radicals.

As under (A-1) room temperature being the bisphenol-type epoxy resin of liquid, can list epoxide equivalent is The bisphenol A type epoxy resin of below 300g/eq, bisphenol f type epoxy resin etc..As concrete example, have three Pedicellus et Pericarpium Trapae KCC manufacture jER825, jER827, jER828, jER828EL, jER828US, JER828XA, Nippon Steel & Sumitomo Metal Corporation manufacture YD-8125, YD-825GS, YD-825GSH, ADEKA Corp. manufacture EP-4100, EP-4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4400, EP-4520S, EP-4530, Dainippon Ink Chemicals manufacture EPICLON 840, EPICLON 840-S、EPICLON 850、EPICLON EXA-850CRP、EPICLON 850-LC The liquid bisphenol A epoxy resin of (being trade name)；Mitsubishi chemical Co., Ltd manufacture jER806, JER806H, jER807, Nippon Steel & Sumitomo Metal Corporation manufacture YD-8170, C, TDF-870GS, EP-4901, the EPICLON of Dainippon Ink Chemicals's manufacture that ZX-1059, ADEKA Corp. manufacture 830、EPICLON 830-S、EPICLON 835、EPICLON EXA-830CRP、EPICLON The liquid bisphenol F type asphalt mixtures modified by epoxy resin of EXA-830LVP, EPICLON EXA-835LV (being trade name) Fat；These can be used alone or mix two or more and use.

As in 1 molecule for solid under (A-2) room temperature, there is the epoxy resin of more than 2 epoxy radicals, Known usual material can be used.Such as, can list: Mitsubishi chemical Co., Ltd manufactures JER1001, jER1004, Dainippon Ink Chemicals manufacture EPICLON 1050, EPICLON 1055, EPICLON 2050、EPICLON 3050、EPICLON 4050、EPICLON 7050、EPICLON The bisphenol A type epoxy resin of HM-091, EPICLON HM-101 (being trade name)；Mitsubishi Chemical EPICLON 152, the EPICLON that the jERYL903 of Co., Ltd.'s manufacture, Dainippon Ink Chemicals manufacture 153, the Epotohto YDB-400 of Toto Kasei KK's manufacture, YDB-500, DOW Chemical public affairs The Araldite8011 of D.E.R.542, Ciba Specialty Chemicals Inc. manufacture of department's manufacture, Sumitomo The Sumi-Epoxy ESB-400 of chemical industry Co., Ltd. manufacture, ESB-700, Asahi Kasei Industrial Co., Ltd A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin that commercial firm manufactures；Rhizoma Sparganii Learn Co., Ltd. manufacture jER152, jER154, Dow Chemical manufacture D.E.N.431, D.E.N.438, Dainippon Ink Chemicals manufacture EPICLON N-660, EPICLON N-665, EPICLON N-670、EPICLON N-673、EPICLON N-680、EPICLON N-690、 EPICLON N-695、EPICLON N-665-EXP、EPICLON N-672-EXP、EPICLON N-665-EXP-S、EPICLON N-662-EXP-S、EPICLON N-665-EXP-S、EPICLON N-670-EXP-S、EPICLON N-685-EXP-S、EPICLON N-730、EPICLON N-770、 EPICLON N-865, Toto Kasei KK manufacture Epotohto YDCN-701, YDCN-704, Ciba Specialty Chemicals Inc. manufacture AralditeECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307, Nippon Kayaku K. K manufacture EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Company Ltd The Sumi-Epoxy ESCN-195X of manufacture, ESCN-220, Asahi Chemical Industry Co., Ltd manufacture A.E.R.ECN-235, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin；Rhizoma Sparganii Learn Co., Ltd. manufacture YL-933, Dow Chemical manufacture T.E.N., EPPN-501, EPPN-502 etc. (being trade name) three hydroxyphenyl methane type epoxy resin；Mitsubishi chemical Co., Ltd's system Di-cresol type or the biphenyl phenolic such as YL-6056, YX-4000, YL-6121 (being trade name) of making Epoxy resin or their mixture；The EBPS-200 of Nippon Kayaku K. K's manufacture, rising sun electrochemical industry The bisphenol Ss such as EPX-30, the EXA-1514 (trade name) of Dainippon Ink Chemicals's manufacture that Co., Ltd. manufactures Type epoxy resin；The bisphenol-A phenolics such as the jER157S (trade name) that Mitsubishi chemical Co., Ltd manufactures are clear Paint shaped epoxy resin；JERYL-931, Ciba Specialty that Mitsubishi chemical Co., Ltd manufactures (being trade name) the four hydroxy phenyl ethane type epoxy resin such as the Araldite163 that Chemicals Inc. manufactures； The AralditePT810 of Ciba Specialty Chemicals Inc. manufacture, Nissan Chemical Ind Ltd's system The TEPIC made etc. (being trade name) hetero ring type epoxy resin；NOF Corp manufactures The o-phthalic acid diglycidyl ester resins such as BLEMMER DDT；Toto Kasei KK manufactures Four glycidyl group dimethylbenzene acyl group ethane resin (the tetraglycidyl xylenoyl ethane such as ZX-1063 resin)；The ESN-190 of Nippon Steel Chemical Co., Ltd's manufacture, ESN-360, Dainippon Ink Chemicals manufacture , EXA-4750, EXA-4700 etc. are containing Naphthol-based Epoxy Resin；Dainippon Ink Chemicals manufacture HP-7200, HP-7200H etc. have the epoxy resin of dicyclopentadiene skeleton；NOF Corp manufactures The glycidyl methacrylate such as CP-50S, CP-50M copolymerization system epoxy resin；And then cyclohexyl horse Carry out the copolymerization epoxy resin of acid imide and glycidyl methacrylate；Epoxide modified polybutadiene rubber Gum derivative (PB-3600 etc. that such as Daisel chemical industry Co., Ltd manufactures), CTBN modification ring Epoxy resins (YR-102, YR-450 etc. that such as Toto Kasei KK manufactures) etc., but be not limited to These.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, particularly preferred phenol Novolac type epoxy resin, modified novolac type epoxy resin, hetero ring type epoxy resin, di-cresol Type epoxy resin or their mixture.

It should be noted that the solid epoxy of the present invention with at 20 DEG C for solid and at 40 DEG C is The semisolid epoxy resin of liquid is different.

(A-1) under room temperature be liquid bisphenol-type epoxy resin and (A-2) room temperature under for 1 point of solid Son has the compounding of epoxy resin of more than 2 epoxy radicals than being preferably (A-1)/(A-2) The scope of=20/80～80/20, the scope of more preferably 30/70～70/30, more preferably The scope of 40/60～60/40.(A-1), when epoxy resin is more than 20, printing is excellent.On the other hand, (A-1) when epoxy resin is less than 80, resistance to anti-thread breakage well.

Stress that (B) filler of the present invention is caused by cure shrinkage for lax, adjust linear expansion coefficient. As this inorganic filler, it is possible to use the known inorganic filler generally used in resin combination. Specifically, include, for example out silicon dioxide, barium sulfate, calcium carbonate, silicon nitride, aluminium nitride, nitrogen Change boron, aluminium oxide, magnesium oxide, aluminium hydroxide, magnesium hydroxide, titanium oxide, Muscovitum, Talcum, organic The metal packings such as the non-metallic fillers such as bentonite, copper, gold, silver, palladium, silicon.These can be used alone Or combine two or more use.

About the shape of inorganic filler, can list spherical, needle-like, lamellar, flakey, hollow form, Amorphous, hexagon shape, cubic, flake etc., go out from the high viewpoint filled of inorganic filler Send out, the most spherical.

In the middle of these, agent of low hygroscopicity, the silicon dioxide of low volumetric expansion excellence, calcium carbonate are preferably used. As silicon dioxide, noncrystalline, crystal, it is also possible to for their mixture.Fill from realizing height Angle set out, the most spherical noncrystalline (melting) silicon dioxide.It addition, as calcium carbonate, sky Right ground calcium carbonate, the winnofil of synthesis.

It addition, mean diameter d50 of (C) filler is preferably 0.1～25 μm.Mean diameter be 0.1 μm with Time upper, it is possible to reduce specific surface area, dispersibility improves, and easily increases the loading of filler.Another Aspect, below 25 μm in the case of, to the filling in the hole portion of the base plate for packaging that carries quasiconductor Property good, when part after filling perforation forms conductor layer, flatness is good.More preferably 0.1～10 μm.

The compounding amount of this (B) filler has more than 2 epoxy radicals relative in 100 parts (A) 1 molecule Epoxy resin be preferably 50 parts～300 parts, more preferably 80 parts～230 parts, more preferably 100 parts ～200 parts.By the compounding amount of (B) filler is set to more than 100 parts, it is possible to the solidfied material that suppression obtains Thermal expansion, resistance to anti-thread breakage excellence, and then sufficient abrasiveness, adaptation can be obtained.On the other hand, By being set under 300 parts, pasteization is easy, it is possible to obtain good printing, filling perforation fillibility.

As (C) thermal curing catalyst of the present invention, include, for example out imidazoles, 2-methylimidazole, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-benzene The imdazole derivatives such as base imidazoles, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole；Dicyandiamide, benzyl two Methyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl Amine, 4-methyl-N, amines, adipic dihydrazide, the sebacic dihydrazide etc. such as N-dimethyl benzyl amine Hydrazine compound；The phosphorus compounds etc. such as triphenylphosphine.It addition, as commercially available product, include, for example out four countries 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ that chemical conversion Industrial Co., Ltd manufactures are (all Trade name for imidazole compound), San-Apro Ltd. manufacture U-CAT (registered trade mark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethyl amine), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc..Limit the most especially Due to these, as long as the thermal curing catalyst of epoxy resin, oxetane compound, it is possible to single Solely use or mix two or more and use.Alternatively, it is also possible to use guanamines, methyl guanamines, benzoguanamine, Tripolycyanamide, 2,4-diaminourea-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diaminourea -s-triazine, 2-vinyl-4,6-diaminourea-s-triazine isocyanuric acid adduct, 2,4-diaminourea-6-methyl These are preferably also made by the Striazine derivatives such as acryloyl-oxyethyl-s-triazine isocyanuric acid adduct Compound for adaptation imparting agent function is applied in combination with aforementioned thermal curing catalyst.

The ratio that compounding amount is common amount of these thermal curing catalysts is sufficient for, relative to 100 mass Part (A) 1 molecule has the epoxy resin of more than 2 epoxy radicals, preferably 0.1～20 mass parts, more It is preferably 0.5～15.0 mass parts.

The state that (D) organic solvent of the present invention is easily coated with for making hardening resin composition become, Make it be dried after coating and carry out film forming.As this organic solvent, it is possible to use known usual thing Matter.As concrete example, the ketone such as butanone, Ketohexamethylene can be listed；Toluene, dimethylbenzene, durene Etc. aromatic hydrocarbon；Methylcellulose, ethyl cellulose, butyl cellulose, methyl carbitol, butyl Carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, DPE, triethylene glycol list second The glycol ethers such as ether；Ethyl acetate, butyl acetate, cellulose acetate, diethylene glycol monoethyl ether acetas The esters such as the carboxylate with above-mentioned glycol ethers；The alcohols such as ethanol, propanol, ethylene glycol, propylene glycol；Pungent The aliphatic hydrocarbon such as alkane, decane；The oil such as petroleum ether, Petroleum, hydrogenated naphtha, solvent naphtha Series solvent etc..

(D) the compounding amount of organic solvent is preferably 1～10 matter relative to hot curing resin composition total amount The scope of amount %, more preferably 3～7 mass %.By organic solvent being set to more than 1 mass %, it is possible to Reducing the viscosity of hot curing resin composition, printing improves.On the other hand, organic solvent is 10 matter During amount below %, it is possible to the generation of the bubble in suppression solidfied material.

The hot curing resin composition of the present invention can also be added as needed on fine particle silica, organic The thixotropic agent such as bentonite, montmorillonite, brucite.From the ageing stability as thixotropic agent, preferably The electrical characteristics of organobentonite, brucite, particularly brucite are excellent.Furthermore it is possible to compounding is as hot polymerization Close defoamer and/or levelling agent, imidazoles system, the thiazoles such as inhibitor, silicon-type, fluorine system, macromolecular The silane couplers such as system, triazole system, antirust agent and then the copper resistant agent such as bis-phenol system, triazine thiol system etc. that The known usual additive kind of sample.It should be noted that the present invention is preferably without reactive diluted material.

For the hot curing resin composition of the present invention, such as, it is adjusted to be suitable to be coated with aforementioned organic solvents The viscosity of cloth method, utilizes dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain to be coated with The methods such as method are applied on base material, and the temperature being then heated to about 130～180 DEG C makes its heat cure, thus Each spies such as resistance to soldering heat performance, chemical proofing, resistance to hygroscopicity, adaptation, electrical characteristics can be formed Property excellent cured coating film.

As above-mentioned base material, have: there is the printed circuit board (PCB) in the hole such as through hole, via portion.Specifically, In addition to can using and being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board, it is also possible to Use copper-clad laminated board and Kapton, PET film, glass substrate, ceramic substrate, crystalline substance Plectane etc..Described copper-clad laminated board is to make paper using-phenolic resin, paper-epoxy resin, glass cloth-asphalt mixtures modified by epoxy resin Fat, glass-polyimides, glass cloth/non-woven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthesis Whole grades (FR-4 etc.) of the composites such as fiber-epoxy resin, fluororesin polyethylene PPO cyanate Copper-clad laminated board.

Embodiment

According to the various compositions shown in table 1 below and table 2 and the ratio (quality shown in Tables 1 and 2 Part) be compounded, after blender premixing, mixing with triple-roller mill, prepare heat-curing resin combination Thing.

Table 1

Table 2

* 1: liquid epoxy resin, the jER828 of Mitsubishi chemical Co., Ltd's manufacture, liquid bisphenol A type ring Epoxy resins, epoxide equivalent 184-194g/eq

* 2: liquid epoxy resin, the EPICLON 830 of Dainippon Ink Chemicals's manufacture, liquid bisphenol F epoxy Resin, epoxide equivalent 165-177g/eq

* 3: EPICLON N-660, cresol novolac that solid epoxy, Dainippon Ink Chemicals manufacture are clear Paint shaped epoxy resin, epoxide equivalent 202-212g/eq

* 4: jER157S, bisphenol-A phenolic that solid epoxy, Mitsubishi chemical Co., Ltd manufacture are clear Paint shaped epoxy resin, epoxide equivalent 200-220g/eq

* 5: filler, the BARIACE B-30 of KCC's manufacture, barium sulfate, mean diameter 0.3μm

* the Softon2200 of 6: filler, SHIRAISHI CALCIUM KAISHA, LTD. manufacture, carbon Acid calcium, mean diameter 1.0 μm

* 7: Admafine SO-C3 that filler, Admatechs Co., Ltd. manufacture, silicon dioxide, flat All particle diameter 0.9 μm

* 8: thermal curing catalyst, four countries are melted into 2PHZ, 2-phenyl-4,5-dihydroxy that Co., Ltd. manufactures Methylimidazole.

* 9: 2MZ-A, 2,4-diaminourea that thermal curing catalyst, Shikoku Chem manufacture -6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine

* 10: organic solvent, dipropylene glycol monomethyl ether

* 11: organic solvent, diethylene glycol monoethyl ether acetas

* 12: EPOLIGHT M-1230 that reactive diluted material, Kyoeisha Chemical Co., Ltd. manufacture, C12, C13 mixing higher alcohol glycidyl ether

* 13: Flowlen AC-902, silicon-type that defoamer, Kyoeisha Chemical Co., Ltd. manufacture disappear Infusion

<printing>

To thickness 1.6mm, plated through hole diameter 0.25mm, double-sided substrate (the non-shape of through-hole spacing 1mm Become pattern, via count 25) carry out the pickling as pre-treatment, then utilize Semi-automatic printer (Seria Co., Ltd. manufactures) carry out filling perforation printing with the hot curing resin composition of previous embodiment and comparative example. Now, hot curing resin composition loading in through hole is evaluated.

◎: hot curing resin composition loading in through hole is abundant and shape is good

Zero: hot curing resin composition loading in through hole is abundant

△: hot curing resin composition loading in through hole is the most insufficient

×: hot curing resin composition loading in through hole is the most insufficient

<bubble>

To thickness 1.6mm, plated through hole diameter 0.25mm, double-sided substrate (the non-shape of through-hole spacing 1mm Become pattern, via count 25) carry out the pickling as pre-treatment, then utilize Semi-automatic printer (Seria Co., Ltd. manufactures) carry out filling perforation printing with the hot curing resin composition of previous embodiment and comparative example. Then, utilize heated air circulation type drying oven carry out at 150 DEG C 30 minutes Cooking/Curing.Cut and obtain Test substrate, uses the quantity of the bubble produced in optical microscope 25 through holes of counting.

The quantity of ◎: bubble is less than 5

Zero: the quantity of bubble is more than 5 and is less than 10

The quantity of △: bubble is more than 10 and is less than 15

×: the quantity of bubble is more than 15

<resistance to soldering heat performance>

The hot curing resin composition of previous embodiment and comparative example is formed by being screen printed onto Carry out pattern coating on the copper clad laminate of pattern, then add at 150 DEG C in heated air circulation type drying oven Heat makes it solidify in 30 minutes, makes evaluation substrate.The substrate obtained is coated with rosin series scaling powder, It is immersed in the solder bath being set in advance as 260 DEG C, after scaling powder being washed with modified alcohol, by visually Cured coating film is heaved and strips off and be evaluated.Determinating reference is as follows.

◎: even if being repeated 4 times above 10 seconds dippings, the most not observing and stripping off

Zero: even if being repeated 3 times 10 seconds dippings, the most not observing and stripping off

△: strip off slightly when being repeated 3 times 10 seconds dippings

×: within being repeated 2 times, during 10 seconds dippings, cured film existence is heaved, is stripped off

<resistance to anti-thread breakage>

To thickness 1.6mm, plated through hole diameter 0.25mm, double-sided substrate (the non-shape of through-hole spacing 1mm Become pattern, via count 25) carry out the pickling as pre-treatment, then utilize Semi-automatic printer (Seria Co., Ltd. manufactures) carry out filling perforation printing with the hot curing resin composition of previous embodiment and comparative example. Then, carry out at 150 DEG C in heated air circulation type drying oven 30 minutes Cooking/Curing.The examination that will obtain Test and impregnated 5 times with 10 seconds in the solder liquid of 288 DEG C with substrate, then naturally cool to room temperature.To To test substrate be ground for cross-section, then with observation by light microscope, evaluation is filled out The number of the crackle of hole solidfied material.

The sum of ◎: crackle is less than 5

Zero: the sum of crackle is more than 5 and is less than 10

The sum of △: crackle is more than 10 and is less than 20

×: the sum of crackle is more than 20

<aerofluxus>

The hot curing resin composition of previous embodiment and comparative example is coated with by entire surface by silk screen printing Cloth is on Copper Foil, and then in heated air circulation type drying oven, at 150 DEG C, heating makes it solidify in 30 minutes. Use cutter to cut the cured coating film of gained, utilize Hitachi High-Technologies Corporation. The differential hot-hot manufactured re-synchronizes determinator STA7200 and heats from room temperature with 10 DEG C/min of programming rate To 300 DEG C, the weight loss at measuring 250 DEG C is as capacity.

: the weightlessness of cured coating film is less than 5.0%

×: the weightlessness of cured coating film is more than 5.0%

Table 3

Table 4

By table 3, table 4 it will be apparent that, the hot curing resin composition of the present invention can obtain aerofluxus, gas Bubble is less and resistance to soldering heat performance, the solidfied material of resistance to anti-thread breakage excellence.In addition we know, the heat of the present invention Hardening resin composition is the most excellent due to printing, and the filling perforation being therefore suitable for use as printed circuit board (PCB) is used.

Claims (4)

1. the Porefilling heat curing resin composition of a printed circuit board (PCB), it is characterised in that contain:

(A) 1 molecule has more than 2 epoxy radicals epoxy resin,

(B) filler,

(C) thermal curing catalyst and

(D) organic solvent,

Described (A) 1 molecule has the epoxy resin of more than 2 epoxy radicals contain under (A-1) room temperature and be For 1 molecule of solid has more than 2 under the bisphenol-type epoxy resin of liquid and (A-2) room temperature The epoxy resin of epoxy radicals.

The Porefilling heat curing resin composition of printed circuit board (PCB) the most according to claim 1, its Being characterised by, described (C) thermal curing catalyst is imidazoles.

3. a solidfied material, it is characterised in that it is by the printed circuit board (PCB) described in claim 1 or 2 Porefilling heat curing resin composition heat cure and obtain.

4. a printed circuit board (PCB), it is characterised in that there is the solidfied material described in claim 3.