CN105802129B - Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board - Google Patents
Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board Download PDFInfo
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- CN105802129B CN105802129B CN201410852265.4A CN201410852265A CN105802129B CN 105802129 B CN105802129 B CN 105802129B CN 201410852265 A CN201410852265 A CN 201410852265A CN 105802129 B CN105802129 B CN 105802129B
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Abstract
The Porefilling heat curing resin composition of present invention offer printed circuit board, solidfied material, and printed circuit board, the Porefilling heat curing resin composition of the printed circuit board is characterized in that, contain: with the epoxy resin of 2 or more epoxy groups in (A) 1 molecule, (B) filler, (C) thermal curing catalyst, and (D) organic solvent, it is the bisphenol-type epoxy resin of liquid that epoxy resin in aforementioned (A) 1 molecule with 2 or more epoxy groups, which contains (A-1) at room temperature, and (A-2) is at room temperature the epoxy resin with 2 or more epoxy groups in 1 molecule of solid.
Description
Technical field
The present invention relates to the Porefilling heat curing resin compositions of printed circuit board, more particularly to as to multilayer
The hole portions such as through-hole, via hole in the printed circuit boards such as substrate, double-sided substrate carry out the composition of permanent filling perforation and useful heat
Hardening resin composition.In turn, permanent the present invention relates to using the composition to carry out the hole portions such as through-hole, via hole
The printed circuit board of filling perforation processing.It should be noted that " hole portion " refers to the manufacture being referred to as in printed circuit board in this specification
The term of the through-hole, the via hole that are formed in the process etc..
Background technique
Printed circuit board is formed with conductor circuit pattern on substrate, is taken in the connection pan portion of conductor circuit using welding
It is loaded with electronic component, in order to protect conductor and the circuit part other than terminal pad is covered with solder mask.In this way, solder mask has
Following function: it prevents solder attachment in unnecessary portion when carrying electronic component to printed circuit board, prevents circuit from aoxidizing
Or corrosion.
In recent years, the downsizing of the graph thinning and mounting area of the conductor circuit pattern of printed circuit board is promoting, and is
It is further to cope with the miniaturization/multifunction for having the equipment of printed circuit board, it is expected that printed circuit board is further light
Thin short and smallization.Therefore, multilayer board below is developed: the potting resin in the through-hole for being set to printed circuit board
Filler makes it be solidified to form even surface, then hands over interlayer resin insulating layers and conductor circuit layers on the circuit substrate
For stacking, thus the multilayer board formed；Or direct shape on the substrate in through-hole etc. filled with resin filler
At the multilayer board of solder mask.In such circumstances it is desirable to develop for being filled into the hole portions such as through-hole, via hole
The permanent filling perforation of the solidfied materials excellents such as printing, resistance to soldering heat performance is with composition (referring to WO2002/044274 public affairs
Report).
Summary of the invention
Problems to be solved by the invention
In turn, electronic equipment is heated cooled according to use environment, accompanying this, printed circuit board also repeat into
Row expansion/contraction.As a result, volatilization (exhaust) occurs, generates filler when remaining volatile ingredient in filler
The failure of crackle, leafing etc.When generating this crackle, leafing, the PCT patience (pressure cooker patience) under high temperature and humidity is reduced,
And lead to the deterioration of the insulating reliability of printed circuit board.
The present invention is made in view of foregoing problem of the prior art, and basic object, which is to provide, to be obtained
It obtains and inhibits the generation of exhaust without cracking in hole portion insulating layer under the hot conditions of curing process, solder leveling etc.
The filling perforation of the solidfied material of the problem of (underbead crack) and the excellent printed circuit board of printing for being filled into hole portion is hot
Hardening resin composition, solidfied material, printed circuit board.
The solution to the problem
To solve the above-mentioned problems, present inventor has performed further investigations.Firstly, in order to reduce as crackle, leafing
The capacity of key factor, it is contemplated that without using reactive diluted material.Reactive diluted material refers to, is at room temperature low viscous
The liquid of degree, the material that reaction can be cured by heating or ultraviolet light irradiation, can replace organic solvent sometimes
It uses.However, this reactivity diluted material can remain not since boiling point is higher than organic solvent when not being fully cured
Reactant volatilizees because of heating process thereafter sometimes.When on the other hand, using reactive diluted material, resin combination
Viscosity becomes excessively high, and printing reduces.
On the other hand, it when largely using organic solvent to reduce the viscosity of resin combination, is generated in solidfied material
Bubble, a problem that cracking.
So, as a result by using specific resin, being successfully not required to present inventor has performed further research
Want reactive diluted material, even if compounded with organic solvent when can prevent the generation of the exhaust from solidfied material, can obtain
Resistance to anti-thread breakage excellent solidfied material and the excellent thermally curable resin composition of printing into hole portion, so as to complete this
Invention.
The present invention is a kind of Porefilling heat curing resin composition of printed circuit board, which is characterized in that is contained: (A) 1
It is preceding with epoxy resin, (B) filler, (C) thermal curing catalyst and (D) organic solvent of 2 or more epoxy groups in molecule
It is the bisphenol-type epoxy resin of liquid that stating in (A) 1 molecule, there is the epoxy resin of 2 or more epoxy groups, which to contain (A-1) at room temperature,
And (A-2) is at room temperature the epoxy resin with 2 or more epoxy groups in 1 molecule of solid.
It is aforementioned (C) according to the Porefilling heat curing resin composition of above-mentioned printed circuit board as the preferred present invention
Thermal curing catalyst is imidazoles.
In turn, the present invention is a kind of solidfied material, which is characterized in that it is by the filling perforation heat cure of aforementioned printed circuit board
Property resin combination carry out heat cure obtained from.
In addition, the present invention is a kind of printed circuit board, which is characterized in that have said curing object.In turn, the present invention one
Kind printed circuit board, which is characterized in that the hole portion of printed circuit board is filled by the solidfied material of aforementioned hot curing resin composition.
The effect of invention
In accordance with the invention it is possible to provide inhibit exhaust from solidfied material, resistance to anti-thread breakage excellent solidfied material can be obtained and
And the hot curing resin composition that printing into hole portion is excellent.In addition, hot curing resin composition of the invention is most
It is suitble to fill in the hole portions such as the through-hole to printed circuit board, via hole, therefore can be used as permanent insulating properties via-fill applications.
In addition, in accordance with the invention it is possible to provide do not damage resistance to soldering heat performance and resistance to anti-thread breakage excellent solidfied material and tool
There is the printed circuit board of the solidfied material.
Specific embodiment
The Porefilling heat curing resin composition of printed circuit board of the invention is characterized in that, is contained: (A) 1 molecule
In with 2 or more epoxy groups epoxy resin, (B) filler, (C) thermal curing catalyst and (D) organic solvent, it is aforementioned (A)
In 1 molecule with 2 or more epoxy groups epoxy resin contain (A-1) at room temperature for liquid bisphenol-type epoxy resin and
It (A-2) is at room temperature the epoxy resin with 2 or more epoxy groups in 1 molecule of solid.
Hot curing resin composition of the invention has in (A) 1 molecule in turn due to combining above-mentioned (A)~(D) ingredient
The epoxy resin of 2 or more epoxy groups contains the bisphenol-type epoxy resin that (A-1) is liquid at room temperature and (A-2) at room temperature
It has the epoxy resin of 2 or more epoxy groups in 1 molecule of solid, therefore is capable of forming following hole portion insulating layer: solidifying
Inhibit under the conditions of the high temperature such as processing, solder leveling exhaust generation without cracked in hole portion insulating layer (underbead crack) or
The removing (leafing) etc between outer insulation (solder mask layer, insulating resin layer) is generated in the peripheral portion of hole portion insulating layer
The problem of, and resistance to soldering heat performance, moisture-proof, PCT patience, insulating reliability etc. are excellent.In addition, Thermocurable of the invention
Resin combination is most suitable for filling in the hole portions such as the through-hole to printed circuit board, via hole since printing is excellent.
Hereinafter, " Porefilling heat curing resin composition of printed circuit board " to be write a Chinese character in simplified form into " heat-curing resin combination
Object ".
Epoxy resin in (A) 1 molecule in hot curing resin composition of the invention with 2 or more epoxy groups contains
Having (A-1) at room temperature, which is the bisphenol-type epoxy resin of liquid, and (A-2) is at room temperature has 2 or more in 1 molecule of solid
The epoxy resin of epoxy group.
It is at room temperature the bisphenol-type epoxy resin of liquid as (A-1), can enumerate epoxide equivalent is that 300g/eq is below
Bisphenol A type epoxy resin, bisphenol f type epoxy resin etc..As concrete example, the jER825 for thering is Mitsubishi chemical Co., Ltd to manufacture,
YD-8125, YD- that jER827, jER828, jER828EL, jER828US, jER828XA, Nippon Steel & Sumitomo Metal Corporation manufacture
EP-4100, EP-4100G, EP-4100E, EP-4100TX, EP- that 825GS, YD-825GSH, ADEKA Corp. manufacture
4300E, EP-4400, EP-4520S, EP-4530, Dainippon Ink Chemicals manufacture EPICLON 840, EPICLON 840-S,
The liquid bisphenol A type asphalt mixtures modified by epoxy resin of EPICLON 850, EPICLON EXA-850CRP, EPICLON 850-LC (being trade name)
Rouge；The YD- that jER806, jER806H of Mitsubishi chemical Co., Ltd's manufacture, jER807, Nippon Steel & Sumitomo Metal Corporation manufacture
8170, C, TDF-870GS, ZX-1059, the EP-4901 of ADEKA Corp.'s manufacture, Dainippon Ink Chemicals manufacture
EPICLON830、EPICLON 830-S、EPICLON 835、EPICLON EXA-830CRP、EPICLONEXA-830LVP、
The liquid bisphenol F type epoxy resin of EPICLON EXA-835LV (being trade name)；These can be used alone or mix 2 kinds
It uses above.
It is at room temperature the epoxy resin with 2 or more epoxy groups in 1 molecule of solid as (A-2), public affairs can be used
Know usual substance.For example, can enumerate: jER1001, jER1004 of Mitsubishi chemical Co., Ltd's manufacture, Dainippon Ink Chemicals
The EPICLON 1050 of manufacture, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050,
The bisphenol A type epoxy resin of EPICLON 7050, EPICLONHM-091, EPICLON HM-101 (being trade name)；Mitsubishi
Learn the jERYL903 of Co., Ltd.'s manufacture, the EPICLON 152 of Dainippon Ink Chemicals's manufacture, EPICLON153, Dongdu chemical conversion strain formula
D.E.R.542, Ciba Specialty that Epotohto YDB-400 of commercial firm's manufacture, YDB-500, Dow Chemical manufacture
The Sumi-Epoxy ESB- that the Araldite8011 of Chemicals Inc. manufacture, Sumitomo Chemical Company Ltd manufacture
400, (being trade name) brominated epoxy such as A.E.R.711, A.E.R.714 that ESB-700, Asahi Chemical Industry Co., Ltd manufacture
Resin；The D.E.N.431 of jER152, jER154, Dow Chemical's manufacture that Mitsubishi chemical Co., Ltd manufactures,
EPICLON N-660, the EPICLON N-665, EPICLON N-670, EPICLON that D.E.N.438, Dainippon Ink Chemicals manufacture
N-673、EPICLON N-680、EPICLON N-690、EPICLON N-695、EPICLON N-665-EXP、EPICLON N-
672-EXP、EPICLONN-665-EXP-S、EPICLON N-662-EXP-S、EPICLON N-665-EXP-S、EPICLONN-
670-EXP-S, EPICLON N-685-EXP-S, EPICLON N-730, EPICLON N-770, EPICLON N-865, Dongdu
It is melted into Epotohto YDCN-701, the YDCN-704, Ciba Specialty Chemicals Inc. system of Co., Ltd.'s manufacture
AralditeECN1235, AralditeECN1273, the AralditeECN1299, AralditeXPY307, Japanese chemical drug strain made
EPPN-201, EOCN-1025, the EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical strain formula meeting of formula commercial firm manufacture
Society manufacture Sumi-Epoxy ESCN-195X, 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；YL-933, the DOW Chemical of Mitsubishi chemical Co., Ltd's manufacture
(being trade name) the three oxybenzene methylmethane type ring oxygen resins such as T.E.N., EPPN-501, EPPN-502 of company's manufacture；Mitsubishi
Learn union IIs cresols type or the xenol type ring oxygen such as YL-6056, YX-4000, YL-6121 (being trade name) of Co., Ltd.'s manufacture
Resin or their mixture；The EBPS-200 of Nippon Kayaku K. K's manufacture, Asahi Denka Kogyo K. K manufacture
The bisphenol-s epoxy resins such as the EXA-1514 (trade name) that EPX-30, Dainippon Ink Chemicals manufacture；Mitsubishi chemical Co., Ltd's system
The phenol novolak type epoxy resin, bisphenol A novolac type epoxy resins such as the jER157S (trade name) made；The jERYL-931 of Mitsubishi chemical Co., Ltd's manufacture,
(being trade name) the four hydroxy phenyl ethane type rings such as the Araldite163 of Ciba Specialty Chemicals Inc. manufacture
Oxygen resin；The AralditePT810 of Ciba Specialty Chemicals Inc. manufacture, Nissan Chemical Ind Ltd
TEPIC of manufacture etc. (being trade name) hetero ring type epoxy resin；The neighbours such as the BLEMMER DDT of NOF Corp's manufacture
Phthalic acid 2-glycidyl ester resin；The four glycidyl groups xyloyls such as the ZX-1063 of Toto Kasei KK's manufacture
Base ethane resin (tetraglycidyl xylenoyl ethane resin)；The ESN- of Nippon Steel Chemical Co., Ltd's manufacture
190, ESN-360, Dainippon Ink Chemicals's manufacture, EXA-4750, EXA-4700 etc. contain Naphthol-based Epoxy Resin；Dainippon Ink Chemicals's system
HP-7200, HP-7200H made etc. has the epoxy resin of dicyclopentadiene skeleton；The CP- of NOF Corp's manufacture
The copolymerization of the glycidyl methacrylate such as 50S, CP-50M is epoxy resin；And then N-cyclohexylmaleimide and metering system
The copolymerization epoxy resin of acid glycidyl ester；Epoxy-modified polybutadiene rubber derivative (such as Daicel chemical industry strain
The PB-3600 etc. of formula commercial firm manufacture), CTBN modified epoxy (such as YR-102, YR- of Toto Kasei KK's manufacture
450 etc.) etc., but it is not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, particularly preferably
Phenolic resin varnish type epoxy resin, modified novolac type epoxy resin, hetero ring type epoxy resin, union II first phenol-type epoxy resin or
Their mixture.
It should be noted that solid epoxy of the invention at 20 DEG C be solid and at 40 DEG C be liquid partly
Solid epoxy resin is different.
(A-1) be the bisphenol-type epoxy resin of liquid at room temperature and (A-2) is at room temperature has 2 in 1 molecule of solid
The mix ratio of the epoxy resin of the above epoxy group is preferably the range of (A-1)/(A-2)=20/80~80/20, more preferably 30/
70~70/30 range, further preferably 40/60~60/40 range.(A-1) when epoxy resin is 20 or more, printing
It is excellent.On the other hand, it is resistance to anti-thread breakage good when (A-1) epoxy resin is 80 or less.
(B) filler of the invention is used for relaxation stress as caused by cure shrinkage, adjustment linear expansion coefficient.As this nothing
The usually well known inorganic filler used in resin combination can be used in machine filler.Specifically, can for example enumerate two
Silica, barium sulfate, calcium carbonate, silicon nitride, aluminium nitride, boron nitride, aluminium oxide, magnesia, aluminium hydroxide, magnesium hydroxide, oxygen
Change the metal packings such as non-metallic fillers, copper, gold, silver, palladium, the silicon such as titanium, mica, talcum, organobentonite.These can individually make
With or combine two or more use.
About the shape of inorganic filler, spherical, needle-shaped, sheet, flakey, hollow form, amorphous, six sides can be enumerated
Shape, cubic, flake etc., it is preferably spherical from the highly filled viewpoint of inorganic filler.
, it is preferable to use the excellent silica of agent of low hygroscopicity, low volume dilatancy, calcium carbonate in these.As dioxy
SiClx, noncrystalline, crystal, or their mixture.From highly filled angle is realized, preferably spherical is non-
Crystalloid (melting) silica.In addition, as calcium carbonate, natural powdered whiting, synthesis winnofil.
In addition, the average grain diameter d50 of (C) filler is preferably 0.1~25 μm.When average grain diameter is 0.1 μm or more, it can drop
Low specific surface area, dispersibility improve, and are easy to increase the loading of filler.On the other hand, in 25 μm of situations below, Xiang Yong
Fillibility in the hole portion of package substrate for carrying semiconductor is good, and flatness is good when the part after filling perforation forms conductor layer
It is good.More preferably 0.1~10 μm.
The compounding amount of this (B) filler is excellent relative to the epoxy resin in 100 parts of (A) 1 molecules with 2 or more epoxy groups
It is selected as 50 parts~300 parts, more preferably 80 parts~230 parts, further preferably 100 parts~200 parts.By by (B) filler
Compounding amount is set as 100 parts or more, the thermal expansion for the solidfied material being able to suppress, resistance to anti-thread breakage excellent, and then can be filled
Abrasiveness, the adaptation divided.On the other hand, by being set as under 300 parts, pasteization is easy, and can be obtained good printing, be filled out
Hole fillibility.
As (C) thermal curing catalyst of the invention, such as imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- can be enumerated
Ethyl -4-methylimidazole, 2- phenylimidazole, 4- phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2- cyanoethyl) -2- second
The imdazole derivatives such as base -4-methylimidazole；Dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl
The amine compounds such as amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine, adipic dihydrazide,
The hydrazine compounds such as sebacic dihydrazide；Phosphorus compounds such as triphenylphosphine etc..In addition, as commercially available product, such as four countries can be enumerated
2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ of chemical conversion industry Co., Ltd. manufacture (are the commodity of imidazole compound
Name), San-Apro Ltd. manufacture U-CAT (registered trademark) 3503N, U-CAT3502T (be the sealing end isocyanide of dimethyl amine
The trade name of ester compound), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compounds and its salt) etc..
These are not particularly limited to, as long as the thermal curing catalyst of epoxy resin, oxetane compound, so that it may individually make
With or mix two or more use.Alternatively, it is also possible to use guanamines, methyl guanamines, benzoguanamine, melamine, 2,4- diamino
Base -6- methacryloxyethyl-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- diamino
Base-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanuric acid add
Striazine derivatives, the compounds for being preferably also used as adaptation imparting agent to function these such as object is closed to urge with aforementioned heat cure
Agent is applied in combination.
The compounding amount of these thermal curing catalysts is the ratio of common amount with regard to enough, relative to 1 point of 100 mass parts (A)
With the epoxy resin of 2 or more epoxy groups, preferably 0.1~20 mass parts, more preferably 0.5~15.0 mass parts in son.
(D) organic solvent of the invention is used to that hardening resin composition to be made to become the state for being easy coating, after coating
It makes it dry to form a film.As this organic solvent, known usual substance can be used.As concrete example, can enumerate
The ketones such as methyl ethyl ketone, cyclohexanone out；Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon；Methylcellulose, ethyl cellulose, fourth
Base cellulose, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, three
The glycol ethers such as ethylene glycol monoethyl ether；Ethyl acetate, butyl acetate, cellulose acetate, diethylene glycol monoethyl ether acetic acid esters and on
State the esters such as the carboxylate of glycol ethers；The alcohols such as ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；
Petroleum series solvent such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha etc..
(D) compounding amount of organic solvent is preferably the model of 1~10 mass % relative to hot curing resin composition total amount
It encloses, more preferably 3~7 mass %.By the way that organic solvent is set as 1 mass % or more, heat-curing resin combination can reduce
The viscosity of object, printing improve.On the other hand, when organic solvent is 10 mass % or less, the bubble that is able to suppress in solidfied material
Generation.
Hot curing resin composition of the invention can also be added as needed fine particle silica, organobentonite,
The thixotropic agent such as montmorillonite, hydrotalcite.From the ageing stability as thixotropic agent, preferably organobentonite, hydrotalcite, especially
Be hydrotalcite electrical characteristics it is excellent.Furthermore it is possible to be compounded as thermal polymerization inhibitor, organic silicon-type, fluorine system, macromolecular etc. defoam
The silane coupling agents such as agent and/or levelling agent, imidazoles system, thiazole system, triazole system, antirust agent and then bis-phenol system, triazine thiol system etc.
Known usual additive kind as copper resistant agent etc..It should be noted that the present invention is preferably free of reactive diluted material.
It is adjusted to for hot curing resin composition of the invention, such as with aforementioned organic solvents suitable for coating method
Viscosity is applied on substrate, then using the methods of dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coating
Being heated to about 130~180 DEG C of temperature makes its heat cure, so as to form resistance to soldering heat performance, chemical resistance, resistance to suction
The cured coating film of each excellent such as moist, adaptation, electrical characteristics.
As above-mentioned base material, have: the printed circuit board with hole portions such as through-hole, via holes.Specifically, in addition to that can make
With being pre-formed with except the printed circuit board of circuit, flexible printed circuit board, copper-clad laminated board and polyamides can also be used
Imines film, PET film, glass substrate, ceramic substrate, wafer board etc..The copper-clad laminated board be using paper-phenolic resin,
Paper-epoxy resin, glass cloth-epoxy resin, glass-polyimides, glass cloth/non-woven fabrics-epoxy resin, glass cloth/paper-ring
Whole grade (FR-4 of the composite materials such as oxygen resin, synthetic fibers-epoxy resin, fluororesin polyethylene PPO cyanate
Deng) copper-clad laminated board.
Embodiment
It is carried out according to ratio (mass parts) shown in various composition shown in following table 1 and table 2 and Tables 1 and 2
Compounding, after being pre-mixed with blender, is kneaded with triple-roller mill, prepares hot curing resin composition.
Table 1
Table 2
* 1: jER828, the liquid bisphenol A epoxy resin, epoxy that liquid epoxy resin, Mitsubishi chemical Co., Ltd manufacture
Equivalent 184-194g/eq
* 2: EPICLON 830, liquid bisphenol F epoxy resin, the epoxy that liquid epoxy resin, Dainippon Ink Chemicals manufacture are worked as
Measure 165-177g/eq
* 3: solid epoxy, EPICLON N-660 of Dainippon Ink Chemicals's manufacture, cresol novolak type epoxy tree
Rouge, epoxide equivalent 202-212g/eq
* 4: jER157S, the bisphenol A novolac type asphalt mixtures modified by epoxy resin that solid epoxy, Mitsubishi chemical Co., Ltd manufacture
Rouge, epoxide equivalent 200-220g/eq
* 5: BARIACE B-30, the barium sulfate, 0.3 μm of average grain diameter that filler, Sakai Chemical Co., Ltd. manufacture
* 6: filler, SHIRAISHI CALCIUM KAISHA, Softon2200, the calcium carbonate, average grain diameter of LTD. manufacture
1.0μm
* 7: Admafine SO-C3, the silica, 0.9 μm of average grain diameter that filler, Admatechs Co., Ltd. manufacture
* 8: thermal curing catalyst, four countries are melted into 2PHZ, 2- phenyl -4,5- bishydroxymethyl imidazoles of Co., Ltd.'s manufacture
* 9: 2MZ-A, 2,4- diamino -6- [2 '-methyl that thermal curing catalyst, Shikoku Chem manufacture
Imidazole radicals-(1 ')]-ethyl-s-triazine
* 10: organic solvent, dipropylene glycol monomethyl ether
* 11: organic solvent, diethylene glycol monoethyl ether acetic acid esters
* 12: reactive diluted material, EPOLIGHT M-1230 of Kyoeisha Chemical Co., Ltd.'s manufacture, C12, C13 are mixed
Close higher alcohol glycidol ether
* 13: Flowlen AC-902, the organic silicon-type defoaming agent that defoaming agent, Kyoeisha Chemical Co., Ltd. manufacture
<printing>
The double-sided substrate of thickness 1.6mm, plated through hole diameter 0.25mm, through-hole spacing 1mm (are unpatterned, through-hole
Number 25) pickling as pre-treatment is carried out, then utilize the aforementioned implementation of Semi-automatic printer (SeriaCo., Ltd. are manufactured)
The hot curing resin composition of example and comparative example carries out filling perforation printing.At this point, evaluating hot curing resin composition to through-hole
In loading.
◎: loading of the hot curing resin composition into through-hole is abundant and shape is good
Zero: loading of the hot curing resin composition into through-hole is abundant
△: loading of the hot curing resin composition into through-hole is slightly insufficient
×: loading of the hot curing resin composition into through-hole is completely insufficient
<bubble>
The double-sided substrate of thickness 1.6mm, plated through hole diameter 0.25mm, through-hole spacing 1mm (are unpatterned, through-hole
Number 25) pickling as pre-treatment is carried out, then utilize the aforementioned implementation of Semi-automatic printer (SeriaCo., Ltd. are manufactured)
The hot curing resin composition of example and comparative example carries out filling perforation printing.Then, using heated air circulation type drying oven at 150 DEG C
Progress 30 minutes Cooking/Curing.The test substrate cut counts the gas generated in 25 through-holes using optical microscopy
The quantity of bubble.
◎: the quantity of bubble is less than 5
Zero: the quantity of bubble is 5 or more and is less than 10
△: the quantity of bubble is 10 or more and is less than 15
×: the quantity of bubble is 15 or more
<resistance to soldering heat performance>
By the hot curing resin composition of previous embodiment and comparative example by being screen printed onto form figuratum copper
Pattern coating is carried out on foil substrate, then heating 30 minutes at 150 DEG C in heated air circulation type drying oven makes its solidification, is made
Substrate is used in evaluation.It is coated with rosin series scaling powder on obtained substrate, is immersed in the solder bath for being set in advance as 260 DEG C, uses
After modified alcohol washs scaling powder, heaving and stripping off and evaluate to cured coating film by visual observation.Determinating reference is as follows.
◎: it is impregnated even if being repeated 4 times above 10 seconds, is also not observed and strips off
Zero: being impregnated even if being repeated 3 times 10 seconds, be also not observed and strip off
△: it is stripped off slightly when being repeated 3 times 10 seconds dippings
×: cured film presence is heaved, is stripped off when 10 seconds dippings within being repeated 2 times
<resistance to anti-thread breakage>
The double-sided substrate of thickness 1.6mm, plated through hole diameter 0.25mm, through-hole spacing 1mm (are unpatterned, through-hole
Number 25) pickling as pre-treatment is carried out, then using Semi-automatic printer (manufacture of Seria Co., Ltd.) with aforementioned reality
The hot curing resin composition for applying example and comparative example carries out filling perforation printing.Then, at 150 DEG C in heated air circulation type drying oven
Lower progress 30 minutes Cooking/Curing.By obtained test substrate with 10 seconds dipping 5 times in 288 DEG C of solder liquid, then
Cooled to room temperature.Obtained test is ground with substrate then to be observed with optical microscopy for cross-section observation,
Evaluate the number of the crackle of filling perforation solidfied material.
◎: the sum of crackle is less than 5
Zero: the sum of crackle is 5 or more and is less than 10
△: the sum of crackle is 10 or more and is less than 20
×: the sum of crackle is 20 or more
<exhaust>
The hot curing resin composition of previous embodiment and comparative example is coated on copper foil by silk-screen printing by entire surface
On, then heating 30 minutes at 150 DEG C in heated air circulation type drying oven makes its solidification.It is cut using cutter resulting solid
Change film, re-synchronizes measurement dress using the differential hot-hot that Hitachi High-Technologies Corporation. is manufactured
It sets STA7200 and is heated to 300 DEG C from room temperature with 10 DEG C/min of heating rate, the weight loss at 250 DEG C of measurement is as capacity.
〇: the weightlessness of cured coating film is lower than 5.0%
×: the weightlessness of cured coating film is 5.0% or more
Table 3
Table 4
By table 3, table 4, it will be apparent that, hot curing resin composition of the invention can be vented, bubble is few and resistance to
Weld hot property, resistance to anti-thread breakage excellent solidfied material.In addition we know, hot curing resin composition of the invention is due to printing
Property it is also excellent, therefore be suitable for use as printed circuit board filling perforation use.
Claims (4)
1. a kind of Porefilling heat curing resin composition of printed circuit board, which is characterized in that contain:
(A) in 1 molecule with 2 or more epoxy groups epoxy resin,
(B) filler,
(C) thermal curing catalyst and
(D) organic solvent,
It is the bis-phenol type ring of liquid that epoxy resin in (A) 1 molecule with 2 or more epoxy groups, which contains (A-1) at room temperature,
Oxygen resin and (A-2) are at room temperature the epoxy resin with 2 or more epoxy groups in 1 molecule of solid,
(A-1) be at room temperature liquid bisphenol-type epoxy resin with (A-2) be at room temperature solid 1 molecule in have
The mix ratio of the epoxy resin of 2 or more epoxy groups is 30/70~60/40,
The compounding amount of (B) filler is 80 parts relative to the epoxy resin in 100 parts of (A) 1 molecules with 2 or more epoxy groups
~230 parts,
The compounding amount of (D) organic solvent is 3~7 mass % relative to the total amount of hot curing resin composition,
(A-2) is that the epoxy resin in 1 molecule of solid with 2 or more epoxy groups is nobolak type epoxy at room temperature
Resin, modified novolac type epoxy resin, hetero ring type epoxy resin, union II first phenol-type epoxy resin or their mixture.
2. the Porefilling heat curing resin composition of printed circuit board according to claim 1, which is characterized in that described
(C) thermal curing catalyst is imidazoles.
3. a kind of solidfied material, which is characterized in that it is by the filling perforation heat cure of printed circuit board of any of claims 1 or 2
Obtained from property resin combination heat cure.
4. a kind of printed circuit board, which is characterized in that have solidfied material as claimed in claim 3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410852265.4A CN105802129B (en) | 2014-12-31 | 2014-12-31 | Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410852265.4A CN105802129B (en) | 2014-12-31 | 2014-12-31 | Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board |
Publications (2)
| Publication Number | Publication Date |
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| CN105802129A CN105802129A (en) | 2016-07-27 |
| CN105802129B true CN105802129B (en) | 2019-05-03 |
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| CN201410852265.4A Active CN105802129B (en) | 2014-12-31 | 2014-12-31 | Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board |
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| CN110431185A (en) * | 2017-03-31 | 2019-11-08 | 日立化成株式会社 | Composition epoxy resin, epoxy resin cured product and electronic part apparatus |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443805A (en) * | 2002-03-08 | 2003-09-24 | 太阳油墨制造株式会社 | Filling material composition for printing distributing board |
| CN102796348A (en) * | 2011-05-27 | 2012-11-28 | 太阳油墨制造株式会社 | Thermosetting resin composition, dry film and printed circuit board (pcb) |
| CN103131132A (en) * | 2011-12-02 | 2013-06-05 | 达航工业股份有限公司 | Hot solidification type component used for filling printed circuit board punched hole |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443805A (en) * | 2002-03-08 | 2003-09-24 | 太阳油墨制造株式会社 | Filling material composition for printing distributing board |
| CN102796348A (en) * | 2011-05-27 | 2012-11-28 | 太阳油墨制造株式会社 | Thermosetting resin composition, dry film and printed circuit board (pcb) |
| CN103131132A (en) * | 2011-12-02 | 2013-06-05 | 达航工业股份有限公司 | Hot solidification type component used for filling printed circuit board punched hole |
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| CN105802129A (en) | 2016-07-27 |
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