CN108203497A - The hole of printed circuit board fills filling composition epoxy resin, solidfied material and has used their printed circuit board - Google Patents
The hole of printed circuit board fills filling composition epoxy resin, solidfied material and has used their printed circuit board Download PDFInfo
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- CN108203497A CN108203497A CN201611182316.2A CN201611182316A CN108203497A CN 108203497 A CN108203497 A CN 108203497A CN 201611182316 A CN201611182316 A CN 201611182316A CN 108203497 A CN108203497 A CN 108203497A
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- Prior art keywords
- epoxy resin
- circuit board
- printed circuit
- hole
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
This application involves the hole landfill filling composition epoxy resin of printed circuit board, solidfied material and their printed circuit board is used.A kind of hole the issue of the present invention is to provide printed circuit board fills filling composition epoxy resin and has used the printed circuit board of the composition epoxy resin, the hole landfill filling of the printed circuit board is wider than through-hole diameter with the composition epoxy resin shape of resin combination (rib) compared with the past for inhibiting to be discharged by through-hole, so as to reduce grinding number, excellent adhesion.The hole landfill filling composition epoxy resin of the printed circuit board is characterized in that, its epoxy resin, (B) monofunctional epoxy compound, (C) boric acid ester compound and (D) inorganic filler for containing more than (A) 2 function form, relative to 100 mass parts of epoxy resin more than above-mentioned (A) 2 function, the blend amount of above-mentioned (B) monofunctional epoxy compound is 5 mass parts20 mass parts.
Description
Technical field
Hole landfill filling the present invention relates to printed circuit board (is hereinafter also referred to as " tree with composition epoxy resin
Oil/fat composition "), solidfied material and used their printed circuit board, specifically, be related to a kind of hole of printed circuit board and fill out
It buries filling composition epoxy resin, solidfied material and has used their printed circuit board, the hole landfill of the printed circuit board
Filling is wider than the diameter of hole portion with composition epoxy resin by the shape of resin combination (rib) for inhibiting to be discharged by hole portion, from
And grinding number can be reduced, excellent adhesion.
Background technology
In recent years, the downsizing of the graph thinning and mounting area of the pattern of printed circuit board is continuously developed, further,
In order to cope with the miniaturization/multifunction for the machine for having printed circuit board, the further frivolous short of printed circuit board it is expected
Smallization.Therefore, printed circuit board develops to the lamination of following manner (Build-up) method, in lamination method, in core substrate
Resin insulating barrier is formed up and down and forms necessary conductor circuit, is further formed resin insulating barrier later, and forms conductor electricity
Road；And installing component develops to area arrays types such as BGA (ball grid array), LGA (land grid array).In this situation
Under, it is expected to develop a kind of resin combination for being used to fill the hole portions such as through-hole or the via hole of printed circuit board, fillibility is ground
Mill property, solidfied material characteristic etc. are excellent.
Hole as printed circuit board fills resin for filling composition, it is however generally that, it is widely used for thermohardening type
Composition epoxy resin because its solidfied material is excellent in terms of engineering properties, electrical properties, chemical property, cementability is also good
It is good.For the permanent hole landfill processing of printed circuit board for using this resin combination, generally by following process structures
Into：Composition epoxy resin is filled in the process of the hole portion of printed circuit board；By the composition heating of filling, precuring is
The precuring process of triturable state；The resin combination of precuring is ground/removed from the part that hole portion surface is overflowed
The process gone；It carries out leading cured process with the resin combination of precuring is further heated.
In the landfill processing of the permanent hole of the printed circuit board, resin combination is filled to the holes such as through-hole or via hole
When in portion, due to being involved in for air, gap can be generated anyway.In addition, it is filled in the permanent hole of printed circuit board
In processing, there is the problem of being cracked in the curing of resin combination.
A kind of composition epoxy resin is proposed in patent document 1, the same of the generation in gap and crackle is being greatly reduced
When, excellent storage stability.The composition epoxy resin of patent document 1 is by adding boric acid ester compound, so as to resin combination
Bubble in object easily removes, and can inhibit the generation of gap and crackle.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-208751 bulletins
Invention content
Problems to be solved by the invention
But for the composition epoxy resin of patent document 1, from the resin combination of hole portion discharge after coating
Shape is wider than the diameter of hole portion, can fill to the place for not needing to filling.If in addition, discharge resin combination expansion it is big,
It then grinds number to increase, poor in processability.In addition, the composition epoxy resin about patent document 1, with the copper in hole portion and admittedly
The problem of adaptation of compound is insufficient.
Therefore, the present invention carries out to solve above-mentioned problem of the prior art, and main purpose is to provide one
The hole of kind printed circuit board fills filling composition epoxy resin, solidfied material and has used their printed circuit board, should
The hole landfill filling composition epoxy resin resin combination compared with the past for inhibiting to be discharged by hole portion of printed circuit board
The shape of (rib) is wider than the diameter of hole portion, so as to reduce grinding number, excellent adhesion.
Solution for solving the problem
The present inventor has made intensive studies to eliminate the above problem, as a result, it has been found that, by with epoxies more than 2 functions
Resin, boric acid ester compound are used together monofunctional epoxy compound, and so as to eliminate the above problem, this completes this hairs
It is bright.
That is, the hole the present invention relates to a kind of printed circuit board fills filling composition epoxy resin, it is for filling out
The recess portion of printed circuit board and the composition epoxy resin of at least one of through hole are charged to, is contained more than (A) 2 function
Epoxy resin, (B) monofunctional epoxy compound, (C) boric acid ester compound and (D) inorganic filler form.
In the hole landfill filling composition epoxy resin of the printed circuit board of the present invention, which is characterized in that relative to
100 mass parts of epoxy resin more than above-mentioned (A) 2 function, the blend amount of above-mentioned (B) monofunctional epoxy compound are
In the hole landfill filling composition epoxy resin of the printed circuit board of the present invention, which is characterized in that above-mentioned (B)
The mixed ratio of monofunctional epoxy compound and above-mentioned (C) boric acid ester compound is 1：0.04~0.12.
In the hole landfill filling composition epoxy resin of the printed circuit board of the present invention, which is characterized in that above-mentioned (B)
Monofunctional epoxy compound is phenylglycidyl ether type monofunctional epoxy compound.
In the hole landfill filling composition epoxy resin of the printed circuit board of the present invention, which is characterized in that relative to
100 mass parts of epoxy resin more than above-mentioned (A) 2 function, above-mentioned (D) inorganic filler are
A kind of moreover, it relates to solidfied material, which is characterized in that the hole of its printed circuit board by the invention described above
Landfill filling is formed with epoxy resin composition.
A kind of moreover, it relates to printed circuit board, which is characterized in that its solidfied material with the invention described above.
The effect of invention
According to the present invention it is possible to provide a kind of hole landfill filling composition epoxy resin of printed circuit board, curing
Object and the printed circuit board for having used them, compared with the past, the hole landfill filling epoxy resin group of the printed circuit board
It closes object and can inhibit the shape of the resin combination discharged by hole portion and be wider than the diameter of hole portion, it is close so as to reduce grinding number
Conjunction property is excellent.In the hole landfill filling composition epoxy resin of the printed circuit board of the present invention, by using simple function
Epoxide so as to which thixotropy improves, can control the shape of resin combination discharged after filling by through-hole, it is possible to reduce
Grind number.In the past in order to improve thixotropy, the levelling agents such as BYK-R606 more than comparison are added to, has and easily generates bubble
Problem.In the present invention, by mixture monofunctional epoxy compound, so as to not generate bubble, thixotropy improves, and can control filling
Afterwards by the shape of the resin combination of through-hole discharge.In addition, for the composition of the present invention, it is closely sealed with the copper in through-hole
Property improve.
Description of the drawings
Fig. 1 is the schematic sectional view of an example of a part for the manufacturing process for showing the printed circuit board of the present invention.
Fig. 2 is the signal of an example for the manufacturing process's about subsequent process for showing the printed circuit board of the present invention shown in FIG. 1
Property sectional view.
Fig. 3 is the schematic sectional view of another of the manufacturing method for showing the printed circuit board of the present invention.
Fig. 4 is the figure for illustrating the performance evaluation related with the shape for lugs of the present invention.
Symbol description
1 substrate
2 copper foils
3 through-holes
4 plated films
5 resin combinations
6 resist layers
7 conductor circuit layers
8 interlayer resin insulating layers
9 openings
10 plating resist layers
11 via holes
12 pads
13 solder masks
14 solder bumps
The base length of the solidfied material of 15 shape for lugs
The diameter length of 16 through-holes
Specific embodiment
In the following, detailed description of embodiments of the present invention.
The composition epoxy resin of the present invention contain more than (A) 2 function epoxy resin, (B) monofunctional epoxy compound,
(C) boric acid ester compound and (D) inorganic filler form.
<(A) epoxy resin more than 2 functions>
Composition epoxy resins more than 2 functions of the present invention can use epoxy resin more than well known 2 function.It can
To enumerate such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, bmminated bisphenol-A type epoxy
Resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol-A phenol
Novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy
Resin, triphenylmenthane type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phosphorous epoxy resin, anthracene type ring
Oxygen resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type epoxy resin, aminobenzene phenol-type epoxy resin, ammonia
Base first phenol-type epoxy resin, alkylbenzene phenol-type epoxy resin etc..
The resin combination of the present invention is preferably solvent-free, thus suitable for epoxy resin more than 2 functions comprising liquid.
It,, can be suitable for using bisphenol-A as epoxy resin more than 2 functions in resin combination of the invention from the aspect of this
In type epoxy resin, bisphenol f type epoxy resin, aminobenzene phenol-type epoxy resin, phenol novolak type epoxy resin at least
It is any.It should be noted that in the resin combination of the present invention, epoxy resin more than these (A) 2 functions can individually make
It is shared with or by two or more.In addition, in the case where using solid epoxy resin rather than liquid-state epoxy resin, only
To utilize solvent that aftermentioned monofunctional epoxy compound, boric acid ester compound and inorganic filler is made to be scattered in solid epoxy resin
In.
As the commercially available product of epoxy resin more than (A) 2 function, it can be cited for example that：As bisphenol A-type liquid epoxy tree
Fat DIC societies manufacture 840, Mitsubishi chemical Co., Ltd manufacture 828, Nippon Steel ＆ Sumitomo Metal Corporation manufacture
YD127；As bisphenol F-type epoxy resin DIC societies manufacture 830, Mitsubishi chemical Co., Ltd manufacture 807, new day
Iron lives in the YD170 of aurification Co., Ltd. manufacture；As aminobenzene phenolic liquid-state epoxy resin (p-aminophenyl phenolic liquid epoxy
Resin) the jER-630 of Mitsubishi chemical Co., Ltd's manufacture, Sumitomo Chemical Co's manufacture ELM-100 etc..
<(B) monofunctional epoxy compound>
It (B), can by the shape of the solidfied material of the resin combination of hole portion discharge after monofunctional epoxy compound control curing
Solidfied material to be inhibited to be wider than the diameter of hole portion.Grinding number is reduced as a result,.In addition, by sharing (B) monofunctional epoxy compound
(C) boric acid ester compound can improve the adaptation of the copper and solidfied material in through-hole.
Well known monofunctional epoxy compound can be used in the composition epoxy resin of the present invention.As the present invention's
(B) monofunctional epoxy compound, it can be cited for example that alkyl list glycidyl ether, alkenyl list glycidyl ether, fragrance
Annulus has phenyl list glycidyl ether of substituent group that carbon atom number is more than 1 etc., as commercially available product, it can be cited for example that
Denacol EX-141 (manufacture of Nagase chemteX societies), ED-509S, ED-509E, ED-529 (being the manufacture of ADEKA societies)
Deng.
Wherein, the shape aspect of resin combination discharged from control by hole portion, preferably phenyl glycidyl base
Ether type monofunctional epoxy compound.By using phenylglycidyl ether type monofunctional epoxy compound, it is easy to control curing
The shape of object, thus preferably.As phenylglycidyl ether type monofunctional epoxy compound, as long as with phenyl glycidyl
Base ether skeleton then, it can be cited for example that ED-509E, ED-529, EX-141 of ADEKA societies.It is it should be noted that of the invention
Resin combination in, (B) monofunctional epoxy compound can be used alone or share two or more.
In the total amount of (B) monofunctional epoxy compound, phenylglycidyl ether type monofunctional epoxy compound is preferred
For more than 60 mass %, more preferably 80 mass %, particularly preferably 100 mass %.
In the resin combination of the present invention, relative to 100 mass parts of epoxy resin more than (A) 2 function, (B) simple function
The additive amount of epoxide is preferablyIf the additive amount for making (B) monofunctional epoxy compound is 5
The mass parts of mass parts~20, then the balance of the diffusivity of shape for lugs, heat resistance and cracking resistance is more excellent.
<(C) boric acid ester compound>
Well known boric acid ester compound can be used in the composition epoxy resin of the present invention.For example, volatilization can be enumerated
The low triphenyl borate of property or cycliborate etc..Preferably cyclic boronate ester compounds.Cyclic boronate ester compounds refer to ring
Substance containing boron in formula structure, particularly preferred 2,2 '-oxo is bis- (5,5 '-dimethyl -1,3,2- oxa-s pentaborane).As boron
Ester compound, other than triphenyl borate or cyclic boronate ester compounds, it can be cited for example that trimethylborate, boric acid three
Ethyl ester, triproylborate, butyl borate etc., the volatility of these boric acid ester compounds is high, thus during especially for high temperature
Composition storage stability, effect is sometimes insufficient.It should be noted that in the resin combination of the present invention, these
Boric acid ester compound can be used alone or share two or more.
As the commercially available product of (C) boric acid ester compound, it can be cited for example that HIBORON BC1, HIBORON BC2,
HIBORON BC3, HIBORON BCN (these are Co., Ltd. boron international manufactures), CUREDUCT L-
07N (Shikoku Chem's manufacture) etc..
In the resin combination of the present invention, the mix ratio of (B) monofunctional epoxy compound and above-mentioned (C) boric acid ester compound
Example be preferably
<(D) inorganic filler>
Used in common resin combination well known can be used inorganic to fill out in the composition epoxy resin of the present invention
Material.It is specific it can be cited for example that silica, barium sulfate, calcium carbonate, silicon nitride, aluminium nitride, boron nitride, aluminium oxide, magnesia,
The non-metallic fillers such as aluminium hydroxide, magnesium hydroxide, titanium dioxide, mica, talcum, Nuo Yibao tripoli, organobentonite；Copper, gold,
The metal packings such as silver, palladium, silicon.The present invention resin combination in, these inorganic fillers can be used alone or by two or more into
Row shares.
Among these, the excellent silica of agent of low hygroscopicity, low volume dilatancy, calcium carbonate are suitable.As dioxy
SiClx can be any one of amorphous state, crystallization, or these mixture.Particularly preferred amorphous state (melting) two
Silica.Can be any one of natural powdered whiting, the precipitated calcium carbonate synthesized in addition, as calcium carbonate.It is inciting somebody to action
In the case that the resin combination of the present invention is used as use in printed circuit board hole landfill packing material, the excellent calcium carbonate of abrasiveness
It is suitable.
The shape of such inorganic filler can enumerate spherical, needle-shaped, plate, flakey, hollow form, amorphous, six
Side shape, cubic, laminar etc., it is preferably spherical from the highly filled aspect of inorganic filler.
In addition, the average grain diameter of these inorganic fillers is preferredIf average grain diameter is 0.1 μm or more,
Specific surface area is small, can be disperseed well by the effect of the mutual agglutination of filler, and easily increases the filling of filler
Amount.On the other hand, if average grain diameter be 25 μm hereinafter, if using the present invention resin combination as use in printed circuit board hole
Packing material is filled in use, the fillibility in the hole portion of printed circuit board is good, has carrying out hole landfill in addition
The effect that flatness improves when part forms conductor layer.More preferablyHerein, average grain diameter refers to averagely primary
Grain size.Average grain diameter (D50) can be measured using laser diffraction/scattering method.
In the resin combination of the present invention, relative to 100 mass parts of epoxy resin more than above-mentioned (A) 2 function, (D) nothing
The content of machine filler is preferably the mass parts of 90 mass parts~200, the mass parts of more preferably 110 mass parts~200.(if D) is inorganic
The content of filler for more than 90 mass parts, then obtained solidfied material shows sufficient low expansion, given play to abrasiveness and
Adaptation.On the other hand, it is below mass part if 200, then liquid thickener is easily generated, can obtain printing, hole landfill
Fillibility etc..
(curing catalysts)
In the resin combination of the present invention, curing catalysts are preferably comprised.As curing catalysts, as long as promoting asphalt mixtures modified by epoxy resin
The curing reaction of fat is just not particularly limited, and can use known usual curing catalysts.
As curing catalysts, it can be cited for example that imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- ethyl -4- methyl miaows
Azoles, 2- phenyl -1- benzyl -1H- imidazoles, 2- phenylimidazoles, 4- phenylimidazoles, 1- cyano ethyl -2- phenylimidazoles, 1- (2- cyanogen
Base ethyl) imdazole derivatives such as -2-ethyl-4-methylimidazole；2,4- diamino -6- [2 '-methylimidazolyl-(1 ')]-ethyl -
S-triazine, 2,4- diamino -6- [2'- undecyl imidazoles base-(1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- second
Base -4'- methylimidazolyls-(1')]-ethyl-s-triazine etc. has the imdazole derivatives of triazine structure；2,4- diamino -6-
The imidazoles such as [2'- methylimidazolyls-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid adducts
The isocyanurate of derivative；The miaows such as 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles
Azoles hydroxymethyl body；Dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl groups-N, N- bis-
The amine compounds such as methylbenzyl amine, 4- methyl-N, N- dimethyl benzyl amine；The hydrazines such as adipic dihydrazide, sebacic dihydrazide
Close object；The phosphorus compounds such as triphenylphosphine；Guanamines, 2,4- diamino -6- methyl-1s, 3,5- triazines, benzoguanamine, melamine, 2,
4- diamino -6- methacryloxyethyls-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6-
Diamino-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyls-s-triazine isocyanide urea
Pyrrolotriazine derivatives such as sour addition product etc..
As commercially available product, it can be cited for example that 1B2PZ, 2E4MZ of chemical conversion industry society of four countries manufacture, 2MZ-A, 2MZ-OK,
2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), the U-CAT (registered trademark) of San-Apro societies manufacture
3503N, U-CAT3502T (being the trade name of the blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102,
U-CAT5002 (being two ring type amidine compounds and its salt) etc..These curing catalysts can be used alone or mix two or more
It closes and uses.
<It is other>
The composition epoxy resin of the present invention contain more than (A) 2 function epoxy resin, (B) monofunctional epoxy compound,
(C) boric acid ester compound and (D) inorganic filler form, and can also add in other known additive as needed.For example, can be with
Addition：Usual colorant known in phthalocyanine blue, phthalocyanine green, iodine are green, two azophosphines, crystal violet, titanium dioxide, carbon black, naphthalene are black etc.；
Amine system catalyst as curing agent；Quinhydrones, hydroquinone monomethyl ether, the tert-butyl o benzene of storage stability when being preserved for assigning
Usual hot polymerization inhibitor known in diphenol, pyrogallol, phenthazine etc.；Known in clay, kaolin, organobentonite, montmorillonite etc.
Usual thickener or thixotropic agent；The antifoaming agent and/or levelling agent of silicone-based, fluorine system, macromolecular etc.；Imidazoles system, thiazole
The known usual additive kind of the adaptations imparting agents such as system, triazole system, silane coupling agent etc.
In the resin combination of the present invention, epoxy resin more than (A) 2 function is suitably the substance of liquid, as described above,
The epoxy resin of solid-like can also be dissolved in solvent to use.In this case, as solvent, can use ketone,
Aromatic hydrocarbon, glycol ethers, glycol ethers acetate esters, esters, alcohols, aliphatic hydrocarbon, oil series solvent etc..It can specifically lift
Go out：The ketones such as methyl ethyl ketone, cyclohexanone；Toluene, dimethylbenzene, durol etc. are aromatic hydrocarbon；The molten fibre of cellosolve, methyl
Agent, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropyl two
The glycol ethers such as diethylene glycol diethyl ether, Triethylene glycol ethyl ether；Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, the third two
Alcohol methylether acetate, propylene glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters, methyl lactate, ethyl lactate, lactic acid fourth
The esters such as ester；The alcohols such as ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, petroleum naphtha,
Oil series solvent such as non-hydrogenated petroleum naphtha, solvent naphtha etc..These solvents can be used alone or close two or more
With.It should be noted that the blend amount of solvent is suitable according to workability etc. in the range of the desired effect of the present invention is obtained
When decision.
The present invention resin combination can utilize all the time used method, such as silk screen print method, rolling method,
Die coating method etc. is easily packed into the hole portions such as via hole or the through-hole of printed circuit board.Next, for example about Heating is aboutLeft and right, makes epoxy resin composition.Such cured epoxy composite
The unnecessary portion that object is discharged from hole portion is few, it is thus possible to it is easily removed by physical grinding with less grinding number, it can
To form flat surface.It should be noted that physical grinding can be carried out using the well known method carried out all the time.
Then, the printed circuit board of the present invention is illustrated.
The printed circuit board of the present invention is obtained using the resin combination of the present invention.In the following, with reference to figureTo this
The manufacturing method of the printed circuit board of invention is described in detail.
<The formation of through-hole>
Fig. 1 is the schematic sectional view of an example of a part for the manufacturing process for showing the printed circuit board of the present invention.It is first
First, as shown in Fig. 1 (a), on the substrate 1 of copper foil 2 has been laminated, through hole is outputed using drill bit, wall surface to through hole and
Copper foil surface imposes electroless plating and forms through-hole 3.As substrate 1, can use glass epoxy substrate or polyimide substrate,
The copper clad laminate of the resin substrates such as bismaleimide-triazine resin substrate, fluororesin substrate or these resin substrates, pottery
Porcelain substrate, metal substrate etc..In the case of the substrate of even plating (つ I ま わ り) difference of the such plating of fluororesin substrate, into
The surface of pretreating reagent, the corona treatment that row is made of organic metal sodium etc. is modified.Then, it is electrolysed to increase thickness
Plating forms plated film 4a as shown in Fig. 1 (b) on the surface of substrate 1 and 3 inner wall of through-hole.As the electrolytic coating, preferably copper plates
It covers.
<Hole fills>
In the through-hole 3 for being formed in substrate 1, the resin combination 5 of the present invention is filled as shown in Fig. 1 (c).Specifically,
The mask for being provided with opening is placed on substrate 1 in 3 part of through-hole, by using the coating of print process etc. or net-point printing method
Etc. can be easily packed into through-hole 3.Then, by resin combination 5 about Heating is aboutLeft and right, makes its curing, later as shown in Fig. 1 (d), by grinding the resin combination that will be overflowed from through-hole 3
The unnecessary portion of object 5 removes, and is planarized.Grinding can utilize the progress such as belt sander or polishing grinding.
<The formation of conductor circuit layers>
On the surface of the substrate 1 of hole landfill for having carried out through-hole 3, plated film 4b is formed as shown in Fig. 1 (e).Thereafter,
Resist layer 6 is formed as shown in Fig. 1 (f), non-formation part is etched to resist.Next, stripping resist layer 6, such as Fig. 1
(g) conductor circuit layers 7a is formed shown in.
<The formation of interlayer resin insulating layers>
Fig. 2 be show the process after the manufacturing process of the printed circuit board of the present invention shown in FIG. 1 an example it is schematic
Sectional view.Interlayer resin insulating layers 8a is formed on conductor circuit layers 7a.As interlayer resin insulating layers 8a, thermosetting can be used
Property resin, light-cured resin, compound or mixture, the resin impregnated glass cloth of thermoplastic resin or these resins are compound
Object, electroless plating bonding agent.
<The formation of via hole>
Then, as shown in Fig. 2 (a), opening 9a is set in interlayer resin insulating layers 8a.Perforation for opening 9a, layer
Between in the case that resin insulating barrier 8a is made of photoresist, carried out by exposure, development treatment, by heat-curing resin
Or it in the case that thermoplastic resin is formed, utilizes laser to carry out.In the case where utilizing laser to setting opening 9a, Ke Yijin
The processing of row desmearing.
Then, as shown in Fig. 2 (b), plated film 4c is formed in entire surface.Also, it as shown in Fig. 2 (c), is formed on plated film 4c
Plating resist layer 10.Plating resist layer 10 by suitably laminated photosensitive dry film and be exposed, development treatment is formed.Into one
Step, is electroplated, and increases conductor circuit segment thickness, as shown in Fig. 2 (c), forms electroplating film 4d.
Next, after stripping plating resist layer 10, the electroless plated film 4c under the plating resist layer 10 is dissolved into removal by etching, such as
Shown in Fig. 2 (d), form independent conductor circuit (comprising via hole 11a).
Fig. 3 is the schematic sectional view of another of the manufacturing method for showing the printed circuit board of the present invention.To Fig. 1 (d)
After shown core substrate manufacture process, if imposing etching as predetermined pattern to the conductor layer on the two sides of core substrate 1,
As shown in Fig. 3 (a), the 1st conductor circuit layers 7b with predetermined pattern is formed, and connect with through-hole 3 on the two sides of substrate 1
A part of conductor circuit layers 7b be formed simultaneously pad 12.
Next, as shown in Fig. 3 (b), interlayer resin insulating layers 8b is formed on the upper and lower surface of substrate 1.In addition, as schemed
Shown in 3 (c), via hole 11b is formed in the resin insulating barrier 8b positioned at the surface of pad 12.Next, in via hole 11b
Coating is formed by copper plating on 8b layers of interlayer insulation resin, etching is imposed after forming resist layer on them.As a result, such as
Shown in Fig. 3 (c), the 2nd conductor circuit layers 7c is formed on interlayer resin insulating layers 8b.1st, the 2nd each conductor circuit layers 7b, 7c by
The mutual conduction by via hole 11b, while the conductor circuit layers 7b on substrate two sides also mutual conductions by through-hole 3.
Also, as shown in Fig. 3 (c), solder mask 13 is formed on each resin insulating barrier 8b and the 2nd conductor circuit layers 7c,
The solder mask 13 of top forms the solder bump 14 for penetrating through the solder mask 13 and being holded up from the surface of conductor circuit layers.In addition,
The conductor circuit layers 7c exposed from the opening 9b being formed between the solder mask 13 of lower section, Au and Ni plating is imposed to its surface,
It can obtain the multi-layered wiring board used as connection terminal.
Embodiment
Embodiment and comparative example is illustrated below the present invention to be specifically described, but the present invention is not limited to following implementations
Example.It should be noted that hereinafter, " part " and " % " is quality criteria as long as not special declaration.
With the various composition shown in ratio (mass parts) the mixture table 1 shown in table 1, composition epoxy resin is prepared.It connects
It, in the through-hole of glass epoxy substrate (plate thickness 1.6mm, through-hole diameter 0.5mm) that through-hole is formd beforehand through panel plating method,
Each resin combination is filled using silk screen print method.It puts it into heated air circulation type drying oven, 30 points is kept at 150 DEG C
Clock produces evaluation sample.About obtained each evaluation sample, using following methods to heat resistance, cracking resistance, protrusion shape
Shape, adaptation, abrasiveness are evaluated.The results obtained are shown in tables 1.
<Performance evaluation>
<Heat resistance>
For each evaluation sample, using grinder, physics is carried out with polishing single shaft by the resin ground for being equivalent to #320
Grinding.Thereafter cut-out evaluation sample, after being ground using grinder with to be equivalent to #600, by the resin for being equivalent to #1000
Grinding pair cross-section is ground, and will evaluate sample with following conditions is impregnated in 288 DEG C of tin soldering liquid and is evaluated.
○：Under conditions of 288 DEG C × 30 seconds × 3 times or more, it is not cured the dissociation of object and through-hole.
×：Under conditions of 288 DEG C × 30 seconds × 3 times, it is cured the dissociation of object and through-hole.
<Crackle>
For each evaluation sample, using grinder, physics is carried out with polishing single shaft by the resin ground for being equivalent to #320
Grinding.Thereafter cut-out evaluation sample, after being ground using grinder with to be equivalent to #600, by the resin for being equivalent to #1000
Grinding pair cross-section is ground, and will evaluate sample with following conditions is impregnated in 288 DEG C of tin soldering liquid and is evaluated.
○：Under conditions of 288 DEG C × 30 seconds × 5 times or more, the solidfied material flawless in through-hole.
△：288 DEG C × 30 seconds × 3 times less than 5 times under conditions of, the solidfied material in through-hole does not crack,
But produce crackle at 5 times or more.
×：288 DEG C × 30 seconds × be less than 3 times under conditions of, the solidfied material in through-hole does not crack, but 3 times or more
When produce crackle.
<Shape for lugs>
In each evaluation sample, as shown in figure 4, confirming the shape of solidfied material discharged by through-hole and being evaluated.This
Place, diffusivity evaluation are represented in filling to the base length 15 of solidfied material of through-hole rearward projection shape divided by the diameter length of through-hole
16 obtained numerical value.
○：Relative to through-hole endoporus 0.5mm, diffusivity evaluation of estimate is less than 2.0.
△：Relative to through-hole endoporus 0.5mm, diffusivity evaluation of estimate is for 2.0 less than 2.5.
×：Relative to through-hole endoporus 0.5mm, diffusivity evaluation of estimate is for 2.0 less than 3.0.
<With the adaptation of the copper in through-hole>
In each evaluation sample, according to following evaluation criteria, pair evaluated with the adaptation of the copper in through-hole.
○：Without dissociation between copper and solidfied material in through-hole.
×：There is dissociation in through-hole between copper and solidfied material.
<Deaeration in through-hole>
In each evaluation sample, according to following evaluation criteria, it is thus identified that whether have bubble in the solidfied material of through-hole.
○：Bubble-free in solidfied material in through-hole.
×：There is bubble in through-hole in solidfied material.
<Abrasiveness>
For evaluating sample, using grinder, physics is carried out with polishing single shaft by the resin ground for being equivalent to #320 and is ground
Mill, compares this road number until resin is completely removed.
○：Less than 2 times
×：3 times or more
Result as shown in Table 1 is it is found that the composition epoxy resin of Examples 1 to 7 can control its solidfied material after hardening
Shape, the generation of crackle lacks, heat resistance and the excellent adhesion with copper.In addition, the shape by controlling solidfied material, so as to grind
Mill property improves.In addition, the deaeration in through-hole might as well.
On the other hand, (B) monofunctional epoxy compound is not used in comparative example 1, thus solidfied material is discharged by through-hole
Shape for lugs it is big, abrasiveness is poor, poor with the adaptation of copper.In comparative example 2,3, since (C) boric acid ester compound is not used,
It is thus poor with the adaptation of copper.In comparative example 3, the additive amount of levelling agent is more, thus deaeration is poor.
Claims (7)
1. a kind of hole landfill filling composition epoxy resin of printed circuit board, is for filling to printed circuit board
The composition epoxy resin of at least one of recess portion and through hole, which is characterized in that
Its contain more than (A) 2 function epoxy resin, (B) monofunctional epoxy compound, (C) boric acid ester compound and (D) it is inorganic
Filler forms.
2. the hole landfill filling composition epoxy resin of printed circuit board as described in claim 1, which is characterized in that phase
For 100 mass parts of epoxy resin more than (A) 2 function, the blend amount of (B) monofunctional epoxy compound is
3. the hole landfill filling composition epoxy resin of printed circuit board as claimed in claim 1 or 2, feature exist
In the mixed ratio of (B) monofunctional epoxy compound and (C) boric acid ester compound is 1：0.04~0.12.
4. the hole landfill filling composition epoxy resin of printed circuit board as claimed in claim 1 or 2, feature exist
In (B) monofunctional epoxy compound is phenylglycidyl ether type monofunctional epoxy compound.
5. the hole landfill filling composition epoxy resin of printed circuit board as claimed in claim 1 or 2, feature exist
In relative to 100 mass parts of epoxy resin more than (A) 2 function, (D) inorganic filler is
6. a kind of solidfied material, which is characterized in that it is by claimAny one of described in printed circuit board hole
Landfill filling is formed with epoxy resin composition.
7. a kind of printed circuit board, which is characterized in that it is with the solidfied material described in claim 6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611182316.2A CN108203497B (en) | 2016-12-20 | 2016-12-20 | Epoxy resin composition for filling holes in printed wiring board, cured product, and printed wiring board using same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611182316.2A CN108203497B (en) | 2016-12-20 | 2016-12-20 | Epoxy resin composition for filling holes in printed wiring board, cured product, and printed wiring board using same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748078A (en) * | 2019-03-26 | 2020-10-09 | 太阳油墨制造株式会社 | Curable resin composition for pore filling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575439A (en) * | 2008-05-07 | 2009-11-11 | 太阳油墨制造株式会社 | Porefilling heat curing resin composition |
| JP2012067255A (en) * | 2010-09-27 | 2012-04-05 | Taiyo Holdings Co Ltd | Thermosetting resin filler |
| CN104072947A (en) * | 2013-03-26 | 2014-10-01 | 太阳油墨制造株式会社 | Epoxy resin composition, composition for filling in hole plugging, and printed wiring board using same |
-
2016
- 2016-12-20 CN CN201611182316.2A patent/CN108203497B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575439A (en) * | 2008-05-07 | 2009-11-11 | 太阳油墨制造株式会社 | Porefilling heat curing resin composition |
| JP2012067255A (en) * | 2010-09-27 | 2012-04-05 | Taiyo Holdings Co Ltd | Thermosetting resin filler |
| CN104072947A (en) * | 2013-03-26 | 2014-10-01 | 太阳油墨制造株式会社 | Epoxy resin composition, composition for filling in hole plugging, and printed wiring board using same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111748078A (en) * | 2019-03-26 | 2020-10-09 | 太阳油墨制造株式会社 | Curable resin composition for pore filling |
| CN111748078B (en) * | 2019-03-26 | 2024-05-17 | 太阳控股株式会社 | Curable resin composition for pore-filling |
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| CN108203497B (en) | 2021-04-13 |
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