CN106916261A - Hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB) - Google Patents
Hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB) Download PDFInfo
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- CN106916261A CN106916261A CN201510990654.8A CN201510990654A CN106916261A CN 106916261 A CN106916261 A CN 106916261A CN 201510990654 A CN201510990654 A CN 201510990654A CN 106916261 A CN106916261 A CN 106916261A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/095—Conductive through-holes or vias
- H05K2201/0959—Plated through-holes or plated blind vias filled with insulating material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB).Hardening resin composition and the solidfied material being made up of it that the present invention provides a kind of hole landfill processing for printed circuit board (PCB), the printed circuit board (PCB) that hole landfill processing is carried out using the solidfied material, the hardening resin composition meets various characteristics required by the embedding material of hole, while especially abrasiveness and cracking resistance is excellent.Landfill hardening resin composition in hole of the invention is the resin combination of compound, (B) titanocenes system Photoepolymerizationinitiater initiater, (C) inorganic filler, (D) thermosetting resin and (E) curing catalysts for having ethylenic unsaturated group comprising (A), characterized in that, being 1000mJ/cm according to light exposure2Mode photocuring film obtained for the ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm to the thickness that is obtained by the resin combination after, the pencil hardness on the surface of the photocuring film determined based on the method described in JIS K 5600-5-4 is F~3H.
Description
Technical field
The present invention relates to hole landfill hardening resin composition and its solidfied material and printed circuit board (PCB).Specifically,
It is related to a kind of hardening resin composition, its through hole for being suitable as multilayer board or double-sided printed-circuit board etc.
Or the permanent hole landfill composition in the hole portion such as via hole.Further, the present invention relates to use said composition to logical
The hole portion such as hole or via hole has carried out the printed circuit board (PCB) of permanent hole landfill disposal.It should be noted that at this
In specification, " hole portion " this term refers to through hole or via hole formed in the manufacturing process of printed circuit board (PCB) etc.
General name.
Background technology
In recent years, the downsizing of the graph thinning and actual installation area of the conductor circuit pattern of printed circuit board (PCB) is continuous
Development, further, possesses the miniaturization/multifunction of the machine of printed circuit board (PCB) in order to tackle, and expects printed circuit
Further compactization of plate.Therefore, multilayer board etc. is developed, it is however generally that, it is being arranged at base
Potting resin composition, is solidified in the through hole of plate, is after even surface, on the substrate alternating layer lamination
Between resin insulating barrier and conductor circuit layers, so as to obtain above-mentioned multilayer board.In this condition, expect out
Send out a kind of for filling the permanent hole landfill hardening resin composition of the hole portions such as through hole or via hole, its filling
Property, abrasiveness, solidfied material characteristic etc. are excellent.
As the permanent hole landfill hardening resin composition of printed circuit board (PCB), it is however generally that, it is widely used for heat
The composition epoxy resin of solidity, because its solidfied material is excellent at aspects such as engineering properties, electrical properties.Print now
The permanent hole landfill of printed circuit board processes the work by composition epoxy resin to be filled in the hole portion of printed circuit board (PCB)
Sequence (filling work procedure), by the operation (heat curing processes) of the composition heat cured of the filling, to what is overflowed from hole portion surface
The operation (grinding/removal step) that solidfied material is ground/removes is constituted.
But, it is hard due to solidfied material as described above, in the case of being ground to solidfied material after heat curing processes
Spend high and there are problems that grinding number is increased.Therefore, it is generally the case that add in the hole landfill of printed circuit board (PCB)
Following methods are employed in work, i.e. composition is filled in after hole portion, according to reaching the easily state that is ground
Precuring is carried out at a lower temperature, after being ground to the precuring thing, carries out main solidification.
However, in the case of method as described above, due to the single curing system as heat cure, therefore hardly possible
So that precuring thing to be controlled to the solid state (hardness) of easy grinding.That is, in precuring, curing reaction exceeds meaning
Carry out and carry out being hardness too low state for the state or curing reaction of excessive high hardness are not achieved one's goal material, produce
Abrasiveness declines so new problem.Heating when further, because of precuring, also generates the viscosity of resin combination
The problem for declining, producing turned-down edge and increase abrasive areas.
In this regard, inventor is conceived to the method for carrying out precuring with photocuring system, main solidification being carried out with heat cured system.
According to the method, precuring is carried out by light irradiation, therefore do not produce the turned-down edge of composition, can easily by precuring
Thing granule surface contral is the solid state (hardness) of easy grinding.As described method, in the past, it is proposed that using following
The method of photo-curable compositions of thermosetting resin, the photo-curable compositions of thermosetting resin includes epoxy resin not
Saturated fat acid moieties addition product, (methyl) esters of acrylic acid, photocrosslinking agent, liquid-state epoxy resin and latent curing agent (ginseng
According to patent document 1).
Prior art literature
Patent document 1：Japanese Unexamined Patent Publication 2003-105061 publications
The content of the invention
Problems to be solved by the invention
However, in the case where precuring is carried out using photocuring system, because of the shape of the hole portion of filling, causing combination
Thing easily produces the difference of curability on solidfied material surface and deep.Therefore, it is known that in heat cure or during soldering
Hot conditions under, for the composition disclosed in the patent document, however it remains generation stress and cause
Crackle as problem, the stress result from surface and deep photo-curable difference.
In addition, for existing photocuring system, in order to fully carry out precuring, generally, using photocuring
Larger internal stress is generated material more than position, but contraction when photocuring, cracking resistance is insufficient.
Therefore, it is a primary object of the present invention to provide a kind of curability of the hole landfill processing for printed circuit board (PCB)
Resin combination, the hardening resin composition meets various characteristics required by the embedding material of hole, while especially grinding
Mill property and cracking resistance are excellent.
In addition, other purposes of the invention are to provide the solidfied material and profit being made up of above-mentioned hardening resin composition
The printed circuit board (PCB) of hole landfill processing has been carried out with the solidfied material.
The means used to solve the problem
Inventor's solution above-mentioned problem and have made intensive studies, its result finds, poly- by using specific light
Initiator is closed, so that internal stress caused by the difference of the photo-curable because of surface and deep is reduced, while can hold
The easily-controllable solid state (hardness) for being made as easy grinding, this completes the present invention.
That is, landfill hardening resin composition in hole of the invention has ethylenic unsaturated group comprising (A)
Compound, (B) titanocenes system Photoepolymerizationinitiater initiater, (C) inorganic filler, (D) thermosetting resin and (E) solidify catalysis
The resin combination of agent, it is characterised in that according to light exposure be 1000mJ/cm2Mode to by the resin combination
The thickness that thing is obtained for the ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm obtain photocuring film it
Afterwards, based on described in JIS K 5600-5-4 method determine the photocuring film surface pencil hardness for F~
3H.Herein, the surface of photocuring film means the face of the carrying out of photocuring film light irradiation.
In landfill hardening resin composition in hole of the invention, the double bond equivalent of composition is preferably 300g/mol
More than.
It is 1000mJ/cm according to light exposure in landfill hardening resin composition in hole of the invention2Mode
Thickness to being obtained by the resin combination is the ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm
And after obtaining photocuring film, the back side of the photocuring film is surveyed based on the method described in JIS K 5600-5-4
Fixed pencil hardness is preferably HB~3H.Herein, the back side of photocuring film means the opposite with surface of photocuring film
The face of side.
In landfill hardening resin composition in hole of the invention, (A) has the chemical combination of ethylenic unsaturated group
Thing preferably includes any at least one selected from following (1)~(3).
The reactant of more than (1) 3 function polyalcohol, epoxyalkane and unsaturated carboxylic acid.That is, more than 3 functions
Polyalcohol on addition epoxyalkane and further reactant obtained from addition unsaturated carboxylic acid.
The reactant of more than (2) 3 functions polyalcohol, caprolactone and unsaturated carboxylic acid.That is, more than 3 functions
Addition caprolactone and reactant obtained from further addition unsaturated carboxylic acid on polyalcohol.
The reactant of more than (3) 3 functions polyalcohol, the reactant of diisocyanate and glycol and unsaturated carboxylic acid.
That is, the reactant of addition diisocyanate and glycol and further addition unsaturation on the polyalcohol more than 3 functions
Reactant obtained from carboxylic acid.
In landfill hardening resin composition in hole of the invention, above-mentioned (A) has the change of ethylenic unsaturated group
Compound does not preferably have carboxyl and epoxy radicals.
In landfill hardening resin composition in hole of the invention, said composition is preferably 2 liquid types.
In addition, solidfied material of the invention is made up of above-mentioned hole landfill of the invention with hardening resin composition.
In addition, printed circuit board (PCB) of the invention has by above-mentioned landfill hardening resin composition in hole of the invention
The solidfied material of composition.
Invention effect
According to the present invention it is possible to provide a kind of curable resin combination of the hole landfill processing for printed circuit board (PCB)
Thing, the hardening resin composition meet various characteristics required by the embedding material of hole, while especially abrasiveness and
Cracking resistance is excellent.
Therefore, according to the hardening resin composition of the invention described above, welding heat resistance when high-temperature process can be provided,
The solidfied material of the various excellents such as cold cycling patience and using the solidfied material carried out hole landfill processing printing
Circuit board.
Brief description of the drawings
Fig. 1 is the formation of the through hole for showing printed circuit board (PCB) and make use of the hole of hardening resin composition of the invention
The schematic sectional view of cave landfill processing.
Fig. 2 is the schematic sectional view for showing to have carried out the through hole of printed circuit board (PCB) the operation after the landfill processing of hole.
Fig. 3 is the formation of the via hole for showing printed circuit board (PCB) and make use of hardening resin composition of the invention
The schematic sectional view of hole landfill processing.
Symbol description
1 substrate, 2 Copper Foils, 3 through holes, 4,6 plated films, 5,5A solidfied materials, 7 etch-resistant coatings, 8 conductor circuit layers,
10 interlayer resin insulating layers, 11 openings, 12 plated films, 13 plating resist layer, 14 electroplating films, 15 via holes.
Specific embodiment
Landfill hardening resin composition in hole of the invention is the chemical combination for having ethylenic unsaturated group comprising (A)
Thing, (B) titanocenes system Photoepolymerizationinitiater initiater, (C) inorganic filler, (D) thermosetting resin and (E) curing catalysts
Resin combination, it is characterised in that according to light exposure be 1000mJ/cm2Mode to being obtained by the resin combination
To thickness obtain photocuring film for the ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm after,
The pencil hardness of the photocuring film determined based on the method described in JIS K 5600-5-4 is preferably F~3H.
In this way, in landfill hardening resin composition in hole of the invention, being drawn by using the photopolymerization of titanocenes system
Hair agent solidifies as Photoepolymerizationinitiater initiater, surface cure (case hardness) and deep such that it is able to ensure easy grinding
Property.
Specifically, it is 1000mJ/cm according to light exposure2Mode be to the thickness obtained by the resin combination
The ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm, so as to obtain photocuring film.Based on JIS K
Method described in 5600-5-4, the pencil hardness to the surface of the photocuring film is measured, and its result is, the pencil
Hardness is F~3H, is preferably F~2H, is more preferably F~H.The pencil hardness on the surface of photocuring film is less than F
In the case of, photocuring film it is excessively soft and be difficult to grinding.On the contrary, in the case that pencil hardness is higher than 3H, light
Cured film it is really up to the mark and be difficult to grinding.On the other hand, in the present invention, the pencil hardness on the surface of photocuring film for F~
3H, therefore the hardness on the surface of photocuring film is suitable, abrasiveness is excellent.
In addition, being 1000mJ/cm according to light exposure similarly2Mode to the thickness that is obtained by the resin combination
The ultraviolet of the dry coating surface illumination wavelength 365nm for 200 μm is spent, after obtaining photocuring film, is based on
Method described in JIS K 5600-5-4, the pencil hardness to the back side of the photocuring film is measured, and its result is,
The pencil hardness is preferably HB~3H, more preferably HB~2H, more preferably HB~H.The pencil is hard
Degree is determined with specific reference to the method described in embodiment described later.Herein, the pencil hardness at the back side of photocuring film is
HB~3H refers to, the center of through hole when hardening resin composition of the invention being filled in into through hole and photocuring is carried out
It is HB~3H to pay near hardness.It follows that according to the present invention, (deep is solid for the curability of the immediate vicinity of through hole
The property changed) it is excellent.
In the present invention, the pencil hardness on the surface of photocuring film is F~3H, the pencil hardness at the back side of photocuring film
It is HB~3H, therefore the state of cure on the surface of photocuring film and the state of cure in deep are almost without difference, cracking resistance
Line is excellent.
According to the present invention, abrasiveness and cracking resistance can be had concurrently first.In addition, according to the present invention, even if in hole portion
Draw ratio it is high in the case of, surface cure (abrasiveness) and deep curability are also excellent, can have concurrently abrasiveness and
Cracking resistance.
On the other hand, by making the double bond equivalent of composition be more than particular value, that is, to reduce the double bond quantity in composition,
Suppress the generation of internal stress so as to the contraction reduced during photocuring.
As the double bond equivalent of composition, more preferably preferably more than 300g/mol, more than 300g/mol 700g/mol
Below, it is more preferably more than 350g/mol below 650g/mol.Herein, the double bond equivalent of composition means
Double bond equivalent under the state (also referred to as organic principle) of the organic solvent in not containing composition and inorganic filler.
Hereinafter, each composition in landfill hardening resin composition in hole of the invention is described in detail.
[(A) has the compound of ethylenic unsaturated group]
There is the compound of ethylenic unsaturated group as (A) that constitutes hardening resin composition of the invention, only
To irradiate the material for solidifying by ultraviolet, it is not particularly limited, it is possible to use known usual material.
Be somebody's turn to do (A) having compound of ethylenic unsaturated group can be independent a kind, or of more than two kinds mixed
Compound, is preferably made up of mixture of more than two kinds.
(A) the double bond equivalent of the compound with ethylenic unsaturated group is preferably more than 100g/mol, is more preferably
More than 120g/mol below 300g/mol.
It is more than 100g/mol by making (A) that there is the double bond equivalent of the compound of ethylenic unsaturated group, so that can
To reduce the double bond quantity during (A) has the compound of ethylenic unsaturated group, contraction during photocuring is reduced.By
This, can suppress the generation of internal stress, improve cracking resistance.
(A) the average functional group number of the compound with ethylenic unsaturated group is preferably more than 3.0.More preferably
It is that the average functional group number is less than more than 3.0 6.0.
Herein, " functional group number " represents the quantity of the ethylenic unsaturated bond in 1 molecule of (A) composition, " average function
Group's number " represents the average value of the ethylenic unsaturated bond quantity of per molecule in (A) composition entirety.
By making average functional group number be more than 3.0, such that it is able to increase the crosslinking of (A) composition and other (A) compositions
And the quantity of the eyed structure for being formed, therefore cracking resistance during high-temperature process is improved.
Then double bond equivalent, to the composition in the present invention, the double bond equivalent of (A) composition and average functional group number
Computational methods and assay method are illustrated.
For example, in the case that resin combination of the invention is the composition shown in table 1 below, can be by following number
Formula (1)~(3) calculate.
【Table 1】
| The species of organic principle | Molecular weight | Functional group number | Blend amount |
| (A1) compound | M1 | N1 | W1 |
| (A2) compound | M2 | N2 | W2 |
| (A3) compound | M3 | N3 | W3 |
| (B) Photoepolymerizationinitiater initiater | - | - | W4 |
| (D) thermosetting resin | - | - | W5 |
| (E) curing catalysts | - | - | W6 |
| Other | - | - | W7 |
The double bond equivalent of composition=(W1+W2+W3+W4+W5+W6+W7)/(N1W1/M1+N2
W2/M2+N3W3/M3) formula (1)
(A) double bond equivalent=(W1+W2+W3)/(N1W1/M1 of the compound with ethylenic unsaturated group
+ N2W2/M2+N3W3/M3) formula (2)
(A) the average functional group number=(N1W1/M1+N2W2/M2 of the compound with ethylenic unsaturated group
+ N3W3/M3)/(W1/M1+W2/M2+W3/M3) formula (3)
In addition, the double bond equivalent of composition in the present invention, the double bond equivalent of (A) composition and average functional group number also may be used
Obtained with by following assay method.
(the double bond equivalent of composition)
(solvent extraction)
The hardening resin composition of the invention of about 3g is measured, in moving to 100mL beakers.It is added to about
The tetrahydrofuran of 20g, is fully dissolved.Afterwards, by centrifugal separator, processed 30 minutes with 1200rpm,
Separate inorganic filler.About 1/10 (g) of the weight of supernatant is measured, for following titration.
The measure of (the 1st equivalent (assuming that double bond equivalent))
During about 1/10 (g) of the weight of supernatant are moved into 100mL beakers, the morpholine of 10mL is added.Afterwards, make
With ultrasonic cleaning equipment, test portion is dissolved using magnetic stirring bar.Also, the mixed liquor 7mL of addition acetic acid/water (1/1),
Covered with aluminium foil etc., heated 30 minutes with 98 ± 2 DEG C in oil bath.Afterwards, room temperature is placed in the state of capping,
Methyl cellosolve, the acetic anhydride of 20mL of 25mL are added, using ultrasonic cleaning equipment, is made using magnetic stirring bar
Test portion dissolves.Afterwards, close the lid, room temperature is placed, and is titrated using the perchloric acid acetic acid solution of 0.1mol/L.
In addition, in addition to not adding supernatant, blank determination has been carried out using method similar to the above.
(computational methods of the 1st equivalent)
The 1st equivalent is obtained by following formula.
1st equivalent (g/eq)=(1000 × w)/N × f × (V-BL)
w：For the weight (about 1/10 (g) of the weight of supernatant) for titrating
N：The concentration (0.1mol/L) of perchloric acid acetic acid solution
f：The titer (f=0.999) of perchloric acid acetic acid solution
V：Titer (mL)
BL：The titer (mL) of blank
(measure of the 2nd equivalent (epoxide equivalent))
During about 1/10 (g) of the weight of above-mentioned supernatant are moved into 100mL beakers, chloroform, the 20mL of 30mL are added
Acetic acid.Afterwards, using ultrasonic cleaning equipment, test portion is dissolved using magnetic stirring bar.Afterwards, 10.0mL is added
Tetraethylammonium bromide solution.Herein, tetraethylammonium bromide solution refers to by tetraethylammonium bromide (powder) 100g dissolvings
The liquid obtained from acetic acid 400mL.
Then, titrated using the perchloric acid acetic acid solution of 0.1mol/L.
In addition, in addition to not adding supernatant, blank determination has been carried out using method similar to the above.
(computational methods of the 2nd equivalent)
The 2nd equivalent is obtained by following formula.
2nd equivalent (g/eq)=(1000 × w)/N × f × (V-BL)
w：For the weight (about 1/10 (g) of the weight of supernatant) for titrating
N：The concentration (0.1mol/L) of perchloric acid acetic acid solution
f：The titer (f=0.999) of perchloric acid acetic acid solution
V：Titer (mL)
BL：The titer (mL) of blank
Double bond equivalent in composition is obtained by following formula.
Double bond equivalent=1/ [(1/ the 1st equivalent)-(1/ the 2nd equivalent)] of composition
((A) has the double bond equivalent and average functional group number of the compound of ethylenic unsaturated group)
By analysis methods such as GPC, MS to composition in (A) have ethylenic unsaturated group compound enter
Row is specific, obtains its blend amount.The blend amount that (A) is had the compound of ethylenic unsaturated group is set to X, group
When the double bond equivalent of composition that the blend amount of compound (organic principle) is set to Y, obtained by said determination is set to Z, (A)
The double bond equivalent of the compound with ethylenic unsaturated group is obtained by following formula.
(A) the double bond equivalent=ZX/Y of the compound with ethylenic unsaturated group
In addition, carrying out specific by the compound to (A) with ethylenic unsaturated group and obtaining molecular weight, function
Group number and blend amount, therefore these numerical value are used, average functional group number has been calculated based on above-mentioned formula (3).
(A) the average functional group number of the compound with ethylenic unsaturated group is preferably more than 3.0, it is therefore desirable for
Comprising compounds more than 3 functions.
As the compounds with ethylenic unsaturated group more than 3 functions, can enumerate for example：3 functions with
On polyalcohol on addition alkylene oxide on compound, the polyalcohol more than 3 functions obtained from addition unsaturated carboxylic acid
Hydrocarbon, caprolactone or diisocyanate and glycol and further compound obtained from addition unsaturated carboxylic acid, have
Compound etc. obtained from addition unsaturated carboxylic acid on the glyceryl compound of more than 3.Particularly, as (A)
Compound with ethylenic unsaturated group, preferably without carboxyl and epoxy radicals.
More specifically, can enumerate：In trimethylolpropane, pentaerythrite, dipentaerythritol, three-ethoxy
The polyalcohol of isocyanates etc. or their ethylene oxide adduct, propylene oxide adduct, caprolactone addition product or
Upper addition (methyl) acrylic acid such as addition product of diisocyanate and glycol (mean acrylic acid, methacrylic acid or they
Mixture) obtained from polynary (methyl) esters of acrylic acid；
In novolak phenolics or its ethylene oxide adduct, propylene oxide adduct, caprolactone addition
Thing or diisocyanate and polynary (methyl) acrylate obtained from upper addition (methyl) acrylic acid such as the addition product of glycol
Class；
In phenol novolak type epoxy resin or cresol novolak type epoxy resin, biphenyl phenolic varnish type asphalt mixtures modified by epoxy resin
It is many obtained from addition (methyl) acrylic acid on the phenolic resin varnish type epoxy resins such as fat, bis-phenol phenolic resin varnish type epoxy resin
First (methyl) esters of acrylic acid；Etc..
Herein, polynary (methyl) esters of acrylic acid this term refers to acrylate, methacrylate and theirs is mixed
The general name of compound, is also same on other similar statements.
It is adjusted to from the viewpoint of more than 100g/mol from by the double bond equivalent of the compound, constitutes solidification of the invention
Property resin combination (A) have ethylenic unsaturated group compound preferably have epoxyalkane addition structure, oneself
Lactone addition structure or isocyanates addition structure.As the commercially available product of these compounds, can enumerate for example：Japan
The KAYARADGPO-303 of chemical drug (strain) society, THE-330, TPA-330, RP-1040, DPCA-20,
DPCA-30、DPCA-60、DPCA-120；East Asia synthesizes M1100, M1200 of (strain) society；Etc..
In addition, from from the viewpoint of the heat resistance for improving composition, constituting (A) of hardening resin composition of the invention
Compound with ethylenic unsaturated group preferably has aromatic rings.As it is this with aromatic rings with ethylenic
The compound of unsaturated group, can enumerate (methyl) acrylate polynary as derived from novolak phenolics
Class, (methyl) esters of acrylic acid polynary as derived from phenolic resin varnish type epoxy resin etc., more specifically, can enumerate
EAM-2160 of Nippon Kayaku (strain) Club etc..
It should be noted that having the compound of ethylenic unsaturated group as (A), can include that there are 2 functions
The known usual compound of the ethylenic unsaturated bond of (being in the molecule less than 2) below.
In terms of solid state component conversion, (A) for constituting hardening resin composition of the invention has ethylenic unsaturated group
The compound of group preferably carries out mixture, more preferably 20~40 mass % with the ratio of 10~50 mass % in the composition
Mixed ratio.By being the mixed ratio, can obtain more excellent surface photo-curable and deep photo-curable,
And heat resistance.
[(B) titanocenes system Photoepolymerizationinitiater initiater]
(B) the titanocenes system Photoepolymerizationinitiater initiater for constituting hardening resin composition of the invention be in order to by with it is above-mentioned
Sharing for (A) composition obtain excellent surface photo-curable and deep photo-curable and carry out mixture.Its result is,
Abrasiveness and cracking resistance can be had concurrently.
As this titanocenes system Photoepolymerizationinitiater initiater, can enumerate：Molybdenyl dichloride (cyclopentadienyl group) titanium, double (rings penta
Dialkylene) diphenyl titanium, double (cyclopentadienyl groups)-bis- (2,3,4,5,6- pentafluorophenyl groups) titaniums, double (cyclopentadienyl groups)-bis- (2,6-
Difluorophenyl) titanium, double (η 5- cyclopentadienyl groups)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles -1- bases) phenyl) titaniums etc., wherein, because
Photo-curable is excellent, double (η 5- cyclopentadienyl groups)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles that particularly preferably following formula (1) is represented
Cough up -1- bases) phenyl) titanium.
Relative to the mass parts of compound 100 that (A) has ethylenic unsaturated group, the titanocenes system photopolymerization triggers
Agent preferably carries out mixture, the more preferably mixed ratio of 1~4 mass parts with the ratio of 0.1~5 mass parts.By for
The mixed ratio, can obtain more excellent abrasiveness and cracking resistance.
It should be noted that in hardening resin composition of the invention, as long as not influenceing effect of the invention, can
To share the other known usual Photoepolymerizationinitiater initiater beyond titanocenes system Photoepolymerizationinitiater initiater.Example can be enumerated
Such as：The benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin alkyl
Ethers；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloro-benzenes
The acetophenones such as ethyl ketone；2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropane -1- ketone, 2- benzyl -2- dimethylaminos
The aminoacetophenone classes such as -1- (4- morphlinophenyls)-butane -1- ketone；2-methylanthraquinone, 2- EAQs, 2- tert-butyl anthracenes
The Anthraquinones such as quinone, 1- chloroanthraquinones；2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, CTX, 2- isopropyls
The thioxanthene ketone class such as base thioxanthones, ITX；Acetophenone dimethyl ketal, benzil dimethyl ketal etc. contract
Ketone；The benzophenones such as benzophenone or xanthene ketone；(2,6- Dimethoxybenzoyls) -2,4,4- amyl groups phosphine oxide,
Double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, ethyl
The acylphosphine oxide class such as -2,4,6- trimethylbenzoyl phenyl phosphites；1,2- octadione- 1- [4- (thiophenyl) -2- (O-
Benzoyl oxime)], the oxime lipid such as ethyl ketone -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1- (O- acetyl oxime)
Deng.
[(C) inorganic filler]
As (C) inorganic filler for constituting hardening resin composition of the invention, it is not particularly limited, can makes
With known usual inorganic filler.As (C) inorganic filler, hole landfill solidfied material can be preferably improved
Heat resistance, the material for reducing linear expansion coefficient, can enumerate for example：Silica or barium sulfate, calcium carbonate, nitridation
Silicon, aluminium nitride, boron nitride, aluminum oxide, magnesia, aluminium hydroxide, magnesium hydroxide, titanium oxide, mica, talcum,
The nonmetallic inorganic filler such as organobentonite；Or, the metal inorganic filler such as copper or gold, silver, palladium.They can
Used with being used alone or combining two or more.
Wherein, from low water absorbable and low heat expansion it is excellent from the viewpoint of, preferably silica；In addition, from low
From the viewpoint of water imbibition and abrasiveness are excellent, preferably calcium carbonate.Can be noncrystalline, knot as silica
Any one brilliant, or their mixture.In addition, as calcium carbonate, can for natural powdered whiting,
Any one of the precipitated calcium carbonate of synthesis.
The shape of this inorganic filler can enumerate spherical, needle-like, tabular, flakey, hollow form, indefinite shape,
Hexagon shape, cubic, spindle shape, flake etc., but from from the viewpoint of filling high in the composition, it is excellent
Elect spherical as.
The average grain diameter (D50) of this inorganic filler is preferably 0.1~25 μm, more preferably 0.1~10 μm.Pass through
In the range of the average grain diameter, more excellent dispersiveness can be obtained, additionally, fillingization high becomes easy, its knot
Fruit is that can obtain the fillibility and reliability in more excellent hole portion.It should be noted that the inorganic filler
Average grain diameter (D50) is by laser diffraction/scattering method.
Relative to the mass parts of (D) thermosetting resin 100, the inorganic fill of hardening resin composition of the invention is constituted
Agent preferably carries out the mixed ratio of mixture, more preferably 50~150 mass parts with the ratio of 30~180 mass parts.It is logical
Cross as the mixed ratio, the low water absorbable and low heat expansion of resulting solidfied material are more excellent, additionally, anti-stomata is produced
Raw or cracking resistance is excellent, can further obtain sufficient abrasiveness and adaptation.
[(D) thermosetting resin]
As (D) thermosetting resin for constituting hardening resin composition of the invention, as long as to be solidified by heat
Material, is not particularly limited, it is possible to use known usual thermosetting resin.As thermosetting resin, preferably
For the heat resistance of solidfied material and the material of adaptation can be improved, can enumerate for example：Block isocyanate compound, ammonia
Base resin, maleimide compound, benzoxazine colophony, carbodiimides resin, cyclic carbonate compound, three
Paracyanogen amine derivative, epoxide, oxetane compound, episulfide resin etc. have the change of ring-type (sulphur) ether
Compound.Among these, preferably there is the ring-type (sulphur) of 3 yuan of rings, 4 yuan of rings or 5 yuan of rings of more than 2 in the molecule
The compound of ether, can enumerate for example：There is the compound, i.e. many of the epoxy radicals of at least more than 2 in the molecule
Functional epoxide compound；There is compound, the i.e. multifunctional oxygen of the oxetanyl of at least more than 2 in the molecule
Oxetane compounds；There is compound, the i.e. episulfide resin of the thioether group of more than 2 in the molecule；Etc..Need
It is noted that ring-type (sulphur) ether refers to any one of ether or cyclic thioether base or both.
As multi-functional epoxy compound, can enumerate for example：Bisphenol A type epoxy resin, bisphenol F type epoxy tree
Fat, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol-s epoxy resin, phenol phenol
Novolac type epoxy resin, cresol novolak type epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, connection
Benzene-type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene-type epoxy resin, triphenyl first
Alkane type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phosphorous epoxy resin, anthracene type asphalt mixtures modified by epoxy resin
Fat, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type epoxy resin, aminobenzene phenol-type epoxy resin,
Amino first phenol-type epoxy resin, alkylbenzene phenol-type epoxy resin etc..It should be noted that in curability tree of the invention
In oil/fat composition, these epoxy resin are can be used alone, or two or more can also be shared.
Herein, hardening resin composition of the invention be used as printed circuit board (PCB) hole landfill use, therefore preferably without
Solvent.Therefore, among above-mentioned multi-functional epoxy compound, the epoxy resin of liquid is preferably used.As this liquid
The epoxy resin of state, can enumerate：Bisphenol A type epoxy resin or bisphenol f type epoxy resin, aminobenzene phenolic ring
Oxygen tree fat etc..It should be noted that hardening resin composition of the invention can contain a small amount of solvent.
As the commercially available product of the epoxy resin of this liquid, can enumerate for example：Society of Mitsubishi Chemical 828, new day
The bisphenol A type epoxy resins such as 840 of YD127, DIC society of Tie Zhujin societies；Society of Mitsubishi Chemical 807,
The bisphenol f type epoxy resins such as 830 of YD170, DIC society of Zhu Jin societies of Nippon Steel；Society of Mitsubishi Chemical
The aminobenzene phenol-type epoxy resin such as jER-630, ELM-100 of Sumitomo Chemical society (p aminophenol epoxy resin).
In addition, in hardening resin composition of the invention, by using the epoxy resin of semisolid as multifunctional ring
Oxygen compound, the cracking resistance of the solidfied material obtained by can improving the anti-turned-down edge of composition or improving.
As this semisolid epoxy resin, can enumerate：The EPICLON860 of DIC societies,
EPICLON900-IM, EPICLONEXA-4816, EPICLONEXA-4822, XuCHIBAShe's
Araldite AER280, Dongdu are melted into EPOTOHTO YD-134, JapanEpoxyResin societies of society
The bisphenol A type epoxy resins such as jER834, jER872, the ELA-134 of Sumitomo Chemical society；DIC societies system
The naphthalene type epoxy resins such as EPICLONHP-4032；DIC societies EPICLONN-740, the RE306 of Japanese chemical drug society
Etc. phenol novolak type epoxy resin etc..
Then, as above-mentioned polyfunctional group oxetane compound, can enumerate for example：Double [(3- methyl -3- oxa-s
Cyclobutane ylmethoxy) methyl] ether, double [(3- ethyl -3- oxetanylmethoxies) methyl] ethers, double [(the 3- methyl of 1,4-
- 3- oxetanylmethoxies) methyl] benzene, 1,4- double [(3- ethyl -3- oxetanylmethoxies) methyl] benzene, third
Olefin(e) acid (3- methyl -3- oxetanyls) methyl esters, acrylic acid (3- ethyl -3- oxetanyls) methyl esters, metering system
Sour (3- methyl -3- oxetanyls) methyl esters, methacrylic acid (3- ethyl -3- oxetanyls) methyl esters or they
The multifunctional oxetanes class such as oligomer or copolymer, in addition to this it is possible to enumerate：Oxa- cyclobutanol and phenolic aldehyde
Varnish gum, poly- (4-Vinyl phenol), Cardo types bisphenols, calixarene kind, resorcinol calixarenes or again
Etherate of the resin with hydroxyl such as half siloxanes etc..In addition, can enumerate：With oxetanes ring
Copolymer of unsaturated monomer and (methyl) alkyl acrylate etc..
Then, as the episulfide resin of the cyclic thioether base in the molecule with more than 2, can enumerate for example：
The YL7000 (bisphenol A-type episulfide resin) of JapanEpoxyResin societies or, Dongdu be melted into society YSLV-120TE
Deng.The oxygen atom of the epoxy radicals of epoxy resin is substituted by episulfide resin of sulphur atom etc. alternatively, it is also possible to use.
In terms of solid constituent conversion, (D) thermosetting resin of hardening resin composition of the invention is constituted preferably in group
Mixture, the more preferably mixed ratio of 20~40 mass % are carried out with the ratio of 10~50 mass % in compound.Pass through
It is the mixed ratio, the balancing good with photo-curable, its result is that heat resistance and cracking resistance are more excellent.
[(E) curing catalysts]
For constituting (E) curing catalysts of hardening resin composition of the invention, as long as to promote (D) thermosetting
The material of the curing reaction of property resin, is not particularly limited, it is possible to use known usual curing catalysts.
As (E) curing catalysts, can enumerate for example：Imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- ethyls -4-
Methylimidazole, 2- phenyl -1- benzyl -1H- imidazoles, 2- phenylimidazoles, 4- phenylimidazoles, 1-cyanoethyl-2-phenylimidazole,
The imdazole derivatives such as 1- (2- cyanoethyls) -2-ethyl-4-methylimidazole；
2,4- diaminourea -6- [2'- methylimidazolyls-(1')]-ethyl-s-triazine, 2,4- diaminourea -6- [2'- undecyl miaows
Oxazolyl-(1')]-ethyl-s-triazine, 2,4- diaminourea -6- [2'- ethyl -4'- methylimidazolyls-(1')]-ethyl-s-triazine etc.
Imdazole derivatives with triazine structure；
2,4- diaminourea -6- [2'- methylimidazolyls-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazoles are different
The isocyanurate of the imdazole derivatives such as cyanurate addition product；
The imidazoles methylol bodies such as 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles；
Dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl groups-N, N- dimethyl
The amines such as benzyl amine, 4- methyl-N, N- dimethyl benzyl amine；
The hydrazine compounds such as adipic dihydrazide, sebacic dihydrazide；
The phosphorus compounds such as triphenylphosphine；
Guanamine, acetyl guanamine, benzo guanamine, melamine, 2,4- diaminourea -6- methyl
Acryloyl-oxyethyl-S- triazines, 2- vinyl -2,4- diaminourea-S- triazines, 2- vinyl -4,6- diaminourea-S- triazines -
The triazines such as isocyanuric acid adduct, 2,4- diaminourea -6- methacryloxyethyls-S- triazines-isocyanuric acid adduct
Derivative；Etc..
As commercially available product, can enumerate for example：The 1B2PZ of chemical conversion industry society of four countries, 2E4MZ, 2MZ-A,
2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), SAN-APRO societies
U-CAT (registration mark) 3503N, U-CAT3502T of system (is the block isocyanate compound of dimethyl amine
Trade name), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compounds and its salt) etc..
These (E) curing catalysts can be used alone or mix two or more and use.
The curing catalysts are preferably powder.By using the curing catalysts of powder, can prevent in reflow process
Plated film on solidfied material is expanded.
In addition, from from the viewpoint of cracking resistance, as curing catalysts, it is however preferred to have the imidazoles of triazine structure spreads out
It is at least any of in the biological, isocyanurate of imdazole derivatives and imidazoles methylol body.Wherein, it is however preferred to have
The compound of triazine structure or benzene structure.
The curing catalysts of hardening resin composition of the invention are constituted with the ratio mixture of common amount, relatively
In the mass parts of (D) thermosetting resin 100, more preferably preferably 0.1~20 mass parts, 0.5~15.0 mass parts.
Further, as needed, hardening resin composition of the invention can add containing carboxy resin, organic solvent,
The thixotropic agent such as organobentonite or montmorillonite, hydrotalcite.Furthermore it is possible to mixture thermal polymerization inhibitor；Silicon-type,
Froth breaking/the levelling agent such as fluorine system, macromolecular；Silane coupler；Antirust agent；And antioxidant etc. is known usual
Additive kind.
The hardening resin composition of present invention mentioned above is protected preferably in the form of the composition being divided into more than 2 liquid
Deposit.In the case of being preserved in the form of composition more than 2 liquid, (A) preferably had into ethylenic insatiable hunger respectively
Compound and (B) titanocenes system Photoepolymerizationinitiater initiater with group are retained separately.Additionally, it is preferred that respectively by (D) thermosetting
Resin and (E) curing catalysts are retained separately.
It should be noted that as the separation method being separated into when more than 2 liquid being preserved, as long as without prejudice to is of the invention
Effect be not particularly limited.
Hereinafter, the method to manufacturing printed circuit board (PCB) of the invention, while one side is specifically described referring to the drawings.Need
It is noted that method described below is to be shown using of the manufacture method of the multilayer board of semi-additive process
In example, but the manufacture method of printed circuit board (PCB) in the present invention, can be known various using fully-additive process etc.
Method.
(1) formation of through hole
First, as shown in Fig. 1 (a), it is being laminated on the substrate 1 of Copper Foil 2, through hole is being outputed using drill bit, it is right
The wall and copper foil surface of through hole impose electroless plating and form through hole 3.As substrate, glass ring epoxide can be used
The resin substrate such as plate or polyimide substrate, bismaleimide-triazine resin substrate, fluororesin substrate, or these
Copper clad laminate, ceramic substrate, metal substrate of resin substrate etc..
Then, electrolytic coating is carried out to increase thickness, wall forms plating in substrate surface and through hole 3 shown in such as Fig. 1 (b)
Film 4.As the electrolytic coating, preferably copper plating.
(2) hole landfill
In through hole 3 formed in above-mentioned (1), filling composition of the invention such as shown in Fig. 1 (c).Specifically,
The mask that will be provided with opening in throughhole portions is placed on substrate, is filled into composition by net-point printing method etc. logical
In hole 3.
Then, make the uncured composition photocuring of filling, obtain photocured product 5.Photo curing condition is without special
Limit, can suitably select, such as with 500~2000mJ/cm2Light irradiation amount illumination wavelength 200~400nm
Ultraviolet.Light irradiation is preferably carried out from two faces of substrate, but it is also possible to carried out from one side.It should be noted that this
The composition of invention preferably carries out photocuring after 30 minutes comprising in the case of solvent in 80 DEG C of dryings.
Afterwards, as shown in Fig. 1 (d), removed by the unnecessary portion for grinding the photocured product 5 that will be overflowed from through hole,
Planarize it.Grinding can suitably be carried out using belt sander or polishing grinding etc..Afterwards, further heating
So as to carry out main solidification.Herein, as heat curing temperature, for example, 150~200 DEG C.It is if the scope, then solid
The heat resistance of compound, moisture-proof are improved, and on the other hand, can prevent the fire damage of substrate.
Afterwards, as needed, the exposing surface to solidfied material 5 carries out roughening treatment.It is dispersed with solidfied material solvable
In the case of the particle of roughening treatment liquid, above-mentioned grain dissolution is removed by the roughening treatment, form anchoring effect
Excellent roughening face, thus plated film after-applied therewith excellent adhesion.
(3) formation of conductor circuit layers
The surface of the substrate filled for the hole that through hole has been carried out in above-mentioned (2), after assigning catalyst core, imposes nothing
Plated film 6 is formed shown in electrolytic coating and electrolytic coating, such as Fig. 1 (e).Afterwards, etch-resistant coating 7 is formed as shown in Fig. 1 (f),
It is etched to not forming etch-resistant coating part.Then, etch-resistant coating 7 is peeled off, shown in such as Fig. 1 (g), formation is led
Body circuit layer 8.As etching solution, it is possible to use the aqueous solution of Sulfuric-acid-hydrogen-peroxide, ammonium persulfate or sodium peroxydisulfate,
The known etching solutions such as the aqueous solution of the persulfate such as potassium peroxydisulfate aqueous solution, iron chloride or copper chloride.
(4) formation of interlayer resin insulating layers
Afterwards, as needed, at the surface by the method for melanism (oxidation)-reduction treatment etc. to conductor circuit layers
After reason, such as shown in Fig. 2 (a), interlayer resin insulating layers 10 are formed.As interlayer resin insulating layers, it is possible to use thermosetting
The compound or mixture, resin impregnated glass cloth of property resin, light-cured resin, thermoplastic resin or these resins
Compound, electroless plating adhesive etc..Interlayer resin insulating layers 10 are by being coated with above-mentioned resin combination
Uncured liquid or the membranaceous resin of hot pressing are simultaneously laminated and are formed.
(5) formation of via hole
Then, as shown in Fig. 2 (a), opening 11 is set in interlayer resin insulating layers 10.For the perforation of the opening 11,
When interlayer resin insulating layers 10 are formed by ultraviolet curable resin, carried out by exposure, development treatment, by thermosetting tree
When fat or thermoplastic resin are formed, utilize laser to carry out.As the laser for now being used, carbon dioxide is there are
Gas laser, ultraviolet laser, excimer laser etc..In the case of utilizing laser to perforate, can be gone
Bore dirty treatment.Desmearing treatment can use the oxidant being made up of the aqueous solution of chromic acid, permanganate etc. to carry out,
Can also be processed using oxygen plasma etc. in addition.
After opening 11 is formed, as needed, the surface to interlayer resin insulating layers 10 carries out roughening treatment.Then,
After to the catalyst core of the electroless plating of surface imparting of interlayer resin insulating layers 10, implement electroless plating, such as
Shown in Fig. 2 (b), plated film 12 is formed in entire surface.
Then, as shown in Fig. 2 (c), the plating resist layer 13 of pattern-like is formed on plated film 12.Plating resist layer is by suitable
Ground laminated photosensitive dry film and be exposed, development treatment and formed.
Further, electroplated, increased conductor circuit segment thickness, shown in such as Fig. 2 (c), formed electroplating film 14.
Then, peel off after plating resist layer 13, the electroless plated film 12 under plating resist layer dissolved into removal by etching,
As shown in Fig. 2 (d), independent conductor circuit (including via hole 15) is formed.As etching solution, sulphur can be suitably used
The persulfate solution such as the aqueous solution of acid-hydrogen peroxide, ammonium persulfate or sodium peroxydisulfate, potassium peroxydisulfate, iron chloride or
Aqueous solution of copper chloride etc..
It should be noted that as shown in Fig. 2 (d), showing by electroplating the operation in filling vias hole 15, but also may be used
With by composition filling vias hole 15 of the invention.
That is, it is same with using Fig. 2 (a), the method illustrated by (b) first, such as Fig. 3 (a), (b) it is shown, according to comprising opening
The mode of mouth 11 forms plated film 12 in entire surface.Afterwards, composition of the invention is filled, light irradiation is carried out so as to obtain
To photocured product 5A.Afterwards, removed by grinding the unnecessary portion of the photocured product 5A that will be overflowed from via hole 5
Go, planarize it, heated to carry out main solidification.
Then, as shown in Fig. 3 (c), the plating resist layer 13 of pattern-like is formed on plated film 12, is electroplated, form electricity
Plated film 14.Afterwards, peel off after plating resist layer 13, the electroless plated film 12 removed under plating resist layer dissolved by etching,
As shown in Fig. 3 (d), independent conductor circuit is formed.
Also, in the manufacture method of above-mentioned printed circuit board (PCB), show leading to substrate as shown in Figure 1, 2
The alternately lamination method of interlayer resin insulating layers and conductor circuit layers on the substrate after the potting resin composition of hole,
But following methods can also be used：On the substrate alternately between laminated layer after resin insulating barrier and conductor circuit layers, formed
The through hole of through substrate, interlayer resin insulating layers and conductor circuit layers, the potting resin composition in the through hole.
Embodiment
(embodiment 1~7, comparative example 1~2；Hole landfill hardening resin composition)
Mixture according to following tables, carries out the mixture of each composition, after being premixed using mixer, uses 3
Three-stage roll mill is disperseed, is kneaded, and is prepared for the 1st combination thing liquid (host) and the 2nd combination thing liquid (curing agent).
Blend amount in table represents mass parts.
(first chamber liquid)
(A) caprolactone modification acrylic monomers：Japanese chemical drug (strain) makes (DPCA-60)
Molecular weight：1262nd, double bond equivalent：210th, average functional group number：6.0
(A) nobolak type epoxy acrylate：Japanese chemical drug (strain) makes (EAM2160W)
Molecular weight：700th, double bond equivalent：230th, average functional group number：3.0
(A) trimethylolpropane trimethacrylate：Japanese chemical drug (strain) makes (TMPTA)
Molecular weight：296th, double bond equivalent：99th, average functional group number：3.0
(C) silica：(strain) imperial gloomy system (A8)
(C) calcium carbonate：White well Calcium (strain) system (ML-2800)
(D) phenol novolak type epoxy resin：Japanese chemical drug (strain) makes (RE306)
(E) imidazoles system curing catalysts：Four countries' chemical conversion (strain) system (2MZ-AP)
Defoamer：BYK-CHEMIE JAPAN (strain) make (KS-66)
Levelling agent：SHIN-ETSU HANTOTAI's chemical industry (strain) makes (R606)
(the 2nd combination thing liquid)
(B) titanocenes system Photoepolymerizationinitiater initiater：BASF JAPAN (strain) make (Irg.784)
Isopropyl thioxanthone：Tokyo chemical conversion industry (strain) makes (ITX)
Acylphosphine oxide system Photoepolymerizationinitiater initiater：BASF JAPAN (strain) make (Irg.TPO)
Aminoacetophenone system Photoepolymerizationinitiater initiater：BASF JAPAN (strain) make (Irg.907)
(D) bisphenol A type epoxy resin：DIC (strain) makes (840)
(D) bisphenol f type epoxy resin：DIC (strain) makes (830)
Fine particle silica：Below 0.1 μm of average grain diameter (D50)
On the embodiment for being mixed to get resulting the 1st combination thing liquid (host) and the 2nd combination thing liquid (curing agent)
1~7 and the hardening resin composition of comparative example 1~2, evaluated according to herein below.The results are shown in table.
From being shown in the result of the table, the hardening resin composition of embodiments in accordance with the present invention 1~7 is used
Titanocenes system Photoepolymerizationinitiater initiater is as Photoepolymerizationinitiater initiater, therefore the pencil hardness on resulting photocuring film surface
In the range of F~3H, the pencil hardness at the photocuring film back side is also in the range of HB~3H.Therefore, it is known that grind
Mill property and cracking resistance are excellent.In addition, other various characteristics such as turned-down edge are also excellent.
On the other hand, for the hardening resin composition of comparative example 1,2, the photopolymerization of titanocenes system is not used
Initiator is used as Photoepolymerizationinitiater initiater, therefore the surface of photocuring film and the pencil hardness at the back side are low, abrasiveness and cracking resistance
Line is insufficient.
Turned-down edge：
Copper clad laminate to having carried out polishing grinding treatment is added dropwise the composition of 0.1mL, and substrate is holded up for 90 °,
After 150 DEG C of dryings 30 minutes, the distance that hangs down from datum line is determined.On metewand, from datum line hang down away from
When during from less than 20mm for zero, for more than 20mm for ×.
Diffusion on through hole：
For the glass epoxy substrate (thickness of slab 1.6mm, through hole footpath 0.3mm) that through hole is formd beforehand through panel plating method,
Each composition is filled in through hole using silk screen print method.For the substrate, using metal halide lamp, in light wave
Under conditions of a length of 300~500nm according to cumulative exposure amount be 800~1200mJ/cm2Mode be exposed, obtain
To photocured product.Afterwards, substrate is inverted, is exposed using metal halide lamp as described above, obtain light
Solidfied material.The cross sectional shape of the photocured product that confirmation is obtained, compared with the footpath of through hole, the diffusion length of photocured product
Be when being more than zero, 3 times when multiplying power is less than 3 times ×.
The crackle in through hole when welding heat-resisting：
For the photocured product obtained according to method similar to the above, using polishing grinding machine, by equivalent to #320
Resin ground carry out physical grinding with polishing single shaft, so as to remove the unwanted cured portion after photocuring.Then,
150 DEG C are warming up to, solidify within 45~60 minutes, obtain evaluating sample (I).Sample (I) will be evaluated and impregnated in 288 DEG C
Soldering fluid in 10 seconds, the dipping is carried out 3 times, carries out placing until for room temperature afterwards.Afterwards, in through-hole section
Cut, observed using light microscope pair cross-section, the through hole that test portion generates crackle (rupture) is NG,
Calculate ratios of the NG relative to observed via count.Judgment standard is as follows.
○：Cracking frequency is less than 10%
△：Cracking frequency is less than more than 10% 25%
×：Cracking frequency is more than 25%
Stomata in through hole：
Above-mentioned evaluation sample (I) is cut in through-hole section, is observed using light microscope pair cross-section, it is thus identified that
There is pore-free in through hole.Leachy through hole will be remained as NG, NG will be calculated relative to observed via count
Ratio.Judgment standard is as follows.
○：Stomata residual rate is 0%
△：Stomata residual rate is less than 25%
×：Stomata residual rate is more than 25%
Abrasiveness：
For the photocured product obtained according to method similar to the above, using polishing grinding machine, by equivalent to #320
Resin ground carry out physical grinding with polishing single shaft, so as to remove the unwanted cured portion after photocuring.As
Grinding condition, load current：1A, transfer rate：0.5m/min.
Now, the easness that grinding is removed is evaluated by proceeding to completion the number of pass times untill removing.Judgment standard
It is as follows.
○：By less than 2 times
×：By more than 3 times or cannot grind
Crackle caused by cold cycling in through hole：
For above-mentioned evaluation sample (I), using 125 DEG C, 30 minutes and -40 DEG C, 30 minutes as 1 circulation, hand over
For being repeated, every 100 recycling light microscopes carry out the surface observation of through hole.Confirm what is cracked
At the moment, stop testing in the circulation, the largest loop to crackle unconfirmed is evaluated.Judgment standard is as follows.
○：More than 2000 times
△：1500 times less than 2000 times
×：Less than 1500 times
Water absorption rate：
Using the curing same with above-mentioned evaluation sample (I), specimen size is obtained for 5cm × 5cm, thickness are
100 μm of cured film.After the weight of the cured film that measure is obtained, impregnated in 24 hours in water, determine cured film
Weight, the water absorption rate of cured film is obtained by following calculating formulas.Judgment standard is as follows.
Water absorption rate (%)=(W2-W1)/(W1) × 100
Herein, W2 is the weight (g) of the cured film after immersion test, and W1 is the weight (g) of the cured film at initial stage.
○：Less than 0.8%
△：More than 0.8% and less than 1.5%
×：More than 1.5%
The pencil hardness of photocuring film：
On glass epoxy substrate, after being coated with each resin combination so as to obtain film using applicator, metal halogen is used
Compound lamp, under conditions of a length of 300~500nm of light wave according to cumulative exposure amount be 800~1200mJ/cm2Side
Formula is exposed to film, obtains photocuring film.
Based on the method described in JIS K 5600-5-4, photocuring film is tested, by the cut on photocuring film surface
Pencil hardness of depth when being less than 100 μm as photocuring film pencil hardness.The depth of cut uses surface
Roughmeter is determined.
The pencil hardness with the back side of plane of exposure opposite side of photocuring film：
200 μm of the Copper Foil with the foursquare opening portions of 5cm × 5cm is overlapped in has carried out the PET of demoulding treatment
Film, each resin combination is coated with so as to obtain film using applicator.Afterwards, PET film is removed, for opening portion
Dry coating, using metal halide lamp, according to cumulative exposure amount under conditions of a length of 300~500nm of light wave
It is 800~1200mJ/cm2Mode be exposed, obtain photocuring film.
Based on the method described in JIS K 5600-5-4, photocuring film and the back side of plane of exposure opposite side are tried
Test, pencil of the pencil hardness when depth using the cut at the photocuring film back side is less than 100 μm as photocuring film
Hardness.The depth of cut is determined using surface roughness meter.
Claims (4)
1. a kind of hole landfill hardening resin composition, it is the change for having ethylenic unsaturated group comprising (A)
Compound, (B) titanocenes system Photoepolymerizationinitiater initiater, (C) inorganic filler, (D) thermosetting resin and (E) curing catalysts
Resin combination, it is characterised in that according to light exposure be 1000mJ/cm2Mode to by the resin combination
The thickness for obtaining is obtained after photocuring film for the ultraviolet of 200 μm of dry coating surface illumination wavelength 365nm,
The pencil hardness on the surface of the photocuring film determined based on the method described in JIS K 5600-5-4 is F~2H.
2. landfill hardening resin composition in hole as claimed in claim 1, it is characterised in that according to exposure
It is 1000mJ/cm to measure2Mode dry coating surface that the thickness obtained by the resin combination is 200 μm is shone
The ultraviolet of ejected wave 365nm long and after obtaining photocuring film, based on the method pair described in JIS K 5600-5-4
The pencil hardness that the back side of the photocuring film determines is HB~3H.
3. a kind of solidfied material, it is characterised in that the solidfied material is filled out by the hole described in claim 1 or 2
Bury obtained from being solidified with hardening resin composition.
4. a kind of printed circuit board (PCB), it is characterised in that the printed circuit board (PCB) has the solidfied material described in claim 3.
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| CN201510990654.8A CN106916261B (en) | 2015-12-25 | 2015-12-25 | Curable resin composition for filling holes, cured product thereof, and printed wiring board |
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| CN201510990654.8A CN106916261B (en) | 2015-12-25 | 2015-12-25 | Curable resin composition for filling holes, cured product thereof, and printed wiring board |
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| CN106916261B CN106916261B (en) | 2020-05-19 |
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|---|---|
| CN106916261B (en) | 2020-05-19 |
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