CN111378253A - Resin filler - Google Patents
Resin filler Download PDFInfo
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- CN111378253A CN111378253A CN201811635559.6A CN201811635559A CN111378253A CN 111378253 A CN111378253 A CN 111378253A CN 201811635559 A CN201811635559 A CN 201811635559A CN 111378253 A CN111378253 A CN 111378253A
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- epoxy resin
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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- 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
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- 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
Abstract
The present invention relates to a resin filler, a cured product, a printed wiring board, and a method for producing a printed wiring board. The resin filler contains (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler.
Description
Technical Field
The present invention relates to a resin filler, and more particularly to a resin filler useful as a composition for permanently filling holes such as through holes and via holes in printed wiring boards such as multilayer boards and double-sided boards. The present invention also relates to a printed wiring board obtained by permanently filling holes and recesses such as through holes and via holes with the composition. In the present specification, the "concave portion" refers to a via hole or the like for the purpose of conduction between layers of the printed wiring board, and the "hole portion" refers to a through hole, for example, a through hole, for the purpose of conduction between the front surface and the back surface of the printed wiring board.
Background
The printed circuit board is provided with a recess between conductor circuits on the surface, and a hole such as a through hole having a conductive layer formed on the inner wall surface. In order to protect the inner wall conductor during etching for forming the conductor pattern and to improve the reliability in mounting, the hole portion is filled with a hole filling material using a thermosetting resin filling material containing an epoxy resin, a curing agent and an inorganic filler.
In recent years, the reduction in the size of conductor circuit patterns and the reduction in the mounting area of printed wiring boards have been advanced, and further reduction in the thickness and size of printed wiring boards have been desired in order to further cope with the miniaturization and high functionality of devices provided with printed wiring boards. Therefore, the following multilayer printed circuit boards were developed: a multilayer printed wiring board formed by filling a resin filler into a through hole provided in a printed wiring board, curing the resin filler to form a smooth surface, and then alternately laminating an interlayer resin insulation layer and a conductor circuit layer on the circuit board; or a multilayer printed wiring board in which a solder resist is directly formed on a substrate having a hole such as a through hole filled with a resin filler. Under such circumstances, it has been desired to develop a composition for permanent hole filling which is excellent in printability for filling holes and recesses such as through holes and via holes and cured product properties such as solder heat resistance (see WO 2002/044274).
In such a multilayer printed wiring board, a hole portion such as a through hole having a copper plating layer formed therein is formed to electrically connect the respective layers. In the process of manufacturing a printed wiring board, a filler of a curable resin composition called a hole-filling ink is filled into a hole portion such as a through hole, from the viewpoint of ensuring the strength of the printed wiring board and preventing contamination.
Disclosure of Invention
Problems to be solved by the invention
As such a resin filler, for example, japanese patent application laid-open No. 11-266078 discloses a resin filler containing a bisphenol epoxy resin, an imidazole curing agent, and an inorganic filler. Jp-a-11-222549 discloses a pore-filling material containing an amine-type epoxy resin, a polyphenol-type epoxy resin, and an inorganic filler. Japanese patent laid-open No. 2003-133672 discloses a filler containing a liquid epoxy resin, an epoxy monomer, a curing agent and a filler.
However, the printing properties of the resin filler of the prior art are not sufficient. Voids may be generated by introducing air during printing, and cracks may be generated during curing of the pore-filling ink. In addition, the peel strength of the copper plating layer is not sufficient.
The present invention has been made in view of the above-described problems of the prior art, and a basic object thereof is to provide a resin filler, a cured product, a printed wiring board, and a method for producing the printed wiring board, which are capable of obtaining a cured product that does not generate voids or cracks under high-temperature conditions such as curing treatment and solder leveling and has excellent adhesion of a copper plating layer, and further, have excellent printability and storage stability.
Means for solving the problems
In order to solve the above problems, the inventors have found that voids and cracks are more likely to occur as the depth of a hole portion is deeper (in the case of a through hole, the thickness of a core substrate is thicker), and have further found that, through extensive and repeated studies, a resin filler which can successfully obtain a cured product having excellent adhesion to a copper plating layer without generating voids and cracks and which is excellent in printability and storage stability by using a specific epoxy resin has been obtained, and have completed the present invention.
That is, the present invention relates to the following.
(1) A resin filler characterized by containing (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler.
(2) The resin filling material according to (1), wherein the (a) liquid epoxy resin having a dicyclopentadiene skeleton has a structure represented by the following formula (I):
wherein R1 represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and m and n are 0 to 2 in total.
(3) The resin filling material according to (2), wherein the (A) liquid epoxy resin having a dicyclopentadiene skeleton has a structure represented by the following formula (II):
(4) the resin filler according to any one of (1) to (3), wherein the curing agent (B) is an imidazole curing agent.
(5) The resin filler according to any one of (1) to (3), wherein the inorganic filler (C) is any one selected from silica and calcium carbonate.
(6) The resin filler according to any one of (1) to (3), which is a resin filler for at least one of a recess or a hole of a printed circuit board.
(7) A printed wiring board using the resin filler according to any one of (1) to (6).
The resin filler for filling holes of the present invention has a low viscosity of resin and high wettability to metal, and therefore has excellent printability. The resin structure is hard to react with the amine-based curing agent, and thus the increase of viscosity with time can be suppressed. In addition, the resin filler for pore filling of the present invention can maintain a state of low viscosity during curing for a long period of time, and bubbles are easily released, thereby suppressing generation of voids and cracks. The alicyclic epoxy resin is easily decomposed by a strong base used for removing the smear, so that a concave portion is easily formed on the surface of the ink, and the peel strength of the copper plating layer is improved by the anchor effect.
The present invention also relates to a cured product obtained by photocuring the resin filler for hole filling, a printed wiring board having the cured product, and a method for producing the printed wiring board.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a resin filler which can provide a cured product having excellent adhesion of a copper plating layer without generating voids or cracks, and further has excellent printability and storage stability. The resin filler of the present invention is most suitable for filling holes and recesses such as through holes and via holes in printed wiring boards, and therefore can be used for permanent insulating hole-filling.
Further, the present invention can provide a cured product which does not cause voids or cracks and has excellent adhesion to a copper plating layer, a printed wiring board having the cured product, and a method for producing the printed wiring board.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a part of a process for manufacturing a printed wiring board according to the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of a process after the process of manufacturing the printed wiring board of the present invention shown in fig. 1.
FIG. 3 is a schematic sectional view showing another example of the method for manufacturing a printed wiring board according to the present invention.
Description of the reference numerals
1 substrate
2 copper foil
3 through hole
4a, 4b, 4c, 4d coating film
5 resin filler
6 Corrosion resistant coating
7a, 7b, 7c conductor circuit layer
8a, 8b interlayer resin insulation layer
9a, 9b openings
10 plating resist
11 through hole
12 bonding pad
13 solder resist layer
14 solder bump
Detailed Description
The present invention provides a resin filler characterized by containing (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler.
The resin filler of the present invention contains a liquid epoxy resin having a dicyclopentadiene skeleton, and therefore, can form a cured product which does not generate voids or cracks and has excellent adhesion to a copper plating layer. The resin filler of the present invention is excellent in printability and storage stability, and therefore, is very suitable for filling holes and recesses such as through holes and via holes in printed wiring boards.
Hereinafter, "resin filling material for filling holes of a printed circuit board" and "resin filling material for filling holes" are sometimes simply referred to as "resin filling material".
The liquid epoxy resin having a dicyclopentadiene skeleton (a) in the resin filler of the present invention is a liquid epoxy resin having 2 ethylene oxide alkylene groups and a dicyclopentadiene skeleton.
The number average molecular weight of the liquid epoxy resin (A) having a dicyclopentadiene skeleton is preferably 300 to 1000, more preferably 300 to 500. The number average molecular weight is preferably 300 or more from the viewpoint of favorably achieving the effects of the present invention. From the viewpoint of improving the workability, the number average molecular weight is preferably 1000 or less.
Here, the number average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene.
The epoxy equivalent of the liquid epoxy resin (A) having a dicyclopentadiene skeleton is preferably 100 to 300, more preferably 120 to 250, and still more preferably 150 to 200.
Here, the epoxy equivalent is a value measured by a potentiometric titration method in accordance with JIS-K-7236.
The liquid epoxy resin (a) having a dicyclopentadiene skeleton of the present invention is preferably an epoxy resin having a structure represented by the following formula (I).
Wherein R1 represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and m and n are 0 to 2 in total.
The liquid epoxy resin (a) having a dicyclopentadiene skeleton of the present invention is preferably an epoxy resin having a structure represented by the following formula (II).
The amount of the liquid epoxy resin having a dicyclopentadiene skeleton (a) in the present invention is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, based on 100 parts by mass of the total amount of the epoxy resins including the liquid epoxy resin having a dicyclopentadiene skeleton (a).
Examples of commercially available products include EP-4088S, EP-4088L manufactured by ADEKA corporation.
(A) an epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton >
In the resin filler of the present invention, a known epoxy resin can be used as the epoxy resin other than the liquid epoxy resin (a) having a dicyclopentadiene skeleton. As (A) an epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton, examples thereof include bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, aminophenol type epoxy resin, aminomethylphenol type epoxy resin, alkylphenol type epoxy resin and the like.
The number average molecular weight of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton (A) is preferably 300 to 1000, more preferably 300 to 500. The number average molecular weight is preferably 300 or more from the viewpoint of improving the soldering heat resistance and toughness of the cured product. From the viewpoint of improving the workability, the number average molecular weight is preferably 1000 or less.
Here, the number average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene.
The epoxy equivalent of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton (A) is preferably 100 to 300, more preferably 120 to 250, and still more preferably 150 to 200. When the epoxy equivalent is 100 or more, toughness tends to be high.
Here, the epoxy equivalent is a value measured by a potentiometric titration method in accordance with JIS-K-7236.
As the commercially available product of the epoxy resin (A) other than the liquid epoxy resin having a dicyclopentadiene skeleton, (A-1) a bisphenol type epoxy resin which is liquid at room temperature can be mentioned. For example, known and conventional epoxy resins such as bisphenol A type epoxy resin, liquid bisphenol E type epoxy resin, liquid bisphenol F type epoxy resin, liquid phenol novolac type epoxy resin, and aminophenol type liquid epoxy resin having an epoxy equivalent of 300g/eq or less. Specific examples thereof include liquid bisphenol A type epoxy resins such as jER825, jER827, jER828EL, jER828US, jER828XA, YD-8125, YD-127, YD-825GS, YD-825GSH manufactured by Mitsubishi chemical corporation, EP-4100 manufactured by ADEKA corporation, EP-4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4400, EP-4520S, EP-4530, EPICLON 840-S, EPICLON 850, EPICLON EXA-850CRP and EPICLON 850-LC (trade names); liquid bisphenol F-type epoxy resins such as jER806, jER806H, jER807 manufactured by Mitsubishi chemical corporation, YD-170 manufactured by Nippon Tekko & materials, YD-8170, YDF-8170C, TDF-870GS, ZX-1059, EP-4901 manufactured by ADEKA corporation, EPICLON 830-S, EPICLON 835, EPICLON EXA-830CRP, EPICLON EXA-830LVP, and EPICLON EXA-835LV (trade names); a liquid phenol novolac type epoxy resin of DEN431 (trade name) manufactured by dow chemical; aminophenol type liquid epoxy resins (p-aminophenol type liquid epoxy resins) of jER630 manufactured by mitsubishi chemical corporation and ELM-100 (both trade names) manufactured by sumitomo chemical corporation; liquid bisphenol E type epoxy resin of R710 (trade name) manufactured by PRINTEC corporation; these can be used alone or in combination of 2 or more.
Further, (a-2) an epoxy resin having 2 or more epoxy groups in 1 molecule which is solid at room temperature is exemplified as a commercially available product of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton (a). As the epoxy resin (A-2) having 2 or more epoxy groups in 1 molecule which is solid at room temperature, those conventionally known in the art can be used. For example, there may be mentioned: bisphenol A type epoxy resins such as jER1001, jER1004 manufactured by Mitsubishi chemical corporation, EPICLON1050, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLONHM-091, and EPICLON HM-101 (all trade names); brominated Epoxy resins such as jERYL903 manufactured by Mitsubishi chemical corporation, EPICLON 152 and EPICLON 153 manufactured by DIC corporation, Epotohto YDB-400 and YDB-500 manufactured by Tokyo chemical Co., Ltd, D.E.R.542 manufactured by Dow chemical Co., Ltd, Araldite8011 manufactured by BASF JAPAN corporation, Sumi-Epoxy ESB-400 and ESB-700 manufactured by Sumitomo chemical Co., Ltd, A.E.R.711 and A.E.R.714 manufactured by Asahi chemical Co., Ltd (trade names); jer152, Jer154, D.E.N.431, D.E.N.438, EPICLON N-660, EPICLON-665, EPICLON-670, EPICLON-673, EPICLON-680, EPICLONN-690, EPICLON-695, EPICLON-665-EXP, EPICLON-672-EXP, EPICLON-665-EXP, EPICLON-662-EXP-S, EPICLON-665-EXP-S, EPICLON-670-EXP-S, EPLON-685-EXP-S, EPICLON-730, EPICLON-865, EPICLON-770-TELEOCLON-EXP-S, EPICLON-1235, EPICLON-1273, EPICLON-O-YD-S, manufactured by Mitsubishi chemical co, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon chemical Co., Ltd., Sumi-EpoxyESCN-195X, ESCN-220 manufactured by Sumitomo chemical Co., Ltd., A.E.R.ECN-235 manufactured by Asahi chemical Co., Ltd., ECN-299, and the like (trade names); trishydroxyphenylmethane-type epoxy resins such as YL-933 manufactured by Mitsubishi chemical corporation, T.E.N. manufactured by Dow chemical Co., Ltd., EPPN-501, EPPN-502, and the like (trade names); bisphenol type or biphenol type epoxy resins such as YL-6056, YX-4000 and YL-6121 (trade names) manufactured by Mitsubishi chemical corporation, or a mixture thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kabushiki Kaisha, EPX-30 manufactured by ADEKA Kaisha, and EXA-1514 (trade name) manufactured by DIC Kaisha; bisphenol a novolac type epoxy resins such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetrahydroxyphenyl ethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi chemical corporation and Araldite163 manufactured by BASF JAPAN corporation (both trade names); heterocyclic epoxy resins such as Araldite PT810 available from BASF JAPAN corporation and TEPIC available from Nissan chemical corporation (trade name); diglycidyl phthalate resin such as BLEMMER DDT manufactured by japan fat and oil co; tetraglycidyl xylenyl ethanolethane resin (tetraglycidyl xylenyl ethanolethein) such as ZX-1063 manufactured by Tokyo Kabushiki Kaisha; naphthyl group-containing epoxy resins such as ESN-190, ESN-360, produced by Nippon Tekko & materials, EXA-4750 and EXA-4700, produced by DIC; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate-copolymerized epoxy resins such as CP-50S, CP-50M manufactured by Nippon fat and oil Co., Ltd; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Celite chemical industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokyo Kasei K.K.), and the like, but are not limited thereto.
These epoxy resins may be used alone or in combination of 2 or more. Among them, at least 1 kind of epoxy resin selected from the group consisting of bisphenol a type epoxy resin, phenol novolac type epoxy resin, and aminophenol type epoxy resin is particularly preferable.
(B) Curing agent
Examples of the curing agent (B) of the present invention include curing agents for resin fillers such as imidazole curing agents.
Examples of the imidazole-based curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole.
Further, examples of commercially available products include 2MZ-A, 2MZA-PW, 2MZ-OK, 2PHZ, 2P4BHZ and 2P4MHZ (both trade names of imidazole compounds) manufactured by Kabushiki Kaisha.
Further, s-triazine derivatives such as guanamine, methylguanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine-isocyanuric acid adduct, and 2, 4-diamino-6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct may be used, and it is preferable to use these compounds also functioning as an adhesion imparting agent in combination with the aforementioned heat curing agent.
The compounding amount of the curing agent may be a conventional amount. The amount of the epoxy resin is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin containing the (A) liquid epoxy resin having a dicyclopentadiene skeleton.
The (C) inorganic filler of the present invention is used for relaxing stress caused by curing shrinkage and adjusting a linear expansion coefficient. As such an inorganic filler, a known inorganic filler used in a general resin filler can be used. Specific examples of the non-metallic fillers include non-metallic fillers such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, and organobentonite; copper, gold, silver, palladium, silicon and other metal fillers. These fillers may be used alone or in combination of 2 or more.
Examples of the shape of the inorganic filler include a spherical shape, a needle shape, a flake shape, a scaly shape, a hollow shape, an irregular shape, a hexagonal shape, a cubic shape, a flake shape, and the like, and a spherical shape is preferable from the viewpoint of high filling of the inorganic filler.
Among them, silica and calcium carbonate having low hygroscopicity and excellent low volume expansibility are preferable. The silica may be either amorphous or crystalline, or a mixture thereof. For high filling purposes, spherical amorphous (fused) silica is preferred. The calcium carbonate may be either natural ground calcium carbonate or synthetic precipitated calcium carbonate. The average particle diameter d50 of the polyurethane particles (C) is preferably 0.1 to 25 μm. More preferably 1 to 10 μm.
The average particle diameter d50 of the inorganic filler (C) is preferably 0.1 to 25 μm. When the average particle diameter is 0.1 μm or more, the specific surface area can be reduced, the dispersibility can be improved, and the filling amount of the filler can be easily increased. On the other hand, when the thickness is 25 μm or less, the filling property into the hole portion of the printed wiring board for mounting a semiconductor becomes good, and the smoothness becomes good when the conductor layer is formed in the hole-filled portion. More preferably 1 to 10 μm.
The compounding ratio of the (C) inorganic filler is 45 to 90% by mass relative to the total amount of the resin filler. By setting the amount to 45 mass% or more, thermal expansion of the obtained cured product can be suppressed, crack resistance is excellent, and sufficient polishing properties and adhesion can be obtained. On the other hand, when the content is 90% by mass or less, pasting is easy, and good printability and filling property of filling holes can be obtained. More preferably 50 to 75 mass%. More preferably 55 to 75 mass%. By setting the compounding ratio of the (C) inorganic filler, the average thermal expansion coefficient of the resin filler can be adapted to the core material of low thermal expansion.
The resin filler of the present invention may further contain a thixotropic agent such as finely powdered silica, organobentonite, montmorillonite or hydrotalcite as required. From the viewpoint of the stability over time as a thixotropic agent, organobentonite and hydrotalcite, particularly hydrotalcite, are preferable to have excellent electrical characteristics. Further, known and conventional additives such as a thermal polymerization inhibitor, a defoaming agent and/or a leveling agent such as a silicone-based, fluorine-based, or polymer-based defoaming agent, a silane coupling agent such as an imidazole-based, thiazole-based, or triazole-based silane coupling agent, a rust inhibitor, and a copper inhibitor such as a bisphenol-based, or triazine-thiol-based agent may be added.
Next, the printed wiring board of the present invention will be explained.
The printed wiring board of the present invention is a printed wiring board having a cured product formed from the resin filler of the present invention in a hole portion formed in a base material. The method for manufacturing the printed wiring board of the present invention will be described in detail below with reference to fig. 1 to 3.
Formation of vias
Fig. 1 is a schematic cross-sectional view showing an example of a part of a process for manufacturing a printed wiring board according to the present invention. First, as shown in fig. 1 (a), a through hole is opened in a substrate 1 on which a copper foil 2 is laminated by a drill or the like, and the wall surface of the through hole and the surface of the copper foil are subjected to electroless plating to form a through hole 3. As the substrate 1, a resin substrate such as a glass epoxy resin substrate, a polyimide substrate, a bismaleimide-triazine resin substrate, or a fluororesin substrate, or a copper-clad laminate of these resin substrates, a ceramic substrate, a metal substrate, or the like can be used. In the case of a substrate having poor throwing power, such as a fluororesin substrate, surface modification such as a pretreatment agent comprising organic metal sodium and plasma treatment is performed. Next, plating is performed to increase the thickness, and as shown in fig. 1 (b), a plating film 4a is formed on the surface of the substrate 1 and on the inner wall of the through-hole 3. As the plating, copper plating is preferable.
Hole filling
As shown in fig. 1 (c), a through-hole 3 formed in a substrate 1 is filled with a resin composition 5 of the present invention. Specifically, a mask having an opening in the through-hole 3 is placed on the substrate 1, and the organic solvent is used to adjust the viscosity to a level suitable for the application method, so that the mask can be easily filled into a hole such as a via hole or a through-hole by screen printing, roll coating, die coating, or the like. Next, after the resin filler 5 is heated at about 80 to 180 ℃ for about 30 to 90 minutes to be cured, unnecessary portions of the resin filler 5 that have overflowed from the through-hole 3 are removed by polishing, and planarization is performed, as shown in fig. 1 (d). The grinding can be performed by a belt sander, a polishing grinder, or the like.
Formation of conductor circuit layer
As shown in fig. 1 (e), a plating film 4b is formed on the surface of the substrate 1 in which the through-hole 3 is filled. Then, as shown in fig. 1 (f), a resist 6 is formed, and a portion where no resist is formed is etched. Next, the resist coating 6 is peeled off, and as shown in fig. 1 (g), a conductor circuit layer 7a is formed.
Formation of interlayer resin insulation layer
Fig. 2 is a schematic cross-sectional view showing an example of a process after the process of manufacturing the printed wiring board of the present invention shown in fig. 1. An interlayer resin insulating layer 8a is formed on the conductor circuit layer 7 a. As the interlayer resin insulation layer 8a, a thermosetting resin, a photocurable resin, a thermoplastic resin, a composite or a mixture of these resins, a glass cloth-impregnated resin composite, or an adhesive for electroless plating can be used.
Formation of via holes
Next, as shown in fig. 2 (a), an opening 9a is provided in the interlayer resin insulation layer 8 a. The opening 9a is perforated by exposure and development treatment when the interlayer resin insulation layer 8a is formed of a photosensitive resin, and by laser light when the interlayer resin insulation layer 8a is formed of a thermosetting resin or a thermoplastic resin. When the opening 9a is provided by laser, desmear treatment can also be performed.
Next, as shown in fig. 2 (b), a plating film 4c is formed over the entire surface. Then, as shown in fig. 2 (c), a plating resist layer 10 is formed on the plated film 4 c. The plating resist layer 10 is preferably formed by laminating photosensitive dry films, and performing exposure and development processes. Further, electroplating is performed to increase the thickness of the conductor circuit portion, thereby forming a plated film 4d as shown in FIG. 2 (c).
Next, after the plating resist layer 10 is peeled off, the electroless plated film 4c under the plating resist layer 10 is removed by etching and dissolution, and as shown in fig. 2 (d), an independent conductor circuit (including a via hole 11a) is formed.
FIG. 3 is a schematic sectional view showing another example of the method for manufacturing a printed wiring board according to the present invention. When the conductor layers on both surfaces of the core substrate 1 are etched in a predetermined pattern after the core substrate manufacturing process shown in fig. 1 (d) is completed, as shown in fig. 3 (a), the 1 st conductor circuit layers 7b having a predetermined pattern are formed on both surfaces of the substrate 1, and the lands 12 are simultaneously formed in a part of the conductor circuit layers 7b connected to the through holes 3.
Next, as shown in fig. 3 (b), interlayer resin insulation layers 8b are formed on both the upper and lower surfaces of the substrate 1. Further, as shown in fig. 3 (c), a via hole 11b is formed in the resin insulating layer 8b located directly above the land 12. Next, plating layers formed by copper plating are formed in the via hole 11b and on the interlayer resin insulation layer 8b, and after a resist coating is formed thereon, etching is performed. Thereby, as shown in fig. 3 (c), the 2 nd conductor circuit layer 7c is formed on the interlayer resin insulation layer 8 b. The 1 st conductor circuit layer 7b and the 2 nd conductor circuit layer 7c are electrically connected to each other through the via hole 11b, and the conductor circuit layers 7b on both surfaces of the substrate are also electrically connected to each other through the through hole 3.
Then, as shown in fig. 3 (c), a solder resist layer 13 is formed on each of the resin insulation layer 8b and the 2 nd conductor circuit layer 7c, and a solder bump 14 is formed in the solder resist layer 13 above, the solder bump 14 penetrating therethrough and standing upright from the surface of the conductor circuit layer. Further, a multilayer circuit board used as a connection terminal can be obtained by performing Au plating and Ni plating on the surface of the conductor circuit layer 7c exposed from the opening 9b formed between the solder resist layers 13 below.
Examples
The respective components shown in table 1 below were compounded in the proportions (parts by mass) shown in table 1, premixed by a stirrer, and kneaded by a three-roll mill to prepare a resin filler. The results are shown in Table 2.
TABLE 1
*1: epoxy resin, EP-4088S manufactured by ADEKA, dicyclopentadiene type epoxy resin, and epoxy equivalent 170
*2: epoxy resin, YX-8000 manufactured by Mitsubishi chemical corporation, hydrogenated bisphenol A epoxy resin, epoxy equivalent 205
*3: epoxy resin, EHPE-3150 manufactured by Dailuo chemical industries, Ltd., polyfunctional alicyclic epoxy resin, epoxy equivalent 177
*4: epoxy resin, R710 manufactured by PRINTEC, bisphenol E epoxy resin, and epoxy equivalent of 160-180
*5: epoxy resin, jER807 manufactured by Mitsubishi chemical corporation, bisphenol F type epoxy resin, epoxy equivalent of 160 to 175
*6: epoxy resin, ELM-100 manufactured by Sumitomo chemical Co., Ltd., aminophenol type liquid epoxy resin, epoxy equivalent of about 106
*7: epoxy resin, DEN431 (produced by Dow chemical Co., Ltd.), phenol novolac type epoxy resin, and epoxy equivalent 172 to 179
*8: curing agent, 2MZA-PW, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine manufactured by Sizhou chemical industry Co., Ltd
*9: curing agent, 2PHZ manufactured by suma chemical co, 2-phenyl-4, 5-dihydroxymethylimidazole 10: an inorganic filler, Softon1500 manufactured by Beibei powdered Industrial Co., Ltd., calcium carbonate, and having an average particle diameter of 1.5 μm
*11: ADMATECHS CO, SO-C5 produced by LTD, fused silica, and having an average particle diameter of 1.3 to 1.7 μm
TABLE 2
< printability >
The liquid resin compositions of examples and comparative examples were filled into through holes of a thick plate substrate (thickness 2.2mm, through hole diameter 0.15mm, through hole pitch 1mm) having through holes in which conductor layers were formed by plate plating (panel plating) by a screen printing method under the following printing conditions. After the filling, the resultant was placed in a hot air circulation type drying furnace, and cured at 130 ℃ for 45 minutes and 150 ℃ for 60 minutes to obtain an evaluation substrate. The filling property was evaluated by the filling degree of the cured product filled in the through hole of the evaluation substrate.
< printing conditions >
Scraping plate: the thickness of the scraper is 20mm, the hardness is 70 degrees, and the inclined grinding: 23 degree
Edition: metal mask, printing pressure: 50kg, blade speed 10mm/s, blade angle: 80 degree
< evaluation criteria for printability >
Confirm 425 holes
◎ filling all through holes with resin
○ through-hole generation 1-2 holes without complete filling with resin
△ through holes not completely filled with resin are 3-50 holes
× through-hole not completely filled with resin occurred over 51 holes
< storage stability >
The initial and viscosity after 7 days of storage at 25 ℃ of each liquid resin composition of comparative examples and comparative examples. The thickening ratio was calculated by the following equation.
A thickening ratio (viscosity after storage at 25 ℃ for 7 days/initial viscosity) × 100
The storage stability was evaluated from the value of thickening ratio as follows.
○ is less than 15%
△：15～40％
× is more than 40%
< voids and cracks after curing >
An evaluation substrate was prepared by the method described in < printability > above, cut at the through hole portion, and the number of voids and cracks was counted by observing the cross section with an optical microscope.
< evaluation criteria for pore-filling voids and cracks >
○ the number of voids and cracks is 5 or less
Δ: the number of voids and cracks is 5 or more and less than 50
× the number of voids and cracks is 50 or more
< peeling Strength >
The liquid resin compositions of examples and comparative examples were applied to the entire surface of a substrate by screen printing, and after heating and curing at 150 ℃ for 60 minutes, they were subjected to a copper plating treatment so as to form a copper thickness of 25 μm on the resin layer by successively carrying out a wet permanganate desmear treatment (commercially available wet permanganate desmear solution: manufactured by ATOTECH), an electroless copper plating treatment (commercially available electroless copper plating solution: THRU-CUP PEA, manufactured by Shanghai industries, Ltd.), and an electrolytic copper plating treatment in this order. A notch having a width of 10mm and a length of 60mm was cut into the copper plating layer of the test substrate, one end portion thereof was peeled off and held by a jig, and the peel strength (N/cm) at the time of peeling off the copper plating layer having a length of 35mm was measured at an angle of 90 degrees and a speed of 50 mm/min by a bench tensile tester (EZ-SX manufactured by Shimadzu corporation).
< evaluation criteria for peeling Strength >
◎ peel strength of 7.0(N/cm) or more
○ peel strength of 5.0(N/cm) or more and less than 7.0(N/cm)
△ Peel Strength of 3.0(N/cm) or more and less than 4.0(N/cm)
× Peel Strength less than 3.0(N/cm)
As is apparent from tables 1 and 2, by containing a liquid alicyclic epoxy resin, a resin filler which is excellent in printability and storage stability, does not cause voids or cracks, and is excellent in adhesion of a copper plating layer can be obtained. Further, the resin filler of the present invention is excellent in both printability and storage stability, and thus is suitably used for filling holes in printed wiring boards.
Claims (7)
1. A resin filler characterized by containing (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler.
2. The resin filling material according to claim 1, wherein the (a) liquid epoxy resin having a dicyclopentadiene skeleton has a structure represented by the following formula (I):
wherein R1 represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and m and n are 0 to 2 in total.
3. The resin filling material according to claim 2, wherein the (a) liquid epoxy resin having a dicyclopentadiene skeleton has a structure represented by the following formula (II):
4. the resin filler according to any one of claims 1 to 3, wherein the curing agent (B) is an imidazole curing agent.
5. The resin filler according to any one of claims 1 to 3, wherein the (C) inorganic filler is any one selected from silica and calcium carbonate.
6. The resin filling material according to any one of claims 1 to 3, which is a resin filling material for at least one of a concave portion or a hole portion of a printed circuit board.
7. A printed wiring board using the resin filling material according to any one of claims 1 to 6.
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