CN111378253B - Resin filling material - Google Patents
Resin filling material Download PDFInfo
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- CN111378253B CN111378253B CN201811635559.6A CN201811635559A CN111378253B CN 111378253 B CN111378253 B CN 111378253B CN 201811635559 A CN201811635559 A CN 201811635559A CN 111378253 B CN111378253 B CN 111378253B
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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 circuit board, and a method for manufacturing a printed circuit 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 in which a hole portion and a recess portion such as a via hole and a via hole are subjected to permanent hole filling treatment using the composition. In the present specification, "concave portion" means a via hole or the like for the purpose of conducting between layers of a printed circuit board, and "hole portion" means a through hole, for example, a via hole for the purpose of conducting between the front surface and the back surface of the printed circuit board.
Background
The printed circuit board is provided with recesses between conductor circuits on the surface and through-holes etc. in which the conductive layers are formed on the inner wall surface. In order to protect the inner wall conductor during etching when forming the conductor pattern and to improve reliability in mounting, the hole is filled with a hole filler using a thermosetting resin filler containing an epoxy resin, a curing agent and an inorganic filler.
In recent years, the conductor circuit pattern of a printed circuit board has been thinned and the mounting area has been reduced, and further reduction in size, thickness, and size of the printed circuit board has been desired in order to further cope with downsizing and higher functionality of a device including the printed circuit board. Thus, the following multilayer printed circuit boards were developed: a multilayer printed circuit board formed by filling resin filler in a through hole provided in a printed circuit board, curing the resin filler to form a smooth surface, and alternately laminating an interlayer resin insulating layer and a conductor circuit layer on the printed circuit board; or a multilayer printed circuit board in which a solder resist is directly formed on a substrate having a resin filler filled in a hole portion such as a through hole. Under such circumstances, it is desired to develop a composition for permanent hole filling which is excellent in properties of cured products such as printability and solder heat resistance for filling into hole portions and recesses such as through holes and via holes (see, for example, WO 2002/044274).
In such a multilayer printed circuit board, a through hole or the like having a copper plating layer applied to the inside thereof is formed in order to electrically connect the layers. In the printed wiring board manufacturing process, a filler of a curable resin composition called a hole-filling ink is filled into the hole portions such as the through holes 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 type epoxy resin, an imidazole curing agent, and an inorganic filler. JP-A11-222549 discloses a pore-filling material comprising an amine-type epoxy resin, a polyphenol-type epoxy resin and an inorganic filler. JP 2003-133672A discloses a filler containing a liquid epoxy resin, an epoxy monomer, a curing agent and a filler.
However, the printability of the resin filling material of the related art is not sufficient. Voids may be generated by introducing air or the like during printing, and cracks may be generated during curing of the hole-filling ink. In addition, the peel strength of the copper plating layer is not yet 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 circuit board, and a method for manufacturing the printed circuit board, which can obtain a cured product that does not generate voids and cracks under high temperature conditions such as a curing process and a solder leveling, has excellent adhesion of a copper plating layer, and further has excellent printability and storage stability.
Solution for solving the problem
In order to solve the above problems, the inventors found that as the depth of the hole portion is deeper (the thickness of the core substrate is thicker in the case of the through hole), voids and cracks are more likely to occur, and further found that, through a great deal of repeated research, a resin filler which can obtain a cured product excellent in adhesion of the copper plating layer without voids and cracks and further excellent in printability and storage stability can be obtained by using a specific epoxy resin, and completed the present invention.
Namely, the present invention relates to the following.
(1) A resin filler characterized by comprising (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler.
(2) The resin filler according to (1), wherein the (A) liquid epoxy resin having a dicyclopentadiene skeleton has a structure shown 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 add up to 0 to 2.
(3) The resin filler 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 (B) curing agent is an imidazole-based 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, wherein the resin filler according to any one of (1) to (6) is used.
In the hole-filling resin filler of the present invention, the viscosity of the resin is low and the wettability to metal is high, so that the resin filler is excellent in printability. The resin structure is less likely to react with the amine-based curing agent, and thus the increase in viscosity with time can be suppressed. In addition, the resin filler for pore filling of the present invention can maintain a low viscosity state during curing for a long period of time, and bubbles are easily escaped, thereby suppressing the occurrence of voids and cracks. The alicyclic epoxy resin is a structure which is easily decomposed by strong alkali for removing the gumming residues, so that the concave part is easily formed on the surface of the ink, and the peeling strength of the copper plating layer is improved by the anchoring effect.
The present invention also relates to a cured product obtained by photocuring the hole-filling resin filler, a printed wiring board having the cured product, and a method for manufacturing the printed wiring board.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin filler which can obtain a cured product having excellent adhesion of a copper plating layer without generating voids and cracks, and which is excellent in printability and storage stability. The resin filler of the present invention is most suitable for filling the hole portions such as the through holes and the via holes of the printed circuit board and the concave portions, and therefore can be used for permanent insulation hole filling treatment.
Further, the present invention can provide a cured product which does not cause voids or cracks and has excellent adhesion of a copper plating layer, a printed wiring board having the cured product, and a method for manufacturing 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 circuit board according to the present invention.
Fig. 2 is a schematic cross-sectional view showing an example of a process subsequent to the manufacturing process of the printed circuit board of the present invention shown in fig. 1.
Fig. 3 is a schematic cross-sectional view showing another example of the method for manufacturing a printed circuit board according to the present invention.
Description of the reference numerals
1. Substrate board
2. Copper foil
3. Through hole
4a, 4b, 4c, 4d coating film
5. Resin filling material
6. Corrosion resistant coating
7a, 7b, 7c conductor circuit layers
8a, 8b interlayer resin insulation layer
9a, 9b openings
10. Plating resist
11. Via hole
12. Bonding pad
13. Solder mask
14. Solder bump
Detailed Description
The present invention provides a resin filler characterized by comprising (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 that does not cause voids and cracks and has excellent adhesion of a copper plating layer. The resin filler of the present invention is excellent in printability and storage stability, and is therefore suitable for filling holes and recesses such as through holes and via holes in a printed wiring board.
Hereinafter, "resin filler for filling holes of printed circuit boards" and "resin filler for filling holes" are sometimes simply referred to as "resin filler".
The liquid epoxy resin (a) having a dicyclopentadiene skeleton in the resin filler of the present invention is a liquid epoxy resin having 2 oxiranylalkylene groups and a dicyclopentadiene skeleton.
The number average molecular weight of the liquid epoxy resin having a dicyclopentadiene skeleton (A) of the present invention is preferably 300 to 1000, more preferably 300 to 500. The number average molecular weight is preferably 300 or more from the viewpoint of facilitating the achievement of the effect of the present invention. From the viewpoint of improving the handleability, the number average molecular weight is preferably 1000 or less.
The number average molecular weight herein refers to a value measured by conversion to polystyrene using gel permeation chromatography.
The liquid epoxy resin having a dicyclopentadiene skeleton in (A) of the present invention preferably has an epoxy equivalent of 100 to 300, more preferably 120 to 250, and still more preferably 150 to 200.
The epoxy equivalent is a value measured by a potentiometric titration method according to JIS-K-7236.
The liquid epoxy resin having a dicyclopentadiene skeleton (A) 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 add up to 0 to 2.
The liquid epoxy resin having a dicyclopentadiene skeleton (A) 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) to be blended in the present invention is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resins containing the liquid epoxy resin having a dicyclopentadiene skeleton (a).
As a commercial product, for example, EP-4088S, EP-4088L manufactured by ADEKA Co., ltd.
(A) epoxy resin other than liquid epoxy resin having dicyclopentadiene skeleton ]
In the resin filler of the present invention, any epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton (a) may be used. Examples of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton 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 type 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, amino cresol 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 in the above (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 weld heat resistance and toughness of the cured product. From the viewpoint of improving the handleability, the number average molecular weight is preferably 1000 or less.
The number average molecular weight herein refers to a value measured by conversion to polystyrene using gel permeation chromatography.
The epoxy equivalent of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton in the above (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.
The epoxy equivalent is a value measured by a potentiometric titration method according to JIS-K-7236.
As the commercial products of the epoxy resins other than the liquid epoxy resin having dicyclopentadiene skeleton, there can be mentioned (A-1) bisphenol type epoxy resins which are liquid at room temperature. For example, a known and conventional epoxy resin such as a bisphenol A type epoxy resin having an epoxy equivalent of 300g/eq or less, a liquid bisphenol E type epoxy resin, a liquid bisphenol F type epoxy resin, a liquid phenol novolac type epoxy resin, or an aminophenol type liquid epoxy resin. 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, EP-4100G, EP-4100E, EP-4100TX, EP-4300E, EP-4400, EP-4520S, EP-4530, epilon 840-S, EPICLON, epilon EXA-850CRP, epilon 850-LC (all trade names) manufactured by mitsubishi chemical company; liquid bisphenol F-type epoxy resins of jER806, jER806H, jER, YD-170, YD-8170, YDF-8170-C, TDF-870GS, ZX-1059, EP-4901, EPICLON 830-S, EPICLON 835, EPICLON EXA-830CRP, EPICLON EXA-830LVP, EPICLON EXA-835LV (all trade names) manufactured by Mitsubishi chemical Co., ltd; liquid phenol novolac type epoxy resin of DEN431 (trade name) manufactured by dow chemical company; an aminophenol type liquid epoxy resin (p-aminophenol type liquid epoxy resin) of jER630 manufactured by mitsubishi chemical corporation, ELM-100 manufactured by sumitomo chemical corporation (all trade names); liquid bisphenol E type epoxy resin of R710 (trade name) manufactured by PRINTEC Co., ltd; these may be used alone or in combination of 2 or more.
As a commercial product of the epoxy resin other than the liquid epoxy resin having a dicyclopentadiene skeleton, there can be mentioned (A-2) an epoxy resin having 2 or more epoxy groups in 1 molecule which is solid at room temperature. As the epoxy resin (A-2) having 2 or more epoxy groups in 1 molecule which is solid at room temperature, a conventional one known in the art can be used. For example, there may be mentioned: bisphenol A type epoxy resins of joR 1001, joR 1004, EPICLON 1050, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101 (all trade names) manufactured by Mitsubishi chemical corporation; brominated Epoxy resins such as joerl 903 manufactured by mitsubishi chemical corporation, EPICLON 152 manufactured by DIC corporation, EPICLON 153 manufactured by tokyo chemical corporation, epotohto YDB-400 manufactured by eastern chemical corporation, YDB-500 manufactured by dow chemical corporation, d.e. r.542 manufactured by BASF JAPAN corporation, araldite8011 manufactured by Sumi chemical corporation, sumi-Epoxy ESB-400 manufactured by Sumi chemical corporation, ESB-700, a.e. r.711 manufactured by xu chemical corporation, a.e. r.714, etc. (all trade names); the "J ER 152", J ER154 ", D.E.N 431", D.E.N 438 ", EPICLON 660", EPICLON-665 ", EPICLON-670, EPICLON-673, EPICLON-680, EPICLON-690, EPICLON-695, EPICLON-665-EXP, EPICLON-672-EXP, EPICLON-665-EXP, EPICLON-662-EXP-S, EPICLON-665-EXP-S, EPICLON-670-EXP-S, EPICLON-685-EXP-S, EPICLON-730, EPICLON-770, EPICN-865, EPICLON-672-EXP-S, EPICLON-665-EXP-S, EPICLON-670-EXP-S, EPICLON-685, EPICLON-770, EPICLON-865" manufactured by Mitsubishi chemical Co., ltd Epotohto YDCN-701, YDCN-704, araldite ECN1235, araldite ECN1273, araldite ECN1299, araldite XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, sumi-Epoxy ESCN-195X, ESCN-220, A.E.R.ECN-235, ECN-299, etc. (all trade names) manufactured by Sumitomo chemical industry Co., ltd; tris (hydroxymethyl) epoxy resins such as YL-933 (manufactured by Mitsubishi chemical corporation), T.E.N., EPPN-501, EPPN-502 (all trade names); YL-6056, YX-4000, YL-6121 (all trade names) and other biphenol-type or biphenol-type epoxy resins manufactured by Mitsubishi chemical corporation or mixtures thereof; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Kagaku Kogyo Co., ltd., EPX-30 manufactured by ADEKA Kagaku Kogyo Co., ltd., EXA-1514 (trade name) manufactured by DIC Kagaku Kogyo Co., ltd.; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetraphenylethane-type epoxy resins such as jERYL-931 manufactured by Mitsubishi chemical corporation and Araldite163 manufactured by BASF JAPAN corporation (all under the trade name); heterocyclic epoxy resins such as araldite pt810, TEPIC (all trade names) manufactured by BASF JAPAN corporation; diglycidyl phthalate resins such as BLEMER DDT manufactured by Japanese fat & oil Co., ltd; tetraglycidyl ditolyl ethane resins (tetraglycidyl xylenoyl ethane resin) such as ZX-1063 manufactured by Tokyo corporation; naphthalene group-containing epoxy resins such as ESN-190, ESN-360, EXA-4750, EXA-4700, etc. manufactured by Nissan iron chemistry & materials Co., ltd; epoxy resins having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Co., ltd; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M manufactured by Japanese fat & oil Co., ltd; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600, manufactured by Kagaku Kogyo Co., ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Tokyo Kagaku Co., ltd.), etc., but are not limited thereto.
These epoxy resins may be used alone or in combination of 2 or more. Among them, at least 1 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
The curing agent (B) of the present invention includes, for example, a curing agent for a resin filler such as an imidazole-based curing agent.
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.
Examples of the commercial products include 2MZ-A, 2MZA-PW, 2MZ-OK, 2PHZ, 2P4BHZ and 2P4MHZ (all trade names of imidazole compounds) manufactured by Kagaku Co., ltd.
In addition, it is also possible to use guanamine, methyl guanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine-isocyanuric acid adducts, 2, 4-diamino-6-methacryloxyethyl-s-triazine-isocyanuric acid adducts and other s-triazine derivatives, and these compounds that also function as adhesion-imparting agents are preferably used in combination with the aforementioned heat curing agent.
The compounding amount of the curing agent is 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, relative to 100 parts by mass of the total amount of the epoxy resin containing (a) the liquid epoxy resin having a dicyclopentadiene skeleton.
The inorganic filler (C) of the present invention is used for relaxing stress caused by curing shrinkage and adjusting the linear expansion coefficient. As such an inorganic filler, a known inorganic filler used for a general resin filler can be used. Specific examples thereof include nonmetallic fillers such as silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, talc, and organobentonite; copper, gold, silver, palladium, silicon, and the like. These fillers may be used alone or in combination of 2 or more.
Examples of the shape of the inorganic filler include spherical, needle-like, flake-like, scale-like, hollow, irregular, hexagonal, cubic, and flake-like, and spherical 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 expansion are preferable. The silica may be amorphous or crystalline, or may be a mixture thereof. Spherical amorphous (fused) silica is preferred for the purpose of high packing. The calcium carbonate may be 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. Mu.m. More preferably 1 to 10. Mu.m.
The average particle diameter d50 of the inorganic filler (C) is preferably 0.1 to 25. Mu.m. 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 of the hole portion of the printed circuit 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. Mu.m.
The compounding ratio of such (C) inorganic filler is 45 to 90 mass% relative to the total amount of the resin filler. By setting the content to 45 mass% or more, thermal expansion of the obtained cured product can be suppressed, crack resistance is excellent, and sufficient polishing property and adhesion can be obtained. On the other hand, if the content is 90 mass% or less, the paste is easy to form, and good printability and hole filling property can be obtained. More preferably 50 to 75 mass%. Further 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 made suitable for a core material having low thermal expansion.
The resin filler of the present invention may be optionally added with a thixotropic agent such as fumed silica, organobentonite, montmorillonite, hydrotalcite, etc. From the viewpoint of the stability with time as a thixotropic agent, organobentonite and hydrotalcite are preferable, and particularly hydrotalcite is excellent in electrical characteristics. Further, known and used additives such as a thermal polymerization inhibitor, an antifoaming agent such as silicone, fluorine, and polymer, a leveling agent, a silane coupling agent such as imidazole, thiazole, and triazole, an anticorrosive agent, and an anti-copper agent such as bisphenol and triazine thiol may be blended.
Next, a printed circuit board of the present invention will be described.
The printed circuit board of the present invention is a printed circuit board having a cured product formed of the resin filler of the present invention in a hole formed in a base material. The method for manufacturing a printed circuit board according to the present invention will be described in detail 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 circuit board according to the present invention. First, as shown in fig. 1 (a), a through hole is formed in a substrate 1 on which copper foil 2 is laminated by a drill or the like, and electroless plating is performed on the wall surface of the through hole and the surface of the copper foil, thereby forming 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 a poor plating ability such as a fluororesin substrate, surface modification such as pretreatment agent made of organic metal sodium or plasma treatment is performed. Next, in order to increase the thickness, plating is performed, and as shown in fig. 1 (b), a plating film 4a is formed on the surface of the substrate 1 and the inner wall of the through hole 3. Copper plating is preferable as this plating.
Hole filling
As shown in fig. 1 (c), the through-hole 3 formed in the substrate 1 is filled with the resin composition 5 of the present invention. Specifically, a mask having an opening at the through hole 3 is placed on the substrate 1, and the viscosity is adjusted to be suitable for the coating method by the organic solvent, so that the mask can be easily filled into the hole portions such as the via hole and the through hole by a screen printing method, a roll coating method, a die coating method, or the like. Next, the resin filler 5 is heated at about 80 to 180 ℃ for about 30 to 90 minutes to be cured, and then unnecessary portions of the resin filler 5 overflowing from the through holes 3 are removed by polishing and planarized as shown in fig. 1 (d). The grinding may be performed by a belt sander, a buffing mill, 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 where the hole filling of the through hole 3 is performed. Then, as shown in fig. 1 (f), a resist layer 6 is formed, and a portion where the resist layer is not formed is etched. Next, the resist layer 6 is peeled off, whereby a conductor circuit layer 7a is formed as shown in fig. 1 (g).
Formation of interlayer resin insulation layer
Fig. 2 is a schematic cross-sectional view showing an example of a process subsequent to the manufacturing process of the printed circuit board of the present invention shown in fig. 1. An interlayer resin insulation layer 8a is formed on the conductor circuit layer 7a. As the interlayer resin insulation layer 8a, a thermosetting resin, a photocurable resin, a thermoplastic resin, or 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 8a. The perforation of the opening 9a is performed by exposure and development processing in the case where the interlayer resin insulation layer 8a is formed of a photosensitive resin, and by laser light in the case where the interlayer resin insulation layer 8a is formed of a thermosetting resin or a thermoplastic resin. When the opening 9a is provided by a 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), an anti-plating layer 10 is formed on the plating film 4c. The plating resist 10 is suitably formed by laminating photosensitive dry films, exposing to light, and developing. Further, electroplating is performed to increase the thickness of the conductor circuit portion, and as shown in fig. 2 (c), a plating film 4d is formed.
Next, after the plating resist 10 is peeled off, the electroless plating film 4c under the plating resist 10 is removed by etching and dissolution, and as shown in fig. 2 (d), an independent conductor circuit (including the via hole 11 a) is formed.
Fig. 3 is a schematic cross-sectional view showing another example of the method for manufacturing a printed circuit board according to the present invention. When the conductor layers on both sides of the core substrate 1 are etched in a predetermined pattern after the core substrate manufacturing process shown in fig. 1 (d), the 1 st conductor circuit layer 7b having a predetermined pattern is formed on both sides of the substrate 1 and the pads 12 are simultaneously formed on a part of the conductor circuit layer 7b connected to the through holes 3 as shown in fig. 3 (a).
Next, as shown in fig. 3 (b), interlayer resin insulation layers 8b are formed on both upper and lower surfaces of the substrate 1. Further, as shown in fig. 3 (c), a via hole 11b is formed on the resin insulation layer 8b located directly above the pad 12. Next, a plating layer obtained by copper plating is formed in the via hole 11b and on the interlayer resin insulation 8b layer, and after a resist coating is formed thereon, etching is performed. Thus, as shown in fig. 3 (c), the 2 nd conductor circuit layer 7c is formed on the interlayer resin insulation layer 8b. The 1 st conductor circuit layer 7b and the 2 nd conductor circuit layer 7c are connected to each other through the via hole 11b, and the conductor circuit layers 7b on both sides of the substrate are also connected to each other through the via 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 and standing vertically from the surface of the conductor circuit layer. Further, au plating and Ni plating are performed on the surface of the conductor circuit layer 7c exposed through the opening 9b formed between the solder resist layers 13 below, whereby a multilayer circuit board used as a connection terminal can be obtained.
Examples
The respective components shown in table 1 below were mixed in the proportions (parts by mass) shown in table 1, and after premixing with a stirrer, they were kneaded with a three-roll mill to prepare a resin filler. The results obtained are shown in Table 2.
TABLE 1
*1: epoxy resin, EP-4088S, dicyclopentadiene type epoxy resin, and epoxy equivalent 170, manufactured by ADEKA Co., ltd
*2: epoxy resin, YX-8000, hydrogenated bisphenol A type epoxy resin, epoxy equivalent 205 manufactured by Mitsubishi chemical Co., ltd
*3: epoxy resin, EHPE-3150 manufactured by Kagaku Kogyo Co., ltd., multifunctional alicyclic epoxy resin, epoxy equivalent 177
*4: epoxy resin, R710, bisphenol E type epoxy resin, and epoxy equivalent 160 to 180 manufactured by PRINTEC Co., ltd
*5: jER807, bisphenol F type epoxy resin, and epoxy equivalent 160 to 175, manufactured by Mitsubishi chemical corporation
*6: epoxy resin, ELM-100 manufactured by Sumitomo chemical Co., ltd., aminophenol type liquid epoxy resin, and about 106 in epoxy equivalent
*7: epoxy resin, DEN431 manufactured by Dow chemical Co., ltd., phenol novolac type epoxy resin, and epoxy equivalent 172-179
*8: curing agent, 2MZA-PW, 2, 4-diamino-6- [2 '-methylimidazole- (1') ] -ethyl-s-triazine manufactured by SiGuo chemical industry Co., ltd
*9: 2PHZ, 2-phenyl-4, 5-dihydroxymethylimidazole, manufactured by four kingdom chemical corporation, 10: inorganic filler, softon1500 manufactured by North pulverization Industrial Co., ltd., calcium carbonate, and average particle diameter of 1.5. Mu.m
*11: ADMATECHS SO-C5, fused silica, and average particle diameter of 1.3 to 1.7 μm manufactured by LTD
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 1 mm) having through holes formed with a conductor layer by panel plating by screen printing under the following printing conditions. After filling, the mixture was put into a hot air circulation type drying oven, and cured at 130℃for 45 minutes and at +150℃for60 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 >
A scraper blade: the thickness of the scraping plate is 20mm, the hardness is 70 degrees, and the inclined grinding is carried out: 23 degree
Version: metal mask, printing pressure: 50kg, scraper speed 10mm/s, scraper angle: 80 degree
< printing evaluation criteria >
Confirm 425 holes
And (3) the following materials: all through holes are completely filled with resin
O: the through holes which are not completely filled with resin are 1-2 holes
Delta: the through holes which are not completely filled with resin are 3 to 50 holes
X: the through holes not completely filled with resin are more than 51 holes
< storage stability >
The viscosity of each of the liquid resin compositions of comparative examples and comparative examples after storage at 25℃for 7 days was as initial. The tackifying ratio was calculated by the following formula.
Viscosity increase = (viscosity after storage at 25 ℃ for 7 days/initial viscosity) ×100
The storage stability was evaluated as follows based on the value of the thickening ratio.
O: below 15%
△：15～40％
X: more than 40%
< voids and cracks after curing >
An evaluation substrate was produced by the method described in the above < printability >, cut through the through-hole, and the cross section was observed with an optical microscope to count voids and cracks.
< evaluation criteria for pore-filling voids and cracks >
O: the number of voids and cracks is less than 5
Delta: the number of voids and cracks is more than 5 and less than 50
X: the number of voids and cracks is 50 or more
< peel Strength >
The liquid resin compositions of examples and comparative examples were coated on the entire surface of the substrate by screen printing, and after heating and curing at 150℃for 60 minutes, the resin composition was subjected to a wet type permanganic acid desmutting treatment (commercially available wet type permanganic acid desmutting liquid: manufactured by ATOTECH Co., ltd.), an electroless copper plating treatment (commercially available electroless copper plating treatment liquid: THRU-CUP PEA, manufactured by Shangcun Industrial Co., ltd.) and an electrolytic copper plating treatment in this order, and copper plating treatment was performed so that a copper thickness of 25 μm was formed on the resin layer. 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 by a bench tensile tester (EZ-SX manufactured by Shimadzu corporation) at an angle of 90 degrees at a speed of 50 mm/min.
< evaluation criteria for peel Strength >
And (3) the following materials: peel strength of 7.0 (N/cm) or more
O: peel strength of 5.0 (N/cm) or more and less than 7.0 (N/cm)
Delta: peel strength of 3.0 (N/cm) or more and less than 4.0 (N/cm)
X: peel strength lower than 3.0 (N/cm)
As is apparent from tables 1 and 2, by containing the alicyclic epoxy resin in a liquid state, a resin filler having excellent printability and storage stability, no voids or cracks, and excellent adhesion of the copper plating layer can be obtained. In addition, it is also known that the resin filler of the present invention is suitable for hole filling of printed wiring boards because of its excellent printability and storage stability.
Claims (3)
1. A resin filler characterized by comprising (A) a liquid epoxy resin having a dicyclopentadiene skeleton, (B) a curing agent, and (C) an inorganic filler,
the liquid epoxy resin (A) having a dicyclopentadiene skeleton has a structure represented by the following formula (II):
the curing agent (B) is an imidazole curing agent,
the inorganic filler (C) is any one selected from silica or calcium carbonate.
2. The resin filling material according to claim 1, which is a resin filling material for at least one of a recess or a hole portion of a printed circuit board.
3. A printed circuit board characterized in that the resin filler material according to claim 1 or 2 is used.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531027A (en) * | 2015-01-21 | 2015-04-22 | 广州聚合电子材料有限公司 | Epoxy resin encapsulating material as well as preparation method and application thereof |
| CN107108982A (en) * | 2014-12-19 | 2017-08-29 | 株式会社Adeka | Polyolefin resin composite |
| JP2018083878A (en) * | 2016-11-22 | 2018-05-31 | 積水化学工業株式会社 | Interlaminar filler for touch panel and touch panel laminate |
| CN108291122A (en) * | 2015-08-08 | 2018-07-17 | 设计分子有限公司 | Anionic curable composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5249170B2 (en) * | 2009-10-26 | 2013-07-31 | パナソニック株式会社 | Epoxy resin composition for sealing semiconductor device and semiconductor device |
| JP5758463B2 (en) * | 2013-03-26 | 2015-08-05 | 太陽インキ製造株式会社 | Epoxy resin composition, hole filling composition, and printed wiring board using the same |
| CN105315614B (en) * | 2014-07-31 | 2018-10-30 | 太阳油墨（苏州）有限公司 | Porefilling heat curing resin composition, solidfied material and the printed circuit board of printed circuit board |
| CN106752703A (en) * | 2016-12-15 | 2017-05-31 | 天长市金陵电子有限责任公司 | A kind of electrostatic spraying powder coating containing modified 2 methylimidazoles |
| CN107915830A (en) * | 2017-11-27 | 2018-04-17 | 陕西生益科技有限公司 | A kind of active ester curing agent and composition epoxy resin |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107108982A (en) * | 2014-12-19 | 2017-08-29 | 株式会社Adeka | Polyolefin resin composite |
| CN104531027A (en) * | 2015-01-21 | 2015-04-22 | 广州聚合电子材料有限公司 | Epoxy resin encapsulating material as well as preparation method and application thereof |
| CN108291122A (en) * | 2015-08-08 | 2018-07-17 | 设计分子有限公司 | Anionic curable composition |
| JP2018083878A (en) * | 2016-11-22 | 2018-05-31 | 積水化学工業株式会社 | Interlaminar filler for touch panel and touch panel laminate |
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