KR20140125356A - Resin composition for plating resist, multilayer printed wiring board, and method for producing multilayer printed wiring board - Google Patents
Resin composition for plating resist, multilayer printed wiring board, and method for producing multilayer printed wiring board Download PDFInfo
- Publication number
- KR20140125356A KR20140125356A KR1020147019958A KR20147019958A KR20140125356A KR 20140125356 A KR20140125356 A KR 20140125356A KR 1020147019958 A KR1020147019958 A KR 1020147019958A KR 20147019958 A KR20147019958 A KR 20147019958A KR 20140125356 A KR20140125356 A KR 20140125356A
- Authority
- KR
- South Korea
- Prior art keywords
- plating resist
- resin composition
- plating
- wiring board
- printed wiring
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/115—Via connections; Lands around holes or via connections
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/429—Plated through-holes specially for multilayer circuits, e.g. having connections to inner circuit layers
-
- 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
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
-
- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- 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
- H05K2201/09645—Patterning on via walls; Plural lands around one hole
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0713—Plating poison, e.g. for selective plating or for preventing plating on resist
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
It is an object of the present invention to provide a multilayer printed wiring board having through-holes in which through-holes are divided, and to provide a multi-layer printed wiring board in which the partial through-holes can be formed easily and exactly as designed. In order to solve this problem, a multilayer printed wiring board in which a conductor layer and an insulating layer on a circuit pattern are alternately laminated and conducts between conductor layers through a through hole is characterized in that a conductor layer in which a through hole is exposed in an opening for a through hole, A plating resist portion provided between at least one of interlayer and interlayer between insulating layers and a plating portion formed in an exposed region other than the plating resist portion, wherein the plating resist portion comprises a plating resist comprising an epoxy resin, an isocyanate compound and a non- A multilayer printed wiring board characterized in that it comprises a cured product of a resin composition for use in a multilayer printed wiring board.
Description
The present invention relates to a multilayer printed wiring board, and more particularly to a multilayer printed wiring board having a through hole in which a through hole is divided by a partial plating resist in a through hole.
On the printed wiring board, a conductor pattern for connection between the parts is formed on the surface of the insulating substrate or on the surface and inside by printing based on the circuit design, and the electronic parts are further disposed and soldered at a predetermined place . BACKGROUND ART [0002] In recent years, miniaturization of electronic products such as cellular phones, portable electronic devices, personal computers, and the like has demanded higher density of printed wiring boards used in electronic products.
The multilayer printed wiring board is formed by alternately laminating an insulating layer made of a resin having insulating properties and a conductor layer (circuit wiring) printed with a circuit pattern in order to cope with increase in mounting density of components and complication of circuit wiring . The plurality of conductor layers are connected by through holes plated with a conductive material through the interlayer. The through hole is formed by laminating an insulating layer and a conductor layer, punching a hole with a drill or the like, and then performing plating, but the entire through hole is plated with a conductive material by the plating treatment.
If the whole through hole is plated, if there is a portion where connection of the conductor layer is not desired, there is a possibility that the undesired portion is plated with a conductive material, thereby hindering the integrity of signal transmission. Further, in order to realize a more complicated circuit pattern by dividing the through holes, it has been investigated to form a plating resist portion in order to form a non-connecting portion (signal unnecessary portion) of the conductor layer in the through hole.
For example, Patent Document 1 discloses a multilayer printed wiring board having a subcomposite structure having a non-conductive dielectric layer sandwiched between conductive layers. The conductive layer includes a gap filled with a plating resist, and a through hole penetrates the plating resist , And a via structure in which a conductive material is plated on a portion where no plating resist is formed to form a divided via structure.
In the multilayered printed circuit board described above, it is possible to prevent the installation of the conductive material by deliberately preparing one or more voids in the via structure, and consequently to limit the installation of the conductive material in the via structure to only the area necessary for transmission of the electric signal Do. In addition, according to a particular embodiment, it is possible to significantly increase the design pattern excellence performance or the wiring density of the printed circuit board by dividing the via structure into physically isolated segments, which is advantageous in that the number of physically isolated segments It is possible to electrically connect signals of a plurality of layers related to the specific segment.
As the plating resist used for forming the multilayered printed circuit board of Patent Document 1, a hydrophobic insulating material such as a silicone resin, a polyethylene resin, a fluorocarbon resin, a polyurethane resin, or an acrylic resin is exemplified. The deposition of the catalyst species (seed) is prevented by the hydrophobicity of the plating resist.
However, in Patent Document 1, the deposition of the catalyst species (seed) is prevented by the hydrophobicity of the plating resist. However, it is not possible to completely prevent deposition, and when a small amount of deposition occurs, It is stated that it needs to be removed. Therefore, further improvement is required in the plating resist in the hole.
An object of the present invention is to provide a resin composition for plating resists used for manufacturing a multilayered printed circuit board having through holes with through holes, and a resin composition for plating resist which can form the partial through holes precisely as designed .
It is also an object of the present invention to provide a multilayered printed circuit board having through-holes with through-holes divided, wherein the partial through-holes can be formed easily and accurately as designed.
It is also an object of the present invention to provide a method of manufacturing the multilayered printed circuit board.
DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above problems and found that a resin composition for a plating resist used in the following multilayer printed wiring board and a multilayer printed wiring board using the composition can solve the above problems, .
That is, the present invention relates to a multilayer printed wiring board in which a conductor layer and an insulating layer on a circuit pattern are alternately stacked, at least one of a layer between a conductor layer and an insulating layer exposed in an opening for a through hole, A resin composition for plating resist for forming a plating resist portion provided between layers,
An epoxy resin, an isocyanate compound, and a non-conductive filler; And
A multilayer printed wiring board in which a conductor layer and an insulating layer on a circuit pattern are alternately laminated and conduct conductor layers through a through hole,
A plating resist portion provided between at least one of a layer between a conductor layer and an insulating layer exposed in a through hole opening portion and an interlayer between insulating layers and a plating portion formed in an exposed region other than the plating resist portion, Wherein the curing agent is a cured product of the resin composition for plating resists.
Preferred embodiments of the resin composition for plating resist for the multilayered printed circuit board of the present invention and the multilayered printed circuit board using the composition are described below.
(1) The isocyanate compound is a block isocyanate compound. The workability is improved because the storage stability is excellent.
(2) The non-conductive filler is an inorganic filler. As the inorganic filler, silicon oxide (silica) and titanium dioxide are preferable. They may be single or in combination. In particular, spherical fillers are preferred. Filler can be replenished. Thereby, the effect of improving the heat resistance is obtained.
(3) The epoxy resin and the isocyanate compound are contained in the resin composition for plating resist in such a ratio that the isocyanate equivalent number of the isocyanate compound becomes 0.5 to 2 per one epoxy equivalent of the epoxy resin. The plating resistance is further improved.
(4) the content of the non-conductive filler is 15 to 60 parts by volume relative to 100 parts by volume of the solid content of the resin composition for plating resist. The plating resistance is further improved.
(5) In the multilayer printed wiring board, the plating is copper plating.
(6) In the multilayer printed wiring board, the plated region of the through hole is divided.
(7) In the multilayer printed wiring board, the insulating layer between the layers provided with the plating resist portions is a prepreg.
In addition, the present invention is characterized in that a conductive layer and an insulating layer on a circuit pattern are alternately stacked, and between at least one of a layer between a conductor layer and an insulating layer exposed in an opening for a through hole, A laminate provided with a plating resist section formed of the resin composition for plating resist of the invention is formed,
A plurality of layers including the conductor layer on the circuit pattern and a plating resist portion provided between the layers,
A step of forming an opening for a through hole with a drill or a laser so as to penetrate through the plating resist portion with respect to the multilayered wiring board,
A step of performing a desmear treatment on the openings for the through holes and
There is also provided a method for manufacturing a multilayer printed wiring board characterized by comprising a step of performing a plating process on an opening portion for a through hole which has been subjected to a desmear treatment.
In the multilayered printed circuit board of the present invention, a plating resist portion is provided between at least one layer between a conductor layer (circuit wiring) on a circuit pattern of a through hole and an interlayer insulating layer and between layers between insulating layers, , A cured product of a resin composition for plating resist comprising an isocyanate compound and a non-conductive filler. The plating resist portion having such a structure is excellent in plating resistance excluding plating, so that plating can be easily and accurately formed in a desired region (area required for transmission of an electric signal). Therefore, the multilayer printed wiring board of the present invention can be said to be a multilayer printed wiring board in which the partial through holes are formed exactly as designed.
Also, by forming the through holes, adverse effects (stub effect) on signals due to unnecessary conductor portions existing in the through holes can be suppressed.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view of an embodiment showing a process of forming a through hole in a multilayer printed wiring board using the resin composition for plating resist of the present invention. Fig.
2 is a schematic cross-sectional view of another embodiment showing a process of forming a through hole in a multilayer printed circuit board using the resin composition for plating resist of the present invention.
3 is a schematic cross-sectional view of another embodiment showing a process of forming a through hole in a multilayer printed wiring board using the resin composition for plating resist of the present invention.
4 is a schematic cross-sectional view showing the middle portion of the through hole forming process of the conventional multilayered printed circuit board.
5 is a schematic cross-sectional view showing the next step of the through-hole forming process of the conventional multilayered printed circuit board shown in FIG.
6 is a schematic cross-sectional view showing a manufacturing process of a multilayer printed wiring board according to a conventional build-up method.
In the multilayered printed circuit board of the present invention, a conductor layer and an insulating layer on a circuit pattern are alternately laminated, a through hole is formed to conduct conductor layers, and at least a layer between the conductor layer and the insulating layer, A plating resist portion is provided between one layer. The plating resist portion is formed of a cured product of the specific resist resin composition of the present invention.
In the present invention, the conductor layer and the insulating layer are alternately laminated, and the conductor layer is formed in a circuit pattern to form a circuit wiring. That is, in the insulating layer provided with the conductor layer on the circuit pattern, there exists a portion where the conductor layer is present and a portion where the insulating layer without the conductor layer is exposed. As a result, even in the openings for the through holes, both exposed portions of the conductor layer and the insulating layer and between the insulating layers are present, and therefore, a plating resist portion is generally provided between the both layers, It may be between the layers with the layers, or may be between layers of the insulating layers.
The resin composition for plating resists of the present invention comprises an epoxy resin, an isocyanate compound and a non-conductive filler.
An embodiment of the resin composition for plating resist of the present invention will be described with reference to Figs. 1, 2, and 3. Fig. These drawings show cross sections of a portion in which a conductor layer (i.e., wiring portion) on a circuit pattern and an insulating layer are alternately stacked.
A
Then, as shown in Fig. 1 (C), an opening for a through hole (a trail through which the
2 (A), a
3, an insulating
Then, as shown in Fig. 2 (C), an opening for a through hole (a trail through which the
On the other hand, as shown in Fig. 4 (A), conventionally, a substrate on which the resin composition for plating resist of the present invention is not applied (conductor layers 31A and 31B on two circuit patterns and an insulating layer The
Further, as shown in Figs. 6A and 6B, a multilayer printed wiring board can be manufactured by a "build-up method" in which lamination, punching, wiring, and the like are repeated for each layer. However, in such a case, it is possible to form a connection between only specific adjacent layers, while complicating the process and requiring a large number of processes.
Hereinafter, each component will be described in detail.
≪ Resin composition for plating resist &
The resin composition for plating resists of the present invention is a resin composition comprising an epoxy resin, an isocyanate compound and a non-conductive filler. The detailed mechanism is not necessarily clear, but it is considered that the isocyanate compound acts as a plating resist by inhibiting the adhesion of a catalyst nucleus such as palladium required for plating.
The resin composition for plating resist needs to contain an epoxy resin and an isocyanate compound. A rigid crosslinked structure formed by an epoxy resin and an isocyanate compound is effective for improving the plating resist resistance. Examples of the epoxy resin include cresol novolak type resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, alkylphenol novolac type epoxy resins, biphenol F type epoxy resins, naphthalene type epoxy resins Dicyclopentadiene type epoxy resins, epoxides of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, triglycidylisocyanurate, alicyclic epoxy resins, and the like.
As the isocyanate compound, a known isocyanate compound such as a monoisocyanate compound having one isocyanate group and a polyisocyanate having two or more isocyanate groups can be used. From the viewpoints of improving the curability of the composition and the toughness of the resulting cured film, preventing the occurrence of cracks during a cooling / heating cycle, and imparting heat resistance, the polyisocyanate compound is more preferable. Also, in the present invention, the use of a block isocyanate compound is also preferable. The use of the block isocyanate compound improves the workability because the storage stability is excellent.
As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, diphenylmethylene diisocyanate and 2,4-tolylene dimer.
The aliphatic polyisocyanate includes, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate.
Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, examples of the above-mentioned isocyanate compound adduct, buret (such as 24A-100, Asahi Kasei Co., Ltd.) and isocyanurate (such as TPA-100, Asahi Kasei Corporation) . Such an alicyclic polyisocyanate is preferable because plating resistance which excludes plating is good.
The block isocyanate group contained in the block isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to form an isocyanate group.
As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the block agent include the polyisocyanate compounds described above.
Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -flareolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scouring, acetal decyl, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine; Pyrazole-based block agents such as dimethylpyrazole; Maleic acid ester block agents such as diethyl maleic acid and the like.
The block isocyanate compound is commercially available, for example, in the form of SUMIJULES BL-3175, BL-4165, BL-1100, BL-1265, DISMODULES (registered trademark) TPLS-2957, TPLS- (All manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513 and Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.) (All manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, and E402-B80T (all manufactured by Mitsui Takeda Chemical Co., Ltd.), B-830, B-815, B-846, B- TRIXEN BI 7982, Tricksen BI 7950, Tricksen BI 7951, Tricksen BI 7960 and Tricksen BI 7961 (manufactured by Baxeneden Chemicals Limited) . Further, Sumijel BL-3175 and BL-4265 are obtained by using methylethyloxime as a block agent.
These isocyanate compounds may be used alone or in combination of two or more.
It is preferable that the epoxy resin and the isocyanate compound in the resin composition for plating resist are contained in a proportion such that the number of isocyanate equivalents of the isocyanate compound is 0.5 to 2 equivalents based on one epoxy equivalent of the epoxy resin. Further, a ratio of 0.8 to 1.5, particularly a ratio of 1.0 to 1.2 is preferable. If the ratio is below the lower limit, the plating resistance becomes insufficient, and if the ratio exceeds the upper limit, the coating becomes excessively hard and the adhesion to the substrate and the durability are lowered.
When a thermosetting resin such as an epoxy resin or an isocyanate compound is used, it is preferable to contain a curing agent. Examples of the curing agent include imidazoles such as 2-ethyl-4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ) and 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) Based curing agent such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, metaoxylenediamine, isophoronediamine, norbornenediamine, 1,3-bisaminomethylcyclohexane, N-aminoethyl Amine-based curing agents such as benzene, toluene, xylene and piperazine; phenol-based curing agents such as polyamide, vinylphenol, aralkyl-type phenol resin, phenolphenylaralkyl resin and phenolbiphenylaralkyl resin; anhydride phthalic acid, tetrahydrophthalic acid, (Anhydroglycine), methylcyclohexene (methylcyclohexene), methylcyclohexene, methylcyclohexene, methylcyclohexene, methylcyclohexene, methylcyclohexene, methylcyclohexene, methylcyclohexene, Tetracar And an acid anhydride-based curing agent such as a carboxylic acid anhydride and a carboxylic acid anhydride. However, such a curing agent needs to be used in consideration of the reactivity and the amount of the isocyanate compound used in the present invention, and it is generally preferable that the curing agent is not used.
The content of the curing agent is preferably 0.5 to 20 parts by mass per 100 parts by mass of the thermosetting resin component. When the blending amount of the curing agent is less than 0.5 parts by mass, the curing of the resin composition may be insufficient, and if it exceeds 20 parts by mass, appropriate effects may not be obtained in some cases.
The resin composition for plating resists of the present invention needs to contain a non-conductive filler. The non-conductive filler of the present invention preferably has a non-conductive property with a volume resistivity (JIS K 6911) of 10 10 ? 占 이상 m or more.
As the material of the filler, an inorganic material may be used, though it may be an inorganic material or an organic material. Examples of the inorganic filler include silicon oxide, amorphous silica, talc, clay, mica powder, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum oxide, aluminum hydroxide, titanium dioxide,
Examples of the organic filler include silicone powder, nylon powder, fluorine powder and the like.
Further, the spherical filler is preferable because it can fill the ink without damaging the fluidity of the ink.
As the spherical filler, spherical silicon dioxide (also referred to as spherical silica), spherical aluminum oxide (also referred to spherical alumina), or spherical titanium dioxide is preferable. Plating resistance is improved by the combined use of spherical silica and spherical titanium dioxide.
The spherical silicon dioxide may be any spherical silicon dioxide that can be used as a filler for electronic materials. The surface may be treated with a silane coupling agent.
The spherical filler may be spherical, and is not limited to spherical spherical spheroid spheres. Suitable spherical fillers include, for example, those having a spherical figure of not less than 0.8 as measured as follows, but are not limited thereto.
The sphericity is measured as follows. The photograph is taken by SEM and is calculated as the value calculated from the area of the observed particle and the circumferential length (sphericity) = {4 pi x (area) / (circumferential length) 2 }. Specifically, an average value measured for 100 particles is adopted by using an image processing apparatus.
The method for producing spherical silica particles and spherical alumina is not particularly limited, and a method known to those skilled in the art can be applied. For example, a silicon powder or an aluminum powder can be produced by burning by a VMC (Vapor-Metal Combustion) method. The VMC method is a method in which a chemical salt is formed by a burner in an atmosphere containing oxygen and a metal powder constituting a part of the objective oxide particles is introduced into the chemical salt in such an amount as to form dust cloud , And knocking is caused to obtain oxide particles.
Examples of commercially available spherical silica include SO series manufactured by Admatex and HPS series (HPS-0500, HPS-1000, HPS3500, etc.) manufactured by Doagose.
The spherical alumina may be any spherical alumina usable as a filler for electronic materials.
Examples of commercially available spherical alumina include AO series manufactured by Admatex, TC-975c manufactured by Admatech, Alunabiz / CB series manufactured by Showa Denko KK, and the like.
The average particle diameter of the filler is preferably 25 占 퐉 or less, more preferably 10 占 퐉 or less, and further preferably 3 占 퐉 or less. It is preferable that the content of the non-conductive filler is 15 to 75 parts by volume based on 100 parts by volume of the solid content of the resin composition for plating resist of the present invention. Particularly preferably 15 to 60 parts by volume. If the amount of the filler to be added exceeds the upper limit, the curability of the cured film is lowered. If the amount is less than the lower limit, the plating resistance tends to become insufficient.
The resin composition may further contain a solvent, a diluent, a curing accelerator, a thickener, a defoaming agent, a leveling agent, a coupling agent, a flame retardant, and a photopolymerization initiator.
The film thickness of the plating resist portion is generally 10 to 100 mu m, preferably 50 to 100 mu m.
<Through hole>
In the multilayered printed circuit board of the present invention, the openings for through holes (through holes before plating) are formed so as to penetrate the plating resist portions formed on the conductor layer on the circuit pattern and / or on the insulating layer. Therefore, the plating resist portion is formed between the conductor layer and the insulating layer and / or between the insulating layers. Through holes are formed by plating the openings for the through holes. As described above, the partial through holes are physically divided through holes by plating resist portions.
The method of forming the plating resist portion on the conductor layer on the circuit pattern is carried out by forming the composition film by applying or printing the resin composition for plating resist of the present invention to a predetermined portion on the conductor layer, and heating and drying. The same applies to the case of the insulating layer. As the coating method, a roll coating method, a spraying method, or the like can be used. As the printing method, a screen printing method, a gravure printing method, or the like can be used. The heating is generally carried out at 80 to 200 ° C, preferably 100 to 170 ° C, for 5 to 60 minutes, preferably 10 to 60 minutes.
≪ Conductor layer on circuit pattern >
The conductor layer in the multilayer printed wiring board of the present invention is a circuit pattern formed by a conductor such as copper, nickel, tin, gold, or an alloy thereof. Any known method may be used for forming the circuit pattern, and examples thereof include a subtractive method and an edited method.
≪ Insulating layer &
The insulating layer between the conductor layers on the circuit pattern of the multilayered printed circuit board of the present invention may be composed of any material as long as it is used as an insulating layer of a multilayered printed circuit board, but is preferably formed by curing the resin composition. The resin composition may be in a liquid form or in a sheet form.
Examples of the interlayer insulating layer include a resin layer in which FR-4, epoxy glass, polyimide glass, ceramic hydrocarbon, polyimide film, resin impregnated glass fiber, resin film, resin impregnated mat material, Kevlar, paper, .
Further, as described above, the prepreg also has a function of insulating the conductor layer, and thus is included in the insulating layer of the present invention.
The prepreg is a sheet obtained by impregnating a substrate such as a glass cloth with a varnish such as an epoxy resin composition, a bismaleimide triazine resin composition or a polyimide resin composition, and heating and drying the same to give a semi-cured, R-1410A, R-5670 (K), R-1650D and R-1551 manufactured by Denki K.K. and GEPL-190 and GHPL-830 manufactured by Mitsubishi Gas Chemical Co., MCL-E-67 and MCL-I-671, which are commercially available.
(Core substrate)
The multilayered printed circuit board of the present invention may have a core substrate. The core substrate is a substrate serving as a base for forming a conductor layer and an interlayer insulating layer on a circuit pattern in a multilayer printed wiring board, and serves as a core. Examples of the material serving as the base of the core substrate include a glass epoxy material, a ceramic, and a metal core substrate obtained by curing a thermosetting resin such as epoxy resin impregnated in glass fiber or the like.
(Plated)
In the multilayer printed wiring board of the present invention, portions other than the plating resist in the openings for the through holes are plated with a conductive material. The plating treatment is carried out by electroless plating, and electrolytic plating may be further carried out after that, if desired. Examples of the catalyst nuclei for electroless plating include palladium, tin, silver, gold, platinum, copper and nickel or a combination thereof, preferably palladium. Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless nickel-tungsten alloy plating, electroless tin plating, and electroless gold plating. Electroless copper plating is preferable. The thickness of the electroless plating is preferably 0.1 to 5 mu m.
≪ Manufacturing Method of Multilayer Printed Circuit Board &
The method for manufacturing a multilayered printed circuit board according to the present invention is a method for manufacturing a multilayered printed circuit board according to the present invention in a predetermined position (conductor layer, insulating layer or both layers) on an insulating layer (including a substrate) on which a conductor layer A step of multilayering a wiring board having a plating resist portion formed by applying and curing a plating resist resin composition to a multilayered structure by, for example, hot pressing through an epoxy prepreg (insulating layer); A step of forming an opening for a through hole by a drill or a laser, a step of performing a desmear treatment, and a step of performing a plating treatment.
(Heating press)
The hot pressing can be carried out using a known method. The pressing condition is preferably 20 to 60 kg /
(Desmear processing)
The desmear process can be performed by a known method. For example, an oxidizing agent containing an aqueous solution of chromic acid, permanganate, or the like can be used. Alternatively, it can be treated by oxygen plasma, mixed plasma of CF 4 and oxygen, corona discharge, or the like.
Example
Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited by the following examples.
(Preparation of resin composition)
Each component was kneaded by a three-roll mill in accordance with the following Tables 1 and 2 to obtain the resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2. The numbers in the table indicate the mass parts.
(Preparation of Evaluation Substrate)
The resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were pattern printed on the FR-4 substrate on the front surface of copper by screen printing so that the film thickness after drying was about 50 占 퐉, The substrate and the FR-4 substrate on the entire surface of the copper substrate were cured at 170 占 폚 for 60 minutes via an epoxy prepreg (R-1650D, manufactured by Panasonic Corporation) 20 kg / cm < 2 >, and finally, drilling was performed to form openings for through-holes having a pore diameter of 0.7 mm to produce test substrates of Examples 1 to 14 and Comparative Examples 1 and 2.
(Desmear treatment process)
(Manufactured by Rohm and Haas Company, 200 ml / l) and Surak Fogitz Z (manufactured by Rohm and Haas Company, 100 ml / l) as the swelling liquid were applied to the test substrates of Examples 1 to 14 and Comparative Examples 1 and 2 The mixture was immersed in a mixed solution at 80 DEG C for 5 minutes and then added to a mixed solution of Surak Fogit MLB Promoter 213A (manufactured by Rohm and Haas Company, 100 ml / l) and Succafogit MLB Promoter 213B (manufactured by Rohm and Haas Company, 150 ml / ° C for 10 minutes and finally immersed in a Sucyl Fogg MLB Neutraliser 216-2 (manufactured by Rohm and Haas Company, 200 ml / l) as a neutralizing solution at 50 ° C for 5 minutes.
(Electroless copper plating process)
After the desmear treatment, the substrate was immersed in a cleaner conditioner process at 50 占 폚 for 5 minutes in a cleaner Securigant P500 (manufactured by Atotech Co., 40 ml / l), followed by pre-dip neogant B (20 ml / (40 ml / l), sodium hydroxide (4 g / l) and boric acid (5 g / l) as a catalyst application step, 1) at 35 ° C for 5 minutes and subsequently subjected to a reduction step in a mixture of Reducer Neogant WA (5 ml / l, manufactured by Atotech Co., Ltd.) and boric acid (25 g / l) for 1 minute at 25 ° C, As the electroless copper plating process, Basic Solution Print Gant MSK (80 ml / l from Atotech) and Copper Solution Print Gant MSK (40 ml / l from Atotech), Reducer Cu (14 ml / l from Atotech) Print Gant MSK (manufactured by Atotech, 3 ml / l) at 35 DEG C for 10 Dipping, and then it dried for 30 minutes at 100 ℃ by a hot air circulation dryer.
(Electrolytic Copper Plating Process)
After electroless copper plating treatment, the substrate was immersed in a mixed solution of an acid cleaning cleaner FR (100 ml / l, manufactured by Atotech Co., Ltd.) and sulfuric acid (100 ml / l) for 1 minute at 30 ° C as an acid cleaning cleaner process, (80 ml / l), sulfuric acid (200 ml / l), chlorine (50 mg / l) and additive cupra (II) as the copper sulfate electroplating process. Was immersed in a mixed solution of Seed HL (manufactured by Atotech Co., Ltd., 10 ml / l) and a correction agent Cupracid GS (0.1 ml / l, manufactured by Atotech) at 23 ° C for 60 minutes (current density of 1 A / dm 2) And dried at 150 DEG C for 60 minutes by a circulating dryer.
(Assessment Methods)
The cross section of the substrate was polished by the cross section after the electrolytic copper plating treatment and the cross section of the through hole section was observed with a microscope to obtain copper plating for the resin composition portion (layer) of the resin composition of Examples 1 to 14 and Comparative Examples 1 and 2 , And evaluated according to the following criteria. The results are shown in Tables 1 and 2 below.
(Criteria)
A: The plating resist portion in the through hole is not plated with a conductive material, but the portion without plating resist portion is plated with a conductive material.
X: Plating resist portion in the through hole is plated with a conductive material.
Remarks)
* 1: jER828 (manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 184 to 194 g / eq, specific gravity 1.17
* 2: Carbitol acetate cut product (solid content 65% by mass) of HF-1M (manufactured by Meiwa Kasei Kabushiki Kaisha), specific gravity 1.28
* 3: Dyuranate TPA-100 (manufactured by Asahi Kasei Chemicals Co., Ltd.), isocyanate equivalent 179, specific gravity 1.16
* 4: Dyuranate 24A-100 (manufactured by Asahi Kasei Chemicals Co., Ltd.), isocyanate equivalent 182, specific gravity 1.13
* 5: 1-Methoxy-2-propanol cut product (solid content: 70% by mass) of BI 7982 (block isocyanate (isocyanate: HDI Buret, block: dimethylpyrazole), manufactured by Parkshan Chemical Industries Co., Ltd.), isocyanate equivalent 477 , Specific gravity 1.1
* 6: SO-C5 (manufactured by Admatechs Kabushiki Kaisha), spherical shape, average particle diameter 1.6 탆, specific gravity 2.2
* 7: Higilite H-42M (manufactured by Showa Denko K.K.), spherical shape, average particle diameter 0.8 to 1.2 탆, specific gravity 2.4
* 8: DAW3 (manufactured by Denki Kagaku Kagaku Co., Ltd.), spherical shape, average particle size 4 탆, specific gravity 3.9
* 9: CR-58 (manufactured by Ishihara Sangyo K.K.), spherical, average particle diameter 0.28 탆, specific gravity 3.9
* 10: μ-powder (POWDER) 3N (manufactured by Asahi Kasei Kabushiki Kaisha), spherical shape, average particle diameter 1.2 μm, specific gravity 2.7
* 11: B-30 (manufactured by Sakai Chemical Industry Co., Ltd.), spherical shape, average particle diameter 0.3 탆, specific gravity 4.5
* 12: SG-2000 (manufactured by Nippon Talc Co., Ltd.), spherical shape, average particle diameter 1 mu m, specific gravity 2.7
It is possible to provide a multilayered printed circuit board which can easily form partial through holes and accurately form according to design.
11A, 11B, 21A, 21B, 31A, 31B conductor layers
12A, 12B, 19, 22A, 22B, 32A, 32B,
13A, 13B, 23A, 23B, 33A, 33B,
14, 24, 34 prepreg
15, 25 plating resist part
16, 26, 30, 36 Printed circuit boards
17, 27, 37, 39 Drill
18, 28, 38 Openings for through holes
Claims (12)
An epoxy resin, an isocyanate compound, and a non-conductive filler.
A plating resist portion provided between at least one of a layer between a conductor layer and an insulating layer exposed in a through hole opening portion and an interlayer between insulating layers and a plating portion formed in an exposed region other than the plating resist portion, A multilayer printed wiring board characterized by containing a cured product of the resin composition for plating resists according to any one of claims 1 to 7.
A plurality of layers including the conductor layer on the circuit pattern and a plating resist portion provided between the layers,
A step of forming an opening for a through hole with a drill or a laser so as to penetrate through the plating resist portion with respect to the multilayered wiring board,
A step of performing a desmear treatment on the openings for the through holes and
A step of performing plating treatment on the openings for the through-holes subjected to the desmear treatment
Wherein the multilayered printed circuit board is manufactured by a method comprising the steps of:
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2012-029081 | 2012-02-14 | ||
| JP2012029081A JP2013168395A (en) | 2012-02-14 | 2012-02-14 | Resin composition for plating resist, multilayer printed wiring board, and manufacturing method of multilayer printed wiring board |
| PCT/JP2012/079754 WO2013121641A1 (en) | 2012-02-14 | 2012-11-16 | Resin composition for plating resist, multilayer printed wiring board, and method for producing multilayer printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20140125356A true KR20140125356A (en) | 2014-10-28 |
Family
ID=48983783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020147019958A KR20140125356A (en) | 2012-02-14 | 2012-11-16 | Resin composition for plating resist, multilayer printed wiring board, and method for producing multilayer printed wiring board |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2013168395A (en) |
| KR (1) | KR20140125356A (en) |
| CN (1) | CN104126334A (en) |
| WO (1) | WO2013121641A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6580033B2 (en) * | 2014-04-25 | 2019-09-25 | 太陽インキ製造株式会社 | RESIN COMPOSITION FOR PERMANENT INSULATION FILM, PERMANENT INSULATION FILM, MULTILAYER PRINTED WIRING BOARD AND METHOD FOR PRODUCING THE SAME |
| JP6198804B2 (en) * | 2015-12-01 | 2017-09-20 | 日本写真印刷株式会社 | Strain sensor for multipoint measurement and its manufacturing method |
| JP6875139B2 (en) * | 2016-02-02 | 2021-05-19 | 積水化学工業株式会社 | Refractory resin composition |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0734022A (en) * | 1993-07-23 | 1995-02-03 | Ajinomoto Co Inc | Heat-hardening ink composition for solder resist |
| JP2001354885A (en) * | 2000-06-15 | 2001-12-25 | Tokushu Shikiryo Kogyo Kk | Blue ink composition for printed circuit board |
| JP2003137945A (en) * | 2001-11-05 | 2003-05-14 | Nippon Shokubai Co Ltd | Radically polymerizable resin, radically polymerizable resin composition and photosensitive resin composition for forming image |
| JP2003177534A (en) * | 2001-12-12 | 2003-06-27 | Nippon Shokubai Co Ltd | Photosensitive resin composition for image formation |
| JP2003204157A (en) * | 2001-12-28 | 2003-07-18 | Toshiba Corp | Multylayer printed-wiring board, manufacturing method thereof and electronic equipment mounting the same |
| JP2003218527A (en) * | 2002-01-18 | 2003-07-31 | Ibiden Co Ltd | Multilayered circuit board and its manufacturing method |
| JP2003229666A (en) * | 2002-02-04 | 2003-08-15 | Ibiden Co Ltd | Wiring board and method of manufacturing the same |
| JP4017451B2 (en) * | 2002-06-19 | 2007-12-05 | イビデン株式会社 | Multi-layer circuit board and manufacturing method thereof |
| JP5011641B2 (en) * | 2004-01-28 | 2012-08-29 | 味の素株式会社 | Thermosetting resin composition, adhesive film using the same, and multilayer printed wiring board |
| JP2005345810A (en) * | 2004-06-03 | 2005-12-15 | Kyocera Chemical Corp | Photosetting/thermosetting resin composition |
| TWI389205B (en) * | 2005-03-04 | 2013-03-11 | Sanmina Sci Corp | Partitioning a via structure using plating resist |
| CN101675089B (en) * | 2007-04-27 | 2015-06-17 | 日本化药株式会社 | (meth)acrylate compound, resin composition containing the same, cured product of the resin composition, and energy ray-curable resin composition for optical lens sheet and cured product thereof |
| JP2009073987A (en) * | 2007-09-21 | 2009-04-09 | Ajinomoto Co Inc | High dielectric resin composition |
| JP2009109833A (en) * | 2007-10-31 | 2009-05-21 | Hitachi Chem Co Ltd | Photosensitive resin composition, and photosensitive film and photosensitive permanent resist using same |
| JP5476649B2 (en) * | 2008-04-03 | 2014-04-23 | 住友電工ウインテック株式会社 | Insulated wire |
| US9075307B2 (en) * | 2008-09-04 | 2015-07-07 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition for protective film of printed wiring board for semiconductor package |
| JP5408655B2 (en) * | 2009-08-10 | 2014-02-05 | 米沢ダイヤエレクトロニクス株式会社 | Printed wiring board and manufacturing method thereof |
-
2012
- 2012-02-14 JP JP2012029081A patent/JP2013168395A/en active Pending
- 2012-11-16 KR KR1020147019958A patent/KR20140125356A/en not_active Application Discontinuation
- 2012-11-16 WO PCT/JP2012/079754 patent/WO2013121641A1/en active Application Filing
- 2012-11-16 CN CN201280069804.6A patent/CN104126334A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN104126334A (en) | 2014-10-29 |
| JP2013168395A (en) | 2013-08-29 |
| WO2013121641A1 (en) | 2013-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5650908B2 (en) | Resin composition and copper foil with resin obtained using the resin composition | |
| CN108588766B (en) | Copper foil with carrier | |
| JP5929219B2 (en) | Printed wiring board and printed wiring board manufacturing method | |
| KR101271008B1 (en) | Resin composition for forming the adhesive layers of a multi-layer flexible printed circuit board | |
| JP5378620B2 (en) | LAMINATED BOARD AND PRINTED WIRING BOARD MANUFACTURING METHOD | |
| TWI756552B (en) | Thermosetting epoxy resin composition, adhesive film for insulating layer formation, prepreg for insulating layer formation, insulator for printed wiring board, multilayer printed wiring board, and semiconductor device | |
| WO2014080959A1 (en) | Copper foil with carrier | |
| JP5521099B1 (en) | Copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and printed wiring board manufacturing method | |
| WO2011068157A1 (en) | Resin composition for use in formation of bonding layer in multilayer flexible printed circuit board, resin varnish, resin-coated copper foil, manufacturing method for resin-coated copper foil for use in manufacturing of multilayer flexible printed circuit board, and multilayer flexible printed circuit board | |
| KR101027303B1 (en) | Resin composition and adhesive film for multi-layered printed wiring board | |
| KR101511495B1 (en) | Epoxy resin composition | |
| CN102474993A (en) | Multilayered wiring board and method for manufacturing multilayered wiring board | |
| KR102429883B1 (en) | Interlayer insulating film and manufacturing method thereof | |
| CN110382589A (en) | Resin material, stack membrane and multilayer printed-wiring board | |
| JPWO2007097209A1 (en) | Epoxy resin composition | |
| KR100776725B1 (en) | Thermosetting epoxy resin composition, its formed article and multilayer printed circuit board | |
| JP5345656B2 (en) | Flame retardant resin composition for multilayer wiring board and multilayer wiring board including the same | |
| JP4345554B2 (en) | Printed wiring board having an auxiliary adhesion layer between insulating layers and method for manufacturing the same | |
| KR20140125356A (en) | Resin composition for plating resist, multilayer printed wiring board, and method for producing multilayer printed wiring board | |
| JP2003138133A (en) | Modified cyanate ester resin composition, resin film, multilayered printed wiring board and method for producing the same | |
| JP6273106B2 (en) | Copper foil with carrier, method for producing copper-clad laminate and method for producing printed wiring board | |
| TW201437277A (en) | Curable resin composition | |
| WO2012169384A1 (en) | Resin composition for plating resist, and multilayer printed wiring board | |
| JP2003138132A (en) | Modified cyanate ester resin composition, flame- retardant resin film, flame-retardant multilayered printed wiring board and method for producing the same | |
| US20100270064A1 (en) | Resin composition for printed circuit board and printed circuit board using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |