CN101798438A - Heat curable resin composition, dry film and printed wiring board and method for preparing the same - Google Patents
Heat curable resin composition, dry film and printed wiring board and method for preparing the same Download PDFInfo
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- CN101798438A CN101798438A CN200910163613A CN200910163613A CN101798438A CN 101798438 A CN101798438 A CN 101798438A CN 200910163613 A CN200910163613 A CN 200910163613A CN 200910163613 A CN200910163613 A CN 200910163613A CN 101798438 A CN101798438 A CN 101798438A
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- resin composition
- hot curing
- insulating barrier
- wiring board
- curing resin
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
Abstract
The invention provides a heat curable resin composition, a dry film and a printed wiring board and a method for preparing the same, and particularly provides a heat curable resin composition capable of obtaining a resin insulating layer with glue residue removing property and glue residue removing resistance, a dry film using the heat curable resin composition, a printed wiring board and a method for preparing the same. The heat curable resin composition is characterized by containing phenolic resin, mixture of liquid epoxy resin at 20 DEG C and solid epoxy resin at 40 DEG C, and inorganic filler, wherein the matching ratio of the phenolic hydroxyl group of the phenolic resin to the epoxy group of the mixture is 0.3 to 1.0 based on an equivalence ratio.
Description
Technical field
The present invention relates to hot curing resin composition, use dry film and the printed-wiring board (PWB) and the manufacture method thereof of this hot curing resin composition.
Background technology
In electronic machine etc., on the employed printed-wiring board (PWB) during packaged electronic components,, in the zone except that connecting hole of the substrate that is formed with circuit for example solder mask of resin insulating barrier is set usually for following purpose.That is, its purpose is, prevents that scolding tin is attached to the unnecessary portions of substrate or printed-wiring board (PWB), and the conductor that prevents circuit set on substrate or the printed-wiring board (PWB) exposes and makes this circuit owing to oxidation, humidity are corroded.
And, when using hot curing resin composition on substrate, to form soldering-resistant pattern (solder mask), to the via (viahole) of this soldering-resistant pattern irradiating laser with formation encapsulation usefulness.At this moment, under the situation that requires fine soldering-resistant pattern,, can use carbon dioxide laser, UV-YAG laser, excimer laser etc. especially as LASER Light Source.
In addition, in this specification sheets, will form circuit but the plate that do not form resin insulating barrier only is called " substrate ".In addition, the plate that has formed circuit and resin insulating barrier is called " printed-wiring board (PWB) ".
When utilizing laser to form via, the composition that can produce solder mask is (hereinafter referred to as " glue slag (smear) ".) be not decomposed remove and in the bottom of via or inside etc. locate (hereinafter referred to as " in the via ") residual phenomenon.Like this, when in via, having the glue slag residual, in thereafter plating is handled, can be created in and produce the not part of plating on the printed-wiring board (PWB), defectives such as bad perhaps take place to engage during packaged electronic components on printed-wiring board (PWB).Therefore, being necessary to remove this glue slag promptly carries out so-called de-smear (desmear) and handles and (followingly will carry out the operation that de-smear handles and be called " de-smear operation ".)。
In the de-smear operation, after employing expands the glue slag with concentrated alkali solution usually, the damp process that utilizes permanganate solution that its decomposition is removed.
But, when adopting damp process to carry out the de-smear processing, attempting to decompose fully when removing glue slag remaining in the via, can produce the surface coarsening of the solder mask that does not form the via part that causes owing to soups such as concentrated alkali solution, permanganate solutions, the problem that perhaps causes these solder masks to be peeled off from printed-wiring board (PWB).On the other hand, attempting to suppress the coarsening phenomenon of solder mask, when peeling off phenomenon, having the problem that the glue slag can not fully be removed (de-smear reduction) on the contrary.
As the existing technology that addresses these problems, proposed on substrate, to form the method for the resin insulating barrier of 2 layers of structure.This method is: easily decomposing the layer that the resin combination of removing (easily de-smear is handled) constitutes with forming by the glue slag as the residual solder mask of glue slag (the 1st layer) of substrate contacts, forming by the difficult layer that (difficult de-smear) resin combination of removing constitutes (for example with reference to patent documentation 1 etc.) that decomposes of glue slag with the 1st layer of top layer that contacts (the 2nd layer).
But, because in this technology, form the resin insulating barrier of 2 layers of structure, so the problem that has tooling cost to rise.
Patent documentation
Patent documentation 1: TOHKEMY 2004-240233 communique (paragraph 0008 etc.)
Summary of the invention
The problem that invention will solve
As known from the above, people seek to have concurrently the character of easy de-smear processing (hereinafter referred to as " de-smear " over against the resin insulating barrier that uses hot curing resin composition.) and the character handled of difficult de-smear (hereinafter referred to as " anti-de-smear ".)。
The objective of the invention is to, the hot curing resin composition of the resin insulating barrier that can obtain to have concurrently de-smear and anti-de-smear is provided, use dry film, printed-wiring board (PWB) and the manufacture method thereof of this hot curing resin composition.
The method of dealing with problems
Hot curing resin composition of the present invention is characterised in that, comprises: resol; Contain at 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy; Inorganic filler, and the proportioning of the epoxy group(ing) of the phenol hydroxyl of above-mentioned resol and said mixture counts 0.3～1.0 with equivalence ratio.
Like this, by limiting proportioning in the equivalence ratio of phenol hydroxyl and epoxy group(ing), in the de-smear operation, can decompose fully and remove glue slag remaining in the via, and can suppress the resin combination layer coarsening phenomenon, peel off phenomenon, can obtain to have concurrently the resin insulating barrier of de-smear and anti-de-smear.
In addition, by use contain 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy, the resin insulating barrier that can obtain to have concurrently de-smear and anti-de-smear and have the good film characteristic.
Hot curing resin composition of the present invention is characterised in that, and is with respect to Resins, epoxy total amount contained in this mixture, described 20 ℃ of ratio cooperations that are the Resins, epoxy of liquid state with 20～80 quality %.
Hot curing resin composition of the present invention is characterised in that with respect to the solids component of hot curing resin composition, the use level of described inorganic filler is 20～100 quality %.
Hot curing resin composition of the present invention is characterised in that the median size of described inorganic filler is below the 5 μ m.
As known from the above, hot curing resin composition of the present invention is applicable to dry film solder resist purposes.
In addition, dry film of the present invention is characterised in that to have the dry coating of this hot curing resin composition.
By such formation, hot curing resin composition of the present invention and dry film can easily form the resin insulating barrier that has de-smear and anti-de-smear concurrently on substrate.
In addition, printed-wiring board (PWB) of the present invention is characterised in that to have: the substrate that forms circuit; Be arranged at resin insulating barrier on this substrate, that constitute by the cured article of above-mentioned hot curing resin composition; Be arranged in the via portion of this resin insulating barrier.
In addition, printed-wiring board (PWB) of the present invention is characterised in that to have: the substrate that forms circuit; Be arranged at resin insulating barrier on this substrate, that constitute by the cured article of the dry coating of above-mentioned dry film; Be arranged in the via portion of this resin insulating barrier.
By such formation, printed-wiring board (PWB) of the present invention can be suppressed at the surface coarsening of resin insulating barrier in the de-smear operation, and because the connection portion of electronic unit can obtain sufficient conducting, so can stablize and obtain the high printed-wiring board (PWB) of reliability simply.
In addition, the manufacture method of printed-wiring board (PWB) of the present invention is characterised in that to have following operation: be formed with the above-mentioned hot curing resin composition of coating on the substrate of circuit; The dry hot curing resin composition that should be coated with; This exsiccant hot curing resin composition is solidified so that resin insulating barrier to be set; This resin insulating barrier is carried out laser radiation to wear via portion; Remove the glue slag of this via portion.
In addition, the manufacture method of printed-wiring board (PWB) of the present invention is characterised in that to have following operation: at the dry coating that is formed with the above-mentioned dry film of crimping on the substrate of circuit; The dry coating of this crimping is solidified so that resin insulating barrier to be set; This resin insulating barrier is carried out laser radiation to wear via portion; Remove the glue slag of this via portion.
By such formation, manufacture method according to printed-wiring board (PWB) of the present invention, the surface coarsening that can suppress resin insulating barrier in the de-smear operation simultaneously because can obtain sufficient conducting in the connection portion of electronic unit, can be stablized and the high printed-wiring board (PWB) of fabrication reliability simply.
The invention effect
Hot curing resin composition of the application of the invention and dry film can obtain to have concurrently the resin insulating barrier of de-smear and anti-de-smear.
In addition, printed-wiring board (PWB) of the present invention can suppress the surface coarsening of resin insulating barrier in the de-smear operation, simultaneously because can obtain sufficient conducting in the connection portion of electronic unit, so can stably obtain the high printed-wiring board (PWB) of reliability.
Further, manufacture method according to printed-wiring board (PWB) of the present invention, can suppress the alligatoring on the surface of resin insulating barrier in the de-smear operation, simultaneously because can obtain sufficient conducting, so the high printed-wiring board (PWB) of fabrication reliability stably in the connection portion of electronic unit.
Description of drawings
The liquid state of Fig. 1 representative ring epoxy resins is judged the simple sectional view of 2 used test tubes.
Nomenclature
The liquid judgement test tube of 10a
10b temperature measuring test tube
11 graticules (A line)
12 graticules (B line)
13a, 13b rubber plug
14 thermometers
Embodiment
Below an example of embodiment of the present invention is described, but the present invention is not limited to this example.
Hot curing resin composition of the present invention is characterised in that, comprises: resol; Contain at 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy; Inorganic filler, and the proportioning of the epoxy group(ing) of the phenol hydroxyl of above-mentioned resol and said mixture counts 0.3～1.0 with equivalence ratio.
In addition, about being included in 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy, with respect to the Resins, epoxy total amount that this mixture contained, preferably with 20～80 quality %, more preferably to be engaged in 20 ℃ with the ratio of 40～60 quality % be the Resins, epoxy of liquid state.With respect to the Resins, epoxy total amount that this mixture contained, when being the use level less than 20 quality % of liquid Resins, epoxy for 20 ℃, so the filming of the hot curing resin composition difficulty that becomes is not preferred.In addition, with respect to the Resins, epoxy total amount that this mixture contained, be the use level of liquid Resins, epoxy when surpassing 80 quality % at 20 ℃, use the surface of the insulation layer that hot curing resin composition forms to become easily by alligatoring, so not preferred.
Here, the decision method for this specification sheets said " liquid state " describes.
Liquid judgement make " confirmation method of liquid state " of the 2nd attached sheet of (put down into the first year autonomous province make No. 1) to carry out based on the province of test that relates to hazardous material and proterties.
(1) device
Water Tank with Temp.-controlled: use possess stirrer, well heater, thermometer, automatic temperature regulator (can at the instrument of ± 0.1 ℃ of scope controlled temperature), the Water Tank with Temp.-controlled that degree of depth 150mm is above.
In addition, in present embodiment and embodiment, as the device of the judgement of " liquid state " of carrying out Resins, epoxy, (model BU300:Yamato Scientific.Co., Ltd. makes can to use Low Constant Temperature Water Baths.Below identical.) with Constant Temperature Devices Thermomate (model BF500:Yamato Scientific.Co., Ltd. make, below identical.) combination, but so long as can carry out the device of the adjusting identical and all can use with these.
In the present embodiment, about 22 liters of tap water of packing in Low Constant Temperature Water Baths are opened the power supply of assembly Thermomate and temperature are set to preset temperature (20 ℃ or 40 ℃).Then, finely tune, so that the water temperature of Low Constant Temperature Water Baths is preset temperature ± 0.1 ℃ with Thermomate.
Test tube:
As shown in Figure 1, as test tube, use liquid judgement test tube 10a and temperature measuring test tube 10b.
Liquid judge with test tube 10a to be the test tube of transparent glass system of the flat round tube type of internal diameter 30mm, height 120mm, distance is managed end 55mm and is highly located to indicate graticule 11 (hereinafter referred to as " A line ".), distance pipe end 85mm highly locates to indicate graticule 12 (hereinafter referred to as " B line ".), the test tube mouth seals with rubber plug 13a.
In addition, temperature measuring judges to have identical size with test tube 10a with test tube 10b with liquid, is indicating A line and B line with the liquid state judgement with the identical position of test tube 10a.And temperature measuring has the rubber plug 13b that is used to insert with the hole of support temperature meter with test tube 10b with central authorities and has sealed the test tube mouth, is inserted with thermometer 14 in this rubber plug 13b.
As thermometer 14, the thermometer (20～50 ℃ of SOP-58 scale ranges) that the cold test that uses JIS B7410 (1982) " petroleum-type test glass thermometer " to stipulate is used, but so long as can measure the thermometer of 0～50 ℃ temperature range and just can be used as thermometer 14 and use.
(2) enforcement of test order
Under the normal atmosphere of 20 ± 5 ℃ of temperature, place the sample ring epoxy resins more than 24 hours.Then, judge with the temperature measuring shown in developmental tube 10a and Fig. 1 (b) in the liquid state shown in Fig. 1 (a) respectively and pack this sample into to the A line in developmental tube 10b.And, test tube 10a and 10b is upright and be statically placed in the Low Constant Temperature Water Baths, make the underwater of the tap water that the B line of each test tube is packed at Low Constant Temperature Water Baths.In addition, thermometer 14 is inserted among the rubber plug 13b, makes the lower end of thermometer 14 be positioned at the following quadrate part that hangs down 30mm than A line.
After the temperature of sample reached design temperature ± 0.1 ℃, the former state state kept 10 minutes.Then, from Low Constant Temperature Water Baths, take out liquid judgement and use test tube 10a, and immediately its level is inverted on the testing table of level.Then, the front end (test tube oral-lateral) of measuring the liquid level of the sample in the test tube 10a with stopwatch moves to the time of B line from the A line.With this minute is to be judged to be " liquid state " with interior sample in 90 seconds, and the sample that minute is surpassed 90 seconds is judged to be " solid state (solid-state) ".
At 20 ℃ is liquid Resins, epoxy
As being liquid Resins, epoxy at 20 ℃, can list 828 (Japan EpoxyResins Co., Ltd makes), YD-128 (Dongdu changes into (strain) and makes), 840,850 bisphenol A type epoxy resins such as (above DIC (strain) manufacturings), 806,807 (above Japan Epoxy Resins Co., Ltd makes), YDF-170 (Dongdu changes into (strain) and makes), 830,835, N-730A bisphenol f type epoxy resins such as (above DIC (strain) manufacturings), the mixture of ZX-1059 dihydroxyphenyl propanes such as (Dongdu change into (strain) and makes) and Bisphenol F, YX-8000,8034 (above Japan Epoxy Resins Co., Ltd makes), ST-3000 bisphenol-A epoxy resins such as (Dongdu change into (strain) and makes) etc.
At 40 ℃ is solid-state Resins, epoxy
As being solid-state Resins, epoxy at 40 ℃, can list EPICLON 1050, EPICLON 3050 (above DIC (strain) manufacturing), EPIKOTE 1001, EPIKOTE1002, EPIKOTE 1003 (above Japan Epoxy Resins Co., Ltd makes), EPOTOHTO YD-011, EPOTOHTO YD-012 bisphenol A type epoxy resins such as (above Dongdu change into (strain) and makes), EPOTOHTO YDF-2001, EPOTOHTO 2004 bisphenol f type epoxy resins such as (above Dongdu change into (strain) and makes), YDB-400 (Dongdu changes into (strain) and makes), EPICLON152, EPICLON153 brominated bisphenol a type epoxy resin such as (DIC (strain) manufacturings), EXA-1514 bisphenol-s epoxy resins such as (DIC (strain) manufacturings), N-770,775 (above DIC (strain) manufacturings), EPPN-201H, RE-306 (above Japanese chemical drug (strain) manufacturing), 152,154 (above Japan Epoxy Resins Co., Ltd makes) etc. phenol novolak type epoxy resin, EOCN-102S, 103S, 104S (above Japanese chemical drug (strain) manufacturing), YDCN-701,702,703,704 (more than, Dongdu changes into (strain) system), N-660,670,680 cresols phenolic resin varnish type epoxy resins such as (above DIC (strain) manufacturings), 157S70 (Japan Epoxy ResinsCo., Ltd makes), N-865 bisphenol-A phenolic varnish type Resins, epoxy such as (DIC (strain) manufacturings), YX-4000 (Japan Epoxy Resins Co., Ltd makes), NC-3000 biphenyl type epoxy resins such as (Japanese chemical drug (strain) manufacturings), NC-7000L naphthalene type Resins, epoxy such as (Japanese chemical drug (strain) manufacturings), HP-7200 (DIC (strain) manufacturing), XD-1000 dicyclopentadiene-type epoxy resin such as (Japanese chemical drug (strain) manufacturings), EPPN-501H, 502H (above Japanese chemical drug (strain) manufacturing), 1031S triphenyl methane type Resins, epoxy such as (JapanEpoxy Resins Co., Ltd makes) etc.
Resol
As the resol among the present invention, specifically, can list PHENOLITE TD-2090, PHENOLITE2131, BESMOL CZ-256-A (above DIC (strain) manufacturing), Shonol BRG-555, Shonol BRG-556 (above clear and polymer (strain) manufacturing), Mirex XLC-4L, MirexXLC-LL (above Mitsui Chemicals (strain) manufacturing), PP-700, PP-1000, DPP-M, DPP-3H, DPA-145, DPA-155 (above Nippon Oil(Nippon Mitsubishi Oil) chemistry (strain) manufacturing), SK-Resin HE100C, SK-Resin HE510, SK-Resin 900 (above Air Water Inc. makes) etc.And these resol can use separately, perhaps multiple being used in combination.
Such resol need cooperate with following ratio: the phenol hydroxyl of resol be the Resins, epoxy of liquid state and is that the epoxy group(ing) of the mixture of solid-state Resins, epoxy count 0.3～1.0 with equivalence ratio at 40 ℃ with containing at 20 ℃.Its proportioning is beyond this scope the time, and in the de-smear operation, the surface of resin insulating barrier is by alligatoring.
Inorganic filler
As the inorganic filler among the present invention, can use barium sulfate, calcium sulfate, silicon-dioxide, clay, talcum, aluminium hydroxide etc.Because these materials are in the infrared absorption spectrum of FT-IR, be wave number 900～1300cm at the wavelength band of carbon dioxide laser
-1Scope in have absorption peak, distillation or decompose during laser processing can suppress the residue after the laser processing.
In these inorganic fillers, especially as (wave number 900～1300cm in the scope of above-mentioned optical maser wavelength band
-1) having strong absorption peak, the material of the residue of inorganic filler can list barium sulfate, calcium sulfate in the time of can suppressing via formation.Wherein, consider from the viewpoint that suppresses residue, more preferably barium sulfate.Also can use metal hydroxidess such as mica, aluminum oxide, titanium oxide, other metal oxides, aluminium hydroxide etc. in addition.And these inorganic fillers can use separately, perhaps make up multiple use.
The median size of inorganic filler is preferably below the 5 μ m.In addition, with respect to the solids component (Resins, epoxy (comprise and contain at 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy), resol) of hot curing resin composition, the use level of inorganic filler is that 20～100 quality % are ideal.With respect to the solids component of hot curing resin composition, during the use level less than 20 quality % of inorganic filler, use the film performances such as hardness of the resin insulating barrier that this resin combination makes insufficient, laser processing is also poor.
On the other hand,, when the use level of inorganic filler surpasses 100 quality %, may become between inorganic filler and resin and produce interface peel, cause the reason of crackle with respect to the solids component of hot curing resin composition.In addition, in this case, coating deteriorations such as the levelling property of hot curing resin composition, in the de-smear operation after laser processing, inorganic filler from the side of via or threshing on every side make the shape instability of via.With respect to the solids component of hot curing resin composition, the preferred use level of inorganic filler is 30～50 quality %.
The hot curing resin composition of present embodiment can also contain phenoxy resin, curing catalysts, additive, solvent etc.
Phenoxy resin
For the film-forming properties that improves hot curing resin composition can cooperate phenoxy resin.As phenoxy resin, can list 1256,4250,4275, YX8100BH30, YX6954BH30 (above Japan Epoxy Resins Co., Ltd makes), YP50, YP50S, YP55U, YP70, ZX-1356-2, FX-316, YPB-43C, ERF-001M30, YPS-007A30, FX-293AM40 (above Dongdu changes into (strain) and makes) etc.These phenoxy resins can use separately, perhaps make up multiple use.
Curing catalysts
As curing catalysts, can use Dyhard RU 100, aromatic amine, imidazoles, acid anhydrides etc.Specifically, can list imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dyhard RU 100, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, hydrazide compounds such as amine compound such as N-dimethyl benzyl amine, adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenylphosphine etc., in addition, as commercially available material, can list four countries and change into U-CAT3503N, U-CAT3502T (all being trade(brand)names of the block isocyanate compound of dimethyl amine), DBU, DBN, U-CATSA102, the U-CAT5002 (all being two ring type amidine compound and salt thereof) etc. that 2MZ-A, 2MZ-OK, 2PHZ, 2P4MHZ (all being trade(brand)names of imidazole compound), SAN-APRO Ltd. that industry (strain) makes make.These curing catalysts can use separately, perhaps make up multiple use.
The adaptation imparting agent
Can cooperate guanamines, methyl guanamines, benzoguanamine, trimeric cyanamide, 2 in the hot curing resin composition of the present invention, 4-diamino-6-methylacryoyloxyethyl-s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine/isocyanuric acid affixture, 2,4-diamino-6-methylacryoyloxyethyl-s-triazine/s-triazine derivatives such as isocyanuric acid affixture.Compound that these work as the adaptation imparting agent and thermal curing catalyst and with being preferred.
Additive
As additive, tinting material (can be any in pigment, dyestuff, the pigment), defoamer, rheology control agent etc. such as can use that phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, Viola crystallina, titanium oxide, carbon black, naphthalene are black.
Solvent
As solvent, can use ketone, aromatic hydrocarbon based, pure ethers, alcohol ether acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More particularly, can list ketones such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Pure ethers such as cellosolve, methylcyclohexane, ethylene glycol butyl ether, Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, dipropylene glycol methyl ether acetic ester, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester, propylene glycol butyl ether acetic ester, methyl lactate, ethyl lactate, n-Butyl lactate; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, petroleum naphtha, hydrogenation petroleum naphtha, solvent naphtha etc.These solvents can use separately, perhaps multiple being used in combination.
In addition, solvent can be the printing that is suitable for hot curing resin composition, the use level of film formation property.
The hot curing resin composition of present embodiment can be coated with on carrier film, and is dried and is made as the dry film that film curls.
Then, the manufacture method to the printed-wiring board (PWB) of the hot curing resin composition that uses present embodiment or dry film describes.
At first, the substrate that is formed with circuit is carried out pre-treatments such as degreasing, soft etching, hot curing resin composition is adjusted to the viscosity that is suitable for coating process, then it is applied on this substrate, make that dry film thickness is 10～50 μ m with solvent.Then, make the solvent evaporates drying (interim dry) of filming and being contained, form tack-free filming (resin layer) by the temperature that this substrate (coating is filmed) is applied 40～100 ℃.
As coating process, can use dip coating, flow coat method, rolling method, rod to be coated with methods such as method, silk screen print method, curtain Tu Fa.
Volatile dry method as solvent, can make with the following method: use heated air circulation type drying oven, IR stove, hot plate, convection furnace etc. to possess the device of the thermal source of the air heating mode of utilizing steam, and the method that the hot blast in the drying machine is contacted with substrate (coating is filmed) convection current; And the method for utilizing nozzle that the hot blast in the drying machine is blowed to substrate (coating is filmed).
In this operation, can on substrate, form film (resin layer) by the dry film lamination that will use hot curing resin composition of the present invention to make.
Then, the substrate of formation is filmed (resin layer) is 150～180 ℃ of down heating 30～120 minutes, makes to film (resin layer) thermofixation and form resin insulating barrier.
Then, (position of the part of exposing corresponding to the circuit of printed-wiring board (PWB)) irradiating laser forms via, and the circuit of printed-wiring board (PWB) is exposed in position that this resin insulating barrier is predesignated.At this moment, in via, there is the residual composition of not removing (glue slag).
And the soup that de-smears such as use permanganate solution are handled decomposes the de-smear of removing this glue slag to be handled, and makes and has used the hot curing resin composition of embodiments of the present invention or the printed-wiring board (PWB) of dry film.
Moreover, though present embodiment is only used and is formed printed-wiring board (PWB) at the substrate (single face substrate) that simultaneously has circuit, for double-sided substrate, multilager base plate, use hot curing resin composition to form resin insulating barrier too, and carry out the de-smear processing after utilizing laser to form via.
The circuit of the printed-wiring board (PWB) of such manufacturing is implemented gold-plated or carried out pre-solder flux (preflux) and handle.After this, electronic units such as the semi-conductor chip of encapsulation engage and carry on printed-wiring board (PWB) by golden projection, solder bump.
Embodiment
Be described more specifically the present invention by the following examples.
The modulation of hot curing resin composition
With each components matching shown in the table 1, and being pre-mixed the back with stirrer, to use 3 roller roller mills to carry out mixing, modulates the hot curing resin composition of embodiment 1～5, comparative example 1～7.
Table 1
* 1: bisphenol A type epoxy resin: at 20 ℃ is liquid Resins, epoxy (JapanEpoxy Resins Co., Ltd makes)
* 2: trihydroxybenzene methylmethane type Resins, epoxy (at 40 ℃ of Resins, epoxy for solid shape) is dissolved in the varnish (Japanese chemical drug (strain) manufacturing) that propylene glycol methyl ether acetate obtains in the mode of non-volatile content 80%
* 3: phenoxy resin (Japan Epoxy Resins Co., Ltd makes)
* 4:1-benzyl-2-phenylimidazole: curing catalysts (four countries change into industry (strain) manufacturing)
* 5: phenol novolac resin (resol) is dissolved in diethylene glycol monoethyl ether in the mode of non-volatile content 65% and the varnish that obtains (bright and change into (strain) make)
Estimate making with sample
Use applicator, the hot curing resin composition of synthetic like this embodiment 1～5, comparative example 1～7 being coated made dried thickness on the pet film of thickness 38 μ m is 30 μ m.And, make this each film (coating is filmed) drying at 40～100 ℃, produce the evaluation dry film of embodiment 1～5, comparative example 1～7.
And, use vacuum laminator ((strain) name mechanism is made made MVLP-500), under 0.8MPa, 110 ℃, 1 minute, the condition of 133.3Pa, each test of making is being formed with on circuit and the FR-4 substrate through the chemical grinding processing with the dry film heated lamination.Then, this substrate 170 ℃ of heating 1 hour, and is solidified to film and forms resin insulating barrier, produce the evaluation wiring board of embodiment 1～5, comparative example 1～7 thus.
Performance evaluation
The film test
For the evaluation dry film of embodiment 1～5, comparative example 1～7, carry out the bending of 90 degree, and estimate the pliability of film with following benchmark.
Zero: resin portion does not have crackle etc. unusual fully
△: the crackle that produces a little
*: resin portion cracks
This evaluation result is as shown in table 1.From the result shown in this table 1 as can be known,, can not confirm that resin portion has crackle etc. unusual, but crack in the comparative example 1～4, comparative example 7 for embodiment 1～5.
Anti-de-smear test
Wiring board is used in the evaluation of embodiment 1～5, comparative example 1～7, and (Rohm and Haas Co. makes at 60～80 ℃ of CIRCUPOSIT MLB Conditioner211, the organic solvent that comprises additive), flooded 3～10 minutes in the mixed solution of CIRCUPO SIT Z (Rohm and Haas Co. makes, and is the solution of principal constituent with sodium hydroxide), distilled water.And further should each estimate with wiring board in 65～85 ℃ of CIRCUPOSIT MLB Promoter213A (Rohm and Haas Co. manufacturing, with the sodium permanganate is the solution of principal constituent), (Rohm and Haas Co. makes CIRCUPOSIT MLB Promoter 213B, with sodium hydroxide is the solution of principal constituent), flooded 3～15 minutes in the mixed solution of distilled water, decompose and remove each and estimate dilated glue slag with wiring board.
Further, above-mentioned each evaluation is immersed in 43～51 ℃ of CIRCUPOSIT MLB neutralizing agents (Neutralizer) 216-2 with wiring board, and (Rohm and HaasCo. makes, with sulfuric acid is the solution of principal constituent), flooded 5～7 minutes in the mixed solution of distilled water, carry out neutralizing treatment.
After these are handled, observe with the condition of surface of the cured coating film (resin insulating barrier) of wiring board and with SEM (scanning electronic microscope) by visual each evaluation, and estimate according to following benchmark.
Zero: do not change fully
△: slight variations only
*: the alligatoring even peel off of filming
Evaluation result is as shown in table 1.From the result shown in this table 1 as can be known,, can not confirm fully to change,, confirm slight variations for comparative example 4,5 for embodiment 1～5, for comparative example 1～3,6, the alligatoring even peel off of filming.
Moreover the present invention is not limited to the above embodiments.
Claims (9)
1. a hot curing resin composition is characterized in that, comprises:
Resol;
Contain at 20 ℃ for liquid Resins, epoxy with at 40 ℃ of mixtures for solid-state Resins, epoxy; And
Inorganic filler,
And the proportioning of the phenol hydroxyl of described resol and the epoxy group(ing) of described mixture counts 0.3～1.0 with equivalence ratio.
2. hot curing resin composition according to claim 1 is characterized in that, and is with respect to Resins, epoxy total amount contained in this mixture, described 20 ℃ of ratio cooperations that are the Resins, epoxy of liquid state with 20～80 quality %.
3. hot curing resin composition according to claim 1 is characterized in that, with respect to the solids component of hot curing resin composition, the use level of described inorganic filler is 20～100 quality %.
4. hot curing resin composition according to claim 1 is characterized in that, the median size of described inorganic filler is below the 5 μ m.
5. a dry film is characterized in that, it has the dry coating that each described hot curing resin composition drying of claim 1～4 is formed.
6. printed-wiring board (PWB) is characterized in that having:
Form the substrate of circuit;
Be arranged at resin insulating barrier on this substrate, that constitute by the cured article of each described hot curing resin composition of claim 1～4; And
Be arranged in the via portion of this resin insulating barrier.
7. printed-wiring board (PWB) is characterized in that having:
Form the substrate of circuit;
Be arranged at resin insulating barrier on this substrate, that constitute by the cured article of the dry coating of the described dry film of claim 5; And
Be arranged in the via portion of this resin insulating barrier.
8. the manufacture method of a printed-wiring board (PWB) is characterized in that,
Be formed with each described hot curing resin composition of coating claim 1～4 on the substrate of circuit;
The dry hot curing resin composition that should be coated with;
This exsiccant hot curing resin composition is solidified so that resin insulating barrier to be set;
This resin insulating barrier is carried out laser radiation to wear via portion;
Remove the glue slag of this via portion.
9. the manufacture method of a printed-wiring board (PWB) is characterized in that,
At the dry coating that is formed with the described dry film of crimping claim 5 on the substrate of circuit;
The dry coating of this crimping is solidified so that resin insulating barrier to be set;
This resin insulating barrier is carried out laser radiation wear via portion;
Remove the glue slag of this via portion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-026308 | 2009-02-06 | ||
| JP2009026308A JP2010180355A (en) | 2009-02-06 | 2009-02-06 | Thermosetting resin composition, dry film, printed wiring board and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101798438A true CN101798438A (en) | 2010-08-11 |
Family
ID=42594290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910163613A Pending CN101798438A (en) | 2009-02-06 | 2009-07-30 | Heat curable resin composition, dry film and printed wiring board and method for preparing the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2010180355A (en) |
| KR (1) | KR101113389B1 (en) |
| CN (1) | CN101798438A (en) |
| TW (1) | TW201030082A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102796348A (en) * | 2011-05-27 | 2012-11-28 | 太阳油墨制造株式会社 | Thermosetting resin composition, dry film and printed circuit board (pcb) |
| CN104448693A (en) * | 2014-11-20 | 2015-03-25 | 深圳市亚太兴实业有限公司 | Epoxy resin composition and preparation method and application thereof |
| CN106364067A (en) * | 2016-08-29 | 2017-02-01 | 上海国纪电子材料有限公司 | P10 copper-clad laminate |
| CN106381111A (en) * | 2016-08-29 | 2017-02-08 | 上海国纪电子材料有限公司 | Glue solution for P10 copper clad laminate |
| CN106398116A (en) * | 2016-08-29 | 2017-02-15 | 上海国纪电子材料有限公司 | Preparation method of adhesive solution used for P10 copper clad laminate |
| CN106393934A (en) * | 2016-08-29 | 2017-02-15 | 上海国纪电子材料有限公司 | Prepreg used for P10 copper clad laminate |
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| JP2013012729A (en) * | 2011-05-27 | 2013-01-17 | Taiyo Ink Mfg Ltd | Dry film and printed wiring board using the same |
| JP2013115368A (en) * | 2011-11-30 | 2013-06-10 | Rohm Co Ltd | Led module |
| JP6268753B2 (en) * | 2012-05-24 | 2018-01-31 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product, and laminate for electric / electronic circuit |
| JP7320191B2 (en) * | 2019-08-01 | 2023-08-03 | 大日本印刷株式会社 | Decorative sheet and display device with decorative sheet |
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| JP3848229B2 (en) * | 2002-09-10 | 2006-11-22 | 太陽インキ製造株式会社 | Insulating resin composition and printed wiring board using the same |
| JP2004161828A (en) * | 2002-11-11 | 2004-06-10 | Nippon Steel Chem Co Ltd | Resin composition for forming film, and film adhesive |
| JP4620967B2 (en) | 2004-04-26 | 2011-01-26 | 太陽ホールディングス株式会社 | Thermosetting resin composition for permanent hole filling |
| JP4992396B2 (en) * | 2005-11-29 | 2012-08-08 | 味の素株式会社 | Resin composition for interlayer insulation layer of multilayer printed wiring board |
| JP2008037957A (en) * | 2006-08-03 | 2008-02-21 | Tamura Kaken Co Ltd | Thermosetting resin composition, b-stage resin film and multilayer build-up substrate |
| JP2009231790A (en) * | 2008-02-27 | 2009-10-08 | Ajinomoto Co Inc | Manufacturing method of multilayer printed wiring board |
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2009
- 2009-02-06 JP JP2009026308A patent/JP2010180355A/en active Pending
- 2009-07-29 TW TW98125528A patent/TW201030082A/en unknown
- 2009-07-30 CN CN200910163613A patent/CN101798438A/en active Pending
- 2009-07-30 KR KR1020090069872A patent/KR101113389B1/en active IP Right Grant
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| CN102796348A (en) * | 2011-05-27 | 2012-11-28 | 太阳油墨制造株式会社 | Thermosetting resin composition, dry film and printed circuit board (pcb) |
| CN104448693A (en) * | 2014-11-20 | 2015-03-25 | 深圳市亚太兴实业有限公司 | Epoxy resin composition and preparation method and application thereof |
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| CN106398116A (en) * | 2016-08-29 | 2017-02-15 | 上海国纪电子材料有限公司 | Preparation method of adhesive solution used for P10 copper clad laminate |
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| CN106364067B (en) * | 2016-08-29 | 2021-10-12 | 上海国纪电子材料有限公司 | P10 copper-clad plate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101113389B1 (en) | 2012-03-05 |
| JP2010180355A (en) | 2010-08-19 |
| KR20100090620A (en) | 2010-08-16 |
| TW201030082A (en) | 2010-08-16 |
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Open date: 20100811 |