KR20100090620A - Heat curable resin composition, dry film and printed wiring board and method for preparing the same - Google Patents

Abstract

PURPOSE: A thermosetting resin composition, a dry film and a printed wiring board including thereof, and a manufacturing method thereof are provided to obtain a resin insulating layer with the desmear property and the desmear resistance. CONSTITUTION: A thermosetting resin composition contains a phenol resin, a mixture including an liquid epoxy resin at 20 deg C and a liquid epoxy resin at 40 deg C, and an inorganic filler. A phenolic -OH of the phenol resin and an epoxy group of the mixture has a combination rate of 0.3~1. A printed circuit board comprises a substrate including a circuit, a resin insulating layer formed with a hardened material of the thermosetting resin composition, and a via hole unit penetrating the resin insulating layer.

Description

Thermosetting resin composition, dry film and printed wiring board and manufacturing method thereof {HEAT CURABLE RESIN COMPOSITION, DRY FILM AND PRINTED WIRING BOARD AND METHOD FOR PREPARING THE SAME}

The present invention relates to a thermosetting resin composition, a dry film and a printed wiring board using the same, and a method for producing the same.

When mounting an electronic component on the printed wiring board used for an electronic device etc., it is common to provide a resin insulation layer, for example a soldering resist layer, in the area | region except the connection hole of the board | substrate with a circuit from the following objectives. That is, the purpose is to prevent solder from adhering to unnecessary portions of the board or printed wiring board, and to prevent the conductors of the circuit provided on the board or printed wiring board from being exposed and corroding the circuit by oxidation or humidity. .

And when a soldering resist pattern (solder resist layer) is formed on a board | substrate using a thermosetting resin composition, a laser hole is irradiated to this soldering resist pattern, and the via hole for mounting is formed. In the case where a fine solder resist pattern is required, a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like is used as the laser light source.

In addition, in this specification, the board in which the circuit is formed but in which the resin insulating layer is not formed is simply called "substrate." In addition, the board in which both the circuit and the resin insulation layer are formed is called "printed wiring board."

When forming the via hole by laser light, the components of the solder resist layer (hereinafter referred to as "smear") are not decomposed and removed, and remain on the bottom or inside of the via hole (hereinafter referred to as "in the via hole"). The phenomenon occurs. In this way, if smears remain in the via holes, in the plating process thereafter, there are problems such as unplated portions on the printed wiring boards, or poor bonding when mounting electronic components on the printed wiring boards. Therefore, what is called a desmear process which removes this desmear is required (henceforth a process which performs a desmear process is called "a desmear process").

Generally in the desmear process, the wet method which swells a smear with a concentrated alkali solution, and then dissolves and removes it with a permanganate solution is used.

However, in the case of performing the desmear process using the wet method, if the smear remaining in the via hole is to be sufficiently decomposed and removed, the surface of the solder resist layer in the portion where the via hole is not formed by a chemical solution such as a concentrated alkali solution or a permanganate solution is The problem arises that it matches, or that these solder resist layers peel from a printed wiring board. On the other hand, when trying to suppress the roughening phenomenon and peeling phenomenon of a soldering resist layer, there exists a problem that smear cannot fully be removed (desmear property falls) on the contrary.

As a conventional technique to solve this problem, a method of forming a resin insulating layer having a two-layer structure on a substrate has been proposed. This forms a layer containing a resin composition in which the smear is easily decomposed and removed (easily desmeared) in the solder resist layer (first layer) in contact with the substrate remaining as a smear, and the surface layer (second layer) in contact with the first layer. ) Is a method of forming a layer containing a resin composition in which smear is hardly decomposed and removed (which is difficult to desmear) (for example, refer to Patent Document 1).

However, there exists a problem that process cost goes up in order to form the resin insulation layer of a two-layer structure as this technique.

Prior art literature

<Patent Documents>

<Patent Document 1> Japanese Unexamined Patent Publication No. 2004-240233 (paragraph 0008, etc.)

As mentioned above, as a resin insulating layer using a thermosetting resin composition, the property which is easy to desmear process (henceforth "desmear resistance"), and the property which is hard to desmear process (henceforth "desmear resistance") are made compatible. Is required.

An object of the present invention is to provide a thermosetting resin composition capable of obtaining a resin insulating layer compatible with desmear and desmear resistance, a dry film, a printed wiring board, and a manufacturing method using the same.

The thermosetting resin composition of this invention contains the mixture containing a phenol resin, a liquid epoxy resin at 20 degreeC, and an epoxy resin solid at 40 degreeC, an inorganic filler, The phenolic hydroxyl group of the said phenol resin, and the epoxy group of the said mixture The compounding ratio of is characterized in that 0.3 to 1.0 in equivalent ratio.

Thus, by specifying the blending ratio in the equivalent ratio of the phenolic hydroxyl group and the epoxy group, the smear remaining in the via hole in the desmear step can be sufficiently decomposed and removed, and the roughening phenomenon and the peeling phenomenon of the resin composition layer can be suppressed. A resin insulating layer capable of achieving both desmear and desmear resistance can be obtained.

Moreover, by using the mixture containing the epoxy resin which is a liquid at 20 degreeC, and the epoxy resin which is solid at 40 degreeC, desmear resistance and a desmear resistance are compatible, and the resin insulating layer which has favorable film characteristics can be obtained. .

As mentioned above, the thermosetting resin composition of this invention can be used suitably for a dry film resist use.

Moreover, the dry film of this invention has a dry coating film of the said thermosetting resin composition, It is characterized by the above-mentioned.

By such a configuration, the thermosetting resin composition and the dry film of the present invention can easily form a resin insulating layer capable of achieving both desmear and desmear resistance on a substrate.

Moreover, the printed wiring board of this invention has a board | substrate with which a circuit is formed, the resin insulating layer which consists of hardened | cured material of the above-mentioned thermosetting resin composition provided in this board | substrate, and the via-hole part provided in this resin insulating layer, It is characterized by the above-mentioned. .

Furthermore, the printed wiring board of this invention has a board | substrate with which a circuit is formed, the resin insulation layer which consists of hardened | cured material of the dry coating film of the dry film mentioned above provided in this board | substrate, and the via hole part provided in this resin insulation layer, It is characterized by the above-mentioned. It is done.

By such a structure, since the roughening of the surface of the resin insulating layer is suppressed at the desmear process, sufficient conductive is obtained at the connection part of an electronic component, and the printed wiring board of this invention stably simplifies a highly reliable printed wiring board. You can get it.

Moreover, the manufacturing method of the printed wiring board of this invention apply | coats the thermosetting resin composition mentioned above to the board | substrate with a circuit, dried this apply | coated thermosetting resin composition, hardens this dry thermosetting resin composition, and installs a resin insulating layer, The resin insulating layer is laser irradiated and drilled through the via hole portion to remove smear from the via hole portion.

Moreover, in the manufacturing method of the printed wiring board of this invention, the dry coating film of the dry film mentioned above was crimped | bonded to the board | substrate with a circuit, hardening this crimped dry coating film, a resin insulating layer is provided, and this resin insulating layer is laser-irradiated, It installs through a via hole part, It is characterized by removing the smear of this via hole part.

According to this structure, according to the manufacturing method of the printed wiring board of this invention, roughening of the surface of a resin insulating layer is suppressed at the desmear process, sufficient conduction is obtained in the connection part of an electronic component, and high reliability printing is carried out. A wiring board can be manufactured simply and stably.

By using the thermosetting resin composition and the dry film of this invention, the resin insulating layer which can satisfy desmear and desmear resistance can be obtained.

In addition, since the roughness of the surface of the resin insulating layer is suppressed in the desmear process and sufficient conduction is obtained in the connection part of an electronic component, the printed wiring board of this invention can obtain a reliable printed wiring board stably.

Moreover, according to the manufacturing method of the printed wiring board of this invention, since the roughening of the surface of the resin insulating layer is suppressed at the desmear process, and sufficient conduction is obtained in the connection part of an electronic component, a highly reliable printed wiring board is stable. It can be prepared by.

Hereinafter, although an example of embodiment of this invention is described, this invention is not limited to this.

The thermosetting resin composition of this invention contains the mixture containing a phenol resin, a liquid epoxy resin at 20 degreeC, and an epoxy resin solid at 40 degreeC, an inorganic filler, The phenolic hydroxyl group of the said phenol resin, and the epoxy group of the said mixture The compounding ratio of is characterized in that 0.3 to 1.0 in equivalent ratio.

Moreover, about the mixture containing the epoxy resin which is liquid at 20 degreeC, and the epoxy resin which is solid at 40 degreeC, 20-80 mass% of liquid epoxy resin at 20 degreeC with respect to the total amount of epoxy resins contained in the said mixture, More preferably, It is preferable to mix | blend in the ratio of 40-60 mass%. When the compounding quantity of the epoxy resin which is liquid at 20 degreeC is less than 20 mass% with respect to the epoxy resin total amount contained in the said mixture, film forming of a thermosetting resin composition becomes difficult and it is unpreferable. Moreover, when the compounding quantity of the epoxy resin which is liquid at 20 degreeC exceeds 80 mass% with respect to the epoxy resin total amount contained in the said mixture, since the surface of the insulating layer formed using the thermosetting resin composition will become easy to harmonize, it is not preferable. not.

Here, the determination method of the "liquid phase" as described in this specification is demonstrated.

The determination of the liquid phase is carried out in accordance with the second "Method for confirming the liquid phase" of the second attached sheet of the Holy Spirit (Pyeonghwa First Year Autonomous Spirit No. 1) concerning the testing and molding of dangerous goods.

(1) device

Constant temperature water bath: Agitator, heater, thermometer, thermostat (with temperature control at ± 0.1 ° C) and having a depth of 150 mm or more.

In addition, in this embodiment and the Example, it is an apparatus which judges the "liquid phase" of an epoxy resin, and it is a low temperature constant temperature water tank (model BU300: Yamato Chemical Co., Ltd. product, hereafter.) And an input-type thermostat thermomate (model). BF500: manufactured by Yamato Chemical Co., Ltd., the same as below.), But any apparatus capable of the same adjustment as these can be used.

In the present example, about 22 liters of tap water was put in a low temperature constant temperature water bath, and the power supply of the assembled thermomate was put into this, and it was set to set temperature (20 degreeC or 40 degreeC). And it adjusted finely with the thermomate so that the water temperature of the low temperature constant temperature water tank might become set temperature +/- 0.1 degreeC.

examiner:

As a test tube, as shown in FIG. 1, the test tube 10a for liquid phase determination and the test tube 10b for temperature measurement are used.

The liquid crystal test tube 10a is a cylindrical transparent glass test tube having a bottom diameter of 30 mm and a height of 120 mm, and a 55 mm height partial mark 11 (hereinafter referred to as "A line") at the bottom of the tube. A mark 12 (hereinafter referred to as "B line") is attached to a height of 85 mm from the bottom of the tube, and the entrance of the test tube is sealed with a rubber stopper 13a.

In addition, the test tube 10b for temperature measurement is the same size as the test tube 10a for liquid phase determination, and A-line and B-line are attached to the same position as this. The test tube 10b for temperature measurement is sealed with a rubber stopper 13b having an opening for inserting and supporting a thermometer in the center thereof, and the inlet of the test tube is sealed, and the thermometer 14 is inserted into the rubber stopper 13b. have.

As the thermometer 14, although the thing for the freezing point measurement (SOP-58 scale range 20-50 degreeC) prescribed | regulated by JIS B7410 (1982) "glass thermometer for petroleum testing" can be used, the temperature range of 0-50 degreeC can be measured. If it exists, it can be used as the thermometer 14.

(2) Procedure of conducting the test

The epoxy resin used as a sample is left to stand for 24 hours or more under atmospheric pressure of the temperature of 20 +/- 5 degreeC. Thereafter, this sample is placed up to the line A in each of the liquid crystal determination test tube 10a shown in FIG. 1 (a) and the temperature measurement test tube 10b shown in FIG. 1 (b). The test tubes 10a and 10b are erected in a low temperature constant temperature water tank so that each B line is under the water surface of the tap water put in the low temperature constant temperature water tank. In addition, the thermometer 14 is inserted in the rubber stopper 13b so that its lower end is 30 mm below the A line.

After the temperature of the sample reaches the set temperature ± 0.1 ° C, the state is maintained for 10 minutes. Thereafter, the liquid phase determination test tube 10a is taken out from the low temperature constant temperature bath and immediately falls horizontally on a horizontal test bench. And the time which the front-end | tip (the entrance side of a test tube) of the sample liquid level in the test tube 10a moved from A line to B line is measured and recorded with a stopwatch. The sample within 90 seconds of this measured time is determined to be "liquid phase", and the sample with the measured time exceeding 90 seconds is determined as "solid state (solid)".

(Epoxy Resin Liquid at 20 ° C)

Bisphenol A type epoxy resins, such as 828 (made by Japan Epoxy Resin Co., Ltd.), YD-128 (made by Toto Kasei Co., Ltd.), 840, 850 (above, DIC Co., Ltd. make) as a liquid epoxy resin at 20 degreeC Bisphenol F-type epoxy such as 806, 807 (above, Japan epoxy resin), YDF-170 (Toto Kasei Co., Ltd.), 830, 835, N-730A (above, DIC Corporation) A mixture of bisphenol A and bisphenol F, such as resin and ZX-1059 (manufactured by Toto Kasei Co., Ltd.), YX-8000, 8034 (above, manufactured by Japan Epoxy Resin Co., Ltd.) ST-3000 (manufactured by Toto Kasei Co., Ltd.) Hydrogenated bisphenol A epoxy resins, such as these, are mentioned.

(Epoxy resin solid at 40 ° C)

As epoxy resin solid at 40 degreeC, Epiclone 1050, copper 3050 (above, DIC Corporation make), Epicoat 1001, copper 1002, copper 1003 (above, Japan Epoxy Resin Co., Ltd. make), Etototo YD-011 Bisphenol A type epoxy resins such as YD-012 (above, manufactured by Toto Kasei Co., Ltd.), bisphenol F type epoxy resins such as Efototo YDF-2001, copper 2004 (above, manufactured by Toto Kasei Co., Ltd.), Bisphenol S type epoxy resins such as brominated bisphenol A type epoxy resins such as YDB-400 (manufactured by Toto Kasei Co., Ltd.), EPICLON 152, and 153 (manufactured by DIC Corporation), and EXA-1514 (manufactured by DIC Corporation); N-770, 775 (above, manufactured by DIC Corporation), EPPN-201H, RE-306 (above, manufactured by Nippon Kayaku Co., Ltd.), 152, 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.) Phenolic novolac type epoxy resin, EOCN-102S, 103S, 104S (above, Nippon Kayaku Co., Ltd.), YDCN-701, 702, 703, 704 (above, Toto Kasei Co., Ltd. product), N-660, Cresol novolac types such as 670, 680 (above, manufactured by DIC Corporation) Bisphenol A novolak-type epoxy resins, such as Foxy resin, 157S70 (made by Japan Epoxy Resin Co., Ltd.), N-865 (made by DIC Co., Ltd.), YX-4000 (made by Japan Epoxy Resin Co., Ltd.), NC-3000 Biphenyl type epoxy resins, such as (made by Nippon Kayaku Co., Ltd.), naphthalene type epoxy resins, such as NC-7000L (made by Nippon Kayaku Co., Ltd.), HP-7200 (made by DIC Corporation), XD-1000 Triphenyl such as dicyclopentadiene type epoxy resins, such as (made by Nippon Kayaku Co., Ltd.), EPPN-501H, 502H (above, Nippon Kayaku Co., Ltd. make), 1031S (Japan Epoxy Resin Co., Ltd. make) Methane type epoxy resin etc. are mentioned.

(Phenolic resin)

Specific examples of the phenol resin in the present invention include phenolite TD-2090, copper 2131, Vesmol CZ-256-A (above, manufactured by DIC Co., Ltd.), siounol BRG-555, copper BRG-556 (above, Showa Kobunshi Co., Ltd.), Mirex XLC-4L, East XLC-LL (above, Mitsui Chemical Industries, Ltd.), PP-700, East 1000, DPP-M, East 3H, DPA-145, Copper 155 (above, manufactured by Shin-Nipbon Sekiyu Chemical Co., Ltd.), SK-resin HE100C, SK-resin HE510, copper 900 (above, manufactured by Air Water Co., Ltd.), and the like. And these phenol resins can be used individually or in combination of several types.

It is necessary to mix | blend such phenol resin in the ratio which the epoxy group of the mixture containing the phenolic hydroxyl group of phenol resin and the epoxy resin which is liquid at 20 degreeC, and the epoxy resin which is solid at 40 degreeC will be 0.3-1.0 in equivalent ratio. If this compounding ratio is out of this range, the surface of a resin insulating layer will be roughened in a desmear process.

(Inorganic filler)

As the inorganic filler in the present invention, barium sulfate, calcium sulfate, silica, clay, talc, aluminum hydroxide and the like can be used. In the infrared absorption spectrum by FT-IR, they have an absorption peak in the range of the wave number 900 to 1300 cm ^-1 , which is the wavelength band of the carbon dioxide laser, and are sublimated or decomposed during laser processing, so that the residue after laser processing can be suppressed. Can be.

Among these inorganic fillers, particularly those having a strong absorption peak within the above-described laser wavelength range (wavelengths 900 to 1300 cm ⁻¹ ) and capable of suppressing the residue of the inorganic filler during the formation of via holes, barium sulfate or calcium sulfate is used. Can be mentioned. Among these, barium sulfate is more preferable from a viewpoint of residue suppression. In addition, a metal hydroxide, such as a miter, alumina, titanium oxide, another metal oxide, and aluminum hydroxide, can also be used. And these inorganic fillers can be used individually or in combination of several types.

It is preferable that the average particle diameter of an inorganic filler is 5 micrometers or less. In addition, the compounding quantity is 20-100 mass% with respect to solid content (the mixture containing an epoxy resin which is a liquid at 20 degreeC, and an epoxy resin which is solid at 40 degreeC), and a phenol resin of a thermosetting resin composition). desirable. When the compounding quantity of an inorganic filler is less than 20 mass% with respect to solid content of a thermosetting resin composition, coating-film performances, such as hardness of the resin insulation layer manufactured using this resin composition, are inadequate, and laser workability is also bad.

On the other hand, when the compounding quantity of an inorganic filler exceeds 100 mass% with respect to solid content of a thermosetting resin composition, interface peeling may arise between an inorganic filler and resin, and there exists a possibility of causing a crack. In addition, in this case, applicability | paintability, such as the leveling property of a thermosetting resin composition, deteriorates, an inorganic filler detach | desorbs in the side surface and periphery of a via hole in the desmear process after laser processing, and the shape of a via hole becomes unstable. The more preferable compounding quantity of an inorganic filler is 30-50 mass% with respect to solid content of a thermosetting resin composition.

The thermosetting resin composition of this embodiment may contain a phenoxy resin, a curing catalyst, an additive, a solvent, etc.

(Phenoxy resin)

Phenoxy resin can be mix | blended in order to improve the film forming property of a thermosetting resin composition. As phenoxy resin, 1256, 4250, 4275, YX8100BH30, YX6954BH30 (above, Japan Epoxy Resin Co., Ltd.), YP50, YP50S, YP55U, YP70, ZX-1356-2, FX-316, YPB-43C, ERF-001M30 YPS-007A30, FX-293AM40 (above, Toto Kasei Co., Ltd. product) etc. are mentioned. These phenoxy resins can be used individually or in combination of multiple types.

(Curing catalyst)

Dicyandiamide, aromatic amine, imidazole, acid anhydride, etc. can be used as a curing catalyst. Specifically, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide and sebacic acid dihydrazide; As commercially available phosphorus compounds such as triphenylphosphine, 2MZ-A, 2MZ-OK, 2PHZ, and 2P4MHZ (all are brand names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and San Apro Co., Ltd. U-CAT3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) and the like. These curing catalysts can be used individually or in combination of multiple types.

(Adhesion imparting agent)

The thermosetting resin composition of the present invention includes guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-dia Mino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine S-triazine derivatives, such as isocyanuric acid adduct, can also be mix | blended. It is preferable to use together the compound which functions also as these adhesive imparting agents with a thermosetting catalyst.

(additive)

Examples of the additive include colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black (foaming agents, dyes, and pigments), antifoaming agents, and rheology. A modifier etc. can be used.

(solvent)

As the solvent, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like can be used. More specifically, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, methyl lactate, ethyl lactate, and butyl lactate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like. These solvents can be used individually or in combination of multiple types.

Moreover, a solvent can be made into the compounding quantity suitable for the printability and film formation property of a thermosetting resin composition.

The thermosetting resin composition of this embodiment is apply | coated on a carrier film, it can be set as the dry film wound up and wound as a film.

Next, the manufacturing method of the printed wiring board using the thermosetting resin composition or dry film of this embodiment is demonstrated.

First, after pretreatment, such as degreasing, soft etching, etc., is performed to the board | substrate formed with a circuit, the thermosetting resin composition adjusted with the solvent with the viscosity suitable for the application | coating method is apply | coated to this board | substrate so that it may become 10-50 micrometers in dry film thickness. Next, a tack free coating film (resin layer) is formed by applying a temperature of 40 to 100 ° C. to the substrate (coating film) to volatilize (temporarily dry) the solvent contained in the coating film.

As the coating method, methods such as dip coating, flow coating, roll coating, bar coater, screen printing and curtain coating can be used.

As the volatilization drying method of the solvent, hot air in the dryer is countercurrently contacted with a substrate (coated coating film) by using a hot air circulation drying furnace, an IR furnace, and a heat source of an air heating system such as a hot plate or a convection oven. The method and the method of spraying the hot air in a dryer to a board | substrate (coating coating film) with a nozzle can be used.

In this process, a coating film (resin layer) can also be formed by laminating the dry film manufactured using the thermosetting resin composition of this invention on a board | substrate.

Next, the board | substrate with which the coating film (resin layer) was formed is heated at 150-180 degreeC for 30 to 120 minutes, and a resin insulating layer is formed by thermosetting a coating film (resin layer).

Next, a via hole is formed by irradiating a laser to a predetermined position (a position corresponding to a portion of the printed wiring board to expose the circuit) of the resin insulating layer to expose the circuit of the printed wiring board. At this time, there is a component (smear) remaining in the via hole and not removed.

And the desmear process which decomposes | disassembles this smear using chemical liquids of desmear processes, such as a permanganate solution, is performed, and the printed wiring board using the thermosetting resin composition or dry film of embodiment of this invention is manufactured.

In addition, in this embodiment, although the printed wiring board was formed using the board | substrate (one side board | substrate) which has a circuit only on one side, also in a double-sided board | substrate and a multilayer board | substrate, the resin insulating layer was formed using the thermosetting resin composition similarly, After forming a via hole with a laser, a desmear process is performed.

The printed wiring board thus produced is subjected to gold plating on the circuit or preflux treatment. After that, electronic components such as semiconductor chips to be mounted are bonded to the printed wiring board by gold bumps or solder bumps and mounted thereon.

<Examples>

Hereinafter, an Example demonstrates this invention concretely.

(Preparation of thermosetting resin composition)

Each component shown in Table 1 was mix | blended, and it premixed with the stirrer, and knead | mixed using the triaxial roll mill, and produced the thermosetting resin composition of Examples 1-5 and Comparative Examples 1-7.

* 1: Bisphenol A epoxy resin: Liquid epoxy resin (made by Japan Epoxy Resin Co., Ltd.) at 20 degreeC.

* 2: Varnish (The Nippon Kayaku Co., Ltd. product) which melt | dissolved trihydroxy phenylmethane type epoxy resin (epoxy resin solid at 40 degreeC) to volatile matter 80%.

* 3: phenoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)

* 4: 1-benzyl-2-phenylimidazole: curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

* 5: Varnish which melt | dissolved phenol novolak resin (phenol resin) with diethylene glycol monoethyl ether so that it might be 65% of non volatile matter (made by Meiwa Kasei Co., Ltd.).

Preparation of Samples for Evaluation

The thermosetting resin compositions of Examples 1 to 5 and Comparative Examples 1 to 7 thus prepared were applied to a polyethylene terephthalate film having a thickness of 38 μm so that the film thickness after drying was 30 μm, respectively, using an applicator. And each said film (coating coating film) was dried at 40-100 degreeC, and the dry films for evaluation of Examples 1-5 and Comparative Examples 1-7 were manufactured.

And each test dry film manufactured was formed into a circuit under the conditions of 0.8 MPa, 110 degreeC, 1 minute, and 133.3 Pa using the vacuum laminator (MVLP-500 by Meisei Seisakusho Co., Ltd.), and the chemical polishing process was carried out. Heat laminated to FR-4 substrate. Then, the board | substrate for evaluation of Examples 1-5 and Comparative Examples 1-7 was manufactured by heating this board | substrate at 170 degreeC for 1 hour, hardening a coating film, and forming a resin insulating layer.

(Performance evaluation)

(Film test)

About the dry films for evaluation of Examples 1-5 and Comparative Examples 1-7, 90 degree | times were bent and the flexibility of the film was evaluated on the following references | standards.

(Circle): There was no abnormality, such as a crack, in a resin part.

△: some crack occurs

X: crack generate | occur | produced in a resin part

The evaluation results are shown in Table 1. As apparent from the results shown in Table 1, no abnormalities such as cracks were observed in the resin portions in Examples 1 to 5, but cracks occurred in Comparative Examples 1 to 4 and Comparative Example 7.

(Measuring resistance test)

Examples 1 to 5 and the wiring boards for evaluation of Comparative Examples 1 to 7 were used for the Succuit MLB Conditioner 211 (an organic solvent containing an additive made by Rohm and Haas Co., Ltd.) and Succuit Z (manufactured by Rohm and Haas Co., sodium hydroxide). 3 to 10 minutes was immersed in the mixed liquid of the solution containing a main component) and distilled water at 60-80 degreeC. In addition, each of the evaluation wiring boards was mainly composed of the Succuit MLB promoter 213A (manufactured by Rohm and Haas, main solution of sodium permanganate) and the Succuit MLB promoter 213B (manufactured by Rohm and Haas company, sodium hydroxide as the main component. Immersed smear of each evaluation wiring board was decomposed and removed by immersing it in a mixed solution of one solution) and distilled water at 65 to 85 ° C for 3 to 15 minutes.

In addition, each said wiring board for evaluation was immersed for 5 to 7 minutes at 43-51 degreeC in the liquid mixture of the Succuit MLB Neutralizer 216-2 (Rom & Haas Co., Ltd., the sulfuric acid based solution), and distilled water, and neutralized. Treated.

After these treatments, the surface state of the cured coating film (resin insulation layer) of each evaluation wiring board was observed by visual observation and SEM (scanning electron microscope), and the evaluation was made according to the following criteria.

○: no change at all

△: barely visible change

×: The coating film is roughened or peeled off

The evaluation results are shown in Table 1. As apparent from the results shown in Table 1, no change was observed in Examples 1 to 5, but barely changed in Comparative Examples 4 and 5, and in Comparative Examples 1 to 3 and 6, the coating was roughened or peeled off. It was found to be.

In addition, this invention is not limited to the above-mentioned embodiment.

1 is a schematic side view showing two test tubes used for liquid phase determination of an epoxy resin.

<Brief description of symbols for the main parts of the drawings>

10a... Test tube for liquid phase determination

10b... Test tube for temperature measurement

11... Mark (A line)

12... Mark line (B line)

13a, 13b... Rubber stopper

14... thermometer

Claims (6)

Phenolic resin, A mixture comprising an epoxy resin liquid at 20 ° C. and an epoxy resin solid at 40 ° C., Contains inorganic fillers, The compounding ratio of the phenolic hydroxyl group of the said phenol resin and the epoxy group of the said mixture is 0.3-1.0 in equivalence ratio, The thermosetting resin composition characterized by the above-mentioned. It consists of a dry coating film obtained by drying the thermosetting resin composition of Claim 1, The dry film characterized by the above-mentioned. A substrate on which a circuit is formed, The resin insulating layer which consists of hardened | cured material of the thermosetting resin composition of Claim 1 provided in this board | substrate, A printed wiring board having a via hole provided in the resin insulating layer. A substrate on which a circuit is formed, Resin insulation layer which consists of hardened | cured material of the dry coating film of the dry film of Claim 2 provided in this board | substrate, The printed wiring board which has a via-hole part provided in this resin insulating layer. The thermosetting resin composition of Claim 1 is apply | coated to the board | substrate with a circuit, This coated thermosetting resin composition is dried, Curing this dry thermosetting resin composition, and providing a resin insulating layer, The resin insulating layer was laser irradiated to drill through holes, and The smear of this via-hole part is removed, The manufacturing method of the printed wiring board characterized by the above-mentioned. The dry coating film of the dry film of Claim 2 is crimped | bonded to the board | substrate with a circuit, The compressed dry coating film is cured to provide a resin insulating layer, The resin insulating layer was laser irradiated to drill through holes, and The smear of this via-hole part is removed, The manufacturing method of the printed wiring board characterized by the above-mentioned.

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