KR101712338B1 - Method for manufacturing printed circuit board - Google Patents

Abstract

A solder resist layer for forming an opening with a small opening diameter for the purpose of solder bonding with a semiconductor chip or the like is intended to have a high internal resistance and an opening with a relatively large opening diameter for connection with a circuit such as a mother board or an electronic component Provided is a printed wiring board manufacturing method capable of forming openings in a solder resist layer to be formed with high working efficiency.
Characterized in that a solder resist layer is formed on both sides of a circuit board and opening formation in the solder resist layer formed on one side is performed by photolithography and opening formation in the solder resist layer formed on the other side is performed by laser irradiation By weight based on the total weight of the printed wiring board.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a printed wiring board and, more particularly, to an improvement of a technique for forming an opening in a solder resist layer.

As a method of forming a pattern of a solder resist by photolithography, there is a problem in that it can not sufficiently cope with thinning and micro-wiring in a recent circuit board and can not sufficiently cope with an increase in the temperature of the solder reflow caused by lead-freeization . This is because photo-solder resists require photosensitivity and developability, so that raw materials that can be used are limited, and cured products capable of sufficiently satisfying heat resistance and mechanical characteristics can not be obtained. Particularly, in the case of a via, which is an opening for connecting with a semiconductor chip, a fine process such as an opening diameter of 100 탆 or less is required, so that the solder resist is required to have high photosensitivity and developability, It is pointed out that cracks are generated when thermal shock is applied after forming the openings. In order to cope with such a problem, for example, in Patent Documents 1 to 4, a thermosetting resin composition is used as the material of the solder resist, and a laser is used as a method of forming the opening, Thereby forming a via hole in the via hole. That is, when such a method is used, the solder resist is not required to have photosensitivity and developability, so that a material having high heat resistance and mechanical characteristics can be selected.

However, in the semiconductor package substrate or the like, the opening diameter of the opening portion is relatively small in the solder resist layer provided on the side on which the semiconductor chip is mounted, so that the laser can be appropriately perforated. However, , The opening diameter of the opening for connecting to the mother board or the like reaches 200 mu m to several millimeters in the solder resist layer, so that a very large number of laser shots are required to be formed with a laser.

[Patent Document 1] JP-A-2000-244125

[Patent Document 2] JP-A-2004-240233

[Patent Document 3] JP-A-2005-347429

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2006-278530

A problem to be solved by the present invention is to provide a method for manufacturing a solder resist of a printed wiring board which is intended to improve the internal resistance of a solder resist layer in which an opening with a small opening diameter for solder bonding with a semiconductor chip or the like is formed, Which can form an opening in a solder resist layer which is required to form an opening of a comparatively large opening diameter for connection with a circuit or an electronic component of a printed wiring board.

As a result of intensive studies for solving the above problems, the present inventors have found that a circuit such as a mother board or the like can be formed by using a laser to form an opening in a solder resist layer formed on one side of a printed wiring board, It has been found that the above problem can be solved by forming openings in the solder resist layer formed on the other side by photolithography in order to form openings of a relatively large opening diameter for connection with electronic parts, Thereby completing the invention.

That is, the present invention includes the following contents.

[1] A solder resist layer is formed on both sides of a circuit board, an opening is formed in the solder resist layer formed on one side by photolithography, and an opening is formed in the solder resist layer formed on the other side by laser Wherein the first and second wiring patterns are electrically connected to each other.

[2] The method according to the above [1], wherein the solder resist layer formed by photolithography for forming the openings is made of a photo-curable resin composition, and the solder resist layer formed by forming the openings by laser is made of a thermosetting resin composition.

[3] The method according to the above [2], wherein the solder resist layer formed on one surface of the circuit board and the solder resist layer formed on the other surface are formed together using a resin composition film having a resin composition layer formed thereon.

[4] In the above-mentioned [3], a solder resist layer formed on one surface and the other surface of the circuit board is formed collectively by a lamination process using a vacuum laminator and a subsequent planarization process by a hot press How to.

[5] The method according to the above [4], wherein the minimum melt temperature of both the photo-curable resin composition and the thermosetting resin composition is in the range of 80 to 160 ° C and the ratio of the minimum melt viscosity of both is 0.01 to 100 .

[6] The method for manufacturing a semiconductor device according to any one of [2] to [5] above, wherein after the opening of the solder resist layer made of the photocurable resin composition by photolithography, the baking process of the solder resist layer made of the photocurable resin composition, A step of thermally curing the solder resist layer made of the resin composition at the same time and thereafter forming an opening in the solder resist layer made of the thermosetting resin composition with a laser.

[7] The method according to any one of [1] to [6], wherein the printed wiring board is a semiconductor package substrate.

[8] The method according to any one of [2] to [6], wherein the printed wiring board is a semiconductor package substrate on which a semiconductor chip is mounted on a solder resist layer made of a thermosetting resin composition.

According to the method of manufacturing a printed wiring board of the present invention, it is possible to provide a printed circuit board having a relatively large opening diameter for connection with a circuit such as a motherboard or an electronic component such as a resistor, a capacitor, An opening portion can be efficiently formed on the solder resist layer to be formed by photolithography and the solder resist layer formed on the other surface of the circuit board for solder bonding with the semiconductor chip or the like It is possible to apply a thermosetting resin composition having excellent heat resistance to a solder resist layer forming an opening (for example, 100 탆 or less) having a relatively small opening diameter, so that it is possible to efficiently manufacture a printed wiring board having more excellent heat resistance .

Hereinafter, the present invention will be described based on a preferred embodiment.

A method of manufacturing a printed wiring board according to the present invention is characterized in that a solder resist layer is formed on both sides of a circuit board and opening portions in a solder resist layer formed on one side are formed by photolithography, Is formed by laser irradiation.

For example, in a semiconductor package substrate, a semiconductor chip is mounted, a solder resist layer on one side (one side) where higher heat resistance is required is formed by a thermosetting resin composition, an opening is formed by a laser, The other one of the solder resist layers is formed by using photolithography using a photocurable resin composition so that high workability can be maintained even in an opening portion having a relatively large opening diameter at the time of forming the opening portion.

The printed wiring board manufactured by the method of the present invention may be a rigid substrate, a flexible substrate, or a rigid flexible substrate. Structurally, it may be a double-sided board or a multi-layer board. Examples of the multilayer substrate include a through multilayer board, an interstitial via hole (IVH) multilayer board, and a build-up board. Among them, a buildup substrate having a high mounting density is preferable, and a semiconductor package substrate is particularly preferable for a build- .

In order to form the solder resist layer in the present invention, any of ink type and dry film type solder resistors can be used. However, in view of good working efficiency and easy thickness control, It is preferable to apply a dry film type solder resist to both of them. The dry film type solder resist is formed by laminating (pressing) a resin composition film on which a resin composition layer is formed on a support, onto a circuit board. In the present invention, the circuit board on which the solder resist layer is formed is a substrate on which conductor circuits are formed on one side or both sides, and is a precursor of the printed circuit board.

In the present invention, a photo solder resist is used for forming an opening portion in the solder resist layer formed on one side of the circuit board by exposure and development (photolithography). For example, in a semiconductor package substrate, an opening is formed by photolithography using a photo solder resist for a solder resist layer on a surface mounted on a mother board. The photo-solder resist has photosensitivity and developability and can be used without particular limitation as long as it is a photo-curable resin composition applicable to photolithography. Preferred examples thereof include resin compositions containing (a) a photocurable alkali-soluble resin, (b) an epoxy resin, (c) a photopolymerization initiator, (d) a curing accelerator and (e) a diluent. The photo-curable resin composition for photo-solder resists is suitably used for the purpose of enhancing heat resistance, reliability, etc., as well as an epoxy resin and the like as described above. However, in the present invention, In the case of a resin composition containing a photosensitive resin component and the like and having photosensitivity and developability, this resin composition is also defined as a " photocurable resin composition " even when it has a thermosetting property.

Examples of the photo-curable alkali-soluble resin include (a) an acid-pendant-type unsaturated epoxy ester resin obtained by reacting an unsaturated carboxylic acid with a polyfunctional epoxy resin and reacting with an acid anhydride, (Meth) acryloyl group and / or an allyl group-containing alkali-soluble resin obtained by reacting an epoxy compound having an acryloyl group and / or an epoxy group having an allyl group.

The polyfunctional epoxy resin may be any compound having two or more epoxy groups in the molecule. Specific examples thereof include a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol Naphthalene type epoxy resins such as bisphenol type epoxy resins such as F type epoxy resin and bisphenol S type epoxy resin, dihydroxynaphthalene type epoxy resin and binaphthol type epoxy resin, and biphenol type epoxy resins such as tetramethyl biphenol type Novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolak type epoxy resin and alkylphenol novolak type epoxy resin, bisphenol F Bisphenol F type epoxy resin modified by three or more functional groups by reacting epichlorohydrin with epoxy resin Any one of them may be used alone or two or more of them may be used in combination. Among them, a cresol novolak type epoxy resin and a bisphenol F type epoxy resin are reacted with epichlorohydrin to obtain a bisphenol F type epoxy resin modified by three or more functionalities, which is a solder resist excellent in developability and insulation reliability From the viewpoint of realizing the above.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and any one of them may be used singly or two or more of them may be used in combination. Among them, acrylic acid and methacrylic acid are preferred from the viewpoint of the photocurability of the composition.

The reaction between the polyfunctional epoxy resin and the unsaturated carboxylic acid is carried out in the range of 0.8 to 1.2, which is a ratio of the number of moles of the epoxy group of the polyfunctional epoxy resin to the number of moles of the carboxyl group of the unsaturated carboxylic acid (number of moles of epoxy group / number of moles of carboxyl group) .

The reaction between the polyfunctional epoxy resin and the unsaturated carboxylic acid is carried out until the acid value in the system (that is, the residual acid value of the carboxylic acid of the unsaturated carboxylic acid) is 5 mgKOH / g or less, preferably 2 mgKOH / g or less. (Unsaturated carboxylic acid-modified epoxy resin).

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenone tetracarboxylic dianhydride , And any one of them may be used singly or two or more of them may be used in combination. Of these, succinic anhydride and anhydrous tetrahydrophthalic acid are preferable from the viewpoints of the developability of the composition and the insulation reliability of the cured coating obtained by curing the composition.

The acid pendant type unsaturated epoxy ester resin can be obtained by reacting the above-mentioned polyfunctional epoxy resin with an unsaturated carboxylic acid in the presence of a catalyst, and then reacting the resultant reacted unsaturated carboxylic acid-modified epoxy resin with an acid anhydride.

The amount of the catalyst to be used at this time is preferably 2 mass% or less, more preferably 0.0005 to 1 mass%, and particularly preferably 0.001 to 0.5 mass%, based on the total mass of the polyfunctional epoxy resin and the unsaturated carboxylic acid and the acid anhydride desirable. Examples of the catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide, Chemical compounds; Phosphines such as trimethylphosphine, tributylphosphine and triphenylphosphine; Phosphonium salts such as tetramethylphosphonium salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl (2-hydroxylpropyl) phosphonium salts, triphenylphosphonium salts and benzylphosphonium salts; Salts, phosphonium salts having a carboxylate, a hydrooxide or the like as typical anions; Sulfonium salts such as trimethylsulfonium salt, benzyltetramethylenesulfonium salt, phenylbenzylmethylsulfonium salt or phenyldimethylsulfonium salt, and representative examples of sulfonium salts include chloride, bromide, carboxylate, hydrooxide, and the like. salts; And acidic compounds such as phosphoric acid, p-toluenesulfonic acid and sulfuric acid.

The reaction temperature of the polyfunctional epoxy resin and the unsaturated carboxylic acid is preferably in the range of 100 to 120 ° C. If the reaction temperature is less than 100 ° C., the reaction rate is slow and the reaction takes a long time, Exceeds 120 캜, the polymerization of the unsaturated carboxylic acid occurs, and there is a fear that the reaction becomes gelled in the course of the reaction. In order to prevent the polymerization of the unsaturated carboxylic acid in the reaction between the polyfunctional epoxy resin and the unsaturated carboxylic acid, it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, benzo Quinone-based polymerization inhibitors such as quinone and p-tert-butyl catechol; Butylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2- Alkylphenol-based polymerization inhibitors such as 2,4,6-tri-tert-butylphenol; Alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy- , 6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy- Amine-based polymerization inhibitors such as 6-tetramethylpiperidine; Tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy- N-oxyl polymerization inhibitors such as 6,6-tetramethylpiperidine-N-oxyl and the like. These may be used alone, or two or more of them may be used in combination. The polymerization inhibitor is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the unsaturated carboxylic acid.

The reaction temperature of the unsaturated carboxylic acid-modified epoxy resin obtained by reacting the polyfunctional epoxy resin with the unsaturated carboxylic acid is preferably 70 to 110 占 폚. When the reaction temperature is less than 70 ° C, the reaction speed is slow and the reaction takes a long time. When the reaction temperature exceeds 110 ° C, polymerization of the unsaturated carboxylic acid-modified epoxy resin occurs and the resin tends to gel.

The use ratio of the acid anhydride is preferably such that the solid dispersion value of the product (acid pendant type unsaturated epoxy ester resin) is from 30 to 150 mgKOH / g, particularly preferably from 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the alkali developability of the target composition tends to be lowered. When the acid value exceeds 150 mgKOH / g, fine patterns of the solder resist formed by development flow, There is a tendency.

The reaction of an acid pendant type unsaturated epoxy ester resin with an epoxy compound having a (meth) acryloyl group and / or an epoxy compound having an allyl group can be carried out by reacting an epoxy compound having a (meth) acryloyl group and / Is preferably in the range of 0.01 to 0.5 equivalent, particularly preferably 0.1 to 0.4 equivalent based on 1 equivalent of the carboxyl group of the acid pendant type unsaturated epoxy ester resin, preferably 60 to 150 ° C, Followed by heating and stirring at 80 to 120 占 폚.

Examples of the epoxy compound having a (meth) acryloyl group include glycidyl (meth) acrylate, -ethylglycidyl acrylate, -n-propylglycidyl acrylate, -n- (Meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, ,? -ethyl-6,7-epoxy-heptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ethyl and p-vinyl benzyl glycidyl ether. Any one of them may be used alone or two or more of them may be used in combination. Among them, glycidyl (meth) acrylate and? -Ethyl glycidyl acrylate are preferable, and glycidyl methacrylate is particularly preferable. Examples of the epoxy compound having an allyl group include allyl glycidyl ether and p-allylbenzyl glycidyl ether, and any one of them may be used singly or both of them may be used in combination.

The epoxy compound having a (meth) acryloyl group and / or the epoxy compound having an allyl group is added to and reacted with a solution of an acid pendant type unsaturated epoxy ester resin, , And 0.01 to 0.5 mol, based on the reaction mixture. Considering the photosensitivity of the intended resin composition, it is advantageous to conduct the reaction at a ratio of preferably 0.1 to 0.4 mol. The reaction temperature is preferably 80 to 120 占 폚. The acid pendant-type unsaturated epoxy ester resin can be used as its own photo-curable resin, but the (meth) acryloyl group-containing epoxy compound and / or the allyl group-containing epoxy compound reacts with the carboxyl group of the acid pendant type unsaturated epoxy ester resin , The (meth) acryloyl group and / or the allyl group is bonded to the side chain of the polymer backbone of the acid pendant type unsaturated epoxy ester resin, the photosensitivity is further improved. From the viewpoint of photosensitivity, the (meth) acryloyl group and / or allyl group-containing alkali-soluble resin thus obtained preferably has a solid dispersion value of 30 to 250 mgKOH / g, more preferably 40 to 110 mgKOH / g.

The epoxy resin (b) is not particularly limited as long as it is suitable as an insulating material in a printed wiring board. Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, A phenol novolak type epoxy resin, a cresol novolak type epoxy resin, an alkylphenol novolak type epoxy resin, a biphenol type epoxy resin (biphenyl type epoxy resin), an aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin , Dicyclopentadiene type epoxy resins, epoxides of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, naphthol type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, anthracene type epoxy resins, And epoxy resins such as epoxy resins. These epoxy resins may be used either singly or in combination of two or more. As the curing agent to be used in combination with these epoxy resins, the same curing agents as those described later can be used.

Among them, a dicyclopentadiene type epoxy resin and a biphenol type epoxy resin (biphenyl type epoxy resin) are preferable. As the dicyclopentadiene type epoxy resin, "HP7200", "HP7200H", "HP7200HH" manufactured by DIC Corporation, Nippon Kayaku Co., Ltd. XD-1000-L ", and" XD-10002L "manufactured by Nippon Kayaku Co., Ltd. as the biphenol type epoxy resin. "NC3000", "NC3000H", "NC3000L", "NC3100", manufactured by Tohto Kasei Co., Ltd. &Quot; GK3207 ", Japan Epoxy Resins Co., Ltd. &Quot; YX4000HK "

The epoxy resin is preferably used in a proportion of 5 to 100 parts by mass, more preferably 10 to 85 parts by mass, per 100 parts by mass of the photocurable alkali-soluble resin (a). When the amount is less than 5 parts by mass, the coating film becomes insufficient in curing, and heat resistance and electrical insulation tend to decrease. When the amount exceeds 100 parts by mass, developability tends to decrease.

(c) Examples of the photopolymerization initiator include benzophenone, methylbenzophenone, o-benzoyl benzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethyl thioxanthone, 2- (4-methylphenyl) methyl] - [4- (4-morpholinyl) phenyl] Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, Ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate, 4,4'-bis (diethylamino) benzophenone, 1 -hydroxy-cyclohexylphenylketone, 2,2- Phenyl-2-hydroxy-2-methyl-1-propan-1-one, bis (2, 4-dihydroxyethoxy) , 6-trimethylbenzoyl) -phenylphosphine oxides, sulfonium salts, and oxime ester-based photopolymerization initiators. The amount of the photopolymerization initiator used is in the range of 0.5 to 30 parts by mass, preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin solid content of the resin composition. If the amount of the photopolymerization initiator to be used exceeds the above range, there is a fear that the composition may have a thermosetting property, a heat resistance property and a deterioration of electric insulation property. If the amount of the photopolymerization initiator used is less than the above range, There is a concern.

(d) The curing accelerator is used for accelerating the thermosetting property in the thermosetting treatment after the photocuring of the composition. Examples thereof include amines, polyamides, imidazoles, and organic phosphine compounds. From the viewpoint of balance of performance, amines and imidazoles are preferable, and specific examples thereof include 2-methylimidazole, triphenylphosphine, ethyl guanidinoamine, diaminodiphenylmethane, melamine, boron trifluoride-amine Complex, dicyandiamide (DICY) and derivatives thereof, and amine imide (AI). Among them, melamine and dicyandiamide (DICY) are particularly preferable. The blending amount of the (d) curing accelerator is preferably in the range of 0.1 to 20 mass% with respect to the epoxy resin (b).

(e) The diluent is formulated for the purpose of improving photoreactivity and the like of the composition. As such a diluent, for example, a liquid, solid or semi-solid photosensitive (meth) acrylate compound may be used at room temperature having at least one (meth) acryloyl group in one molecule. Representative examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol Or polyhydric alcohols such as polyhydric acrylates of ethylene oxide, adducts of propylene oxide or? -Caprolactone, phenols such as phenoxy acrylate and phenoxyethyl acrylate, and ethylene oxide or propylene oxide adduct thereof Acrylate, trimethylol propane triglycidyl ether and the like, Epoxy acrylates derived from diesters, melamine acrylates, and / or methacrylates corresponding to the above acrylates. Among these, polyhydric acrylates or polyhydric methacrylates are preferable, and examples of the trivalent acrylates or methacrylates include trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Trimethylolpropane EO addition tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (Meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylol propane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylol Methane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N ', N'- tetrakis (Meth) acrylic acid esters of triethanolamine or triethanolamine, and (meth) acrylic acid esters of triethanolamine or triethanolamine. Examples of the acrylates or methacrylates having three or more valences include tri (2- (meth) acryloyloxyethyl) (Meth) acryloyloxypropyl) phosphate, di (3- (meth) acryloyloxypropyl) phosphate, tri (Meth) acryloyl-2-hydroquinyloxypropyl) di (2- (meth) acryloyloxypropyl) (Meth) acrylate such as acryloyloxyethyl) phosphate. Any of these photosensitive (meth) acrylate compounds may be used singly or two or more of them may be used in combination.

The amount of the diluent (e) to be used is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of (a) the photocurable alkali-soluble resin and (b) . If the amount is less than 1 part by mass, the effect of improving the photoreactivity is difficult to obtain. If the amount is more than 50 parts by mass, stickiness of the coating film by the composition increases, and the workability tends to deteriorate.

The resin composition containing the components (a) to (e) may also contain (f) a filler. An inorganic filler and / or an organic filler may be used for the filler.

Examples of inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica, mica, silicate, barium sulfate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Barium, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate and calcium zirconate. Silica and barium sulfate are preferable, and amorphous silica, fused silica, Silica such as silica and synthetic silica is preferred. From the viewpoint of insulation reliability, the inorganic filler preferably has an average particle diameter of not more than 3 mu m, and more preferably an average particle diameter of not more than 1.5 mu m. The inorganic fillers may be used alone or in combination of two or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured by using a laser diffraction particle size distribution measuring apparatus, and the median diameter is determined as an average particle diameter. The measurement sample can be preferably those obtained by dispersing an inorganic filler in water by ultrasonic waves. As a laser diffraction particle size distribution measuring apparatus, HORIBA, Ltd. LA-500 manufactured by Mitsui Chemicals, Inc. can be used.

The inorganic filler is preferably selected from the group consisting of aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (amino Ethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, glycidylbutyltrimethoxysilane, Epoxy silane coupling agents such as silane and (3,4-epoxycyclohexyl) ethyl trimethoxy silane, mercapto silane coupling agents such as mercaptopropyl trimethoxy silane and mercaptopropyl triethoxy silane, Silane-based coupling agents such as methoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolylsilane and triazinilane, hexamethylsilazane, hexaphenyldisilazane,Organosilazane compounds such as methylaminotrimethylsilane, trisilazane, cyclotrisilazane, and 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimers, titanium octylen glycolate , Diisopropoxytitanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxybis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis Tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra-n-butoxytitanium monostearate, (Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, Millepe Isopropyl tributyl titanate, isopropyl tributyl titanate, isopropyl tributyl titanate, isopropyl tributyl titanate, isopropyl tributyl titanate, isopropyl tributyl titanate, isopropyl triisostearoyl titanate, isopropyl diisostearoyldiacrylate, Titanate-based coupling agents such as isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-amide ethyl aminoethyl) titanate, silica-alumina surface treatment agents and the like Or may be treated with one or more kinds of surface treating agents.

Examples of the organic filler include acrylic rubber particles, polyamide fine particles and silicone particles. As specific examples of the acrylic rubber particles, there may be mentioned a resin crosslinkable resin such as acrylonitrile butadiene rubber, butadiene rubber and acrylic rubber, which is chemically crosslinked to form a resin fine particle chain which is insoluble in an organic solvent and is not melted. (Manufactured by Japan Synthetic Rubber Co., Ltd.), stapyloids AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Chemical Co., Ltd.) ) Pararoid EXL2655, EXL2602 (manufactured by Kureha Corporation), and the like. Specific examples of the polyamide fine particles may be any fine particles of an amide bond-containing resin such as aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar, and polyamideimide. For example, VESTOSINT 2070 (Daicel Daicel- Manufactured by Huels Ltd.) and SP500 (manufactured by Toray Industries, Inc.). The average particle diameter of the organic filler is preferably in the range of 0.005 to 1 mu m, more preferably in the range of 0.2 to 0.6 mu m. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.) is used, the particle size distribution of the organic filler is prepared on the basis of mass, It can be measured by setting the diameter to an average particle diameter.

The amount of the filler (f) to be used is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the nonvolatile matter of the resin composition.

The opening of the solder resist layer formed on the other surface of the circuit board is formed by a laser. For example, in a semiconductor package substrate, a solder resist layer on a surface on which a semiconductor chip is mounted, which is required to have higher heat resistance, is formed of a thermosetting resin composition, and an opening is formed by a laser. By forming openings with a laser, it is not necessary to use a photo-curable resin composition, and a thermosetting resin composition having superior heat resistance can be used. A resin composition having both a photo-curable property and a thermosetting property including a developable photo-curable resin component such as a photo-curable alkali-soluble resin as described above may be used. In general, however, such a photo- It is preferable to use a thermosetting resin composition that can be cured only by thermal curing.

In the present invention, when a thermosetting resin composition is referred to, it means a thermosetting resin composition having substantially no photocurability. Examples of the thermosetting resin as a main component include thermosetting resins such as epoxy resin and bismaleimide-triazine resin. Preferable examples of the thermosetting resin composition include a resin composition containing an epoxy resin and a curing agent, and a resin composition containing (A) an epoxy resin, (B) a high molecular component and (C) a curing agent is preferable.

Examples of the epoxy resin (A) include bisphenol A type epoxy resin, biphenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, A cyclic epoxy resin, an alicyclic epoxy resin, an aliphatic chain epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, an alkylphenol novolac type epoxy resin, a fluorene type epoxy resin, an anthracene type epoxy resin, Resins, phosphorus-containing epoxy resins, epoxy resins having a butadiene structure, and alkyl-substituted products and hydrogenated products of these epoxy resins. These epoxy resins may be used either singly or in combination of two or more.

Among these epoxy resins, bisphenol A type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and epoxy resins having a butadiene structure are preferable from the viewpoints of heat resistance, insulation reliability and adhesion. Specifically, for example, a liquid bisphenol A type epoxy resin ("Epicoat 828EL" manufactured by Japan Epoxy Resins Co., Ltd.), diglycidyl ether of naphthalene diol (bifunctional type) (HP4700 manufactured by DIC Corporation), naphthol type epoxy resin (ESN-475V manufactured by Tohto Kasei Co., Ltd.), butadiene type epoxy resin (HP4032D manufactured by Tohto Kasei Co., ("PB-3600" manufactured by Daicel Daicel-Huels Ltd.), an epoxy resin having a biphenyl structure ("NC3000", "NC3000H", "NC3000L", " NC3100 " manufactured by Japan Epoxy Resins Co., Ltd., and " YX4000HK "

(B) polymer component is blended for the purpose of imparting suitable flexibility to the composition after curing, and includes, for example, phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone , An aliphatic polyester-based polyol, a polyether polyol, a polycarbonate-based polyol, a polyethylene terephthalate polyol, and an acrylic resin. Any one of them may be used alone or two or more of them may be used in combination. The polymer component is preferably blended in a proportion of 0.5 to 60 mass%, more preferably 3 to 30 mass%, based on 100 mass% of the nonvolatile component of the resin composition. When the blend ratio of the polymer component is less than 0.5 mass%, it is difficult to form a uniform thickness layer because the viscosity of the resin composition is low, and when it exceeds 60 mass%, the viscosity of the resin composition becomes excessively high , It tends to be difficult to embed in the wiring pattern on the circuit.

Specific examples of the phenoxy resin include Tohto Kasei Co., Ltd. FX280, FX293, Japan Epoxy Resins Co., Ltd. For example, YX8100, YL6954, YL6974 and the like.

The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and specific examples of the polyvinyl acetal resin include Denki Kagaku Kogyo Kabushiki Kaisha, telephone Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co ., Ltd. BREX series, BX series, KS series, BL series, BM series, and so on.

Specific examples of the polyimide include New Japan Chemical Co., Ltd. Quot; Rika coat SN20 " and " Rika coat PN20 " Further, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A No. 2006-37083), a polysiloxane skeleton-containing polyimide Japanese Patent Application Laid-Open No. 2002-12667, Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of the polyamideimide include Toyobo Co., Ltd. Polyamideimide " Viromax HR11NN ", " Viromax HR16NN ", and the like. Examples of the modified polyamideimide include polysiloxane skeleton-containing polyamideimide "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

Specific examples of polyethersulfone include Sumitomo Chemical. Co., Ltd. And polyethersulfone " PES5003P "

Specific examples of the polysulfone include polysulfone "P1700" and "P3500" manufactured by Solvent Advanced Polymers Co.

Examples of the curing agent (C) include, but are not limited to, amine curing agents, guanidine curing agents, imidazole curing agents, phenol curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, Benzoxazine resin, cyanate ester resin, and the like. Among them, a phenol-based curing agent, a naphthol-based curing agent and a cyanate ester resin are preferable. The curing agent may be one kind or two or more kinds thereof.

MEH-7810, MEH-7851 (manufactured by Meiwa Plastic Industries, Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), and the like, as specific examples of the phenol type curing agent and the naphthol type curing agent. (Manufactured by Tohto Kasei Co., Ltd.), LA7052, LA7054, LA3018, and LA1356 (manufactured by DIC Corporation), and the like .

Specific examples of the cyanate ester resin include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2 , 6-dimethyl phenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3- Cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., Examples of commercially available cyanate ester resins include phenol novolak type polyfunctional cyanates ("PT30" manufactured by Lonza Japan Ltd., cyanate equivalent 124) or a prepolymer obtained by trimerization of a part or all of bisphenol A dicyanate ("BA230" manufactured by Lonza Japan Ltd., cyanate Equivalent to 232).

The mixing ratio of the epoxy resin (A) to the curing agent (C) is such that the phenolic hydroxyl group equivalent of these curing agents is in the range of 0.4 to 2.0, in the case of the phenolic curing agent or the naphthol curing agent, , And more preferably in the range of 0.5 to 1.0. In the case of the cyanate ester resin, the proportion of the cyanate equivalent to the epoxy equivalent of 1 is preferably in the range of 0.3 to 3.3, more preferably in the range of 0.5 to 2.

The thermosetting resin composition can further contain (D) a curing accelerator in addition to the (C) curing agent. Examples of such a curing accelerator include an imidazole-based compound and an organophosphine-based compound. Specific examples thereof include 2 Methylimidazole, 2-ethyl 4-methylimidazole, triphenylphosphine, and the like. When a curing accelerator is used, it is preferably used in an amount of 0.1 to 3.0% by mass based on the epoxy resin (A). When a cyanate ester resin is used as the curing agent (C), for the purpose of shortening the curing time, even if an organometallic compound conventionally used as a curing catalyst in a system using an epoxy resin composition and a cyanate compound is added good. Examples of the organometallic compound include organic dyes such as copper (II) acetylacetonate, organic zinc compounds such as zinc (II) acetylacetonate, organic cobalt compounds such as cobalt (II) acetylacetonate and cobalt (III) . The amount of the organometallic compound to be added is preferably 10 to 500 ppm, more preferably 25 to 200 ppm, in terms of the metal, based on the cyanate ester resin.

The thermosetting resin composition may further contain a filler. An inorganic filler and / or an organic filler may be used for the filler. Examples of the inorganic filler are as described above. Among these inorganic fillers, silica and alumina are preferable, and silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, spherical silica, and pulverized silica is particularly preferable. The average particle diameter of the inorganic filler and the surface treatment are also the same as described above. The types and average particle diameters of the organic fillers are as described above. The content of the inorganic filler in the thermosetting resin composition is preferably 20 to 80 mass%, more preferably 30 to 70 mass%, based on 100 mass% of the nonvolatile component of the thermosetting resin composition. The content of the organic filler is preferably 1 to 10% by mass, more preferably 2 to 5% by mass, based on 100% by mass of the nonvolatile component of the thermosetting resin composition.

The thermosetting resin composition may contain a thermosetting resin other than an epoxy resin such as a maleimide compound, a bisallylnadiimide compound, a vinylbenzyl resin, and a vinyl benzyl ether resin. These thermosetting resins may be used in combination of two or more kinds. As the maleimide resin, BMI1000, BMI2000, BMI3000, BMI4000 and BMI5100 (manufactured by Daiwakasei Industry Co., Ltd.), BMI, BMI-70 and BMI-80 (manufactured by KI Chemical Industry Co., M (manufactured by Maruzen Petrochemical Co., Ltd.), and V5000 (manufactured by Showa Highpolymer Co., Ltd., manufactured by Mitsui Fine Chemical Co., Ltd.) as the bisallylnadimide compound; BANI- ) And vinyl benzyl ether resin (V1000X, V1100X (manufactured by Showa Highpolymer Co., Ltd.)).

The photocurable resin composition and / or thermosetting resin composition of the present invention may contain a flame retardant. Two or more flame retardants may be used in combination. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon-based flame retardants and metal hydroxides. Organic phosphorus flame retardants include Sanko Co., Ltd. HCA, HCA-HQ and HCA-NQ manufactured by Showa Highpolymer Co., Ltd .; Phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Ajinomoto Fine-Techno Co., Inc. TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Hokko Chemical Industry Co., Ltd. PPQ manufactured by Daihachi Chemical Industry Co., Ltd., OP930 manufactured by Clariant Co., Ltd. Phosphoric acid ester compounds such as PX200 manufactured by Tohto Kasei Co., Ltd. Phosphorus-containing epoxy resins such as FX289 and FX310 manufactured by Tohto Kasei Co., Ltd. Phosphorus-containing phenoxy resins such as ERF001 manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Examples of the organic nitrogen-containing phosphorus compound include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Chemicals Corporation; And phosphazene compounds such as SPB100 and SPE100 manufactured by Shin-Etsu Chemical Co., Ltd. The metal hydroxides include Ube Material Industries, Ltd. Magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Tomoe Engineering Co., Ltd. Aluminum hydroxide such as B-30, B-325, B-315, B-308, B-303 and UFH-

The photocurable resin composition and / or thermosetting resin composition of the present invention may contain a thickening agent such as an orthovane or a benton, a defoaming agent or leveling agent of a silicon type, a fluorine type or a high molecular type, an imidazole type, a thiazole type, a triazole type or a silane type coupling agent And other components such as a colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black.

In the present invention, both the solder resist layer formed on one side of the circuit board and the solder resist layer formed on the other side may be formed of an ink type solder resist or a dry film type solder resist. That is, even when the varnish of the resin composition is coated on the circuit board and dried, a resin composition film having the resin composition layer formed on the support is produced, and the resin composition film is laminated . In addition, it is preferable to form the dry film type solder resist on both sides of the circuit board in view of good working efficiency and easy thickness control.

The solder resist layer made of the photo-curable resin composition formed on one side of the circuit board and the solder resist layer made of the thermosetting resin composition formed on the other side of the circuit board are made of the photo-curable resin composition and the thermosetting resin composition The minimum melt viscosity of both the thermosetting resin composition and the photocurable resin composition is in the range of 80 to 160 占 폚 and the minimum melt viscosity of both of them is 0.01 To 100. The ratio of the lowest melt viscosity is more preferably 0.05 to 20, and particularly preferably 0.1 to 7. [ This is because when the solder resist layer is formed using a dry film type solder resist, the resin composition film can be continuously pressed and flattened to a circuit board by a vacuum laminator as described later, When the temperature is lower than 80 ° C, the viscosity of the resin is excessively low in a vacuum press or a planarizing press, and the resin is pushed out. When the minimum melting temperature exceeds 160 ° C, the fluidity is insufficient and poor compression or flattening may occur. In the case where the other resin composition layers (the photocurable resin composition layer and the thermosetting resin composition layer) are laminated on one side and the other side of the circuit board simultaneously, if the ratio of the lowest melt viscosity of both layers is out of the above range, There is a tendency that an appropriate temperature setting becomes difficult in a flattening process by thermal press, and the fluidity of one of the layers is too low at a predetermined temperature, so that the filling property of the circuit and the flatness of the resin are lowered, The fluidity is too high and the resin tends to be pushed out.

The " minimum melt viscosity " referred to herein is a temperature at which the resin composition is heated and melted at a constant heating rate. In the initial stage, the melt viscosity decreases with increasing temperature, , And is a value measured by measuring dynamic viscoelasticity using, for example, Rheosol-G3000, a product of Yu-Bi Co., Ltd. Specifically, it means the lowest melt viscosity value measured using a parallel plate at an initial temperature of 60 占 폚, a temperature rising rate of 5 占 폚 / min, a measurement interval of 2.5 占 폚, a frequency of 1 Hz / deg, and a constant load of 100 g. In addition, the temperature of the minimum point indicating the lowest melt viscosity is the " minimum melting temperature ".

The method of adjusting the lowest melt viscosity ratio of the photo-curable resin composition and the thermosetting resin composition is not particularly limited, and the mixing of the photo-curable resin composition or the mixing of the thermosetting resin composition may be adjusted. However, since the photo-curable resin composition must satisfy both photosensitivity and developability, and addition of a polymer component and a curing accelerator is limited, it is preferable to control and adjust the addition amount of the polymer component or the curing accelerator of the thermosetting resin composition. In general, when the amount of the polymer component, the curing accelerator, and the like is increased, the lowest melt viscosity is increased.

Examples of the support for the dry film type solder resist include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as " PET ") and polyethylene naphthalate (hereinafter abbreviated as " PEN " (TAC), polyether sulfone (PES), polyether ketone, polyimide, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone And the like.

It is preferable that a plastic film on which the contact surface with the solder resist layer is subjected to release treatment is used as the support. This is because it is generally difficult to peel the plastic film from the surface of the solder resist layer after the thermal curing if the surface of the plastic film serving as the support of the resin composition film is not subjected to the release treatment on the contact surface with the thermosetting resin composition layer to be. The releasing agent used in the releasing treatment is not particularly limited as long as the plastic film can be peeled off from the surface of the solder resist layer, and examples thereof include a fluorine releasing agent, a silicone releasing agent and an alkyd resin releasing agent. The releasing agent may be used by mixing with other kinds of the releasing agent. The surface of the plastic film may be subjected to a matte treatment, a corona treatment, or the like, and the corona-treated surface may be further subjected to a release treatment. In addition, the plastic film may contain a laser energy absorbing component such as carbon powder such as carbon black, metal compound powder, metal powder, and black dye.

The thickness of the plastic film (total thickness including the release layer in the case of the release-treated plastic film) is preferably in the range of 10 to 50 탆, more preferably in the range of 12 to 45 탆, more preferably in the range of 16 to 38 탆 Particularly preferred. If the thickness of the plastic film is less than 10 mu m, the flatness of the circuit tends to decrease. If the thickness exceeds 50 mu m, the price tends to become high. The thickness of the release layer in the release-treated plastic film is preferably 0.05 to 2 占 퐉.

It is preferable that the dry film type solder resist has a protective film for covering and protecting the resin composition layer until lamination to a circuit board is carried out. The protective film is advantageous in that the surface of the resin composition layer is protected from physical damage, and adhesion of dust and the like is prevented. Examples of such a protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, and films such as polyester, polycarbonate (PC) and polyimide such as PET and PEN. In addition to the matte treatment and the corona treatment, the protective film may be subjected to a release treatment in the same manner as the plastic film used for the support film. The thickness of the protective film is preferably in the range of 5 to 30 mu m.

The dry film type solder resist can be formed by a method known to those skilled in the art, for example, by preparing a varnish of a photocurable resin composition or a thermosetting resin composition, applying the varnish on a support using a die coater or the like, And drying the organic solvent by hot blowing or the like to form a resin composition layer.

In the present invention, the operation of laminating the dry film type solder resist on the circuit board and forming the solder resist layer can be performed according to the conventional method. For example, it can be manufactured using a vacuum laminator. The resin composition film is heated and pressed under reduced pressure to laminate an adhesive film on the circuit board. The lamination is performed at a temperature of preferably 60 to 140 占 폚 and a pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ). The air pressure is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. After the lamination process, the laminated resin composition film is preferably planarized by hot pressing with a metal plate. The planarization step is performed by heating and pressing the adhesive sheet with a metal plate such as a heated SUS mirror plate under atmospheric pressure (under atmospheric pressure). The heating and pressurizing conditions can be the same as those in the lamination process. The lamination process and the planarization process can be continuously performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, Meiki Co., Ltd. Manufacture of vacuum pressurized laminator, Nichigo-Morton Co., Ltd. An applicator for manufacturing, and the like.

In the present invention, the thickness of the solder resist layer is preferably 10 to 50 mu m, more preferably 20 to 40 mu m. When the thickness of the solder resist layer is less than 10 mu m, it tends to be difficult to laminate the circuit board smoothly depending on the thickness of the conductor layer. When the thickness exceeds 50 mu m, the multilayer printed wiring board tends not to be thin .

After a solder resist layer is formed on both sides of the circuit board, exposure and development (lithography) is performed in order to form openings in the photo-solder resist layer (solder resist layer formed of the photo-curable resin composition) on one side. In the exposure step, exposure is performed with an active energy ray using a negative mask in which only the portion which becomes an opening portion does not pass through the active energy ray. Further, it is also possible to directly paint with a beam of an active energy ray without using a negative mask. The exposure method includes a contact exposure method in which a negative mask is brought into close contact with a circuit board and a non-contact exposure method in which a negative light is used to expose a negative mask. The dose of ultraviolet radiation is approximately 10 to 1000 mJ / cm ² .

After the exposure process, the development process is started. The developing step is carried out by means of spraying, immersion or the like using an alkaline solution such as an aqueous solution of sodium carbonate, an aqueous solution of sodium hydroxide or the like as a developer, and the unexposed portions are removed by the action of dissolution, swelling, peeling or the like.

In the exposure and / or development process, the solder resist layer formed of the thermosetting resin composition that is opened using the laser may be protected with a protective film or the like, if necessary, in order to avoid damage by a roller or the like, good. When the solder resist layer is formed of a dry film type solder resist, the support of the resin composition film may be used as a protective film in the exposure or development process as it is without peeling off the support.

After the developing process, the baking process is started. The bake has a role of post-baking the solder resist layer (photo-solder resist) formed of the photo-curable resin composition and also serves as a step of thermally curing the solder resist formed of the thermosetting resin composition. The baking may be performed at a temperature and for a time at which a thermosetting component such as an epoxy resin in the solder resist sufficiently reacts in a hot air furnace or a far infrared ray furnace. Depending on the kind of the solder resist used, it is preferable to perform the process in the range of 120 to 200 DEG C for 30 to 120 minutes.

After baking, the surface of the solder resist layer formed of the thermosetting resin composition is irradiated with laser light to form openings. The size of the opening portion is selected according to the fineness of the component to be mounted, but the range of the column diameter is preferably from 40 to 100 탆. Examples of the laser light source include a carbon dioxide gas laser, a YAG laser, and an excimer laser, and a carbon dioxide gas laser is preferably used in terms of workability and cost.

When a carbon dioxide gas laser device is used, it is preferable to use a laser beam having a wavelength of 9.3 to 10.6 mu m. It is preferable that the number of shots is selected from 1 to 10 shots although it depends on the depth and hole diameter of the via hole to be formed. From the viewpoint of speeding up the processing speed of the via and improving the productivity of the circuit board, the number of shoots is preferably small, preferably 1 to 5 shots, more preferably 1 to 3 shots. The energy of the laser beam in the case of using a carbon dioxide gas laser device is preferably set to 0.5 mJ or more, more preferably 1 mJ or more, and more preferably 1 mJ or more, depending on the number of blades, the depth of the blind via, the thickness of the metal film layer, Still more preferably 2 mJ or more. The upper limit is preferably 20 mJ or less, more preferably 15 mJ or less, even more preferably 10 mJ or less, and most preferably 5 mJ or less. If the energy of the laser light is too high, the underlying conductor layer of the via hole is liable to be damaged. Therefore, it is preferable to select an optimum energy value within the above range in accordance with the number of turns. Further, in the case of machining into a plurality of shots, the continuous burst-type burst mode tends to be filled with machining heat in the hole, and a difference in via machining property tends to easily occur. Therefore, .

The pulse width of the laser light used for the irradiation is not particularly limited and can be selected from a wide range from a mid range of 28 μs to a short pulse of about 4 μs. In general, in the case of high energy small diameter processing, Is excellent. As a commercially available carbon dioxide gas laser device, for example, Mitsubishi Electric Corporation ML605GTWII, Hitachi Via Mechanics, Ltd. LC-G series, Matsushita Welding System Co., Ltd., and a laser drilling machine.

After formation of openings in the solder resist layer, desmear treatment is carried out on both sides or one side as required for the purpose of removing the smear and improving the wetting component of the underfill. The desmear treatment in the present invention can be carried out by various known methods, and it is preferable to use a commonly used dry method using a plasma and a wet method using an oxidizing agent solution such as an alkaline permanganic acid solution.

As the plasma desmear device, Ebara-Udylite Co., Ltd. &Quot; Daishi, " manufactured by Sekisui Chemical Co., Ltd. A commercially available atmospheric plasma processing apparatus, or the like can be used.

In the case of desmear treatment with an oxidizing agent such as an alkaline permanganic acid aqueous solution, swelling treatment with a swelling liquid is preferably carried out prior to treatment. Examples of the swelling liquid include Swelling Dip Securiganth P and Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd. (Swelling Dip Securiganth SBU) . The swelling treatment is preferably performed by adding an insulating layer to the swelling liquid heated at 60 to 80 캜 for 5 to 10 minutes. Examples of the alkaline permanganic acid aqueous solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an alkaline permanganic acid aqueous solution is preferably carried out by adding it at 60 to 80 캜 for 10 to 30 minutes. Commercially available alkaline permanganic acid aqueous solutions include Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solution Cecrigin P, and the like.

In the desmear process, the solder resist layer (the solder resist layer formed on one side of the circuit board) on the opening side using the exposure and development is removed as needed to avoid damage by rollers, etc., It may be protected with a protective film or the like.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the following description, " part " used when referring to the amount of the material means " part by mass ". The dynamic viscoelasticity was measured using a Rheosol-G3000 manufactured by Yu-Bi Co., Ltd. The measurement was carried out at an initial temperature of 60 占 폚, a heating rate of 5 占 폚 / min, a measurement interval of 2.5 占 폚 and a frequency of 1 Hz / deg.

(Synthesis Example of Resin Solution (A)) [

430 parts of ethylcarbitol acetate, 430 parts of o-cresol novolak type epoxy resin (epoxy equivalent 215, average of six phenolic nuclei in one molecule), and 144 parts of acrylic acid were placed in a flask and stirred at 120 ° C for 10 hours Lt; / RTI > Once the reaction product was cooled to room temperature, 288.8 parts of anhydrous tetrahydrophthalic acid was added and the mixture was heated to 80 占 폚 and stirred for 4 hours. The reaction product was cooled to room temperature again, and 105 parts of glycidyl methacrylate and 161 parts of propylene glycol methyl ether acetate were added and reacted at 110 ° C for 6 hours under stirring. The reaction product was cooled to room temperature to obtain a resin solution (A) (nonvolatile matter content 62.9%, acid value 70 [KOH mg / g]).

(Production Example of Photocurable Resin Composition Film (1)) [

, 100 parts of the resin solution (A), 18 parts of an ethylcarbitol acetate solution having a solid content of 70% of biphenyl type epoxy resin (epoxy equivalent 291, "NC-3000H" manufactured by Nippon Kayaku Co., Ltd.), 18 parts of dicyclopentadiene 18 parts of an ethylcarbitol acetate solution having a solid content of 70% of an epoxy resin (epoxy equivalent 277, "EPICLON HP-7200H" manufactured by DIC Corporation), 18 parts of a photopolymerization initiator ("2-methyl- , 7 parts of [4- (methylthio) phenyl] -2-morpholino-1-propanone "), a photosensitizer (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) , 16 parts of an acrylic monomer ("M-310" manufactured by Toagosei Co., Ltd.), 0.5 part of a curing accelerator ("Epicure DICY-7" manufactured by Japan Epoxy Resins Co., Ltd.) 2 parts of "AEROXIL # 200" manufactured by Nippon Aerosil Co., Ltd.), 10 parts of spherical silica ("QOURTON SP-1" manufactured by Fusou Chemical Co., Ltd.), 10 parts of pigment ((Toyo Ink Mfg Co., Ltd.) " FG7351 ") were mixed , Uniformly dispersed in a high-speed rotary mixer to prepare a photocurable resin composition varnish.

The varnish was coated on the release-treated surface of a 25-μm release PET film (manufactured by Lintec Corporation, PET25-AL-5) which had been subjected to release treatment with an alkyd resin on one side so that the thickness of the resin composition layer after drying became 27 μm, Dried in a hot-air circulating dryer at 80 DEG C for 20 minutes, and then wound in a roll form while bonding a polypropylene film having a thickness of 15 mu m as a protective film. The roll-type adhesive film was slit with a width of 507 mm to obtain a film (photo-curable resin composition film (1)) having a size of 507 x 336 mm. The lowest melt viscosity of the obtained film was 540 poise and the lowest melt temperature was 148 占 폚.

(Production Example of Photocurable Resin Composition Film (2)) [

, 13 parts of a liquid bisphenol F type epoxy resin (epoxy equivalent 170, "Epicoat 807" manufactured by Japan Epoxy Resins Co., Ltd.), 10 parts of a dicyclopentadiene type epoxy resin (epoxy equivalent 277 , 12 parts of an ethylcarbitol acetate solution having a solid content of 70% (manufactured by DIC Corporation, "EPICLON HP-7200H"), 2 parts of a photopolymerization initiator (2-methyl- [4- (methylthio) Phenyl] -2-morpholino-1-propanone), 7 parts of a photosensitizer (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.), 1 part of acrylic monomers (Toagosei (Manufactured by Japan Epoxy Resins Co., Ltd., "Epicure DICY-7" manufactured by Japan Epoxy Resins Co., Ltd.), 20 parts of fine silica ), 10 parts of spherical silica (" Q-ballon SP-1 ", manufactured by Fusou Chemical Co., Ltd.) and 0.5 parts of pigment (Toyo Ink Mfg. Co., Ltd. " FG7351 " Dispersed uniformly with a high-speed rotary mixer, To prepare a resin composition varnish.

The varnish was coated on the release-treated surface of a 25-μm release PET film (manufactured by Lintec Corporation, PET25-AL-5) which had been subjected to release treatment with an alkyd resin on one side so that the thickness of the resin composition layer after drying became 27 μm, Dried in a hot-air circulation dryer at 80 DEG C for 20 minutes, and wound into a rolled form while bonding a polypropylene film having a thickness of 15 mu m as a protective film. The roll-shaped adhesive film was slit with a width of 507 mm to obtain a sheet-like adhesive film (photo-curable resin composition film (2)) of 507 x 336 mm size. The lowest melt viscosity of the obtained film was 120 poise and the lowest melt temperature was 128 占 폚.

(Production example of thermosetting resin composition film (3)) [

, 26 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Japan Epoxy Resins Co., Ltd.) and 26 parts of a naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" ) Was dissolved by heating in a mixed solvent of 15 parts of methyl ethyl ketone and 15 parts of cyclohexanone with stirring. Thereafter, 25 parts of a methyl ethyl ketone solution having a solid content of 60% of phenol novolak type curing agent ("TD2090" manufactured by DIC Corporation, phenolic hydroxyl group equivalent 105), 25 parts of a curing accelerator ("2E4MZ" , 45 parts of spherical silica (average particle diameter 0.5 탆, "SOC2" manufactured by Admatechs Company Limited), 15 parts of a polyvinyl butyral resin solution (ethoxylate of 15% solids in "KS1" manufactured by Sekisui Chemical Co., ) And 23 parts of a phenoxy resin solution ("FX293" manufactured by Tohto Kasei Co., Ltd., a solid content of 40% methyl ethyl ketone and cyclohexanone 2: 3 solution) And uniformly dispersed in a mixer to prepare a thermosetting resin composition varnish.

The varnish was applied uniformly on a release-treated surface of a 38 占 퐉 -thick release PET film (manufactured by Lintec Corporation, PET38-AL-5) with a die coater so that the thickness of the resin composition layer after drying became 27 占 퐉, (Average 100 ° C) for 6 minutes (amount of residual solvent in the resin composition layer: 1.5% by mass). Then, a polypropylene film having a thickness of 15 占 퐉 was bonded to the surface of the resin composition layer as a protective film and wound in a roll form. The roll-shaped adhesive film was slit with a width of 507 mm to obtain a sheet-like adhesive film (thermosetting resin composition film (3)) having a size of 507 x 336 mm. The lowest melt viscosity of the obtained film was 3310 poise and the lowest melt temperature was 135 占 폚.

(Production example of thermosetting resin composition film (4)) [

, 26 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Japan Epoxy Resins Co., Ltd.) and 26 parts of a naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" ) Was dissolved by heating in a mixed solvent of 15 parts of methyl ethyl ketone and 15 parts of cyclohexanone with stirring. Thereafter, 25 parts of a methyl ethyl ketone solution having a solid content of 60% of phenol novolak type curing agent ("TD2090" manufactured by DIC Corporation, phenolic hydroxyl group equivalent 105), 25 parts of a curing accelerator ("2E4MZ" 45 parts of spherical silica (average particle diameter 0.5 탆, manufactured by "SOC2" Admatechs Company Limited), 15 parts of a polyvinyl butyral resin solution ("KS1" manufactured by Sekisui Chemical Co., Ltd., 40 parts of a phenol resin solution (a 1: 1 solution of novolak and toluene) and 46 parts of a phenoxy resin solution ("FX293" manufactured by Tohto Kasei Co., Ltd., solid content 40% methyl ethyl ketone and cyclohexanone 2: 3 solution) , And the mixture was uniformly dispersed in a high-speed rotary mixer to prepare a thermosetting resin composition varnish.

The varnish was applied uniformly on a release-treated surface of a 38 占 퐉 -thick release PET film (manufactured by Lintec Corporation, PET38-AL-5) with a die coater so that the thickness of the resin composition layer after drying became 27 占 퐉, (Average 100 ° C) for 6 minutes (amount of residual solvent in the resin composition layer: 1.5% by mass). Then, a polypropylene film having a thickness of 15 占 퐉 was bonded to the surface of the resin composition layer as a protective film and wound in a roll form. The roll-shaped adhesive film was slit with a width of 507 mm to obtain a sheet-like adhesive film (thermosetting resin composition film (4)) of 507 x 336 mm size. The lowest melt viscosity of the obtained film was 13210 poise and the lowest melt temperature was 135 占 폚.

≪ Example 1 >

The protective film of the photo-curable resin composition film (1) and the thermosetting resin composition film (3) (size 507 x 336 mm, respectively) was peeled off, For, under the condition of temperature 70 ℃, pressure 7kgf / cm ^2, pressure 5mmHg below, copper-clad circuit (銅張) laminate (thickness of conductor circuit 18㎛, external size 510 × 340mm, thickness 0.2mm) are formed by a vacuum laminator for manufacturing Respectively, and laminated on both sides at the same time. Further, hot pressing was carried out continuously under the conditions of a temperature of 70 DEG C and a pressure of 5 kgf / cm < ² > by an SUS hard plate. The pushed-out of the resin of the photo-curable resin composition film 1 from the end face of the PET film after hot pressing to the peripheral edge of the copper clad laminate was 0.67 mm and the pushed out of the resin of the thermosetting resin composition film 3 was 0.18 mm.

Next, the photocurable resin composition film (1), the diameter by using the fixed pattern of a photomask is subjected to circular 600㎛, and a high pressure mercury lamp exposure apparatus was subjected to photocuring by exposure 200mJ / cm ^2. Next, the PET film on the side of the photocurable resin composition film (1) was peeled and then developed in a developer of 1.0% sodium carbonate aqueous solution (liquid temperature: 30 DEG C) for 60 seconds at a spray pressure of ² kg / dissolving and removing the light parts, and the screen was also the exposed portion using a high pressure mercury lamp exposure apparatus 1000mJ / cm ² using an exposure optical path. Then, the PET film on the side of the thermosetting resin composition film (3) was peeled off and then heated at 180 캜 for 60 minutes to thermoset.

After cooling to room temperature, a carbonic acid gas laser device (ML605GTWII-P) manufactured by Mitsubishi Electric Corporation was used to form a cured layer of a thermosetting resin composition film (3) mJ, a pulse width of 4 占 퐏, and a number of times of one shot to form a via hole (top diameter 60 占 퐉).

After the solder resist was formed on both sides in this manner, the substrate was transferred to ESPEC Corp. A thermal shock test was conducted under the conditions of a low-temperature bath temperature of -65 占 폚, a high-temperature bath temperature of 150 占 폚, an exposure time interval of 5 minutes, and a cycle of 1000 cycles, using a liquid bath thermo-shock testing apparatus (TSB-51) The presence of cracks was investigated. No cracks were observed in any of the solder resists on both sides.

≪ Comparative Example 1 &

Two pieces of the above-mentioned photo-curable resin composition film (1) were prepared and both protective films were peeled off to form a film on both sides of a circuit-laminated copper clad laminate (circuit conductor thickness 18 占 퐉, outer size 510 占 340mm, thickness 0.2mm) ) Was attached, and Nichigo-Morton Co., Ltd. The thermocompression bonding was carried out at 70 캜 by a varnish applicator of the manufacture. Next, with fixing the photomask subjected to a circular pattern having a diameter of 60㎛ on one side using a high pressure mercury lamp exposure apparatus and exposure 200mJ / cm ^2, it was subjected to photocuring. On the other side, a photomask having a circular pattern with a diameter of 600 mu m was fixed and photocuring was carried out in the same manner. After the PET films on both sides were peeled off, a 0.85% sodium hydroxide aqueous solution (liquid temperature: 30 캜) was used for the developer and developed for 60 seconds at a spray pressure of ² kg / cm ² to dissolve and remove the unexposed portions, Respectively. Thereafter, the exposed portion was exposed to 1000 mJ / cm ² using a high-pressure mercury lamp exposing apparatus to be photo-cured, and further heated at 180 캜 for 60 minutes for thermal curing. Thereafter, a thermal shock test was conducted in the same manner as in Example 1 to investigate the occurrence of cracks. No crack was observed on the side having the opening of 600 mu m in diameter, but a crack was observed in the vicinity of the opening of 60 mu m in diameter.

≪ Comparative Example 2 &

Two sheets of the thermosetting resin composition films 3 were prepared and both protective films were peeled off and attached to both surfaces of a copper clad laminate (circuit conductor thickness 18 占 퐉, external size 510 占 340mm, thickness 0.2mm) Meiki Co., Ltd. By means of a vacuum laminator for manufacturing, temperature 100 ℃, pressure 7kgf / cm ^2, pressure laminate on both sides, and under the conditions of 5mmHg below also conditions of continuous temperature 100 ℃, Pressure 5kgf / cm ² for hot press according to the SUS hard decision . Thereafter, the PET film was peeled off and then heated at 180 캜 for 60 minutes to effect thermal curing. After cooling to room temperature, an opening was made on the one surface with a carbon dioxide gas laser device (ML605GTWII-P) manufactured by Mitsubishi Electric Corporation under the condition of laser light wavelength of 9.3 탆, energy of 2.50 mJ, pulse width of 4 s, A top diameter of 60 mu m). On the other side, 10 shots were irradiated under the condition that the wavelength of the laser beam was 9.3 탆, the energy was 2.50 mJ, and the pulse width was 4 s while aiming for an opening with a diameter of 600 탆 in the top, but a desired opening could not be obtained. Thereafter, a thermal shock test was conducted in the same manner as in Example 1 to investigate the occurrence of cracks. No cracks were observed in any of the solder resists.

≪ Comparative Example 3 &

Each of the protective films of the photo-curable resin composition film (2) and the thermosetting resin composition film (4) was peeled off to obtain a circuit-laminated plate (circuit conductor thickness 18 占 퐉, outer size 510 占 340mm, thickness 0.2mm) And placed on one side. Both sides of the laminate were simultaneously laminated under the conditions of a temperature of 70 DEG C, a pressure of 7 kgf / cm < ² >, and an air pressure of 5 mmHg or less. Further, hot pressing was carried out continuously under the conditions of a temperature of 70 DEG C and a pressure of 5 kgf / cm < ² > by an SUS hard plate. The pushed out of the resin of the thermosetting resin composition film (4) was 0.17 mm and the pushed out of the resin of the photocurable resin composition film (2) was 3.10 mm. The resin was pushed out so that the experiment was completed when the solder resist could not be appropriately formed.

Table 1 summarizes the above results.

The acceptability of the resin in the opening forming process was evaluated by SEM observation and BSE observation using a scanning electron microscope (SU-1500 manufactured by Hitachi High-Technologies Corporation) (∘), and when the resin is not removed and the copper of the lower circuit is not visible, it is judged to be rejected (×).

The determination of whether or not the crack after the cold / heat impact was successful was determined by observing the presence or absence of cracks using a CCD type microscope (VHX-900, manufactured by Keyence Corporation) If any one of them occurred, it was rejected (×).

According to the present invention, it is possible to prevent the high internal resistance of the solder resist layer for forming the openings with a small opening diameter for the purpose of solder bonding with the semiconductor chip or the like and the relatively large opening diameter It is possible to achieve an efficient formation of openings in the solder resist layer forming the openings.

This application is based on Japanese Patent Application No. 2009-105100, the contents of which are incorporated herein by reference.

Claims (8)

A resin composition film formed by forming a resin composition layer made of a photo-curable resin composition before curing on a support is laminated on one side of a circuit substrate, a solder resist layer is formed by the resin composition layer, and a thermosetting resin A step of laminating a resin composition film having a resin composition layer made of a composition on the other side of a circuit board and forming a solder resist layer using the resin composition layer as a lamination treatment of the resin composition film using a vacuum laminator And a step of collectively forming the solder resist layer formed on one surface and the other surface of the circuit board by a planarization process by a hot press followed by the step,
Wherein the minimum melting temperature of both the photocurable resin composition before curing and the thermosetting resin composition before curing is in the range of 80 to 160 캜 and the ratio of the minimum melt viscosity of both is 0.01 to 100,
Characterized in that opening formation in the solder resist layer formed on one side of the circuit board is performed by photolithography and formation of openings in the solder resist layer formed on the other side of the circuit board is performed by laser Way. The method according to claim 1, wherein the ratio of the minimum melt viscosity of both the photo-curable resin composition before curing and the thermosetting resin composition before curing is 0.05 to 20. The method according to claim 1 or 2, wherein a baking step of a solder resist layer formed on one surface of the circuit board and having an opening formed by photolithography, and a thermosetting step of a solder resist layer formed on the other surface of the circuit board are simultaneously performed And then forming an opening in the solder resist layer formed on the other surface of the circuit board with a laser. The method according to claim 1 or 2, wherein the contact surface of the support with the resin composition layer is subjected to a release treatment. The method according to claim 1 or 2, wherein the printed wiring board is a semiconductor package substrate. The method according to claim 1 or 2, wherein the printed wiring board is a semiconductor package substrate on which the semiconductor chip is mounted on the other surface of the circuit board. delete delete