KR20100117035A - Method for manufacturing printed circuit board - Google Patents

Abstract

PURPOSE: A method for manufacturing a printed wiring plate is provided to secure the high heat-resistance property of a solder resist layer by differentiating an opening part forming process with respect to a solder resist layer according to the size of a diameter. CONSTITUTION: Solder resist layers are formed on both sides of a circuit board. An opening part with a large diameter is formed on one side of the solder resist layers using a photo-lithography method. An opening part with a small diameter is formed on the other side of the solder resist layer using laser. One side of the solder resist layer is made of a photo curable resin composition. The other side of the solder resist layer is made of a heat curable resin composition.

Description

Method for manufacturing printed circuit board

TECHNICAL FIELD This invention relates to the manufacturing method of a printed wiring board. Specifically, It is related with the improvement of the technology of forming opening part in a soldering resist layer.

The method of pattern formation of the solder resist by photolithography causes a problem that it cannot sufficiently cope with thinning and fine wiring in a recent circuit board, or can not sufficiently cope with an increase in solder reflow temperature due to lead freeization. . This is because photo-resist resists require photosensitivity and developability, and thus the raw materials that can be used are limited, and hardened materials that can sufficiently satisfy heat resistance and mechanical properties cannot be obtained. Particularly, in the case of Via, which is an opening for connecting with a semiconductor chip, fine processing such as an opening diameter of 100 μm or less is required, the solder resist requires high photosensitivity and developability. It has been pointed out that a crack is generated when heat shock is applied after the opening is formed. In order to cope with such a problem, for example, Patent Literatures 1 to 4 use a thermosetting resin composition as a material of a solder resist, and use a laser as a method of forming an opening, where the solder resist layer corresponds to a solder land. Disclosed is a method for forming a via hole in a. That is, when such a method is used, since a photoresist and developability are not required for a soldering resist, the material which has high heat resistance and a mechanical characteristic can be selected.

However, in a semiconductor package substrate or the like, the opening diameter of the opening is relatively small in the solder resist layer provided on the side of the side where the semiconductor chip is mounted, so that the punching by the laser can be performed suitably. In the solder resist layer described above, since the opening diameter of the opening for connecting to the motherboard or the like reaches from 200 µm to several mm, there is a drawback that the work efficiency is greatly reduced, for example, a very large number of laser shots are required to form the laser.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2000-244125

[Patent Document 2] Japanese Unexamined Patent Publication No. 2004-240233

[Patent Document 3] Japanese Unexamined Patent Publication No. 2005-347429

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

Problems to be Solved by the Invention The problem to be solved by the present invention is to achieve high heat resistance of a solder resist layer in which openings having a small opening diameter are formed for solder bonding with a semiconductor chip or the like, in forming a solder resist of a printed wiring board, It is to provide a method for producing a printed wiring board that can form an opening in a solder resist layer that needs to form an opening having a relatively large opening diameter for connection with a circuit or an electronic component.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors used a laser, such as a motherboard, for the formation of the opening part to the soldering resist layer formed in the one side which requires fine opening part formation in a printed wiring board, or It has been found that the above-mentioned problem is solved by performing photolithography to form an opening in the solder resist layer formed on the other side, which needs to form an opening having a relatively large opening diameter for connection with an electronic component. The invention was completed.

That is, this invention includes the following content.

[1] A solder resist layer is formed on both sides of a circuit board, photolithography is used to form openings in the solder resist layer formed on one side, and laser forming is performed in the solder resist layer formed on the other side. The manufacturing method of the printed wiring board characterized by the above-mentioned.

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

[3] The method of [2], wherein the solder resist layer formed on one side and the other side of the circuit board is formed by using a resin composition film in which a resin composition layer is formed on a support.

[4] The solder resist layer formed on one side and the other side of the circuit board is collectively formed by the lamination process using the vacuum laminator and the planarization process by the heat press following this in [3]. How to.

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

[6] The baking step and the thermosetting of any one of the above [2] to [5], after forming the opening by photolithography of the solder resist layer made of the photocurable resin composition, and forming the photoresist composition. The method of simultaneously performing the thermosetting process of the soldering resist layer which consists of a resin composition, and then forming an opening part with a laser in the soldering resist layer which consists of a thermosetting resin composition.

[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 manufacturing method of the printed wiring board of the present invention, an opening having a relatively large opening diameter for the purpose of connecting to a circuit such as a motherboard or an electronic component such as a resistor, a capacitor, a coil, etc. For example, an opening can be efficiently formed by photolithography in the solder resist layer to be formed at 200 μm or more, and a solder joint with a semiconductor chip formed on the other side of the circuit board can be used. Since the thermosetting resin composition excellent in heat resistance can be applied to the soldering resist layer which forms the opening part (for example, 100 micrometers or less) with a relatively small opening diameter, it becomes possible to manufacture a printed wiring board excellent in heat resistance more efficiently.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on suitable embodiment.

The manufacturing method of the printed wiring board of this invention forms a soldering resist layer on both surfaces of a circuit board, forms the opening part in the soldering resist layer formed in one side by photolithography, and the opening part in the soldering resist layer formed in the other side It is a main feature to perform formation by laser irradiation.

For example, in a semiconductor package board | substrate, a semiconductor chip is mounted and the soldering resist layer of the side (one side) where higher heat resistance is calculated | required is formed with a thermosetting resin composition, an opening part is formed by a laser, and it mounts on a motherboard Formation of the other solder resist layer by employing photolithography using a photocurable resin composition enables high workability even in an opening having a relatively large opening diameter at the time of forming the opening.

The printed wiring board manufactured by the method of this invention may be a rigid board | substrate, a flexible board | substrate, or a rigid flexible board | substrate. In addition, the structure may be a double-sided substrate or a multilayered substrate. Examples of the multilayer substrate include through-layer multilayer boards, interstitial via hole (IVH) multilayer substrates, build-up substrates, and the like. Among them, build-up substrates having a high mounting density are preferable, and in particular, semiconductor package substrates are preferable. .

Although any solder resist of an ink type and a dry film type can be used for formation of the soldering resist layer in this invention, since the work efficiency is good and thickness control is easy, the soldering resist layer formed on both surfaces of a circuit board is used. It is preferable to apply a dry film type soldering resist to both. A dry film soldering resist is formed by laminating (pressing) a resin composition film on which a resin composition layer is formed on a support. Moreover, in this invention, the circuit board in which a soldering resist layer is formed is a board | substrate with which the conductor circuit is formed in one side or both surfaces, and becomes a precursor of the said printed wiring board.

In this invention, in order to form an opening part by exposure and image development (photolithography), the photo solder resist is used for the soldering resist layer formed in one surface of a circuit board. For example, in a semiconductor package board | substrate, opening formation is formed by photolithography using a photo solder resist for the soldering resist layer of the surface mounted on a motherboard. The photo solder resist has photosensitivity and developability, and can be used without particular limitation as long as it is a photocurable resin composition applicable to photolithography. As a preferable example, the resin composition containing (a) photocurable alkali-soluble resin, (b) epoxy resin, (c) photoinitiator, (d) hardening accelerator, and (e) diluent is mentioned. In order to improve heat resistance, reliability, etc., the photocurable resin composition for photo solder resist contains epoxy resin as mentioned above, and what has thermosetting property is used suitably, but in this invention, it is a photoinitiator and developable sight. If it contains the resin component etc. of a ignition type, and is a resin composition which has photosensitivity and developability, such a resin composition is defined as "photocurable resin composition", even if it has thermosetting property.

(a) As a photocurable alkali-soluble resin, For example, the acid pendant type | mold unsaturated epoxy ester resin which made unsaturated carboxylic acid react with the polyfunctional epoxy resin, and made the acid anhydride react, and also said acid pendant type unsaturated epoxy ester resin ( (Meth) acryloyl group and / or allyl group containing alkali-soluble resin etc. which are obtained by making the epoxy compound which has a meta) acryloyl group, and / or the epoxy compound which has an allyl group react.

As the polyfunctional epoxy resin, any compound having two or more epoxy groups in the molecule can be used. Specifically, a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a hydrogenated bisphenol Non-phenol type epoxy resins, such as bisphenol type epoxy resins, such as an F type epoxy resin and a bisphenol S type epoxy resin, a naphthalene type epoxy resin, such as a dihydroxy naphthalene type epoxy resin and a vinapthol type epoxy resin, and a tetramethyl biphenol type Novolak-type epoxy resins, such as resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol A novolak-type epoxy resin, naphthol novolak-type epoxy resin, and alkylphenol novolak-type epoxy resin, bisphenol F Bisphenol F type epoxy resin etc. which modified | denatured to trifunctional or more by making epichlorohydrin react with a type | mold epoxy resin are mentioned. These may be used individually by 1 type, or may use 2 or more types together. Especially, the bisphenol F-type epoxy resin which modified | denatured trifunctional or more by making epichlorohydrin react with cresol novolak-type epoxy resin and bisphenol F-type epoxy resin is a soldering resist excellent in developability, insulation reliability, etc. It is preferable from the viewpoint of realizing.

Moreover, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, etc. are mentioned, for example, These may be used individually by 1 type, or may use 2 or more types together. Especially, acrylic acid and methacrylic acid are preferable at the point of photocurability of a composition.

The reaction between the polyfunctional epoxy resin and the unsaturated carboxylic acid is in the range of 0.8 to 1.2, wherein the ratio of the number of moles of the epoxy group of the polyfunctional epoxy resin and the number of moles of the carboxyl group of the unsaturated carboxylic acid (moles of the epoxy group / moles of the carboxyl group) is almost one. It is preferable to perform at.

In addition, the reaction product between the polyfunctional epoxy resin and the unsaturated carboxylic acid is reacted 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. It is preferable at the point of stability of (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 benzophenonetetracarboxylic dianhydride. These may be used individually by 1 type, or may use 2 or more types together. Especially, succinic anhydride and tetrahydrophthalic anhydride are preferable at the point of the insulation reliability of the cured coating film obtained by hardening the developability of a composition and a composition.

An acid pendant type unsaturated epoxy ester resin can be obtained by making said polyfunctional epoxy resin and unsaturated carboxylic acid react in presence of a catalyst, and then making unsaturated carboxylic acid modified epoxy resin and acid anhydride which are obtained reactants react.

As for the quantity of the catalyst used at this time, 2 mass% or less is preferable with respect to the total mass of a polyfunctional epoxy resin, unsaturated carboxylic acid, and an acid anhydride, 0.0005-1 mass% is more preferable, The range of 0.001-0.5 mass% especially desirable. As the catalyst, for example, N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 ( DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole , 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N- Various amines such as phenyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide Compounds; Phosphines such as trimethyl phosphine, tributyl phosphine and triphenyl phosphine; Phosphoniums such as tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxypropyl) phosphonium salt, triphenylphosphonium salt, benzylphosphonium salt As a salt and a typical large anion, Phosphonium salt which has a carboxylate, a hydroxide, etc .; Sulfonium salts such as trimethylsulfonium salt, benzyl tetramethylenesulfonium salt, phenylbenzylmethylsulfonium salt, or phenyldimethylsulfonium salt, which are representative anti-anions, and sulfonium having chloride, bromide, carboxylate, and hydroxide salts; Acid compounds, such as phosphoric acid, p-toluene sulfonic acid, and sulfuric acid, etc. are mentioned.

Although these reaction can be performed at 50-150 degreeC, as for the reaction temperature of a polyfunctional epoxy resin and unsaturated carboxylic acid, 100-120 degreeC is preferable, when it is less than 100 degreeC, reaction rate is slow, reaction requires a long time, and reaction temperature When exceeds 120 degreeC, superposition | polymerization of unsaturated carboxylic acid arises and there exists a possibility of gelatinizing in a reaction process. Moreover, in order to prevent superposition | polymerization of unsaturated carboxylic acid in reaction of such a polyfunctional epoxy resin and unsaturated carboxylic acid, it is preferable to add a polymerization inhibitor, As a polymerization inhibitor, hydroquinone, methoxy hydroquinone, benzo, for example. Quinone-based polymerization inhibitors such as quinone and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, Alkylphenol 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-2,2 , 6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy-2,2,6, Amine polymerization inhibitors such as 6-tetramethylpiperidine; 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2, N-oxyl polymerization inhibitors, such as 6, 6- tetramethyl piperidine-N-oxyl, etc. are mentioned. These may be used independently and may use 2 or more types together. 0.01-1 mass% is preferable with respect to unsaturated carboxylic acid, and, as for a polymerization inhibitor, 0.05-0.5 mass% is more preferable.

The reaction temperature of the unsaturated carboxylic acid-modified epoxy resin obtained by reacting the polyfunctional epoxy resin with the unsaturated carboxylic acid and the acid anhydride is preferably 70 to 110 ° C. If it is less than 70 degreeC, reaction rate will be slow, reaction will require a long time, and if reaction temperature exceeds 110 degreeC, superposition | polymerization of unsaturated carboxylic acid modified epoxy resin may arise, and resin may gelatinize.

As a usage ratio of an acid anhydride, the range whose solid dispersion value of a product (acid pendant unsaturated epoxy ester resin) becomes 30-150 mgKOH / g is preferable, and 50-120 mgKOH / g is especially preferable. When the acid value is less than 30 mgKOH / g, the alkali developability of the target composition tends to decrease, and when the acid value exceeds 150 mgKOH / g, the fine pattern of the formed solder resist flows due to development, or the characteristics such as insulation reliability decrease. There is a tendency.

The reaction between the acid pendant unsaturated epoxy ester resin and the epoxy compound having a (meth) acryloyl group and / or the epoxy compound having an allyl group includes an epoxy compound having a (meth) acryloyl group and / or an epoxy compound having an allyl group, With respect to 1 equivalent of the carboxyl group of the acid pendant unsaturated epoxy ester resin, preferably from 0.01 to 0.5 equivalents, particularly preferably from 0.1 to 0.4 equivalents, by the usual method, preferably from 60 to 150 ° C, particularly preferably It can carry out by heating and stirring at 80-120 degreeC.

As an epoxy compound which has a (meth) acryloyl group, For example, glycidyl (meth) acrylate, (alpha)-ethylglycidyl acrylate, (alpha)-n-propyl glycidyl acrylate, (alpha)-n-butylglycol. Cydyl acrylate, β-methylglycidyl (meth) acrylate β-ethylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate 6,7-epoxyheptyl (meth) acrylate , α-ethyl-6,7-epoxy-heptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ethyl, p-vinyl benzyl glycidyl ether, and the like. These may be used individually by 1 type, or may use 2 or more types together. Especially, glycidyl (meth) acrylate and (alpha)-ethylglycidyl acrylate are preferable, and glycidyl methacrylate is especially preferable. Moreover, as an epoxy compound which has an allyl group, allyl glycidyl ether, p-allyl benzyl glycidyl ether, etc. are mentioned, for example, These may use any 1 type individually or may use both together.

The epoxy compound having a (meth) acryloyl group and / or the epoxy compound having an allyl group is added to the solution of the acid pendant unsaturated epoxy ester resin and reacted, but with respect to 1 mol of the carboxyl group introduced into the acid pendant unsaturated epoxy ester resin. It is preferable to make it react in the ratio of 0.01-0.5 mol. Considering the photosensitivity of the target resin composition, it is advantageous to make it react in the ratio of 0.1-0.4 mol preferably. As for reaction temperature, 80-120 degreeC is preferable. The acid pendant unsaturated epoxy ester resin can be used as a photocurable resin itself, but the (meth) acryloyl group-containing epoxy compound and / or allyl group-containing epoxy compound react with the carboxyl group of the acid pendant unsaturated epoxy ester resin. Since the (meth) acryloyl group and / or allyl group couple | bond with the side chain of the polymer skeleton of an acid pendant type unsaturated epoxy ester resin, photosensitivity is further improved. From the viewpoint of photosensitivity, the (meth) acryloyl group and / or allyl group-containing alkali-soluble resin obtained in this way have a solid dispersion value of preferably 30 to 250 mgKOH / g, more preferably 40 to 110 mgKOH / g.

(b) As epoxy resin, if it is suitable for the insulating material in a printed wiring board, it can use without a restriction | limiting especially, For example, bisphenol A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, complex Cyclic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkylphenol novolak type epoxy resin, biphenol type epoxy resin (biphenyl type epoxy resin), aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin , Dicyclopentadiene type epoxy resin, epoxide of condensate of phenol with aromatic aldehyde having phenolic hydroxyl group, naphthol type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, anthracene type epoxy resin, xanthene type Epoxy resins, such as an epoxy resin, are mentioned. Such epoxy resin may use any 1 type, or may use 2 or more types together. The hardening | curing agent used together with these epoxy resins can use the same thing as the hardening | curing agent described later.

Among the epoxy resins, dicyclopentadiene type epoxy resins and biphenol type epoxy resins (biphenyl type epoxy resins) are preferable. As a dicyclopentadiene type epoxy resin, "HP7200", "HP7200H", "HP7200HH" by Nippon Kayaku Co., Ltd. make by DIC Corporation. "XD-1000", "XD-1000-L", "XD-10002L" etc. of manufacture are mentioned, Nippon Kayaku Co., Ltd. as a non-phenol type epoxy resin is mentioned. "NC3000", "NC3000H", "NC3000L", "NC3100" of manufacture, Tohto Kasei Co., Ltd. `` GK3207 '' of manufacture, Japan Epoxy Resins Co., Ltd. "YX4000HK" etc. of manufacture are mentioned.

It is preferable to use the said epoxy resin in the ratio of 5-100 mass parts with respect to 100 mass parts of (a) photocurable alkali-soluble resin, and 10-85 mass parts is more preferable. If it is less than 5 mass parts, a coating film will become inadequate in hardening, and heat resistance, electrical insulation, etc. will tend to fall, and if it exceeds 100 mass parts, developability will fall.

(c) As a photoinitiator, benzophenone, methyl benzophenone, o-benzoyl benzoic acid, benzoyl ethyl ether, 2, 2- diethoxy acetophenone, 2, 4- diethyl thioxanthone, 2-benzyl-2, for example. -Dimethyl amino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-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-cyclohexyl-phenylketone, 2,2-dimethoxy-1 , 2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4 And 6-trimethylbenzoyl) -phenylphosphine oxide, and sulfonium salt-based and oxime ester-based photopolymerization initiators. As the usage-amount of the said photoinitiator, it is 0.5-30 mass parts with respect to 100 mass parts of resin solid content of a resin composition, Preferably it exists in the range of 1-15 mass parts. If the amount of the photopolymerization initiator is used in excess of the above range, there is a fear of deterioration of the heat curability, heat resistance, electrical insulation of the composition, etc., and if the amount of the photopolymerization initiator is less than the above range, the curing is insufficient when the composition is photocured. There is concern.

(d) A hardening accelerator is used in order to promote thermosetting in the thermosetting process after photocuring of a composition, For example, although amines, polyamides, imidazole, an organic phosphine type compound, etc. are mentioned, a coating film From the viewpoint of the balance of performance, amines and imidazoles are preferable, and specific examples thereof include 2-methylimidazole, triphenylphosphine, ethylguanidinoamine, diaminodiphenylmethane, melamine, and boron trifluoride-amine. Complexes, dicyandiamide (DICY) and derivatives thereof, and amineimide (AI). Especially, melamine and dicyandiamide (DICY) are especially preferable. (d) It is preferable to use the compounding quantity of a hardening accelerator in 0.1-20 mass% with respect to (b) epoxy resin.

(e) Diluent is mix | blended for the purpose of improvement of the photoreactivity of a composition, etc. As such a diluent, a liquid, solid, or semisolid photosensitive (meth) acrylate compound can be used, for example at room temperature which has one or more (meth) acryloyl groups in 1 molecule. Typical examples include mono or diacrylates of hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, glycols such as ethylene glycol, methoxy tetraethylene 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 Polyhydric alcohols such as these, polyhydric acrylates such as ethylene oxide, propylene oxide or ε-kaflolactone, phenols such as phenoxyacrylate and phenoxyethyl acrylate, or ethylene oxide or propylene oxide adducts thereof Glycines, such as acrylates and trimethylolpropane triglycidyl ether Epoxy acrylates, melamine acrylates, and / or methacrylates corresponding to the above acrylates may be cited. Among these, polyhydric acrylates or polyhydric methacrylates are preferable, and as trivalent acrylates or methacrylates, for example, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate , Trimethylolpropane EO addition tri (meth) acrylate, glycerin PO addition tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethylcarbitol oligo (meth) Acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethol Methanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N ', N'-tetrakis (β-hydr (Meth) acrylic acid ester of the ethyl ethyl) diamine, etc. are mentioned, and tri (2- (meth) acryloyloxyethyl) phosphate and tri (2- (meth) are mentioned as trivalent or more acrylates or methacrylates. ) Acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyl-2-hydroquinyloxypropyl) phosphate, di (3- (meth) ) Acryloyl-2-hydroquinyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) acryloyl-2-hydroquisiloxypropyl) di (2- (meth) Phosphoric acid triester (meth) acrylate, such as acryloyloxyethyl) phosphate, is mentioned. These photosensitive (meth) acrylate compounds may be used individually by 1 type, or may use 2 or more types together.

(e) It is preferable to use the diluent in 1-50 mass parts with respect to 100 mass parts of total amounts of (a) photocurable alkali-soluble resin and (b) epoxy resin, and 5-30 mass parts is more preferable. . If it is less than 1 mass part, the effect of improving light reactivity will be hard to be acquired, and if it exceeds 50 mass parts, the stickiness of the coating film by a composition will become large and workability will tend to deteriorate.

The resin composition containing such (a)-(e) component may contain (f) filler further. Inorganic fillers and / or organic fillers may be used for the filler.

As the inorganic filler, for example, 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, titanium titanate Barium, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like, and silica and barium sulfate are preferable, and in particular, amorphous silica, fused silica, and crystals. Silica, such as silica and synthetic silica, is preferable. Moreover, it is preferable that an average particle diameter is 3 micrometers or less, and, as for an inorganic filler, it is more preferable that an average particle diameter is 1.5 micrometers or less. The inorganic fillers may be used alone, or two or more kinds thereof may be used in combination. The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the laser diffraction particle size distribution measuring device can measure the particle size distribution of the inorganic filler on a volume basis and make the median diameter the average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As a laser diffraction particle size distribution measuring device, HORIBA, Ltd. Manufactured LA-500 etc. can be used.

Inorganic fillers include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (amino to improve moisture resistance, dispersibility, etc.). Aminosilane-based coupling agents such as ethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxy Epoxysilane coupling agents, such as a silane and (3, 4- epoxycyclohexyl) ethyltrimethoxysilane, mercapto silane coupling agents, such as mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane, and methyl tree Silane coupling agents such as methoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methoxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethylsilazane, hexaphenyldisilazane,Organosilazane compounds such as methylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimer, titanium octylene glycolate , Diisopropoxy citan bis (triethanol aluminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyro Phosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra Octylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyl triku Milpe Titanate, Isopropyl triisostearoyl titanate, Isopropyl isostaroyl diacrylitanate, Isopropyl dimethacrylic isostaroyl titanate, Isopropyl tri (dioctyl phosphate) titanate, Isopropyl Such as tridodecylbenzenesulfo titanate, isopropyl tris (dioctylpyrophosphate) titanate, titanate coupling agent of isopropyl tri (N-amide ethyl aminoethyl) titanate, silica-alumina surface treatment agent You may be processed by 1 type or 2 or more types of surface treating agents.

Examples of the organic filler include acrylic rubber particles, polyamide fine particles, silicon particles, and the like. Specific examples of the acrylic rubber particles are a fine particle body of a resin which is subjected to chemical crosslinking treatment to resins exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, acrylic rubber, and the like and are insoluble and insoluble in organic solvents. Any one may be used, for example, XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Stapiroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Ganz Chemical Co., Ltd.) ) Pararoid EXL2655, EXL2602 (above, Kureha Corporation) etc. are mentioned. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, aromatic polyamide such as Kevlar, or fine particles of a resin having an amide bond such as polyamideimide. For example, VESTOSINT 2070 (Daicel Daicel- Huels Ltd.) and SP500 (made by Toray Industries, Inc.) etc. are mentioned. The range of 0.005-1 micrometer is preferable, and, as for the average particle diameter of an organic filler, the range of 0.2-0.6 micrometer is more preferable. The average particle diameter of the organic filler can be measured using the 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, and the particle size distribution of the organic filler is prepared on a mass basis, and the median is used. It can measure by making diameter into an average particle diameter.

When the non-volatile content of the resin composition is 100% by mass, the amount of the filler used (f) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass.

The solder resist layer formed on the other side of the circuit board performs the opening formation by a laser. For example, in a semiconductor package board | substrate, the soldering resist layer of the surface in which a semiconductor chip is mounted which requires more heat resistance is formed with a thermosetting resin composition, and an opening part is formed by a laser. By forming an opening part with a laser, it is not necessary to use a photocurable resin composition, and the thermosetting resin composition excellent in heat resistance can be used. As mentioned above, although the resin composition which has photocurable property and thermosetting property, including developable photocurable resin component, such as photocurable alkali-soluble resin, etc. can also be used, generally such a photocurable resin composition is a thermosetting resin composition. Since heat resistance is inferior, it is preferable to use the thermosetting resin composition which can be hardened only by thermosetting.

In the present invention, the term thermosetting resin composition means a thermosetting resin composition having substantially no photocurability. As thermosetting resin used as a main body, thermosetting resins, such as an epoxy resin and bismaleimide triazine resin, are mentioned, for example. As a preferable thermosetting resin composition, it is a resin composition containing an epoxy resin and a hardening | curing agent, and especially the resin composition containing (A) epoxy resin, (B) polymer component, and (C) hardening | curing agent is preferable.

Here, as the (A) epoxy resin, for example, bisphenol A epoxy resin, biphenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and complex Cyclic epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkylphenol novolak type epoxy resin, fluorene type epoxy resin, anthracene type epoxy resin, xanthene type epoxy The resin, the phosphorus containing epoxy resin, the epoxy resin which has butadiene structure, the alkyl substituent of these epoxy resins, a hydrogenated substance, etc. are mentioned. These epoxy resins may use any 1 type, or may mix and use 2 or more types.

Among them, epoxy resins having a bis phenol A type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a butadiene structure are preferable from the viewpoints of heat resistance, insulation reliability, and adhesion. Specifically, for example, liquid bisphenol A epoxy resin ("Epicoat 828EL" made by Japan Epoxy Resins Co., Ltd.), diglycidyl ether compound (bifunctional type) of naphthalenediol (DIC Corporation) "HP4032", "HP4032D"), naphthalene type tetrafunctional epoxy resin ("HP4700" by DIC Corporation), naphthol type epoxy resin ("ESN-475V" by Tohto Kasei Co., Ltd.), butadiene structure Epoxy resin ("PB-3600" manufactured by Daicel Daicel-Huels Ltd.), epoxy resin having a biphenyl structure ("NC3000", "NC3000H", "NC3000L", "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) NC3100 "," YX4000HK "by Japan Epoxy Resins Co., Ltd.), etc. are mentioned.

(B) A polymer component is mix | blended for the purpose of giving a suitable flexibility to the composition after hardening, For example, a phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyether sulfone, polysulfone And aliphatic polyester polyols, polyether polyols, polycarbonate polyols, polyethylene terephthalate polyols, and acrylic resins. These may be used individually by 1 type, or may use 2 or more types together. When the said non-volatile component of a resin composition is 100 mass%, the said polymeric component is mix | blended in the ratio of 0.5-60 mass%, More preferably, it is 3-30 mass%. When the blending ratio of the polymer component is less than 0.5% by mass, since the viscosity of the resin composition is low, it becomes difficult to form a layer having a uniform thickness, and when it exceeds 60% by mass, the viscosity of the resin composition becomes too high. This tends to make embedding in the wiring pattern on the circuit difficult.

As a specific example of a phenoxy resin, Tohto® Kasei® Co., Ltd., for example. FX280, FX293, Japan Epoxy Resins Co., Ltd. Manufactured YX8100, YL6954, YL6974, etc. are mentioned.

The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and specific examples of the polyvinyl acetal resin are manufactured by Denki Kagaku Kogyo Kabushiki Kaisha, telephone butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co. ., Ltd. Esque BH series, BX series, KS series, BL series, BM series etc. of manufacture are mentioned.

Specific examples of the polyimide include New Japan Chemical Co., Ltd. The polyimide "Rika coat SN20" and "Rika coat PN20" of manufacture are mentioned. In addition, linear polyimide (described in JP 2006-37083) and polysiloxane skeleton-containing polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic anhydride Modified polyimide such as those described in Japanese Patent Application Laid-Open No. 2002-12667, Japanese Unexamined Patent Application Publication No. 2000-319386, and the like.

Specific examples of the polyamide-imide include Toyobo Co., Ltd. The polyamide-imide "Biromax HR11NN" of manufacture, "Biromax HR16NN", etc. are mentioned. Moreover, modified polyamideimide, such as polysiloxane frame | skeleton containing polyamideimide "KS9100" and "KS9300" by Hitachi Chemical Co., Ltd, is mentioned.

Specific examples of the polyether sulfone include Sumitomo Chemical. Co., Ltd. Polyether sulfone "PES5003P" etc. of manufacture are mentioned.

As a specific example of polysulfone, polysulfone "P1700", "P3500", etc. made by Solver Advanced Polymers Co., Ltd. are mentioned.

As the (C) hardener, for example, an amine hardener, guanidine hardener, imidazole hardener, phenol hardener, naphthol hardener, acid anhydride hardener, active ester hardener, or these epoxy adducts or microencapsulated The thing, benzoxazine resin, cyanate ester resin, etc. are mentioned. Especially, a phenol type hardening | curing agent, a naphthol type hardening | curing agent, and cyanate ester resin are preferable. The hardener may be used alone or in combination of two or more.

As a specific example of a phenol type hardening | curing agent and a naphthol type hardening | curing agent, for example, MEH-7700, MEH-7810, MEH-7851 (above, manufactured by Meiwa Plastic Industries, Ltd.), NHN, CBN, GPH (above, Nippon Kayaku Co., Ltd.) Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (above, manufactured by Tohto® Kasei Co., Ltd.), LA7052, LA7054, LA3018, LA1356 (manufactured by DIC Corporation), etc. Can be.

Moreover, as a specific example of cyanate ester resin, bis phenol A dicyanate, polyphenol cyanate (oligo (3-methylene- 1, 5- phenylene cyanate), 4,4'- methylene bis (2, for example) , 6-dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis ( Bifunctional cyanate resins such as 4-cyanatephenyl) thioether and bis (4-cyanatephenyl) ether, polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and these cyanate resins are partially tria Evolved prepolymer, etc. Commercially available cyanate ester resins include phenol novolac-type polyfunctional cyanates. Terpolymer ("PT30" manufactured by Lonza Japan Ltd., cyanate equivalent 124) and some or all of bisphenol A dicyanate are triazines to form a trimer ("BA230" manufactured by Lonza Japan Ltd., cyanate And equivalents 232).

In the case of a phenolic hardener or a naphthol hardener, the compounding ratio of (A) epoxy resin and (C) hardening | curing agent is the ratio which the phenolic hydroxyl group equivalent of these hardening | curing agents becomes the range of 0.4-2.0 with respect to the epoxy equivalent of epoxy resin 1 This is preferable and the ratio which becomes the range of 0.5-1.0 is more preferable. In the case of cyanate ester resin, the ratio in which cyanate equivalent is 0.3 to 3.3 with respect to epoxy equivalent 1 is preferable, and the ratio in the range of 0.5-2 is more preferable.

In addition to (C) hardening | curing agent, (D) hardening accelerator can be further mix | blended with thermosetting resin composition, As such a hardening accelerator, an imidazole compound, an organic phosphine type compound, etc. are mentioned, As a specific example, it is 2, for example. -Methylimidazole, 2-ethyl4-methylimidazole, triphenylphosphine, etc. are mentioned. When using a hardening accelerator, it is preferable to use in 0.1-3.0 mass% with respect to (A) epoxy resin. Moreover, when using cyanate ester resin for (C) hardening agent, even if it adds the organometallic compound currently used as a hardening catalyst in the system which used together an epoxy resin composition and a cyanate compound for the purpose of shortening hardening time. good. Examples of the organometallic compound include organic copper compounds such as copper (II) acetylacetonite, organic zinc compounds such as zinc (II) acetylacetonite, organic cobalt compounds such as cobalt (II) acetylacetonite and cobalt (III) acetylacetonite. Can be mentioned. As for the addition amount of an organometallic compound, 10-500 ppm is preferable in conversion of metal with respect to cyanate ester resin, and the range of 25-200 ppm is more preferable.

The thermosetting resin composition may contain the filler further. Inorganic fillers and / or organic fillers may be used for the filler. Examples of the inorganic filler are as described above. In addition, among the inorganic fillers, silica and alumina are preferable, and silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, spherical silica, pulverized silica is particularly preferable. The average particle diameter, surface treatment, and the like of the inorganic filler are the same as described above. In addition, the kind and average particle diameter of an organic filler are mentioned above. When content of the inorganic filler in a thermosetting resin composition is 100 mass% of non volatile components of a thermosetting resin composition, Preferably it is 20-80 mass%, More preferably, it is 30-70 mass%. When content of an organic filler is 100 mass% of non volatile components of a thermosetting resin composition, Preferably it is 1-10 mass%, More preferably, it is 2-5 mass%.

The thermosetting resin composition can also mix | blend thermosetting resins other than epoxy resins, such as a maleimide compound, a bisallyl naimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin. You may use these thermosetting resins in mixture of 2 or more types. As the maleimide resin, BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (above, manufactured by Daiwakasei Industry Co., Ltd), BMI, BMI-70, BMI-80 (above, manufactured by KI Chemical Industry Co., Ltd.), ANILIX- MI (manufactured by Mitsui Fine Chemical Inc.), BANI-M, BANI-X (above, manufactured by Maruzen Petrochemical Co., Ltd.) as the bisallynalimide compound, and V5000 (manufactured by Showa Highpolymer Co., Ltd.) as the vinyl benzyl resin. ) And vinyl benzyl ether resin include V1000X and V1100X (above, manufactured by Showa Highpolymer Co., Ltd.).

The photocurable resin composition and / or thermosetting resin composition of this invention may contain a flame retardant. A flame retardant may mix and use 2 or more types. As a flame retardant, an organophosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide, etc. are mentioned, for example. As organophosphorus flame retardant, Sanko Co., Ltd. Phosphine compounds such as HCA, HCA-HQ, HCA-NQ, manufactured by Showa Highpolymer Co., Ltd. Phosphorus-containing benzoxazine compounds such as manufactured HFB-2006M, Ajinomoto Fine-Techno Co., Inc. Leopard 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Hokko Chemical Industry Co., Ltd. PPＱ of manufacture, OP930 of Clariant Co., Ltd., Daihachi Chemical Industry Co., Ltd. Phosphate ester compounds, such as PX200, Tohto Kasei Co., Ltd. Phosphorus containing epoxy resins, such as FX289 and FX310, Tohto Kasei Co., Ltd. Phosphorus containing phenoxy resins, such as manufactured ERF001, etc. are mentioned. Examples of the organic nitrogen-containing phosphorus compound include phosphate esteramide compounds such as SP670 and SP703 manufactured by Shikoku Chemicals Corporation, Otsuka Chemical Co., Ltd. Phosphazene compounds, such as SPB100 and SPE100 of manufacture, etc. are mentioned. As the metal hydroxide, Ube Material Industries, Ltd. Magnesium hydroxide, such as UD65, UD650, UD653, manufactured by Tomoe Engineering Co., Ltd. The aluminum hydroxides, such as manufactured B-30, B-325, B-315, B-308, B-303, UFH-20, etc. are mentioned.

The photocurable resin composition and / or thermosetting resin composition of the present invention may be a thickener such as orbene or benton, a silicone-based, fluorine-based, anti-foaming agent or leveling agent, an imidazole-based, thiazole-based, triazole-based, silane-based coupling agent, or the like. It may contain other components, such as an adhesive imparting agent, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and coloring agents, such as carbon black.

In the present invention, all of the solder resist layers formed on one side and the other side of the circuit board may be formed of an ink type solder resist or a dry film type solder resist. That is, even if it forms by coating and drying varnish of the resin composition on a circuit board, it forms by producing the resin composition film which formed the resin composition layer on the support body, and laminating | stacking (compressing) the said resin composition film on a circuit board. You may also do it. Moreover, since work efficiency is good and thickness control is easy, it is preferable to form both sides of a circuit board by the dry film type soldering resist.

Moreover, the soldering resist layer which consists of a soldering resist layer which consists of a photocurable resin composition formed in one side of a circuit board, and the thermosetting resin composition formed in the other side of a circuit board is made of the photocurable resin composition and a thermosetting resin composition. The minimum melt temperature of both is in the range of 80 degreeC-160 degreeC, and also the relationship which ratio of the minimum melt viscosity of both (the minimum melt viscosity of the thermosetting resin composition / the minimum melt viscosity of the photocurable resin composition) becomes 0.01-100, It is preferable that it is the relationship which the ratio of said minimum melt viscosity becomes 0.05-20, It is more preferable, Especially preferably, it is 0.1-7. When forming a soldering resist layer using a dry-film soldering resist, as mentioned later, although the crimping and flattening press of a resin composition film to a circuit board can be performed continuously by a vacuum laminator, the minimum melt temperature is If the temperature is less than 80 ° C, the resin may be pushed out due to the resin having a too low viscosity in a vacuum press or a flattening press, or if the minimum melting temperature exceeds 160 ° C, fluidity may not be sufficient, resulting in poor crimping or flattening. In addition, when laminating | stacking another resin composition layer (photocurable resin composition layer and thermosetting resin composition layer) simultaneously on one side and the other side of a circuit board, if the ratio of the minimum melt viscosity of both layers is out of the said range, it will laminate. In the flattening step by hot press, proper temperature setting tends to be difficult, and at a predetermined temperature, the fluidity of either layer is too low, so that the embedding of the circuit and the flatness of the resin are reduced, or The fluidity is too high and the resin tends to push out.

The term "lowest melt viscosity" as used herein means that when the resin composition is heated and melted at a constant temperature increase rate, the melt viscosity decreases with temperature rise in the initial stage, and after that, if the temperature exceeds a certain temperature, the melt viscosity increases with temperature rise. It is a melt viscosity of the minimum at the time of showing the characteristic to be mentioned, and is a value measured by measuring dynamic viscoelasticity, for example using the type | mold Rheosol-G3000 by Yu B. Co., Ltd. product. Specifically, using a parallel plate, it means the minimum melt viscosity value measured at the initial temperature of 60 degreeC, the temperature increase rate of 5 degree-C / min, on the conditions of a measurement interval temperature of 2.5 degreeC, the frequency of 1 Hz / deg, and a constant load of 100 g. In addition, the temperature of the minimum point which shows a minimum melt viscosity is "minimum melt temperature."

The adjustment method of the minimum melt viscosity ratio of a photocurable resin composition and a thermosetting resin composition is not specifically limited, You may adjust the compounding of a photocurable resin composition, or the compounding of a thermosetting resin composition. However, since the photocurable resin composition must make photosensitive and developability compatible, and there is a limit to addition of a polymer component and a hardening accelerator, it is preferable to control and adjust the addition amount of the polymer component and hardening accelerator of a thermosetting resin composition. Generally, increasing the addition amount of a polymer component, a hardening accelerator, etc. increases the minimum melt viscosity.

As a support body in a soldering film of a dry film type | mold, polyester, such as polyethylene terephthalate (it may abbreviate as "PET" hereafter), polyethylene naphthalate (it may abbreviate as "PEN" hereafter), poly Carbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide A plastic film which consists of these etc. is mentioned.

Moreover, it is preferable that the support body uses the plastic film by which the contact surface with a soldering resist layer was mold-released. This is generally because it is often difficult to peel the plastic film from the surface of the solder resist layer after thermal curing unless the release surface is subjected to the contact surface with the thermosetting resin composition layer of the plastic film serving as the support for the resin composition film. to be. The mold release agent used in the mold release 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 mold release agent, a silicone mold release agent, and an alkyd resin mold release agent. A mold release agent may mix and use different types of things. In addition, the matte process, corona treatment, etc. may be given to the plastic film surface, and the mold release process may be performed further on the said corona treatment surface. The plastic film may also contain laser energy absorbing components 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 a release-treated plastic film) is preferably in the range of 10 to 50 µm, more preferably in the range of 12 to 45 µm, particularly preferably in the range of 16 to 38 µm. . If the thickness of the plastic film is less than 10 µm, the flatness on the circuit tends to be lowered, and if it exceeds 50 µm, the price tends to be expensive. Moreover, as for the thickness of a mold release layer in a mold release processed plastic film, 0.05-2 micrometers is preferable.

It is preferable that a dry film-type soldering resist has a protective film for covering and protecting a resin composition layer until lamination | stacking on a circuit board. A protective film has the advantage of protecting the surface of a resin composition layer from physical damage, and preventing foreign material adhesion, such as dust. As such a protective film, films, such as polyolefin, such as polyethylene, a polypropylene, and polyvinyl chloride, polyester, such as PET and PEN, a polycarbonate (PC), and a polyimide, are mentioned. Moreover, in addition to a mat process and a corona treatment, the mold release process may be given to the protective film similarly to the plastic film used for a support film. It is preferable that the thickness of a protective film is the range of 5-30 micrometers.

The dry film solder resist is prepared by a method known to those skilled in the art, for example, a varnish of a photocurable resin composition or a thermosetting resin composition, and the varnish is applied onto a support using a die coater or the like, and heated or It can manufacture by drying an organic solvent by hot air blowing, etc., and forming a resin composition layer.

In this invention, the operation | work which laminates a dry film type soldering resist on a circuit board and forms a soldering 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, and an adhesive film is laminated on the circuit board. The lamination is preferably carried out at a temperature in the range of 60 to 140 ° C. and a pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ). Pneumatic pressure is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less. After the lamination step, the laminated resin composition film is preferably flattened by hot pressing with a metal plate. The said planarization process is performed by heating and pressurizing an adhesive sheet with metal plates, such as a heated SUS hard plate, under normal pressure (at atmospheric pressure). Heating and pressurization conditions may use the same conditions as the lamination process. The lamination step and the planarization step can be performed continuously by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, Meiki Co., Ltd. Vacuum Press Laminator, Nichigo-Morton Co., Ltd. Manufacture change application, etc. are mentioned.

In this invention, 10-50 micrometers is preferable and, as for the thickness of a soldering resist layer, 20-40 micrometers is more preferable. If the thickness of the solder resist layer is less than 10 µm, the thickness of the conductor layer tends to be difficult to make it flat on the circuit board. If the thickness of the solder resist layer exceeds 50 µm, the thickness of the multilayer printed wiring board is not suitable.

After forming a soldering resist layer on both surfaces of a circuit board, exposure and image development (lithography) are performed in order to form an opening part in the photo soldering resist layer (solder resist layer formed from the photocurable resin composition) of one side. In an exposure process, exposure by an active energy ray is performed using the negative mask which only the part used as an opening part does not pass an active energy ray. In addition, you may draw directly by the 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 exposed using parallel rays without being in close contact with each other. The irradiation amount of ultraviolet rays is approximately 10 to 1000 mJ / cm ² .

After the exposure process, the development process is started. In the developing step, alkaline liquids such as aqueous sodium carbonate solution and aqueous sodium hydroxide solution are used as the developing solution, and the unexposed portion is removed by the action of dissolution, swelling, peeling, or the like.

In the exposure and / or developing step, the solder resist layer formed of the thermosetting resin composition on the side of opening using a laser may be protected with a protective film or the like as necessary in order to avoid damage by a roller or the like or damage by a chemical or the like. good. In addition, when the said soldering resist layer is formed from the dry-film soldering resist, you may use as a protective film in an exposure or image development process as it is, without peeling off the support body of a resin composition film.

After a developing process, it enters into a baking process. Bake has the role of post-baking of the soldering resist layer (photo soldering resist) formed from the photocurable resin composition, and also has the process of thermosetting the soldering resist formed from the thermosetting resin composition. Baking may be performed in a hot air furnace, a far-infrared furnace, or the like at a temperature and a time at which a thermosetting component such as an epoxy resin in a solder resist sufficiently reacts. Although based also on the kind of soldering resist used, it is preferable to carry out for 30 to 120 minutes in 120-200 degreeC.

After baking, a laser beam is irradiated to the surface of the soldering resist layer formed from the thermosetting resin composition, and an opening part is formed. Although the size of an opening part is selected according to the fineness of the component to mount, the range of the tower diameter of 40-100 micrometers is preferable. As a laser light source, a carbon dioxide gas laser, a YAG laser, an excimer laser, etc. are mentioned, A carbon dioxide gas laser is used preferably from a viewpoint of workability and cost.

When using a carbon dioxide gas laser apparatus, it is preferable to use the laser beam of the wavelength of 9.3-10.6 micrometers. The number of shots also varies depending on the depth of the via hole to be formed and the hole diameter, but is preferably selected from 1 to 10 shots. From the viewpoint of increasing the via processing speed and improving the productivity of the circuit board, the number of shots is preferably smaller, preferably 1 to 5 shots, and more preferably 1 to 3 shots. The energy of the laser light in the case of using the carbon dioxide laser device is based on the number of shots, the depth of the blind via, the thickness of the metal film layer, and the thickness of the release layer, but is preferably set to 0.5 mJ or more, more preferably 1 mJ or more, Even more preferably, it is set to 2 mJ or more. The upper limit is preferably 20 mJ or less, more preferably 15 mJ or less, still 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 optimal energy value in the above range according to the number of shots. In the case of processing into a plurality of shots, the burst mode, which is a continuous shot, is a plurality of shots having a time interval because the processing heat is filled in the holes and tends to cause a difference in via workability. Is preferred.

The pulse width of the laser beam used for irradiation is not particularly limited and can be selected in a wide range from a middle range of 28 μs to a short pulse of about 4 μs, but in general, in the case of high-diameter small diameter machining, the short pulse side has a via processing shape. This is excellent. In addition, as a commercially available carbon dioxide gas laser apparatus, for example, Mitsubishi Electric Corporation ML605GTWII, Hitachi Via Mechanics, Ltd. LC-G series, Matsushita Welding System Co., Ltd. board | substrate drilling laser processing machine, etc. are mentioned.

After formation of the openings in the solder resist layer, desmear treatment is performed on both sides or one side as necessary for the purpose of removing smear and improving the wettability of the underfill. The desmear process in this invention can be performed by various well-known methods, Preferably the dry method by plasma generally used and the wet method using the oxidizer solution, such as alkaline permanganic acid solution, can be used.

As the plasma desmear apparatus, Ebara-Udylite Co., Ltd. Sea of manufacture, Sekisui Chemical Co., Ltd. A commercially available one can be used, such as the atmospheric pressure plasma processing apparatus of manufacture.

In the case of desmear treatment with an oxidizing agent such as an aqueous alkaline permanganate solution, it is preferable to perform a swelling treatment with a swelling liquid prior to the treatment. Examples of the swelling liquid include swelling dip Securiganth P (Swelling Dip Securiganth P), Swelling Dip Securiganth SBU (manufactured by Atotech Japan), and the like. . It is preferable to perform a swelling process by adding an insulating layer for 5 to 10 minutes to the swelling liquid heated at 60-80 degreeC. As alkaline aqueous permanganate solution, the solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. It is preferable to perform roughening process by alkaline permanganic acid aqueous solution by adding 60 to 80 degreeC for 10 to 30 minutes. Examples of commercially available aqueous alkaline permanganic acid include Agate Tech Compact CP, Dosing Solution Securigans P and the like manufactured by Atotech Japan.

In the desmear process, the solder resist layer (the solder resist layer formed on one side of the circuit board) on the side that is opened by exposure and development is used as necessary to avoid damage caused by rollers or the like, or chemicals. You may protect with a protective film.

[Example]

Hereinafter, an Example and a comparative example are shown and this invention is demonstrated further more concretely. In addition, in the following description, the "part" used when it means the compounding quantity of a material means a "mass part." The melt viscosity measured the dynamic viscoelasticity using the type | mold Rheosol-G3000 by Yu B. Co., Ltd. make. The measurement was measured at a temperature increase rate of 5 ° C./min from the initial temperature of 60 ° C., at a measurement interval temperature of 2.5 ° C. and at a frequency of 1 Hz / deg.

(Synthesis example of resin solution (A))

411 parts of ethyl carbitol acetate, 430 parts of o-cresol novolak-type epoxy resin (epoxy equivalent 215, having 6 phenol nuclei on average in 1 molecule), and 144 parts of acrylic acid were placed in a flask, and stirred at 120 ° C. for 10 hours. Reacted. The reaction product was cooled to room temperature once, 288.8 parts of tetrahydro phthalic anhydride were added, it heated at 80 degreeC, and stirred for 4 hours. Again, this reaction product was cooled to room temperature, 105 parts of glycidyl methacrylate and 161 parts of propylene glycol methyl ether acetate were added, and the mixture was reacted at 110 ° C for 6 hours under stirring. This reaction product was cooled to room temperature to obtain a resin solution (A) (62.9% nonvolatile content, acid value 70 [KOHmg / g]).

(Manufacture example of photocurable resin composition film (1))

100 parts of resin solution (A), 18 parts of ethyl carbitol acetate solutions of 70% of solid content of diphenylpentadiene of biphenyl-type epoxy resin (epoxy equivalent 291, "NC-3000H" by Nippon Kayaku Co., Ltd. product) 18 parts of ethyl carbitol acetate solutions of 70% of solid content of type epoxy resin (epoxy equivalent 277, "EPICLON HP-7200H" by DIC Corporation), photoinitiator ("2-methyl-" of Chiba Specialty Chemical Co., Ltd. product) 7 parts of [4- (methylthio) phenyl] -2-morpholino-1-propanone], photosensitizer ("2, 4- diethyl thioxanthone" of Nippon Kayaku Co., Ltd.) 1 part, 16 parts of acrylic monomers ("M-310" made by Toagosei Co., Ltd.), 0.5 parts of hardening accelerators ("Epicure DICY-7" made by Japan Epoxy Resins Co., Ltd.), finely divided silica ( 2 parts of "Aerosil # 200" manufactured by Nippon Aerosil Co., Ltd., 10 parts of spherical silica ("Quartron SP-1" manufactured by Fusou Chemical Co., Ltd.), and a pigment ((Toyo Ink Mfg) Co., Ltd.) 「FG7351」) 0.5 parts , Uniformly dispersed in a high-speed rotary mixer to prepare a photocurable resin composition varnish.

The varnish was applied to a release treated surface of a 25 μm release PET film (Lintec Corporation, PET25-AL-5) release-treated with an alkyd resin on one side, so that the thickness of the resin composition layer after drying was 27 μm, and hot air circulation After predrying at 80 ° C. for 20 minutes in a mold dryer, the film was wound in a roll while bonding a polypropylene film having a thickness of 15 μm as a protective film. The roll-shaped adhesive film was slitted at a width of 507 mm to obtain a film (photocurable resin composition film (1)) having a size of 507 × 336 mm. The minimum melt viscosity of the obtained film was 540 poise, and the minimum melt temperature was 148 degreeC.

(Manufacture example of photocurable resin composition film (2))

100 parts of resin solution (A), 13 parts of liquid bisphenol F-type epoxy resins (epoxy equivalent 170, "Epicoat 807" by Japan Epoxy Resins Co., Ltd.), dicyclopentadiene type epoxy resin (epoxy equivalent 277 , 12 parts of ethylcarbitol acetate solution of 70% of solid content of "EPICLON HP-7200H" made by DIC Corporation), photoinitiator ("2-methyl- [4- (methylthio) by Chiba Specialty Chemical Co., Ltd. make) Phenyl] -2-morpholino-1-propanone ") 7 parts, a photosensitizer (" 2, 4- diethyl thioxanthone "by Nippon Kayaku Co., Ltd.) 1 part, an acrylic monomer (Toagosei 16 parts of "M-310" made by Co., Ltd., 0.5 parts of hardening accelerators ("Epicure DICY-7" made by Japan Epoxy Resins Co., Ltd.), finely divided silica (made "aerosil # 200 '') 2 parts, spherical silica ("Quoronon SP-1" manufactured by Fusou Chemical Co., Ltd.), 0.5 parts of pigment (Toyo Ink Mfg. Co., Ltd. "FG7351") are mixed, Evenly distributed with high speed rotary mixer To prepare a resin composition varnish.

The varnish was applied to a release treated surface of a 25 μm release PET film (Lintec Corporation, PET25-AL-5) release-treated with an alkyd resin on one side, so that the thickness of the resin composition layer after drying was 27 μm, and hot air circulation After preliminary drying for 20 minutes in 80 degreeC with a type | mold dryer, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film as a protective film. The roll-shaped adhesive film was slitted at a width of 507 mm to obtain a sheet-shaped adhesive film (photocurable resin composition film (2)) having a size of 507 × 336 mm. The minimum melt viscosity of the obtained film was 120 poise and the minimum melt temperature was 128 degreeC.

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

26 parts of liquid bis phenol A type epoxy resin (epoxy equivalent 180, "epoch 828EL" made by Japan Epoxy Resins Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" made by DIC Corporation) ) 20 parts were dissolved by heating in 15 parts of methyl ethyl ketone and 15 parts of cyclohexanone while stirring. There, 25 parts of methyl ethyl ketone solutions of 60% of solid content of the phenol novolak-type hardening | curing agent ("TD2090" made by DIC Corporation, phenolic hydroxyl group equivalent 105), a hardening accelerator ("2E4M '" made by Shikoku Chemicals Corporation) 0.1 Part, 45 parts of spherical silica (average particle diameter: 0.5 micrometer, made by "SOC2" Admatechs Company Limited), ethanol and toluene of 15% of solid content of polyvinyl butyral resin solution ("KS1" made by Sekisui Chemical Co., Ltd.) 1 part solution) and 20 parts phenoxy resin solution (23 parts of 40% of methyl ethyl ketone and cyclohexanone 2: 3 solution of 40% of solid content of "FX293" manufactured by Tohto Kasei Co., Ltd.) It disperse | distributed uniformly with the mixer and the thermosetting resin composition varnish was produced.

The varnish was uniformly applied to a mold release surface of a 38 μm release PET film (Lintec Corporation, PET38-AL-5) with a die coater so that the thickness of the resin composition layer after drying was 27 μm, and was 80 to 120 ° C ( It dried at average 100 degreeC) for 6 minutes (amount of residual solvent in resin composition layer: 1.5 mass%). Then, it wound in the roll shape, bonding a 15-micrometer-thick polypropylene film as a protective film on the surface of a resin composition layer. The roll-shaped adhesive film was slitted at a width of 507 mm to obtain a sheet-shaped adhesive film (thermal curable resin composition film (3)) having a size of 507 × 336 mm. The minimum melt viscosity of the obtained film was 3310 poise, and the minimum melt temperature was 135 ° C.

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

26 parts of liquid bisphenol A-type epoxy resin (epoxy equivalent 180, "epoch 828EL" made by Japan Epoxy Resins Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "HP4700" made by DIC Corporation) ) 20 parts were dissolved by heating in 15 parts of methyl ethyl ketone and 15 parts of cyclohexanone while stirring. There, 25 parts of methyl ethyl ketone solutions of 60% of solid content of phenol novolak-type hardener ("TD2090" made by DIC Corporation, phenolic hydroxyl group equivalent 105), hardening accelerator (manufactured by Shikoku Chemicals Corporation, "2E4M '") 0.5 45 parts of spherical and spherical silica (average particle diameter: 0.5 µm, manufactured by "SOC2" Admatechs Company Limited), ethane of 15% solid content of polyvinyl butyral resin solution ("KS1" manufactured by Sekisui Chemical Co., Ltd.) 40 parts of a 1: 1 solution of knol and toluene) and 46 parts of a phenoxy resin solution (40% of methyl ethyl ketone and cyclohexanone 2: 3 solution of 40% solids of FX293 manufactured by Tohto Kasei Co., Ltd.) It uniformly disperse | distributed with the high speed rotary mixer, and produced the thermosetting resin composition varnish.

The varnish was uniformly applied to a release treatment surface of a 38 μm release PET film (Lintec Corporation, PET38-AL-5) with a die coater so that the thickness of the resin composition layer after drying was 27 μm, and was 80 to 120 ° C ( It dried at average 100 degreeC) for 6 minutes (amount of residual solvent in resin composition layer: 1.5 mass%). Then, it wound in the roll shape, bonding a 15-micrometer-thick polypropylene film as a protective film on the surface of a resin composition layer. The roll-shaped adhesive film was slitted at a width of 507 mm to obtain a sheet-shaped adhesive film (heat curable resin composition film (4)) having a size of 507 × 336 mm. The minimum melt viscosity of the obtained film was 13210 poise, and the minimum melt temperature was 135 ° C.

≪ Example 1 >

The protective film of the said photocurable resin composition film 1 and the said thermosetting resin composition film 3 (each size 507 * 336mm) is peeled off, and these are removed from Meiki Co., Ltd. The copper lamination board (circuit conductor thickness 18 micrometers, external size 510 * 340mm, thickness 0.2mm) formed in a circuit by conditions of the temperature of 70 degreeC, the pressure of 7 kgf / cm <^2> , and the atmospheric pressure of 5 mmHg or less by the vacuum laminator of manufacture, respectively. It arrange | positioned on one side and laminated both surfaces simultaneously. Moreover, the hot press by the SUS hard plate was performed on the conditions of the temperature of 70 degreeC, and the pressure of 5 kgf / cm <^2> continuously. The extrusion of the resin of the photocurable resin composition film 1 from the PET film cross section after the hot press to the outer peripheral layer of the copper clad laminate was 0.67 mm, and the extrusion of the resin of the thermosetting resin composition film 3 was 0.18 mm.

Next, with respect to the photocurable resin composition film 1, the photomask which gave the circular pattern of 600 micrometers in diameter was fixed, and it was 200mJ / cm <^2> using a high pressure mercury lamp exposure apparatus. It exposed and photocured. Next, after peeling the PET film of the photocurable resin composition film 1 side, it uses for developing solution of 1.0% sodium carbonate aqueous solution (liquid temperature 30 degreeC), and develops for 60 second by the spray pressure of ² kg / cm <^2> , The light portion was dissolved and removed, and the exposed portion was photocured by exposure to 1000 mJ / cm ² using a high pressure mercury lamp exposure apparatus. Then, after peeling off the PET film on the thermosetting resin composition film 3 side, it heated at 180 degreeC for 60 minutes, and performed thermosetting.

After cooling to room temperature, the carbon dioxide laser device (ML605GTWII-P) by Mitsubishi Electric Corporation made on the surface which forms the hardened | cured material layer derived from the thermosetting resin composition film 3, the wavelength of a laser beam is 9.3 micrometers, energy 2.50. An opening was made under the conditions of mJ, pulse width of 4 mus, and the number of shots once, to form a via hole (top diameter of 60 mu m).

In this way, the board | substrate after forming a soldering resist on both surfaces was made into ESPEC Corp. Using a liquid bath cold impact test apparatus (TSB-51) manufactured, a thermal shock test was conducted under conditions of a low temperature bath temperature of -65 ° C, a high temperature bath temperature of 150 ° C, an exposure time of 5 minutes and 1000 cycles, The presence of cracks was examined. No crack was found in any of the solder resists on both sides.

Comparative Example 1

Two photocurable resin composition films 1 were prepared, both protective films were peeled off, and both sides of the copper-clad laminate (circuit conductor thickness 18 μm, outline size 510 × 340 mm, thickness 0.2 mm) formed on a circuit were temporarily added. And Nichigo-Morton Co., Ltd. It thermocompression-bonded at 70 degreeC with the manufacturing applicator. Next, the photomask which gave the circular pattern of 60 micrometers in diameter was fixed to one side, 200mJ / cm <^2> exposure was performed using the high pressure mercury lamp exposure apparatus, and photocuring was performed. On the other side, the photomask which gave the circular pattern of 600 micrometers in diameter was fixed, and photocuring was similarly performed. After peeling off both sides of the PET film, 0.85% aqueous sodium hydroxide solution (liquid temperature: 30 ° C) was used for the developer, followed by development for 60 seconds at a spray pressure of ² kg / cm ² , dissolving and removing the unexposed portions, and forming an opening. It was. Thereafter, the exposed portion was photocured by exposure to 1000 mJ / cm ² using a high pressure mercury lamp exposure apparatus, and further heated at 180 ° C. for 60 minutes to perform thermal curing. Then, the thermal shock test was done similarly to the said Example 1, and the presence or absence of the occurrence of a crack was investigated. Although no crack was observed on the side having an opening having a diameter of 600 µm, a crack was observed in the vicinity of the opening having a diameter of 60 µm.

Comparative Example 2

Two thermally curable resin composition films 3 were prepared, and both protective films were peeled off, and they were temporarily attached to both surfaces of a copper-clad laminate (circuit conductor thickness 18 μm, external size 510 × 340 mm, thickness 0.2 mm) formed with a circuit, and 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 It was done. Then, after peeling a PET film, it heated at 180 degreeC for 60 minutes, and thermosetted it. After cooling to room temperature, an opening was performed on one surface by a carbon dioxide gas laser device (ML605GTWII-P) manufactured by Mitsubishi Electric Corporation under conditions such that the wavelength of the laser beam was 9.3 μm, energy 2.50 mJ, pulse width 4 μs, and the number of shots once. Column diameter 60 µm). On the other side, 10 shots were irradiated on the condition of an aperture having a tower diameter of 600 µm under the conditions of a wavelength of 9.3 µm, an energy of 2.50 mJ, and a pulse width of 4 µs of the laser beam, but the target aperture could not be obtained. Thereafter, a thermal shock test was conducted in the same manner as in Example 1, and the presence or absence of crack occurrence was examined. No crack was found in any of the solder resists on either side.

Comparative Example 3

Each of the said protective film of the said photocurable resin composition film 2 and the said thermosetting resin composition film 4 was peeled off, and each of the copper clad laminated boards (circuit conductor thickness 18 micrometers, external size 510 * 340mm, thickness 0.2mm) which were formed in a circuit Placed on one side, Meiki Co., Ltd. Both sides were laminated simultaneously by the vacuum laminator of manufacture on the conditions of the temperature of 70 degreeC, the pressure of 7 kgf / cm <^2> , and the atmospheric pressure of 5 mmHg or less. Moreover, the hot press by the SUS hard plate was performed on the conditions of the temperature of 70 degreeC, and the pressure of 5 kgf / cm <^2> continuously. The extruded resin of the thermosetting resin composition film 4 was 0.17 mm, and the extruded resin of the photocurable resin composition film 2 was 3.10 mm. Since the resin was largely pushed out, the experiment was terminated when the solder resist could not be formed properly.

The following results are summarized in Table 1 below.

The passability determination in the opening forming process is performed by SEM observation and BSE observation using a scanning electron microscope (SU-1500 manufactured by Hitachi High-Technologies Corporation) to determine the removal state of the resin, and the bottom circuit of the opening When copper was seen, it was set as pass ((circle)), and when resin was not removed and copper of the underlying circuit is not seen, it was set as rejected (x).

In addition, the determination of the acceptance of the crack after the cold shock was observed using a CCD microscope (VHX-900, manufactured by Keyence Corporation) and judged according to the presence or absence of a crack. When any one of these occurred, it was set as fail (x).

According to the present invention, a high heat resistance of a solder resist layer forming an opening having a small opening diameter for solder bonding with a semiconductor chip or the like, and a relatively large opening diameter for connection with a circuit or an electronic component such as a motherboard The efficiency of opening formation in the soldering resist layer which forms an opening can be made compatible.

This application is based on Japanese Patent Application No. 2009-105100 filed in Japan, the contents of which are included in the present specification.

Claims (8)

Solder resist layers are formed on both sides of the circuit board, the openings are formed by the photolithography in the solder resist layer formed on one side, and the openings are formed by the laser in the solder resist layer formed on the other side. The manufacturing method of the printed wiring board to say. The manufacturing method of the printed wiring board of Claim 1 in which the soldering resist layer which performs opening formation by photolithography consists of a photocurable resin composition, and the soldering resist layer which performs opening formation by a laser consists of a thermosetting resin composition. The manufacturing method of the printed wiring board of Claim 2 which forms the soldering resist layer formed in one side and the other side of a circuit board using the resin composition film which formed the resin composition layer on the support body together. 4. The printed wiring board according to claim 3, wherein the solder resist layer formed on one side and the other side of the circuit board is collectively formed by a lamination process using a vacuum laminator and a planarization process by a heat press subsequent thereto. Manufacturing method. The manufacturing method of the printed wiring board of Claim 4 whose minimum melt temperature of both a photocurable resin composition and a thermosetting resin composition exists in the range of 80 degreeC-160 degreeC, and ratio of the minimum melt viscosity of both is 0.01-100. The baking process of the soldering resist layer which consists of photocurable resin compositions, and the thermosetting resin composition of Claim 2 to 5 after formation of the opening part by photolithography of the soldering resist layer which consists of photocurable resin compositions. The thermosetting process of the soldering resist layer which consists of simultaneously is performed, and the manufacturing method of the printed wiring board which forms an opening part with a laser in the soldering resist layer which consists of a thermosetting resin composition after that. The manufacturing method of the printed wiring board of any one of Claims 1-6 whose printed wiring board is a semiconductor package board | substrate. The manufacturing method of the printed wiring board of any one of Claims 2-6 whose printed wiring board is a semiconductor package board | substrate with which a semiconductor chip is mounted in the soldering resist layer which consists of a thermosetting resin composition.