JP6958189B2 - A photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, a solder resist, an interlayer insulating film, a method for forming an interlayer insulating film, a method for manufacturing a printed wiring board, and a printed wiring board. - Google Patents

Description

The present invention comprises a photosensitive resin composition suitable for forming an insulating layer such as a multilayer printed wiring board, a photosensitive element using the same, a method for forming a resist pattern, a solder resist, an interlayer insulating film, and an interlayer insulating film. The present invention relates to a method, a method for manufacturing a printed wiring board, and a printed wiring board and a printed wiring board.

In recent years, the miniaturization and high performance of electronic devices have progressed, and the density of multilayer printed wiring boards has been increasing due to the increase in the number of circuit layers and the miniaturization of wiring. In particular, the density of semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted has been remarkably increased. The diameter of the is being reduced. In such a semiconductor package substrate, a semi-additive method in which a circuit is formed by plating has become the mainstream as the circuit becomes finer.

In the semi-additive method, for example, (1) after forming an insulating film on the conductor circuit, laser irradiation is performed for via processing for interlayer connection, and desmear treatment is performed as resin residue removal. (2) After that, the substrate is subjected to electroless copper plating treatment, a pattern is formed with a dry film resist, and then electrolytic copper plating is performed to form a copper circuit layer. (3) Finally, a copper circuit is formed by resist peeling and flash etching of the electroless layer.
However, recently, due to the high density, the via processing size by laser irradiation has reached the limit, and the photolithography method, which collectively forms smaller diameter vias by the photolithography method, is attracting attention.

On the other hand, in the case of a photosensitive resin composition compatible with the photolithography method, it was not sufficient to satisfy the characteristics required for a semiconductor package substrate that requires high reliability.

Japanese Unexamined Patent Publication No. 2010-128317

INDUSTRIAL APPLICABILITY The present invention has photosensitivity capable of forming a cured film having excellent adhesion (peel strength) with a conductor layer formed on an insulating base material and having excellent insulation reliability (HAST resistance). It is an object of the present invention to provide a resin composition, a photosensitive element, and a photovia material.

As a result of diligent research, the present inventors have found that (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a polyfunctional maleimide, and (E). A photosensitive resin composition containing a phosphorus-based curing accelerator and (A) a photopolymerizable compound having an ethylenically unsaturated group containing an acid-modified epoxy (meth) acrylate compound having a carboxyl group in the molecule. However, it has been found that a cured product having excellent adhesion (peel strength) to the conductor layer and having excellent insulation reliability can be formed.

That is, the present invention provides the following photosensitive resin compositions and the like.
[1] Contains (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a polyfunctional maleimide compound, and (E) a phosphorus-based curing accelerator. The photosensitive resin composition, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group contains an acid-modified epoxy (meth) acrylate compound having a carboxyl group in the molecule.
[2] The photosensitive resin composition according to [1], wherein the (E) phosphorus-based curing accelerator is an adduct of a tertiary phosphine and quinones.
[3] (F) The photosensitive resin composition according to [1] or [2], which further contains an organic peroxide having a 1-hour half-life temperature of 100 to 180 ° C.
By containing such an organic peroxide, the Tg of the cured product can be increased, and the insulation reliability and the like can be further improved.
[4] Described in any one of [1] to [3] used as a photosensitive resin composition for forming an interlayer insulating film in a method for manufacturing a multilayer printed wiring board including a step of forming a conductor layer on the interlayer insulating film. Photosensitive resin composition.
[5] A photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition according to any one of [1] to [3].
[6] The photosensitive element according to [5], which is used as a photosensitive element for forming an interlayer insulating film in a method for manufacturing a multilayer printed wiring board including a step of forming a conductor layer on the interlayer insulating film.
[7] A laminating step of laminating a photosensitive layer formed of the photosensitive resin composition according to any one of [1] to [3] on a conductor layer of a substrate having a conductor layer on an insulating base material.
An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to photo-cure the exposed portion.
A developing process for removing a portion of the photosensitive layer other than the exposed portion, and
A method for forming a resist pattern including.
[8] The method for forming a resist pattern according to [8], which has a post-curing step of further curing the exposed portion of the photosensitive layer after the developing step.
[9] A solder resist made of a cured product of the photosensitive resin composition according to any one of [1] to [3], which is formed on the conductor layer of a substrate having a conductor layer on an insulating base material.
[10] An interlayer insulating film made of a cured product of the photosensitive resin composition according to any one of [1] to [3], which is formed on a conductor layer of a substrate having a conductor layer on an insulating base material.
[11] A laminating step of laminating a photosensitive layer formed of the photosensitive resin composition according to any one of [1] to [3] on a conductor layer of a substrate having a conductor layer on an insulating base material.
An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to photo-cure the exposed portion.
A developing process for removing a portion of the photosensitive layer other than the exposed portion, and
A method for forming an interlayer insulating film including.
[12] The method for forming an interlayer insulating film according to [11], which comprises a post-curing step of further curing the exposed portion of the photosensitive layer after the developing step.
[13] A method for manufacturing a printed wiring board, which comprises a step of plating a substrate on which an interlayer insulating film is formed by the method for forming an interlayer insulating film according to [11] or [12].
[14] A substrate having an interlayer insulating film formed by the method for forming an interlayer insulating film according to [11] or [12] and / or an interlayer insulating film is surface-roughened to roughen the substrate and / or interlayer insulation. A method for manufacturing a printed wiring board, which includes a step of plating a film.
[15] The method for manufacturing a printed wiring board according to [15], wherein the surface roughening is performed by a treatment with an alkaline permanganate etching solution, and the plating is performed by a copper plating process.
[16] A printed wiring board comprising a substrate having a conductor layer on an insulating base material and a cured product of the photosensitive resin composition according to [1] to [3].

According to the present invention, a photosensitive product capable of forming a cured product having excellent adhesion (peel strength) with a conductor layer formed on various insulating base materials and having excellent insulation reliability can be formed. A resin composition, a photosensitive element, and a photovia material can be provided.
In particular, it is suitable when used as a resin for an interlayer insulating base material of a multilayer printed wiring board in which wiring is formed on a resist by a copper plating process after treatment with an alkaline permanganate etching solution (desmia solution).

Hereinafter, preferred embodiments of the present invention will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a polyfunctional maleimide compound, and (E). Contains a phosphorus-based curing accelerator. Further, if necessary, (F) organic peroxide, (G) inorganic filler and the like can be contained. Hereinafter, each component will be described.

<(A) Photopolymerizable compound having an ethylenically unsaturated group>
The (A) photopolymerizable compound having an ethylenically unsaturated group (hereinafter, may be referred to as a component (A)) used in the present invention is an acid-modified epoxy having an ethylenically unsaturated group and a carboxyl in the molecule. It contains a (meth) acrylate compound as an essential component. In the present specification, (meth) acrylate means acrylate and / or methacrylate. As the ethylenically unsaturated group as the photosensitive group, those derived from the (meth) acryloyl group are preferable. In the present specification, the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
The acid-modified epoxy (meth) acrylate compound is, for example, a reaction product (A') of (a1) an epoxy resin and (a2) an unsaturated group-containing monocarboxylic acid (that is, an epoxy resin and an unsaturated monocarboxylic acid). A compound obtained by reacting (a3) a saturated or unsaturated group-containing polybasic acid anhydride with an esterified hydroxyl group-containing compound (that is, the hydroxyl group-containing (A') component and the polybasic acid anhydride. (Additional compound with) is preferably used.
The epoxy resin (a1) is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule. For example, novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S. Examples thereof include type epoxy resin, salicylaldehyde type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, biphenyl novolac type epoxy resin, and rubber-modified epoxy resin. Further, an epoxy resin-based polyurethane resin obtained by reacting the reaction product (A') with isocyanate may be used. These are used alone or in combination of two or more.

Examples of the acid-modified epoxy (meth) acrylate compound described above include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, UXE-3024, and ZFR-1185. And ZCR-1569H, ZCR-6000, ZCR-8000 (above, manufactured by Nippon Kayaku Co., Ltd., trade name), UE-9000, UE-EXP-2810PM, UE-EXP-3045 (above, manufactured by DIC Corporation, product name). Name) etc. are commercially available.
The above-mentioned (a2) unsaturated group-containing monocarboxylic acid is not particularly limited as long as it is a compound having one carboxyl group in the molecule and one or more ethylenically unsaturated bonds. For example, (meth). ) Acrylic acid, crotonic acid, cinnamic acid and derivatives thereof and the like can be mentioned. In addition, in this specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid. (Meta) acrylic acid means acrylic acid and / or methacrylic acid.
(A3) As the saturated or unsaturated group-containing polybasic acid anhydride, for example, anhydrides of polybasic acids such as phthalic acid, tetrahydrophthalic acid, maleic acid, and succinic acid may be used alone or in combination of two or more. Can be used.

Further, in the present invention, as the component (A), a photopolymerizable compound having no carboxyl group can be used in addition to the above-mentioned acid-modified epoxy (meth) acrylate compound, if necessary. Examples of photopolymerizable compounds having no carboxyl group include dipentaerythritol hexaacrylate and its similar structure, and commercially, for example, KAYARAD DPHA, KAYARAD D-310, KAYARAD D-330, KAYARAD. It is available as DPCA-20, 30, KAYARAD DPCA-60, 120 (all manufactured by Nippon Kayaku Co., Ltd., trade name). As a polyfunctional photopolymerized compound having three or more ethylenically unsaturated groups in one molecule, trimethylolpropane triethoxytriacrylate (SR-454, manufactured by Nippon Kayaku Co., Ltd., trade name) and the like are commercially available. It is possible.

Further, as the photopolymerizable compound having no carboxyl group, a photopolymerizable compound having a bisphenol A structure can also be used. Examples of such a photopolymerizable compound include FA-321M (manufactured by Hitachi Chemical Industry Co., Ltd., trade name) or BPE-500 (new) which is 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane. BPE-1300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trade name) which is commercially available as 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl), which is commercially available as Nakamura Chemical Industry Co., Ltd. ) Is commercially available.
The photopolymerizable compound may be an acid-modified epoxy (meth) acrylate compound alone or in combination of two or more, or at least one acid-modified epoxy (meth) acrylate compound and the above-mentioned light having no carboxyl group. It is used in combination with one or more polymerizable compounds. In particular, it is preferable to contain at least one polyfunctional photopolymerized monomer having three or more ethylenically unsaturated groups in one molecule. Among them, a polyfunctional photopolymerizable compound having 6 or more ethylenically unsaturated groups in one molecule is effective for improving crack resistance at the time of reflow mounting.

The content of the component (A) is preferably 30 to 80 parts by mass, preferably 40 to 70 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition excluding the inorganic filler and the solvent component (F). More preferably, it is by mass. If the content of the component (A) is less than 30 parts by mass, the CTE tends to increase and solder cracks tend to occur, and if it exceeds 80 parts by mass, the copper plating peel strength decreases. Therefore, the copper plating line tends to fly easily. When a photopolymerizable compound other than the acid-modified epoxy (meth) acrylate compound is used as an optional component, the amount of the acid-modified epoxy (meth) acrylate compound in the component (A) is 50 to 50 in the total amount of the component (A). It is preferably 95% by mass, more preferably 70 to 90% by mass. If the amount of the acid-modified epoxy (meth) acrylate compound is 95% or more, it tends to swell during development, so that sufficient adhesion tends not to be obtained. If it is less than 50% by mass, development cannot be performed and vias. It tends to be unable to form a shape.

<(B) Photopolymerization Initiator>
Examples of the (B) photopolymerization initiator (hereinafter, may be referred to as the (B) component) used in the present invention include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1,4,4'-bis Aromatic ketones such as (dimethylamino) benzophenone (Miherer ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, quinones such as alkylanthraquinone and phenanthrenquinone, benzoin, alkyl Benzoin compounds such as benzoin, benzoin ether compounds such as benzoin alkyl ethers and benzoin phenyl ethers, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-). Chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2 , 4,5-Triarylimidazole dimer, N-phenylglycine, N-phenylglycine derivative, aclysine derivatives such as 9-phenylacridin, 1,2-octanedione, 1- [4- (phenylthio) −, 2 -(O-benzoyloxime)] and other oxime esters, 7-diethylamino-4-methylcoumarin and other coumarin compounds, 2,4-diethylthioxanthone and other thioxanthone compounds, 2,4,6-trimethylbenzoyl-diphenyl -Acylphosphine oxide-based compounds such as phosphine oxide can be used in combination.
Commercially, there are the IRGACURE series manufactured by BASF, and for example, they are commercially available as IRGACURE 369, IRGACURE 907, IRGACURE TPO, IRGACURE 819, IRGACURE OXE01, and IRGACURE OXE02 (all manufactured by BASF, trade name). Is. These are used alone or in combination of two or more.

The content of the (B) photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 mass by mass of the total solid content of the photosensitive resin composition excluding the (G) inorganic filler and solvent component. It is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.2 to 6 parts by mass. When the content of the photopolymerization initiator (B) is within this range, the photosensitive resin composition is excellent in photosensitivity and internal photocurability, and as a result, the resolution and the via shape are improved.

<(C) Epoxy resin>
The (C) epoxy resin (hereinafter, may be referred to as (C) component) used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule, but bisphenol A. Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin , Biphenyl type epoxy resin, biphenyl aralkyl epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, epoxidized polybutadiene resin and the like. .. These may be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type, in particular, from the viewpoint of improving heat resistance, insulation reliability, and adhesion to copper. Epoxy resin is preferred. Specifically, for example, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "Epicoat 828EL", "YL980"), bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER806H", " YL983U ”), naphthalene type epoxy resin (manufactured by DIC Co., Ltd., trade name“ HP4032D ”,“ HP4710 ”), naphthalene skeleton-containing polyfunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name“ NC7000 ”), naphthol type epoxy Resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name "ESN-475V"), epoxy resin with biphenyl structure (manufactured by Nippon Kayaku Co., Ltd., trade names "NC3000H", "NC3500"), manufactured by Mitsubishi Chemical Co., Ltd. Product name "YX4000HK", "YL6121"), anthracene type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "YX8800"), glycerol type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., product name "ZX1542"), Nafuchi Lene ether type epoxy resin (manufactured by DIC Co., Ltd., trade name "EXA7311-G3"), epoxidized polybutadiene resin (manufactured by Daicel Chemical Co., Ltd., trade name "PB3600") and the like can be mentioned.
Two or more types of epoxy resins may be used in combination. Further, it is preferable to use an epoxy resin that is liquid at room temperature and an aromatic epoxy resin that is solid at room temperature in combination.
The content of the epoxy resin (C) is preferably 5 to 70 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition excluding the inorganic filler and the solvent component (F). It is 10 to 50 parts by mass, and particularly preferably 15 to 40 parts by mass. When the content of the epoxy resin (C) is less than 5 parts by mass, sufficient cross-linking of the photosensitive resin composition cannot be obtained, and there is a tendency that adhesion to copper and insulation reliability cannot be obtained. On the other hand, if it exceeds 70 parts by mass, the resolution and developability tend to be insufficient.

<(D) Polyfunctional maleimide compound>
The polyfunctional maleimide compound used in the present invention is not particularly limited, but for example, bismaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N'-m-phenylene bismaleimide, N, N'-. p-Phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4'-[3,3'-dimethylbiphenylene ] Bismaleimide, N, N'-4,4'-[3,3'-dimethyldiphenylmethane] Bismaleimide, N, N'-4,4'-[3,3'-diethyldiphenylmethane] Bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-diphenylpropan bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, 2,2-bis [4-( 4-maleimide phenoxy) phenyl] propane, 1,1-bis [2-methyl-4- (4-maleimide phenoxy) -5-t-butylphenyl] -2-methylpropane, 4,4'-methylene-bis [ 1- (4-maleimide phenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4'-(1-methylethylidene) -bis [1- (maleimide phenoxy) -2,6- Bis (1,1-dimethylethyl) benzene], 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimide phenoxy) phenyl] Propane, 2,2-bis [3,5-dimethyl-4- (4-maleimide phenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimide phenoxy) phenyl] propane, bis [ 3-Methyl-4- (4-maleimide phenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-maleimide phenoxy) phenyl] methane, bis [3-ethyl-4- (4-maleimide phenoxy) Phenyl] Phenyl] methane, phenylmethane maleimide and the like can be mentioned. These can be used alone or in combination of two or more.
Commercially available, for example, as the BMI series manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-1000, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5000, BMI-5100, BMI-7000, BMI-TMH (manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name) and the like are available. Among these, it is preferable to use BMI-5100, BMI-4000, and BMI-2300 from the viewpoint of solubility in a solvent.
The content of the (D) polyfunctional maleimide compound is preferably 2 to 40 parts by mass with respect to 100 mass by mass of the total solid content of the photosensitive resin composition excluding the (G) inorganic filler and solvent component. , More preferably 5 to 30 parts by mass, and particularly preferably 10 to 25 parts by mass. When the content of the polyfunctional maleimide compound (D) is less than 2 parts by mass, the insulation reliability tends to decrease. On the other hand, if it exceeds 40 parts by mass, the resolution and developability tend to be insufficient.

<(E) Phosphorus-based curing accelerator>
The (E) phosphorus-based curing accelerator used in the photosensitive resin composition according to the present invention is not particularly limited as long as it contains a phosphorus atom and accelerates the curing reaction of the epoxy resin. .. Further, the phosphorus-based curing accelerator may be used alone, or other curing accelerators may be used alone or in combination of two or more. Examples of phosphorus-based curing accelerators include triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, and tris. (Trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine Examples thereof include organic phosphines such as, a complex of these organic phosphines and organic borons, and an adduct of a tertiary phosphine and quinones.
As the (E) phosphorus-based curing accelerator used in the present invention, for example, an adduct of a third phosphine and quinones capable of exhibiting high adhesiveness by sufficiently advancing the curing reaction of the adhesive auxiliary layer for the plating process. Is preferable. The third phosphine is not particularly limited, but is, for example, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine. A tertiary phosphine having an aryl group such as is preferable. Examples of quinones include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like.
Among these, for example, an adduct of triphenylphosphine and p-benzoquinone is preferable from the viewpoint of heat resistance and storage stability in addition to adhesiveness. As a method for producing an adduct of the tertiary phosphine and quinones, for example, a method of stirring and mixing the three phosphine and quinones as raw materials in a solvent in which both of them are dissolved, subjecting them to an addition reaction, and then isolating them. And so on. In this case, the production conditions are in the range of room temperature to 80 ° C. in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, and ketones such as acetone, which have high solubility of the raw material and low solubility of the produced adduct, for 1 to 12 hours. It is preferable to stir and carry out an addition reaction.
In the photosensitive resin composition of the present invention, the curing reaction proceeds sufficiently by using the (E) phosphorus-based curing accelerator.
The reason for this is not always clear, but in the conventional nitrogen-based curing accelerator typified by imidazole, the nitrogen atom of the nitrogen-based curing accelerator is affected by the copper atom of the copper foil, and the curing acceleration is suppressed. On the other hand, the phosphorus-based curing accelerator is not easily affected by this, so it is presumed that a sufficient curing reaction occurs.
(E) content of the phosphorus-based curing accelerator, (G) based on 100 parts by weight of the solid content of the photosensitive resin composition excluding the inorganic filler and a solvent component, preferably 0.01 to 20 parts by weight, More preferably, 0.1 to 10 parts by mass is preferable.

<(F) Organic peroxide>
The photosensitive resin composition of the present invention may further contain an organic peroxide, if necessary. The organic peroxide functions as a thermal radical initiator that generates radicals by heat, and in the present invention, it is preferable to use an organic peroxide having a one-hour half-life temperature of 100 to 180 ° C.
By using an organic peroxide having such a one-hour half-life temperature, it is possible to improve the crosslink density and storage stability of the photosensitive resin composition, and to have a wide lamination temperature margin. Specifically, dicumyl peroxide (manufactured by Nippon Oil & Fat Co., Ltd., trade name "Park Mill D"), α, α'-bis (t-butylperoxy-m-isopropyl) benzene (manufactured by Nippon Oil & Fat Co., Ltd., product) Name "Perbutyl P"), 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perhexin 25B"), t-butyl peroxybenzoate ( Nippon Oil & Fat Co., Ltd., trade name "Perbutyl Z"), t-Butyl Cumyl Peroxide (Manufactured by Japan Oil & Fat Co., Ltd., Trade Name "Perbutyl C"), Cyclohexane Peroxide, 1,1-Bis (t-Butyl Peroxy) ) Cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-) Butyl peroxy) Valerate, di-t-butyl peroxide, benzoyl peroxide, cumylperoxyneodecanate, 2,5-dimethyl-2,5-di (benzoylperoshi) hexane, t-butylperoxyisopropyl carbonate , T-butylperoxyallyl carbonate, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, di-t-butylperoxyisophthalate and t-butylperoxymaleic acid. Can be done. These can be used alone or in combination of two or more.
When (F) an organic peroxide is used, the content is preferably 0.01 to 5 mass with respect to 100 mass by mass of the total solid content of the photosensitive resin composition excluding (G) the inorganic filler and the solvent component. Parts, more preferably 0.1 to 3 parts by mass. (F) If the content of the organic peroxide is less than 0.01 parts by mass, it becomes difficult to complete the curing in a short time, and the cured product tends to be non-uniform. On the other hand, when the content exceeds 5 parts by mass, the margin of the drying temperature and the laminating temperature tends to decrease. Further, the organic peroxide remaining without decomposition tends to reduce the insulation reliability and crack resistance of the insulating film after curing.

<(G) Inorganic filler>
The photosensitive resin composition of the present invention preferably further contains (G) an inorganic filler for the purpose of improving various properties such as adhesion and coating film hardness, if necessary. For example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (Si 3 N 4). BaO / TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum oxide, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO / TiO ₂ ), lead zirconate titanate (PZT), zirconic acid titanate lead lanthanum (PLZT), gallium oxide _{(Ga 2 O} 3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite _{(2MgO · 2Al 2 O 3 /} 5SiO 2) , talc _{(3MgO · 4SiO 2 · H 2} O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), nitride Boron (BN), Calcium Carbonate (CaCO ₃ ), Barium Sulfate (BaSO ₄ ), Calcium Sulfate (CaSO ₄ ), Zirconium Oxide (ZnO), Magnesium Titanium (MgO / TiO ₂ ), Hydrotalcite, Mica, Calcined Kaolin , Carbon and the like can be used. These inorganic fillers can be used alone or in combination of two or more.
The content of the inorganic filler (G) is preferably 0 to 80% by mass, more preferably 10 to 70% by mass, and 20 to 60% by mass based on the total solid content of the photosensitive resin composition. It is particularly preferably%, and most preferably 30 to 50% by mass. When the content is within the above range, the film strength, heat resistance, insulation reliability, heat impact resistance, resolution and the like can be further improved. The maximum particle size of the inorganic filler is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm, particularly preferably 0.1 to 5 μm, and 0.1 to 1 μm. And most preferable. If the maximum particle size exceeds 20 μm, the insulation reliability tends to be impaired.
Among the inorganic fillers (G), it is preferable to use silica fine particles from the viewpoint of improving insulation reliability.

In the photosensitive resin composition used in the present invention, various organic solvents can be used as a diluent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. Glycol ethers such as propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, octane, Examples thereof include aliphatic hydrocarbons such as decane, petroleum ethers, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum-based solvents such as solvent naphtha.
Further, the photosensitive resin composition of the present invention may further use a (H) cyanamide compound such as dicyanamide or a (I) triazine compound such as melamine, if necessary.
The photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing the above-mentioned various compounding components with a roll mill, a bead mill or the like.

<Photosensitive element and its manufacturing method>
The photosensitive element of the present invention comprises a support and a photosensitive layer formed on the support using the photosensitive resin composition of the present invention. If necessary, a protective film may be further provided on the surface of the photosensitive layer.

Examples of the support include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polystyrene. The thickness of the support is not particularly limited, but is preferably 5 to 100 μm, and more preferably 10 to 30 μm. Examples of the protective film include a polymer film such as polypropylene.
The photosensitive element of the present invention can be manufactured, for example, as follows. That is, the obtained photosensitive resin composition is prepared as a coating liquid having a solid content of about 30 to 60% by mass, and the coating liquid is applied onto a support such as a support film to form a coating layer, and the coating is applied. The photosensitive element of the present invention can be produced by drying the layer to form a photosensitive layer.

The coating liquid can be applied onto the support by, for example, a known method of a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater.

Further, the drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it is preferably performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of residual organic solvent in the photosensitive layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in a later step.

The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the intended use, but the thickness after drying is preferably 1 to 100 μm, more preferably 1 to 50 μm, and 5 to 40 μm. Is even more preferable. When the thickness of the photosensitive layer is 1 μm or more, industrial coating is facilitated and productivity is improved. Further, when it is 100 μm or less, the adhesion and the resolution are improved.
The form of the photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in a state of being wound around a winding core in a roll shape.

When winding in a roll shape, it is preferable to wind the support such as a support film so that the support is on the outside. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). It is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained from the viewpoint of end face protection, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Further, as a packing method, it is preferable to wrap the product in a black sheet having low moisture permeability.

The photosensitive element of the present invention can be particularly preferably used in, for example, a method for manufacturing an interlayer insulating film by a photovia method described later and a method for manufacturing a printed wiring board. Above all, it is suitable for application to a method for manufacturing a printed wiring board in which a circuit is formed on a conductor layer by plating.

[Method of forming resist pattern]
The method for forming a resist pattern of the present invention includes a laminating step of laminating a photosensitive layer formed of the photosensitive resin composition of the present invention on a conductor layer of a substrate having a conductor layer on an insulating base material, and a laminating step of laminating the photosensitive layer. An exposure step of irradiating a predetermined portion with active light to photocure the exposed portion, a developing step of removing a portion of the photosensitive layer other than the exposed portion, and, if necessary, an exposure of the photosensitive layer after the developing step. It includes a post-curing step of further curing the portion.

Examples of the insulating base material include glass epoxy base materials used in MCL-E-700G and MCL-E-705G (both manufactured by Hitachi Kasei Co., Ltd., trade names). The conductor layer on the insulating base material is not particularly limited, and examples thereof include copper foil, electroless plated copper, plated copper, and sputtered copper.

As a method of laminating the photosensitive layer on the conductor layer, a photosensitive resin composition is prepared as a coating liquid having a solid content of about 30 to 60% by mass, and this coating liquid is applied onto the conductor layer to form a coating layer. Then, it may be dried to form a photosensitive layer, or the photosensitive layer of the photosensitive element of the present invention may be laminated on a conductor layer. Details of the photosensitive layer laminating step, the exposure step, the developing step, the post-curing step, and the like will be described in the method for manufacturing the printed wiring board by the photovia method, which will be described later as one aspect of the method for manufacturing the printed wiring board of the present invention.
The resist pattern thus formed can be used as the solder resist of the present invention, the interlayer insulating film, and the like.

[Method for forming interlayer insulating film]
The method for forming the interlayer insulating film of the present invention can also be carried out in the same manner as the method for forming the resist pattern described above.

Details of the method for forming the photosensitive element and the method for forming the interlayer awning will be described in [Method for manufacturing a printed wiring board by the photovia method] described later as one aspect of the method for manufacturing a printed wiring board of the present invention.

[Printed wiring board and its manufacturing method]
The printed wiring board of the present invention includes a substrate having a conductor layer on an insulating base material and a cured product of the photosensitive resin composition of the present invention. For example, it can be manufactured by a method including a step of plating a substrate on which an interlayer insulating film is formed by the above-mentioned method of forming an interlayer insulating film. Further, before the plating step of the above-mentioned substrate, the substrate and / or the interlayer insulating film may be surface-roughened, and the roughened substrate and / or the interlayer insulating film may be plated. As a preferable method of surface roughening and plating, for example, it is preferable to carry out the treatment with an alkaline permanganate etching solution and to carry out the above plating by a copper plating process. The details of the method for manufacturing the printed wiring board will be described later in [Method for manufacturing the printed wiring board by the photovia method] as one aspect of the method for manufacturing the printed wiring board of the present invention.

<Manufacturing method of printed wiring board by photovia method>
An example of a method for producing an interlayer insulating film using the photosensitive resin composition of the present invention is shown below. The present invention is not limited to the following methods. For example, in the step of forming the interlayer insulating film, in addition to the method using a photosensitive element, a method by applying and drying a coating liquid containing the photosensitive resin composition of the present invention may be used.

This embodiment is a semi-additive construction method based on the photovia method, and includes, for example, the following steps.
(1) Step of forming interlayer insulating film After forming a photosensitive element on a conductor circuit which is a conductor layer of a substrate by vacuum press lamination, via processing for interlayer connection is performed by exposure and development, and then post-UV cure and post-UV cure. / Or the process of curing the resin by heat curing.
(2) Surface roughening by desmear treatment and formation process of copper circuit layer A step of roughening the surface of the interlayer insulating film by desmear treatment and then applying electroless copper plating treatment to the substrate. Further, after that, a pattern is formed on the electroless copper plating with a dry film resist, and then the electrolytic copper plating is performed to form a copper circuit layer.
(3) Resist stripping and copper circuit forming step Finally, a step of forming a copper circuit by stripping the dry film resist and removing the electroless plating layer by flash etching.

Hereinafter, preferred embodiments will be described for each step.
(1) Layer Insulating Film Forming Step In the interlayer insulating film forming step, the photosensitive element is pressure-bonded by a known vacuum press laminating method. After removing the protective film from the photosensitive element of the present invention, the photosensitive layer of the photosensitive element is heated and pressure-bonded to the substrate under reduced pressure. The photosensitive layer and / or the substrate is preferably heated at a temperature of 70 to 130 ° C. during crimping. The crimping is preferably performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ), but these conditions are appropriately selected as necessary.
In the exposure and development steps, by irradiating at least a part of the photosensitive layer formed on the substrate with the active light beam, the portion irradiated with the active light beam is photocured to form a pattern.

The exposure method is not particularly limited, and examples thereof include a method of irradiating an active ray in an image form through a negative or positive mask pattern called artwork (mask exposure method). Further, a method of irradiating an active ray in an image shape by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be adopted.

As the light source of the active light, a known light source can be used, for example, a carbon arc lamp, a mercury steam arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid-state laser such as a YAG laser, a semiconductor laser, or the like. Those that effectively emit the ultraviolet rays and visible light of the above are used. The exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, when the thickness of the photosensitive layer is 1 to 100 μm, it is usually about ^{10 to 1000 J / m 2.} It is more preferably 15 to 500 J / m ^2.
In development, the uncured portion of the photosensitive layer is removed from the substrate, so that an interlayer insulating film made of a photocured cured product is formed on the conductor layer of the substrate.

When a support such as a support film is present on the photosensitive layer, the support film is removed, and then the unexposed portion other than the exposed portion is removed (developed). There are two types of development methods, wet development and dry development, and wet development is widely used.

In the case of wet development, development is carried out by a known developing method using a developing solution corresponding to the photosensitive resin composition. Examples of the developing method include a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like, and the high-pressure spray method is the most suitable from the viewpoint of improving the resolution. Development may be performed by combining these two or more methods.

The composition of the developing solution is appropriately selected according to the composition of the photosensitive resin composition. For example, an alkaline aqueous solution such as a TMAH aqueous solution (tetramethylammonium hydroxide aqueous solution), an aqueous developer, and an organic solvent developer can be mentioned.

In the present invention, after removing the unexposed portion in the developing step, the insulating substrate is prepared by performing post-UV curing of about ^{0.2 to 10 J / cm 2 and heating of about 60 to 250 ° C. as necessary.} It may be further cured.

(2) Surface roughening by desmear treatment and copper circuit layer forming process If necessary, the surface of the interlayer insulating film can be roughened by desmear treatment. Examples of the desmear treatment liquid (oxidizing roughening liquid) include chromium / sulfuric acid roughening liquid, alkaline permanganate roughening liquid (sodium permanganate roughening liquid, etc.), and sodium fluoride / chromium / sulfuric acid roughening liquid. Etc. can be used.
After the desmear treatment, circuit formation and via conduction are performed by a semi-additive process. In the semi-additive process, first, an electroless copper treatment using a palladium catalyst or the like is applied to the via bottom, the via wall surface, and the entire surface of the insulating film after the desmear treatment to form a seed layer. The electroless copper plating of the seed layer is for forming a feeding layer for applying electrolytic copper plating, and is usually formed to a thickness of about 0.1 to 2.0 μm. If the seed layer is too thin, the connection reliability during subsequent electroplating tends to decrease, and if the seed layer is too thick, the etching amount when flash-etching the seed layer between the wires later must be increased, and the etching amount must be increased. In some cases, the damage to the wiring tends to be large.
The electroless copper treatment is performed by depositing metallic copper on the resin surface by the reaction of copper ions and a reducing agent. The electroless plating and electroplating may be any known method and are not limited to a specific method. However, the catalyst in the electroless plating process is composed of a palladium-tin mixed catalyst, and the primary particle size of the catalyst is large. It is preferably 10 nm or less. Further, it is preferable that the plating composition of the electroless plating treatment step contains hypophosphorous acid as a reducing agent.
Examples of the electroless copper plating include "MSK-DK" manufactured by Atotech Japan Co., Ltd. and "Sulcup PEA ver.4" manufactured by Uemura Kogyo Co., Ltd.
After the electroless copper plating treatment, the dry film resist is thermocompression bonded on the electroless copper plating with a roll laminator. The thickness of the dry film resist must be in a range higher than the wiring height after electrolytic copper plating, and a dry film resist having a thickness of 5 to 30 μm is preferably used.
The dry film resist is not particularly limited, and for example, the "Fortec" series (trade name) manufactured by Hitachi Kasei Co., Ltd. is used. After forming the dry film resist, the dry film resist is exposed through a mask on which a wiring pattern is drawn. The exposure can also be performed with the same device and light source as the photosensitive element. After the exposure, the support film is peeled off and developed with an alkaline aqueous solution to remove the unexposed portion to form a pattern. After that, if necessary, the work of removing the development residue of the dry film resist using plasma or the like may be performed. After development, electrolytic copper plating is performed to form a copper circuit layer and via filling.

(3) Resist stripping and copper circuit forming step After electrolytic copper plating, the dry film resist is stripped using an alkaline aqueous solution or an amine-based stripping agent. After peeling the dry film resist, flash etching is performed for the purpose of removing the seed layer between the wirings. Flash etching is performed using an acidic or oxidizing solution such as sulfuric acid and hydrogen peroxide. Specific examples thereof include "SAC" manufactured by Ebara Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company. After flash etching, if necessary, remove palladium or the like adhering to the portion between the wirings. Palladium is preferably removed using an acidic solution such as nitric acid or hydrochloric acid. Specific examples include the EBARA Eujilite "PJ" solution.
After stripping the dry film resist or after the flash etching step, post-curing is performed by a post-baking step. The post-baking process completely heat-cures the unreacted thermosetting components, thereby improving insulation reliability, curing properties, and plating adhesion. The thermosetting conditions vary depending on the type of the resin composition and the like, but the curing temperature is preferably 150 to 240 ° C. and the curing time is preferably 15 to 100 minutes.
Post-baking completes the manufacturing process of the printed wiring board by the photovia method, but the substrate is manufactured by repeating this process according to the required number of insulating layers. In addition, a solder resist layer is formed on the outermost layer.

The photosensitive resin composition of the present invention can be used in the production of printed wiring boards, but is not limited thereto, and can be used in the production process of wafer processes such as FOWLP (Fan Out Wafer Level Package). May be good.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the synthesis example, the part in the example, and the compounding amount in the table show the part by mass.

(Synthesis Example 1; Synthesis of Acid-Modified Epoxy (Meta) Acrylate Compound)
Bisphenol F novolak type epoxy resin (trade name: EXA-7376, manufactured by DIC Corporation) 350 parts by mass, 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, 120 parts by mass of carbitol acetate are charged and heated to 90 ° C. The reaction was carried out by stirring to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. and reacted until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, and then cooled to have a solid content concentration of 73 parts by mass. A solution of the acid-modified epoxy (meth) acrylate compound (A-1) as the component (A) in% was obtained.

Examples 1 and 2 and Comparative Examples 1 to 3 were mixed in the blending amounts (parts by mass) shown in Table 1 and kneaded with a three-roll mill to obtain a photosensitive resin composition solution. Finally, propylene glycol monomethyl ether acetate was added so that the solid content concentration became 60% by mass to prepare a photosensitive resin composition solution.
Next, the prepared photosensitive resin composition solution was uniformly applied onto a 25 μm-thick polyethylene terephthalate film (G2-25, manufactured by Teijin Limited, trade name) as a support, and then it was applied to a hot air convection dryer. Was dried at 100 ° C. for about 10 minutes. The film thickness of the photosensitive resin composition layer after drying, that is, the photosensitive layer obtained by drying the photosensitive resin composition solution was 25 μm.

Subsequently, an OPP biaxially stretched polypropylene film (MA-411, manufactured by Oji Special Paper Co., Ltd., trade name) is bonded as a protective film on the surface opposite to the side in contact with the support of the photosensitive layer. A photosensitive element was obtained.

A-2: Kayarad DPHA: Dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name)
B-1: Irgacure 907: 2-Methyl- [4- (Methylthio) Phenyl] Morpholino-1-Propanone (manufactured by BASF Japan Ltd., trade name)
B-2: DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name)
C-1: Epicoat 806: Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)
C-2: Epicoat 828: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name)
C-3: NC-3000H: Biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)
C-4: PB3600: Epoxidized polybutadiene (manufactured by Daicel Chemical Co., Ltd., trade name)
D-1: BMI-4000: Bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name)
E-1: TBP2: Tributylphosphonium p-benzoquinone (manufactured by Kurokin Kasei Co., Ltd., trade name)
E-2: 2MZ-CN: 1-cyanoethyl-2-methylimidazole (manufactured by Shikoku Chemicals Corporation, trade name)
F-1: Perhexin 25B: 2,5-dimethyl-2,5-bis (tert-butylperoxy) -3-hexyne (manufactured by NOF CORPORATION, trade name)
G-1: MEK slurry: silica slurry (manufactured by Admatex Co., Ltd., sample name)

[Evaluation of minimum development time, sensitivity, and resolution]
Pretreatment liquid CZ-8100 (Mech Co., Ltd.) for roughening the copper surface of a printed wiring board substrate (MCL-E-679, manufactured by Hitachi Kasei Co., Ltd., trade name) in which a 12 μm thick copper foil is laminated on a glass epoxy base material. It was treated with (manufactured by), washed with water, and dried. Using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name) on this printed wiring board substrate, press hot plate temperature 70 ° C., vacuuming time 20 seconds, laminating press time 30 seconds, Evaluation that a photosensitive layer (photosensitive resin composition layer) was formed on a printed wiring board substrate by peeling and laminating the protective film of the photosensitive element under the conditions of an atmospheric pressure of 4 kPa or less and a crimping pressure of 0.4 MPa. A laminate for use was obtained.

Then, after leaving it at room temperature for 1 hour or more, the support film was peeled off and removed, a 41-step step tablet was placed on the photosensitive layer, and a direct imaging exposure device DXP-3512 (Oak Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Exposure was performed using (manufactured by Mfg. Co., Ltd.). As the exposure pattern, a pattern in which dots having a diameter of 30 to 100 μm were arranged in a grid pattern was used.

After the exposure, the mixture was left at room temperature for 30 minutes, and then the photosensitive layer (photosensitive resin composition) in the unexposed portion was spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. At this time, the minimum time during which the unexposed portion can be developed is defined as the minimum development time. The evaluation substrate was developed in twice the minimum development time. After development, the amount of exposure energy at which the number of remaining glossy steps of the 41-step step tablet was 8.0 was defined as the sensitivity (unit: mJ / cm ² ) of the photosensitive layer (photosensitive resin composition layer). The photosensitive resin composition layer was evaluated using the pattern exposed with this sensitivity.

The resolution was evaluated by exposing and spray-developing with an exposure energy amount such that the number of step steps was 8.0, and observing a via pattern using an optical microscope after the development treatment. When the via (60 μm diameter portion) of the dot pattern was open, it was determined as “A”, and when it was not opened, it was determined as “B”. The judgment of "A" with the via opening shows good characteristics. The results are shown in Table 2.

[Evaluation of peel strength]
Pretreatment liquid CZ-8100 (Mech Co., Ltd.) for roughening the copper surface of a printed wiring board substrate (MCL-E-679, manufactured by Hitachi Kasei Co., Ltd., trade name) in which a 12 μm thick copper foil is laminated on a glass epoxy base material. It was treated with (manufactured by), washed with water, and dried. Using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name) on this printed wiring board substrate, press hot plate temperature 70 ° C, vacuuming time 20 seconds, laminating press time 30 seconds, Under the conditions of an atmospheric pressure of 4 kPa or less and a crimping pressure of 0.4 MPa, the protective film of the photosensitive element was peeled off and laminated to obtain a laminate for evaluation.

Then, after leaving it at room temperature for 1 hour or more, the support film was peeled off and removed, a 41-step step tablet was installed, and a parallel light exposure machine EXM-1201 (manufactured by ORC Manufacturing Co., Ltd.) using an ultra-high pressure mercury lamp as a light source was installed. The entire surface was exposed with an exposure energy amount such that the number of steps with residual gloss was 10.0. After the exposure, the mixture was allowed to stand at room temperature for 30 minutes, and then the photosensitive resin composition in the unexposed portion of the photosensitive layer was sprayed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for 60 seconds to remove and develop.

^{After that, post-UV cure is performed at a conveyor speed of 2} J / cm 2 with a high-pressure mercury lamp lamp irradiation type UV conveyor device (manufactured by ORC Manufacturing Co., Ltd.), and then with a hot air circulation dryer (manufactured by Futaba Kagaku Co., Ltd.). Post-heat curing was performed at 170 ° C. for 1 hour.
As the roughening treatment of the above substrate, the swelling liquid "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) was used at 70 ° C. for 5 minutes, and the roughening liquid (permanganate etching solution (Desmia solution)) "Dosing Securigant P500J" was used. (Atotech Japan Co., Ltd.) was used at 70 ° C. for 10 minutes, and the neutralizing solution "Reduction Conditioner Securigant P500" (manufactured by Atotech Japan Co., Ltd.) was used at 40 ° C. for 5 minutes to carry out desmear treatment.
After that, the electroless plating solution "Prigant MSK-DK" (manufactured by Atotech Japan Co., Ltd.) was applied at 30 ° C. for 20 minutes, and the electroplating solution "Capallaside HL" (manufactured by Atotech Japan Co., Ltd.) was applied at 24 ° C., 2A / dm ² . Two hours were carried out to prepare an evaluation substrate for peel measurement.
For the measurement of the plating peel strength, the thickness of the plated copper was set to 35 μm, and the conductor peeling strength of the evaluation sample was measured. For peeling, the vertical peeling strength was measured. The measurement was carried out at room temperature of 23 ° C. The measuring method was based on JIS-C-6481. If the peel strength was 0.4 kN / m or more, it was judged to be good. The results are shown in Table 2.

[Evaluation of HAST resistance]
Printed circuit board board (MCL-E-679FG, manufactured by Hitachi Kasei Co., Ltd., trade name) in which 12 μm thick copper foil is laminated on a glass epoxy base material, build-up material for semi-adive wiring formation (AS-Z6, A comb-shaped electrode having a line / space of 12 μm / 12 μm was produced using Hitachi Kasei Co., Ltd. (trade name), and this was used as an evaluation substrate.
An interlayer insulating film made of a cured product of the photosensitive element is formed on the comb-shaped electrode on this evaluation substrate in the same manner as in the above-mentioned "evaluation of resolution" (exposure is performed so that the insulating film remains on the comb-shaped electrode portion). It was formed by developing, irradiating with ultraviolet rays, and heat-treating), and then exposed under the conditions of 130 ° C., 85% RH, and 6 V for 200 hours. Then, the resistance value was measured and the HAST resistance of the interlayer insulating film was evaluated. The time when the resistance value becomes ^10-6 Ω or less is defined as the migration occurrence time, the one in which no migration occurs after 200 hours is "A", and the one in which the migration occurs between 100 hours and 200 hours is "B". , The one that occurred in less than 100 hours was judged as "C". The results are shown in Table 2.

As is clear from the results shown in Table 2, the photosensitive layer of the photosensitive element of the present invention of Examples 1 and 2 (the photosensitive layer formed of the photosensitive resin composition of the present invention) has excellent resolution. However, it was confirmed that it had excellent peel strength with the conductor layer formed on the insulating base material, and also had excellent insulation reliability (HAST resistance).

According to the present invention, a photosensitive resin composition suitable for forming an insulating layer of a multilayer printed wiring board or the like having excellent resolution, adhesion and insulation reliability, forming an insulating layer of a printed wiring board of an electronic device, or the like. A photosensitive element can be provided. Further, the photosensitive resin composition and the photosensitive element of the present invention are also effective as an interlayer insulating base material of FOWLP (Fan Out Wan Out Wafer Package).

Claims (9)

A laminating step of laminating a photosensitive layer formed of a photosensitive resin composition on a conductor layer of a substrate having a conductor layer on an insulating base material.
An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to photo-cure the exposed portion.
A developing process for removing a portion of the photosensitive layer other than the exposed portion, and
In the method for manufacturing a printed wiring board, which comprises a step of surface-roughening an interlayer insulating film formed by a method including the above with an alkaline permanganate etching solution and plating the roughened interlayer insulating film by a copper plating process. A photosensitive resin composition used for forming a layer.
It contains (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, (C) an epoxy resin, (D) a polyfunctional maleimide compound, and (E) a phosphorus-based curing accelerator. (A) The photopolymerizable compound having an ethylenically unsaturated group contains an acid-modified epoxy (meth) acrylate compound having a carboxyl group in the molecule .
The (C) epoxy resin contains a bisphenol F type epoxy resin and contains
A photosensitive resin composition in which the phosphorus-based curing accelerator (E) is an adduct of a tertiary phosphine and quinones. (G) The photosensitive resin composition according to claim 1, further containing an inorganic filler . (F) The photosensitive resin composition according to claim 1 or 2, further containing an organic peroxide having a 1-hour half-life temperature of 100 ° C. to 180 ° C. The content of the (C) epoxy resin in the photosensitive resin composition is 5 to 70 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition excluding the (G) inorganic filler and solvent component. The photosensitive resin composition according to any one of claims 1 to 3, which is a part by mass. The content of the (D) polyfunctional maleimide compound in the photosensitive resin composition is 2 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition excluding (G) the inorganic filler and the solvent component. The photosensitive resin composition according to any one of claims 1 to 4, which is ~ 40 parts by mass. The content of the (E) phosphorus-based curing accelerator in the photosensitive resin composition is 100 parts by mass of the total solid content of the photosensitive resin composition excluding the (G) inorganic filler and solvent component. The photosensitive resin composition according to any one of claims 1 to 5, which is 0.01 to 20 parts by mass. A laminating step of laminating a photosensitive layer formed of a photosensitive resin composition on a conductor layer of a substrate having a conductor layer on an insulating base material.
An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to photo-cure the exposed portion.
A developing process for removing a portion of the photosensitive layer other than the exposed portion, and
In the method for manufacturing a printed wiring board, which comprises a step of surface-roughening an interlayer insulating film formed by a method including the above with an alkaline permanganate etching solution and plating the roughened interlayer insulating film by a copper plating process. A photosensitive element used to form a layer.
A photosensitive element comprising a support and a photosensitive layer formed on the support using the photosensitive resin composition according to any one of claims 1 to 6. A laminating step of laminating a photosensitive layer formed of the photosensitive resin composition according to any one of claims 1 to 6 on a conductor layer of a substrate having a conductor layer on an insulating base material.
An exposure step of irradiating a predetermined portion of the photosensitive layer with active light to photo-cure the exposed portion.
A developing process for removing a portion of the photosensitive layer other than the exposed portion, and
A printed wiring board including a step of forming an interlayer insulating film by a method including the above , roughening the surface of the interlayer insulating film with an alkaline permanganate etching solution, and plating the roughened interlayer insulating film by a copper plating process. Manufacturing method . The method for manufacturing a printed wiring board according to claim 8 , further comprising a post-curing step of further curing the exposed portion of the photosensitive layer after the developing step.