CN113614639A - Laminated structure, cured product, printed circuit board, and electronic component - Google Patents

Abstract

The laminated structure of the present invention, which suppresses the occurrence of static electricity, prevents defective peeling, and has excellent long-term reliability, sequentially comprises: a conductive layer having a surface resistance of 1.0 × 10, a support film, a photosensitive resin layer and a protective film¹⁰Omega or less and the surface resistance value of the supporting film is 1.0 x 10¹²Omega or more, the photosensitive resin layer comprises: a carboxyl group-containing resin, a photopolymerization initiator, a thermosetting component and an inorganic filler, and dissolvedThe ratio of the residual content of the agent is less than 5% by mass based on the total amount of the resin layer containing the aforementioned solvent.

Description

Laminated structure, cured product, printed circuit board, and electronic component

Technical Field

The present invention relates to: a laminated structure, a cured product obtained by curing a photosensitive resin layer of the laminated structure, a printed wiring board having the cured product, and an electronic component having the cured product or the printed wiring board.

Background

Conventionally, dry films have been used as one of the means for forming protective films and insulating layers such as solder resists and interlayer insulating layers provided on printed wiring boards used in electronic devices and the like. The dry film has: a support film (carrier film); and a resin layer obtained by applying a curable resin composition to the support film and drying the resin layer, and further, the resin layer is distributed in the market as a laminated structure in which a protective film for protecting the surface of the resin layer opposite to the support film is laminated. The protective film of the dry film is peeled off, and after a resin layer is attached (hereinafter, also referred to as "laminated") to a substrate, patterning and curing treatment are performed, thereby forming the protective film and the insulating layer of the printed wiring board.

After the dry film is attached to a substrate such as a printed circuit board, there is a concern that a surface of the solder resist layer may be scratched by static electricity generated when the support film is peeled off, or an IC chip mounted on the printed circuit board may be damaged. In order to suppress the static electricity generated when peeling off the supporting film, the surface resistivity of the supporting film is 1X 10¹³Omega or lessA photosensitive film with a support (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-169547

Disclosure of Invention

Problems to be solved by the invention

In the photosensitive film with a support described in patent document 1, the antistatic agent is applied to the surface of the support film, and the like, whereby the surface resistance value of the support film is 1 × 10¹³Omega is less than or equal to. The support film has a low surface resistance value, can suppress the generation of static electricity, and has excellent flexibility.

However, when the protective film is peeled off from the photosensitive film with a support described in patent document 1, a phenomenon called poor peeling may occur in which a part of the photosensitive resin layer adheres to the protective film and is peeled off, and there is a problem in moisture resistance and further long-term reliability.

Accordingly, an object of the present invention is to provide: a laminated structure which suppresses generation of static electricity, prevents defective peeling, and has excellent long-term reliability, a cured product obtained by curing a photosensitive resin layer of the laminated structure, a printed wiring board having the cured product, and an electronic component having the cured product or the printed wiring board.

Means for solving the problems

The inventors have repeatedly studied the defective peeling of the laminated structure used as a dry film and found that: if the content of the solvent is less than 5% by mass, poor peeling can be prevented. Further, it was found that: in order to effectively suppress the generation of static electricity, it is important to specify the surface resistance value of the conductive layer formed on the surface of the support film opposite to the resin layer and the surface resistance value of the support film to predetermined ranges, respectively, rather than simply reducing the surface resistance value of the support film containing the antistatic agent.

Based on the above findings, the laminated structure of the present invention is characterized by comprising, in order: a conductive layer, a support film, a photosensitive resin layer and a protective film,

the surface resistance of the conductive layer is 1.0 × 10¹⁰Omega or less, and the surface resistance value of the support film is 1.0X 10¹²The content of the carbon dioxide is more than omega,

the photosensitive resin layer comprises: a carboxyl group-containing resin, a photopolymerization initiator, a thermosetting component and an inorganic filler, and the ratio of the residual content of the solvent is less than 5% by mass based on the total amount of the resin layer containing the aforementioned solvent.

In the laminated structure of the present invention, the thickness of the conductive layer is preferably 2 μm or less, the gardner color number of the thermosetting component of the photosensitive resin layer is preferably 3 or less, and the electrostatic potential of the surface of the photosensitive resin layer when the support film is peeled off from the photosensitive resin layer is preferably 250kV or less.

The cured product of the present invention is obtained by curing the photosensitive resin layer of the laminated structure.

The printed wiring board of the present invention is characterized by having the cured product.

The electronic component of the present invention is characterized by having the cured product or the printed wiring board.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the laminated structure of the present invention, it is possible to suppress generation of static electricity when peeling the support film, to prevent scratching of the solder resist and damage of the IC chip, and to suppress defective peeling when peeling the protective film, to maintain long-term reliability. Here, the poor peeling means that a part of the photosensitive resin layer is peeled off by adhering to the protective film.

Drawings

Fig. 1 is a schematic cross-sectional view of a dry film of one embodiment of the laminated structure of the present invention.

Detailed Description

The laminated structure, the solder resist, the cured product, the printed wiring board, and the electronic component of the present invention will be described in more detail with reference to the drawings.

Fig. 1 is a schematic cross-sectional view showing a dry film 10 of one embodiment of the laminated structure of the present invention. Figure 1 stemThe film 10 includes a conductive layer 11, a support film 12, a photosensitive resin layer 13, and a protective film 14 in this order, and has a structure in which at least 4 layers are stacked. The surface resistance of the conductive layer 11 was 1.0X 10¹⁰Omega is less than or equal to. Further, the surface resistance value of the support film 12 was 1.0X 10¹²Omega or more. Further, the photosensitive resin layer 13 includes: a carboxyl group-containing resin, a photopolymerization initiator, a thermosetting component and an inorganic filler, and the ratio of the residual content of the solvent is less than 5% by mass based on the total amount of the resin layer containing the aforementioned solvent. Further, an uneven layer may be provided between the support film 12 and the photosensitive resin layer 13.

The laminated structure of the present invention comprises a support film and a conductive layer, wherein the conductive layer is laminated on the support film, and the surface resistance value of the conductive layer is 1.0X 10¹⁰Omega or less, and the surface resistance of the supporting film is set to 1.0 × 10¹²Omega or more, the occurrence of static electricity when peeling the support film can be effectively suppressed by the conductive layer having a low surface resistance value. Specifically, the static electricity can be suppressed such that the static electricity potential of the surface of the photosensitive resin layer when the support film is peeled from the photosensitive resin layer becomes 250 kV.

In addition, the ratio of the residual content of the solvent in the photosensitive resin layer is less than 5% by mass of the total resin layer, whereby defective peeling can be prevented.

The layers of the dry film 10 will be described below.

[ conductive layer ]

The conductive layer is a layer having a property of improving conductivity in order to prevent static electricity from occurring when the support film is peeled from the dry film, and may be formed on the surface of the support film formed of a resin. Specifically, an antistatic agent may be used for the conductive layer. Examples of the antistatic agent include quaternary ammonium salt type cationic polymer compounds, sulfonic acid group-containing anionic polymer compounds, ether type nonionic surfactants, and the like. In addition to these antistatic agents, as the conductive layer, a layer in which a conductive filler containing powder, fibers, flakes, or the like of graphite, metal oxide, or the like is dispersed in a thermoplastic resin can be used. In addition, a resin composition in which a conductive polymer such as polyacetylene or polyaniline is mixed with another resin may be used as the conductive layer.

In any material, the surface resistance of the conductive layer must be 1.0 × 10¹⁰Omega is less than or equal to. Passing surface resistance value of 1.0X 10¹⁰The conductivity can be further improved and the generation of static electricity can be effectively suppressed by not more than Ω.

The conductive layer is formed on the opposite side of the photosensitive resin layer to the support film. The conductive layer is formed on the side opposite to the photosensitive resin layer with respect to the support film, whereby peeling marks on the surface of the photosensitive resin layer after the support film is peeled from the photosensitive resin layer together with the conductive layer can be suppressed. Further, if the support film, the conductive layer and the photosensitive resin layer are sequentially laminated, the B-HAST property indicating the moisture resistance of the photosensitive resin layer is poor, and the long-term reliability is insufficient.

The thickness of the conductive layer is preferably 2 μm or less. When the thickness is 2 μm or less, static electricity can be effectively prevented, and since the conductive layer is thin, deterioration in resolution of the photosensitive resin layer can be suppressed by the color depth of the conductive layer or the conductive particles included in the conductive layer. Preferably 1 μm or less.

[ supporting film ]

The support film has a function of supporting the photosensitive resin layer of the dry film, and is a film coated with the photosensitive resin composition when the photosensitive resin layer is formed. As the support film, for example, there can be used: polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, films made of thermoplastic resins such as polyethylene films, polytetrafluoroethylene films and polypropylene films, and surface-treated papers. Among them, polyester films can be suitably used from the viewpoint of heat resistance, mechanical strength, handling properties, and the like. The thickness of the support film is not particularly limited, and may be appropriately selected within a range of about 10 to 150 μm depending on the application. The surface of the support film on which the resin layer is provided may be subjected to a mold release treatment. Further, a sputtered or extra thin copper foil may be formed on the surface of the carrier film on which the resin layer is provided.

[ photosensitive resin layer ]

The photosensitive resin layer is preferably formed from a photosensitive resin composition containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, a thermosetting component, and an inorganic filler.

(carboxyl group-containing photosensitive resin)

The carboxyl group-containing photosensitive resin may be any of various conventionally known carboxyl group-containing photosensitive resins having a carboxyl group in the molecule, and a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is particularly preferable from the viewpoints of photocurability and resolution. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. When only the carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used, a compound having an ethylenically unsaturated group in the molecule, that is, a photopolymerizable monomer, which will be described later, must be used in combination in order to make the composition photocurable.

Specific examples of the carboxyl group-containing resin include the following compounds (either oligomers or polymers).

(1) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid and reacting the obtained reaction product with a polybasic acid anhydride.

(2) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional (solid) epoxy resin having 2 or more functional groups described later with (meth) acrylic acid to add a dibasic acid anhydride to a hydroxyl group present in a side chain.

(3) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional (solid) epoxy resin described later with epichlorohydrin with (meth) acrylic acid to add a dibasic acid anhydride to the resulting hydroxyl group.

(4) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with an unsaturated group-containing monocarboxylic acid, and reacting the resultant reaction product with a polybasic acid anhydride.

(5) A carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate, a (meth) acrylate ester or a partial acid anhydride modified product thereof with a 2-functional epoxy resin such as a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bixylenol epoxy resin, or a diphenol epoxy resin, a carboxyl group-containing diol compound, and a diol compound.

(6) A carboxyl group-containing non-photosensitive resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.

(7) A carboxyl group-containing non-photosensitive polyurethane resin obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(8) A carboxyl group-containing non-photosensitive polyester resin obtained by reacting a 2-functional oxetane resin described later with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to add a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the resulting primary hydroxyl group.

(9) In the synthesis of the resin of the above (5) or (7), a carboxyl group-containing photosensitive polyurethane resin is added which has been (meth) acrylated at the end by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate.

(10) In the synthesis of the resin of the above (5) or (7), a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, is added to carry out terminal (meth) acrylation to obtain a carboxyl group-containing photosensitive polyurethane resin.

(11) A carboxyl group-containing photosensitive resin obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule to the resins (1) to (10) above.

In the present specification, the term (meth) acrylate is a term generally referring to acrylate, methacrylate and a mixture thereof, and the same applies to similar expressions.

Since the above-mentioned carboxyl group-containing resin has a plurality of carboxyl groups in the side chain of the main chain polymer, development can be performed with a dilute aqueous alkali solution.

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. The acid value of the carboxyl group-containing resin is preferably 40mgKOH/g or more because alkali development is easy, and 200mgKOH/g or less because drawing of a normal resist pattern is easy.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually in the range of 2000 to 150000, and more preferably 5000 to 100000. When the weight average molecular weight is 2000 or more, the moisture resistance of the coating film after exposure is good, and the film loss at the time of development is suppressed, whereby the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150000 or less, the developability is good and the storage stability is also excellent. The weight average molecular weight can be determined by GPC.

The amount of the carboxyl group-containing resin is suitably in the range of 15 to 60 mass%, preferably 20 to 50 mass%, of the entire composition of the photosensitive resin layer. When the amount of the carboxyl group-containing resin is within the above range, the coating strength is not reduced, and the viscosity, the coatability and the like of the composition become good.

These carboxyl group-containing resins may be used without being limited to those listed above, and may be used alone in 1 kind or in a mixture of plural kinds. In particular, among the above-mentioned carboxyl group-containing resins, those having an aromatic ring are preferable because they have a high refractive index and excellent resolution, and further, those having a novolak structure are preferable because they are excellent not only in resolution but also in PCT and crack resistance, and among them, the carboxyl group-containing photosensitive resins (1) and (2) satisfy various characteristics such as PCT resistance and are preferable because they can provide a solder resist having excellent resolution.

(photopolymerization initiator)

The photosensitive resin composition for forming the photosensitive resin layer contains a photopolymerization initiator. As the photopolymerization initiator, 1 or more kinds of photopolymerization initiators selected from the group consisting of oxime ester type photopolymerization initiators having an oxime ester group, alkylbenzene type photopolymerization initiators, α -aminoacetophenone type photopolymerization initiators, acylphosphine oxide type photopolymerization initiators, and titanocene type photopolymerization initiators can be suitably used.

In particular, the amount of the oxime ester photopolymerization initiator added is not particularly limited, and is preferable because the exhaust gas can be suppressed, and thus, PCT resistance and crack resistance are effective.

Examples of oxime ester photopolymerization initiators that are commercially available include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF JAPAN, N-1919 manufactured by ADEKA, and NCI-831. Further, a photopolymerization initiator having 2 oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula can be mentioned.

(wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), Y, Z represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), Anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond or an alkylene group having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thienyl, anthracenylene, thienylene, furanylene, 2, 5-pyrrolediyl, 4 '-stilbenediyl, 4, 2' -styryl, n is an integer of 0 or 1. )

Particularly preferably, in the above formula, X, Y is methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is a bond, or phenylene, naphthylene, thienyl, or thienylene, respectively.

Further, preferable examples of the carbazole oxime ester compound include compounds represented by the following general formula.

(in the formula, R¹Represents an alkyl group having 1 to 4 carbon atoms or a phenyl group optionally substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

R²Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms.

R³Represents an alkyl group having 1 to 20 carbon atoms which is optionally substituted with a phenyl group and is optionally bonded to an oxygen atom or a sulfur atom, or a benzyl group which is optionally substituted with an alkoxy group having 1 to 4 carbon atoms.

R⁴Represents a nitro group, or an acyl group represented by X — C (═ O) -.

X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, the aryl group being optionally substituted with an alkyl group having 1 to 4 carbon atoms. )

Examples of the carbazole oxime ester compounds include those described in Japanese patent laid-open Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770, 2008-509967, 2009-040762, and 2011-80036.

The amount of the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.25 to 3 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

By setting the amount to 0.01 to 5 parts by mass, a solder resist having excellent photocurability and resolution, improved adhesion and PCT resistance, and further excellent chemical resistance such as electroless gold plating resistance can be obtained.

On the other hand, if the amount is less than 0.01 parts by mass, the photocurability of copper is insufficient, the solder resist coating film is peeled off, and the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes rapid, and deep curability tends to decrease.

Commercially available products of the alkylphenone photopolymerization initiator include α -hydroxyalkylphenone types such as Omnirad 184, Darocure 1173, Irgacure2959, and Omnirad 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one), manufactured by IGM Resins, for example.

Specific examples of the α -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, and N, N-dimethylaminoacetophenone. Commercially available products include Omnirad 907, Omnirad 369 and Omnirad 379 manufactured by IGM Resins.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Omnirad TPO manufactured by IGM Resins, Omnirad 819 manufactured by IGM Resins, and the like.

The amount of the α -aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

By 0.1 to 25 parts by mass, a solder resist having excellent photocurability and resolution, improved adhesion and PCT resistance, and further excellent chemical resistance such as electroless gold plating resistance can be obtained.

On the other hand, if it is less than 0.1 part by mass, the photocurability on copper is similarly insufficient, the solder resist is peeled off, and the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 25 parts by mass, the effect of reducing outgassing cannot be obtained, and further, light absorption on the surface of the solder resist becomes rapid, and deep curability tends to decrease.

Further, Omnirad 389 manufactured by IGM Resins company can be suitably used as the photopolymerization initiator. The amount of Omnirad 389 added is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

Furthermore, a titanocene-based photopolymerization initiator such as Omnirad 784 (bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) can also be suitably used. The amount of the titanocene-based photopolymerization initiator is preferably 0.01 to 5 parts by mass and more preferably 0.01 to 3 parts by mass per 100 parts by mass of the carboxyl group-containing resin.

By appropriately blending these photopolymerization initiators, a solder resist having excellent photocurability and resolution, improved adhesion and PCT resistance, and further excellent chemical resistance such as electroless gold plating resistance can be formed.

On the other hand, if the amount is less than the appropriate amount, the photocurability on copper is insufficient, the solder resist peels off, and the coating film properties such as chemical resistance are degraded. On the other hand, if the amount exceeds the appropriate amount, the effect of reducing outgassing cannot be obtained, and further, the light absorption on the surface of the solder resist becomes rapid, and the deep curing property tends to decrease.

Among the above photopolymerization initiators, compounds containing nitrogen, phosphorus, sulfur and titanium atoms are particularly preferable.

(auxiliary component for photocuring)

The photosensitive resin composition may use a photo-initiation aid or a sensitizer in addition to the photopolymerization initiator. Examples of the photopolymerization initiator, the photoinitiator aid, and the sensitizer that can be suitably used in the photosensitive resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

Specific examples of the thioxanthone compound include 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, and 2, 4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzil dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 ' -methyldiphenyl sulfide, 4-benzoyl-4 ' -ethyldiphenyl sulfide, and 4-benzoyl-4 ' -propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure, and examples of commercially available products include dialkylaminobenzophenones such as 4,4 '-dimethylaminobenzophenone (Nis Cure MABP manufactured by Nippon Kazakh Co., Ltd.) and 4, 4' -diethylaminobenzophenone (EAB manufactured by Baoka chemical Co., Ltd.), dialkylamino-containing coumarin compounds such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kaya Cure EPA manufactured by Nippon Kagaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthesis Co., Ltd.), and the like, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-Synthesis), isoamyl p-dimethylaminobenzoate (Kaya Cure DMBI, manufactured by Nippon Kagaku K.K.), 2-ethylhexyl 4-dimethylaminobenzoate (esol 507, manufactured by Van Dyk K.K.), 4' -diethylaminobenzophenone (EAB, manufactured by Gekko Kagaku K.K.).

Among them, a thioxanthone compound and a tertiary amine compound are preferable. From the viewpoint of deep curability, it is particularly preferable to contain a thioxanthone compound. Among them, preferred are thioxanthone compounds such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone.

The amount of the thioxanthone compound to be blended is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. If the compounding amount of the thioxanthone compound exceeds 20 parts by mass, thick film curability decreases, and the cost of the article increases. More preferably 10 parts by mass or less.

The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, and particularly preferably a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450nm, and ketocoumarins.

As the dialkylaminobenzophenone compound, 4, 4' -diethylaminobenzophenone is preferable because of its low toxicity. Since the maximum absorption wavelength of the dialkylamino group-containing coumarin compound is 350 to 410nm in the ultraviolet region, it is possible to provide a colorless and transparent photosensitive composition with little coloring, and it is also possible to provide a colored solder resist using a coloring pigment or reflecting the color of the coloring pigment itself. The 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is particularly preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the tertiary amine compound to be blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, if it exceeds 20 parts by mass, light absorption on the surface of the dry solder resist by the tertiary amine compound becomes rapid, and deep curability tends to decrease. More preferably 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator aids, and sensitizers may be used alone or as a mixture of 2 or more kinds.

The total amount of such a photopolymerization initiator, a photoinitiator aid and a sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

Since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, the sensitivity may be lowered and they may function as ultraviolet absorbers in some cases.

(thermosetting component)

In the photosensitive resin composition, a thermosetting component may be added. By adding a thermosetting component, improvement in heat resistance was confirmed. As the thermosetting component, known thermosetting resins such as an amino resin such as a melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivative, etc., a blocked isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin, bismaleimide, carbodiimide resin, etc. can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and/or cyclic thioether groups (hereinafter, referred to as cyclic (thio) ether groups) in the molecule.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having any one or 2 kinds of cyclic (thio) ether groups having a plurality of 3-, 4-or 5-membered rings in the molecule, and examples thereof include: a polyfunctional epoxy compound which is a compound having a plurality of epoxy groups in the molecule, a polyfunctional oxetane compound which is a compound having a plurality of oxetane groups in the molecule, an episulfide resin which is a compound having a plurality of thioether groups in the molecule, and the like.

Examples of the polyfunctional epoxy compound include: epoxidized vegetable oils such as Adeka sizer O-130P, Adeka sizer O-180A, Adeka sizer D-32 and Adeka sizer D-55 manufactured by ADEKA; JeR828, JeR834, JeR1001, JeR1004, Daicel Chemical Industries, Ltd., EHPE3150, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055, Epotohto YD-011, YD-013, YD-127, YD-128, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664, Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, SUMI-ESEPOXY-011, ESEPELA 115-014, Araldite A115-014, bisphenol A (bisphenol A) resins such as bisphenol A manufactured by Sumitomo Chemical Industries, Ltd; YDC-1312, hydroquinone type epoxy resin, YSLV-80XY bisphenol type epoxy resin, YSLV-120TE thioether type epoxy resin (all manufactured by Tokyo Kasei Co., Ltd.); brominated EPOXY resins such as jERYL903 manufactured by Mitsubishi Chemical corporation, EPICLON152 manufactured by DIC corporation, EPICLON165, Epotohto YDB-400 manufactured by Tokyo Kaisha, YDB-500, D.E.R.542 manufactured by Dow Chemical Company, Araldite 8011 manufactured by BASF JAPAN corporation, SUMI-XY ESB-400 manufactured by Sumitomo Chemical industry Co., Ltd, and ESB-700 (trade names in each case); novolac type EPOXY resins such as JeR152, JeR154 manufactured by Mitsubishi Chemical corporation, D.E.N.431, D.E.N.438, EPICLON-730 manufactured by DIC, EPICLON-770, EPICLON-865, Epotohto YDCN-701 manufactured by Tokyo Kaisha, YDCN-704, Araldite ECN1235 manufactured by HUNTSMAN, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201 manufactured by Nippon Kaisha, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, SUMI-EPOXY-195X, ESCN-220 manufactured by Sumitomo Chemical industry Co., Ltd (trade name); bisphenol novolac type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon chemical Co., Ltd; bisphenol F type epoxy resins such as EPICLON830 manufactured by DIC, jER807 manufactured by Mitsubishi chemical corporation, Epotohto YDF-170, YDF-175, YDF-2004 manufactured by Tokyo Kaisha, Araldite XPY306 manufactured by BASF JAPAN, and the like (trade names); hydrogenated bisphenol A type epoxy resins such as Epotohto ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokyo chemical Co., Ltd; glycidyl amine type EPOXY resins such as jER604 manufactured by Mitsubishi chemical corporation, Epotohto YH-434 manufactured by Tokyo chemical corporation, Araldite MY720 manufactured by Huntsman corporation, SUMI-EPOXY ELM-120 manufactured by Sumitomo chemical industry Co., Ltd; hydantoin-type epoxy resins such as Araldite CY-350 (trade name) manufactured by HUNTSMAN; alicyclic epoxy resins such as CELLOXIDE 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 and CY179 manufactured by HuntSMAN (trade name); trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical corporation, T.E.N. manufactured by Dow Chemical Company, EPPN-501, EPPN-502, and the like (trade names); dixylenol-type or diphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (trade names) available from Mitsubishi chemical corporation, or a mixture thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kabushiki Kaisha, EPX-30 manufactured by ADEKA, and EXA-1514 (trade name) manufactured by DIC Kabushiki Kaisha; bisphenol a novolac type epoxy resins such as jER157S (trade name) manufactured by mitsubishi chemical corporation; tetrahydroxyphenylethane-type epoxy resins such as jERYL-931 manufactured by Mitsubishi chemical corporation and Araldite 163 manufactured by HUNTSMAN corporation; heterocyclic epoxy resins such as Araldite PT810 manufactured by Huntsman corporation and TEPIC manufactured by Nissan chemical industries, all of which are trade names; diglycidyl phthalate resins such as BLEMMER DGT manufactured by NOF corporation; tetraglycidyl ditoluoylethane resins such as ZX-1063 manufactured by Tokyo Kabushiki Kaisha; naphthyl group-containing epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750 and EXA-4700, manufactured by NITRI CHEMICAL CORPORATION; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resins such as CP-50S, CP-50M manufactured by Nippon fat and oil Co., Ltd; further a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives (e.g., Daicel Chemical Industries, Ltd., PB-3600, and the like), CTBN-modified epoxy resins (e.g., YR-102, YR-450, and the like, manufactured by Tokyo Kabushiki Kaisha), and the like, but are not limited thereto. These epoxy resins may be used alone or in combination of 2 or more. Among them, particularly preferred are novolak type epoxy resins, bixylenol type epoxy resins, biphenol novolak type epoxy resins, naphthalene type epoxy resins, or mixtures thereof.

Examples of the polyfunctional oxetane compound include bis [ (3-methyl-3-oxetanylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetanylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl ] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, methyl (3-methyl-3-oxetanyl) methacrylate, methyl (3-ethyl-3-oxetanyl) methacrylate, methyl (3-oxetanyl) acrylate, and the like, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, there can be mentioned: and etherates of oxetanol with hydroxyl group-containing resins such as novolak resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, and silsesquioxanes. Further, there can be mentioned: and copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

Examples of the compound having a plurality of cyclic sulfide groups in the molecule include bisphenol a type cyclic sulfide resin YL7000 manufactured by mitsubishi chemical corporation. In addition, it is also possible to use: and episulfide resins obtained by replacing an oxygen atom of an epoxy group of a novolac epoxy resin with a sulfur atom by the same synthesis method.

The amount of the thermosetting component added is preferably 0.6 to 2.5 equivalents based on1 equivalent of the carboxyl group-containing resin. When the amount of the compound is 0.6 or more, no carboxyl group remains in the solder resist, and the solder resist is excellent in heat resistance, alkali resistance, electrical insulation property, and the like. On the other hand, when the amount is 2.5 equivalents or less, low-molecular-weight cyclic (thio) ether groups and the like in the thermosetting component do not remain in the dried coating film, and the strength and the like of the coating film are improved. More preferably 0.8 to 2.0 equivalent.

Further, as other thermosetting components, amino resins such as melamine derivatives and benzoguanamine derivatives can be cited. Examples thereof include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds. Further, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are obtained by converting the methylol group of each of the methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound into an alkoxymethyl group. The kind of the alkoxymethyl group is also not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less which is safe for human and environment is preferable.

Examples of commercially available products thereof include: cymel 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 327, Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 1141, Cymel 272, Cymel 202, Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 300 (both manufactured by Mitsui Cyanamid), Nicaraq Mx-750, Nicaraq Mx-032, Nicaraq Mx-270, Nicaraq Mx-280, Nicaraq Mx-290, Nicaraq Mx-706, Nicaraq Mx-708, Nicaraq Mx-40, Nicaraq Mx-31, Nicaraq-11, Nicaraq-30, Nicaraq Mw-30, Nicaraq Mx-750, Nicaraq LM-5, Nicaraq-11, Nicaraq Mx-290, and Mw-30. Such thermosetting components may be used singly or in combination of 2 or more.

The thermosetting component may affect the resolution of the photosensitive resin layer when the color is dark. In particular, the residual content of the solvent in the photosensitive resin composition of the photosensitive resin layer is less than 5% by mass, and therefore, poor peeling is good, and the residual content of the solvent is small, but this may cause the color of the photosensitive resin layer to be dark, and the resolution may be insufficient. Therefore, the heat-curable component preferably has a gardner color number of 3 or less as an index of the color depth. When the gardner color number is 3 or less, the light transmittance of the thermosetting component is high, and the resolution of the photosensitive resin layer can be improved. Defective peeling can be prevented. Here, the gardner color number can be measured in accordance with JIS K6901.

A compound having a plurality of isocyanate groups or blocked isocyanate groups in 1 molecule may be added to the photosensitive resin composition. Examples of the compound having a plurality of isocyanate groups or blocked isocyanate groups in 1 molecule include polyisocyanate compounds and blocked isocyanate compounds. The blocked isocyanate group is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated, and the blocking agent is dissociated to generate an isocyanate group when heated to a predetermined temperature. It was confirmed that the addition of the polyisocyanate compound or the blocked isocyanate compound improves curability and toughness of the resulting cured product.

As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate can be used.

Specific examples of the aromatic polyisocyanate include 4, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, naphthalene-1, 5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and 2, 4-tolylene diisocyanate dimer.

Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and the like.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. And adducts, biurets, isocyanurates and the like of the above-exemplified isocyanate compounds.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent may be used. Examples of the isocyanate compound capable of reacting with the blocking agent include the polyisocyanate compounds described above.

Examples of the isocyanate blocking agent include: phenol-based end-capping agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam and beta-propiolactam; an active methylene-based blocking agent such as ethyl acetoacetate or acetylacetone; alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; oxime blocking agents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, and cyclohexane oxime; thiol-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, and ethyl thiophenol; acid amide-based blocking agents such as acetamide and benzamide; imide-based terminal-blocking agents such as succinimide and maleimide; amine-based blocking agents such as dimethylaniline, aniline, butylamine, and dibutylamine; imidazole-based capping agents such as imidazole and 2-ethylimidazole; and imine-based blocking agents such as methylene imine and propylene imine.

The blocked isocyanate compound may be a commercially available product, and examples thereof include: sumidure BL-3175, BL-4165, BL-1100, BL-1265, Dismodule TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosam 2170, Desmosam 2265 (both manufactured by Sumitomo Bayer Urethane Co., Ltd.), corona 2512, corona 2513, corona 2520 (both manufactured by Nippon polyurethane Industrial Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (both manufactured by Mitsui Wutian chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (both manufactured by Asahi Kasei Co., Ltd.), and the like. Sumidure BL-3175 and BL-4265 were obtained by using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in 1 molecule may be used alone in 1 kind or in combination with 2 or more kinds.

The amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in 1 molecule is preferably 1 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount of the component is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained. On the other hand, if it exceeds 100 parts by mass, the storage stability is lowered. More preferably 2 to 70 parts by mass.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include: imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and the like. Further, examples of commercially available products include: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Sizhou chemical industry Co., Ltd., U-CAT (registered trademark) 3503N, U-CAT3502T (all trade names of blocked isocyanate compounds of dimethylamine) manufactured by San-apro Co., Ltd., DBU, DBN, U-CATA SA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof), and the like. These are not particularly limited as long as they are thermal curing catalysts for epoxy resins and oxetane compounds, or promote the reaction of epoxy groups and/or oxetane groups with carboxyl groups, and they may be used alone or in combination of 2 or more. Further, an s-triazine derivative such as guanamine, methylguanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine/isocyanuric acid adduct, or 2, 4-diamino-6-methacryloyloxyethyl-s-triazine/isocyanuric acid adduct may be used, and it is preferable to use a compound functioning as an adhesion imparting agent in combination with a heat curing catalyst.

The amount of the thermosetting catalyst to be blended may be in a usual amount ratio, and is, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the carboxyl group-containing resin or the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule.

(inorganic Filler)

The photosensitive resin composition preferably contains an inorganic filler. The inorganic filler is used for suppressing curing shrinkage of a cured product of the photosensitive resin composition and improving properties such as adhesion and hardness. Examples of the inorganic filler include: barium sulfate, barium titanate, amorphous silica, crystalline silica, Nojenberg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, and the like.

The average particle diameter of the inorganic filler is preferably 5 μm or less. The compounding ratio is preferably 75% by mass or less, more preferably 0.1 to 60% by mass, based on the total solid content of the photosensitive resin composition. If the blending ratio of the inorganic filler exceeds 75% by mass, the viscosity of the composition increases, and the coatability decreases, or the cured product of the photosensitive resin composition becomes brittle.

(coloring agent)

A colorant may be further added to the photosensitive resin composition. The colorant may be any of commonly known colorants such as red, blue, green and yellow, and may be any of pigments, dyes and pigments. Specifically, there may be mentioned those with The following color index (C.I.; issued by The Society of Dyers and Colourists). However, it is preferable not to contain halogen from the viewpoint of reducing environmental load and affecting human body.

Red colorant:

the red colorant includes monoazo-based, disazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridone-based, and the like, and specific examples thereof include the following.

Mono-azo series: pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268, 269.

A bisazo system: fragment Red 37,38, 41.

Monoazo lakes system: pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1, 68.

Benzimidazolone series: segment Red 171, segment Red 175, segment Red 176, segment Red 185, segment Red 208.

Perylene series: solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole series: segment Red 254, segment Red 255, segment Red 264, segment Red 270, segment Red 272.

Condensation azo system: segment Red 220, segment Red 144, segment Red 166, segment Red 214, segment Red 220, segment Red 221, segment Red 242.

Anthraquinone series: pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone series: pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

examples of the blue colorant include phthalocyanine-based colorants and anthraquinone-based colorants, and the Pigment-based colorants are compounds classified into pigments (pigments), and specifically, the following may be mentioned: pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds may be used.

Green colorant:

examples of the Green coloring agent include phthalocyanine-based, anthraquinone-based, and perylene-based ones, and specifically Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, and Solvent Green 28 can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds may be used.

Yellow colorant:

the yellow coloring agent includes monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, and the like, and specific examples thereof include the following.

Anthraquinone series: solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensation azo system: pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Mono-azo series: pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182, 183.

A bisazo system: pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188, 198.

Further, for the purpose of adjusting the color tone, colorants of violet, orange, brown, black, etc. may also be added.

As specific examples, there are Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet13, 36, c.i. Pigment orange 1, c.i. Pigment orange 5, c.i. Pigment orange 13, c.i. Pigment orange 14, c.i. Pigment orange 16, c.i. Pigment orange 17, c.i. Pigment orange 24, c.i. Pigment orange 34, c.i. Pigment orange 36, c.i. Pigment orange 38, c.i. Pigment orange 40, c.i. Pigment orange 43, c.i. Pigment orange 46, c.i. Pigment orange 49, c.i. Pigment orange 51, c.i. Pigment orange 61, c.i. Pigment orange 63, c.i. Pigment orange 64, c.i. Pigment orange 71, c.i. Pigment orange 73, c.i. Pigment brown 23, c.i. Pigment orange 25, c.i. Pigment black 1, c.i. Pigment black 7, and the like.

The colorant may be appropriately blended, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin or the thermosetting component. More preferably 0.1 to 5 parts by mass.

(other Components)

The photosensitive resin composition may contain a compound having an ethylenically unsaturated group in the molecule as a photosensitive monomer. The compound having an ethylenically unsaturated group in the molecule is photo-cured by irradiation with active energy rays, making the photosensitive resin composition insoluble in an aqueous alkali solution, or contributing to insolubilization. As such a compound, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate can be used, and specific examples thereof include: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, and N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexane diol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, and polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts, and e-caprolactone adducts thereof; polyvalent acrylates such as phenoxy acrylate, bisphenol a diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; polyacrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and acrylates and melamine acrylates obtained by direct acrylation of a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or by urethane acrylation with a diisocyanate, and/or methacrylates corresponding to the above acrylates.

Further, there may be mentioned: an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, an epoxy urethane acrylate compound obtained by further reacting a hydroxyl group of the epoxy acrylate resin with a half urethane compound formed from a hydroxyl acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate, and the like. The epoxy acrylate resin can improve photocurability without reducing finger-touch dryness.

The above-mentioned compounds having an ethylenically unsaturated group in the molecule may be used alone in 1 kind, or may be used in combination with 2 or more kinds. From the viewpoint of photoreactivity and resolution, a compound having 4 to 6 ethylenically unsaturated groups in 1 molecule is particularly preferable, and if a compound having 2 ethylenically unsaturated groups in 1 molecule is used, the linear thermal expansion coefficient of the cured product is lowered, and the occurrence of peeling at the time of PCT is reduced, which is more preferable.

The amount of the compound having an ethylenically unsaturated group in the molecule is preferably 5 to 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is 5 parts by mass or more, the photocurability improves, and the pattern formation is facilitated by alkali development after the irradiation with active energy rays. On the other hand, when the amount is 100 parts by mass or less, the solubility in a dilute aqueous alkali solution is not lowered, and the coating film is not embrittled. More preferably 10 to 70 parts by mass.

An elastomer having a functional group may be further added to the photosensitive resin composition. By adding an elastomer having a functional group, improvement in coatability and improvement in strength of a coating film can be expected. Examples of the elastomer having a functional group include, for example, trade names such as: r-45HT, Poly bd HTP-9 (manufactured by Shikino Corporation), Eporide PB3600(Daicel Chemical Industries, Ltd.), Denarex R-45EPT (manufactured by Nagase ChemteX Corporation), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 181, Ricon 184, Ricon 130MA8, Ricon 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon 6, Ricon 184MA 17 (manufactured by Sarton Corporation). Polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyester amide elastomers, acrylic elastomers, olefin elastomers may be used. Further, a resin obtained by modifying a part or all of epoxy groups of epoxy resins having various skeletons with a butadiene-acrylonitrile rubber modified with a carboxylic acid at both ends, or the like can be used. Further, an epoxy-containing polybutadiene elastomer, an acrylic-containing polybutadiene elastomer, a hydroxyl-containing isoprene elastomer, or the like can be used. The amount of the elastomer is preferably in the range of 3 to 124 parts by mass per 100 parts by mass of the carboxyl group-containing resin. These elastomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

A mercapto compound may be added to the photosensitive resin composition as necessary. In particular, by adding a mercapto compound to a photosensitive resin composition for forming a photosensitive resin layer on the side in contact with a substrate, improvement in PCT resistance and B-HAST resistance can be expected. This is considered to be because the adhesion to the substrate is improved.

Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxythiobenzenethiol, and derivatives thereof, such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2- (ethylenedioxy) diethylalkanethiol, ethanethiol, 4-methylphenylthiol, dodecylthiol, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, and 4, 4-thiobisbenzenethiol.

Examples of commercially available products of these compounds include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (made by Sakai chemical industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz-NR1 (made by Showa Denko K.K.).

Further, examples of the heterocyclic mercapto compound include mercapto-4-butyrolactone (alternatively referred to as 2-mercapto-4-butanol), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, and mixtures thereof, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4, 6-trimercapto-s-triazine (trade name Gisnet F, manufactured by Tri Kagaku K.K.), 2-dibutylamino-4, 6-dimercapto-s-triazine (trade name Gisnet DB, manufactured by Triplex corporation), 2-anilino-4, 6-dimercapto-s-triazine (trade name Gisnet AF, manufactured by Triplex corporation), and the like.

Among them, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (product name Axel M, product of Kayokoku K.K.), 3-mercapto-4-methyl-4H-1, 2, 4-triazole, 5-methyl-1, 3, 4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole are preferable.

The amount of the mercapto compound added is preferably 0.01 part by mass or more and 10.0 parts by mass or less, and more preferably 0.05 part by mass or more and 5 parts by mass or less, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the mercapto compound is 0.01 parts by mass or more, the adhesion to the substrate is improved, while when the amount is 10.0 parts by mass or less, there is no fear that development failure or reduction in the drying control range of the photosensitive resin composition occurs. These mercapto compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

An antioxidant such as a radical extender or a peroxide decomposer may be added to the photosensitive resin composition. In addition, a known ultraviolet absorber may be used in addition to the antioxidant.

The photosensitive resin composition may further contain known additives such as a known thermal polymerization inhibitor, an adhesion promoter, a thickener such as fine powder silica, organobentonite and montmorillonite, a defoaming agent and/or a leveling agent such as a silicone-based, fluorine-based and polymer-based defoaming agent, a silane coupling agent such as a imidazole-based, thiazole-based and triazole-based silane coupling agent, and a rust preventive agent, if necessary.

The photosensitive resin composition may further contain a flame retardant. As the flame retardant, a commonly known phosphorus compound such as a phosphonate, a phosphate derivative, or a phosphazene compound can be used. The preferable phosphorus element concentration is preferably within a range of not more than 3% in the photosensitive resin composition.

(solvent)

In addition, in the photosensitive resin composition, an organic solvent may be used for the synthesis of the carboxyl group-containing resin, the preparation of the composition, or the adjustment of viscosity for application to a substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone are removed; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, and N, N-Dimethylformamide (DMF), tetrachloroethylene, turpentine, and the like can be given. Further, organic solvents such as Swazole 11000, Swazole 11500, Solvesso 100, Solvesso 150, solvent #100, solvent #150, Shersol A100, Shersol A150, Ipsol No. 100, Ipsol No. 150, manufactured by Takara petrochemical Co., Ltd, manufactured by Standard Osaka Seisakusho, and Ipsol No. 150, manufactured by Sholl Chemicals JAPAN may be used. Such organic solvents may be used alone in 1 kind, or 2 or more kinds may be used as a mixture.

The residual content of the solvent in the aforementioned resin layer is preferably less than 5 mass%. The residual content of the solvent is less than 5 mass%, so that poor peeling can be prevented. The lower limit of the residual content of the solvent is not particularly limited, and if it is 0.1 mass% or more, the fluidity at the time of lamination is good, and the flatness and embeddability become better.

The residual content of the solvent in the photosensitive resin layer in the laminated structure used as a dry film may be set to less than 5% by mass depending on the amount of the solvent used in the preparation of the photosensitive resin composition constituting the photosensitive resin layer. However, when a photosensitive resin composition having a solvent content of 5 mass% or more is prepared and the photosensitive resin composition is applied to a support film, and then the solvent is evaporated by heating in a drying furnace, the residual content of the solvent in the photosensitive resin layer is less than 5 mass%, good workability can be obtained in the preparation of the photosensitive resin composition, and the residual content of the solvent can be easily controlled to be less than 5 mass%, which is preferable.

The thickness of the photosensitive resin layer of the laminated structure used as the dry film is not particularly limited, and may be, for example, 1 to 200 μm. When the thickness is large, the flatness is more excellent, and therefore, for example, a thickness of 30 μm or more, further 50 μm or more, and further 100 μm or more can be suitably used. In addition, a plurality of resin layers of the dry film are laminated, and a resin layer having a thickness of more than 200 μm can be formed. In this case, a roll laminator or a vacuum laminator can be used.

The photosensitive resin layer of the laminated structure used as a dry film is in a semi-cured state generally called a B-stage state, and is obtained from a photosensitive resin composition. Specifically, the photosensitive resin layer of the laminated structure used as a dry film is obtained by applying a photosensitive resin composition to a support film and then subjecting the resultant to a drying step.

[ protective film ]

The protective film is provided on the surface of the photosensitive resin layer opposite to the support film in the laminated structure used as a dry film, for the purpose of preventing dust from adhering to the surface of the photosensitive resin layer and improving the handling properties. As the protective film, for example, a biaxially stretched polypropylene film can be used. By biaxially stretching the polypropylene film, the cooling shrinkage after the resin layer is laminated can be reduced. The thickness of the protective film is not particularly limited, and may be appropriately selected within a range of approximately 10 to 100 μm depending on the application. The surface of the protective film provided with the resin layer is preferably subjected to embossing, corona treatment, treatment for improving adhesiveness such as micro-adhesion treatment, or release treatment.

As shown in fig. 1, a laminated structure in which the conductive layer, the support film, the photosensitive resin layer, and the protective film are laminated in this order can be used as a dry film. The dry film can be used preferably for forming a protective film and an insulating layer of an electronic component, particularly preferably for forming a permanent protective film of a printed wiring board, and can be used preferably for forming a solder resist layer, an interlayer insulating layer, and a cover layer of a flexible printed wiring board, in the form of a cured product obtained by curing a photosensitive resin layer from which a support film and a protective film are peeled. The wiring is attached using the dry film, so that a circuit board can be formed. Further, the resin composition can be used as a sealing material for semiconductor chips.

Examples

The present invention will be specifically described below by showing examples of the present invention and comparative examples at the same time, but the present invention is not limited to the following examples, as a matter of course. In the following description, "part" and "%" are all based on mass unless otherwise specified.

< adjustment of conductive Polymer A >

Conductive polymer a was obtained by mixing 2 parts of polyester resin Byronal MD16 (manufactured by toyoyo seiki corporation), 2 parts of urethane resin H-38 (manufactured by seiko showa koku corporation), 0.8 part of anionic polymer antistatic agent WS134 (manufactured by shinkamura chemical corporation: sulfonic acid group-containing acrylic polymer antistatic agent), 43 parts of water, and 43 parts of isopropyl alcohol (hereinafter, referred to as IPA).

< adjustment of conductive Polymer B >

A conductive polymer B was prepared by mixing 35 parts (solid content ratio, the same shall apply hereinafter) of a quaternary ammonium salt type cationic polymer compound (PAS-10L, manufactured by Nidoku corporation) having the following formula as a main component, 50 parts of a copolyester resin, 10 parts of a methylolated melamine resin (SUMIMALM-40W, manufactured by Sumitomo chemical Co., Ltd.), and 5 parts of an epoxy-modified silicone (PolnMF-18, manufactured by shin chemical Co., Ltd.) to obtain a2 wt% aqueous solution.

< adjustment of conductive Polymer C >

Conductive polymer C was obtained in the same manner as the adjustment of conductive polymer B except that a quaternary ammonium salt type cationic polymer compound (manufactured by first industrial pharmaceutical company, Syroll DM-283P) containing the following formula as a main component was used instead of the quaternary ammonium salt type cationic polymer compound of conductive polymer B.

< adjustment of conductive Polymer D >

Amidia G-821-60 (isobutylated melamine resin, solid content 60%) manufactured by DIC and Acridic A-405 (acrylic resin for melamine sintering, solid content 50%) manufactured by DIC were mixed in a mass ratio of 25: 75, the resulting acrylic melamine resin was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35 mass%. To this resin solution, methyl ethyl ketone was further added so as to have an appropriate solid content concentration depending on the thickness of the coating film, and then a silicone resin (Cymac US-270 manufactured by east asia synthetic company) and Ag particles having an average primary particle diameter of 0.1 μm were added so that the mass ratio of the acrylic melamine resin to the silicone resin to the Ag particles became 79.7: 0.3: 20, at room temperature, fully stirring, get conductive polymer D.

< adjustment of carboxyl group-containing resin >

Into a flask equipped with a condenser and a stirrer, 456 parts of bisphenol a, 228 parts of water and 649 parts of 37% formalin were charged, and the mixture was kept at a temperature of 40 ℃ or lower, and 228 parts of a 25% aqueous sodium hydroxide solution was added, and after the addition, the reaction was carried out at50 ℃ for 10 hours. After completion of the reaction, the reaction mixture was cooled to 40 ℃ and then neutralized to pH4 with 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ℃. Then, the mixture was allowed to stand, and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed 3 times with 500 parts of distilled water, and water, solvent and the like were removed under reduced pressure at a temperature of 50 ℃ or lower. The resulting polyhydroxymethyl compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanolic solution of polyhydroxymethyl compound.

A part of the obtained methanol solution of the polyhydroxymethyl compound was dried in a vacuum dryer at room temperature, and the solid content was 55.2%.

500 parts of the obtained methanol solution of the polyhydroxymethyl compound and 440 parts of 2, 6-xylenol were put into a flask equipped with a condenser and a stirrer, and were uniformly dissolved at50 ℃. After the homogeneous dissolution, methanol was removed under reduced pressure at a temperature of 50 ℃ or lower. Then, 8 parts of oxalic acid was added thereto, and the mixture was reacted at 100 ℃ for 10 hours. After the completion of the reaction, the distillate was removed under reduced pressure of 50mmHg at 180 ℃ to obtain 550 parts of novolak a resin.

130 parts of novolak resin a, 2.6 parts of a 50% aqueous sodium hydroxide solution, and 100 parts of toluene/methyl isobutyl ketone (mass ratio: 2/1) were charged into an autoclave equipped with a thermometer, a nitrogen gas introducing device and an alkylene oxide introducing device, and a stirring device, and the inside of the system was replaced with nitrogen gas while stirring, followed by heating to raise the temperature, and 8kg/cm at 150 ℃²Then, 45 parts of ethylene oxide was gradually introduced and reacted. The reaction was continued for about 4 hours until a gauge pressure of 0.0kg/cm was reached²After that, it was cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed, and sodium hydroxide was neutralized. The neutralized reaction product was diluted with toluene, washed with water 3 times, and desolventized in an evaporator to obtain an ethylene oxide adduct of novolak a resin having a hydroxyl value of 175g/eq. The average amount of the epoxy resin is 1 mole of ethylene oxide added to 1 equivalent of phenolic hydroxyl group.

175 parts of the obtained ethylene oxide adduct of novolak a resin, 50 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 130 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, stirred while blowing air, heated to 115 ℃ and reacted for 4 hours while removing water produced by the reaction and toluene as an azeotropic mixture by distillation, and then cooled to room temperature. The resulting reaction solution was washed with 5% NaCl aqueous solution, toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a nonvolatile content of 68%.

Then, 312 parts of the obtained acrylic resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were put into a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was heated to 110 ℃, 45 parts of tetrahydrophthalic anhydride was added thereto, reacted for 4 hours, cooled, and then taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 72% and a solid acid value of 65 mgKOH/g. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as a carboxyl group-containing resin a.

As in the examples and comparative examples shown in tables 1 and 2, a laminated structure was produced. The laminated structures were used as dry films, and a photosensitive resin layer was formed on a test substrate and photocured to obtain a cured product. The steps for producing the photosensitive resin compositions, the steps for producing the laminated structures, the steps for forming the photosensitive resin layers, and the steps for curing the photosensitive resin layers in the examples and comparative examples are as follows.

< production Process of photosensitive resin composition >

The respective components shown in tables 1 and 2 were mixed at the ratios (parts by mass) shown, premixed in a mixer, and dispersed by a bead mill to prepare a photosensitive resin composition. The ratio (parts by mass) in the table is the amount of nonvolatile solid components. The dispersion of the filler was passed through a10 μm filter and then blended in the amounts shown in the table in terms of solid content.

< production Process of laminated Structure >

A conductive layer was formed on one surface of a support film, and a photosensitive resin composition containing the components shown in tables 1 and 2 was applied to the other surface of the support film at a speed of 10 m/min by means of a die coater, and then heated to 60 to 120 ℃ in a drying furnace to volatilize the solvent in the photosensitive resin layer, thereby forming a predetermined photosensitive resin layer. A protective film is laminated on the photosensitive resin layer to obtain a laminated structure used as a dry film. In addition, for some of the comparative examples, a laminated structure having a structure different from that of the example was obtained.

< step of Forming photosensitive resin layer >

The protective film was peeled off using the laminated structure obtained in the above-described manner as a dry film, and the resultant was laminated on each test substrate described later by a vacuum laminator CVP-300 (manufactured by Nikko Materials), to obtain a laminated body of the conductive layer and the support film, and the photosensitive resin layer and the test substrate.

< curing step of photosensitive resin layer >

The laminate was subjected to a predetermined pattern exposure according to evaluation items so that the Stouffer41 stage stepwise exposure table was 10 stages of the number of curing stages in an ultrahigh pressure mercury lamp DI exposure machine DXP-3580 (manufactured by ORC corporation). After 10 minutes of exposure, the support film was peeled off, and developed in a1 mass% aqueous solution of sodium carbonate at 30 ℃ for a development time 2 times the development point (shortest development time). After that, the substrate was exposed to UV CONVEYOR (manufactured by ORC, Metal halide Lamp) at 2000mJ, and then cured in a thermal cycle oven at 170 ℃ for 60 minutes to obtain an evaluation substrate.

In each of examples and comparative examples, the surface resistance value of the conductive layer, the surface resistance value of the support film, the electrostatic potential of the photosensitive resin layer, the IC dielectric breakdown property of the photosensitive resin layer, the defective peeling of the photosensitive resin layer, and the adhesion of the photosensitive resin layer in the laminated structure used as a dry film were examined to evaluate, and the resolution and the B-HAST property of a cured product obtained by curing the photosensitive resin layer were examined to evaluate. The results of these evaluations are shown in tables 1 and 2. The evaluation results in tables 1 and 2 were evaluated as follows.

< ratio of residual solvent amount in photosensitive resin layer >

A photosensitive resin layer of a dry film was laminated on a copper foil (1) having a thickness of 35 μm at 70 ℃ for 60 seconds by using a CVP-300 manufactured by Nikko Material. Subsequently, the support film was peeled off (2), dried at 100 ℃ for 30 minutes, and the solvent was completely removed (3).

The ratio of the amount of the residual solvent in the photosensitive resin layer was calculated based on the following equation for calculating the ratio of the amount of the residual solvent. (calculation formula of ratio of residual solvent amount)

The ratio (%) of the residual solvent amount was ((mass of (2) — (mass of (3)/((2) — (mass of (1)) × 100)

(1) The mass of (A): weight of copper foil

(2) The mass of (A): weight of photosensitive resin layer combining copper foil and dry film

(3) The mass of (A): combining the weight of the copper foil and the dried photosensitive resin layer

< surface resistance value of conductive layer >

The surface resistance of the material to be measured was measured by R8340(500V pressure) manufactured by Advantest corporation. Here, the surface resistance value of the conductive layer is measured as a value obtained by forming the conductive layer on the support film. The evaluation criteria are as follows.

◎…1.0×10⁹Omega or less

O … exceeding 1.0X 10⁹Omega and 1.0X 10¹⁰Omega or less

X … exceeds 1.0X 10¹⁰Ω

< surface resistance value of supporting film >

The surface resistance of the material to be measured was measured by R8340(500V pressure) manufactured by Advantest corporation. The evaluation criteria are as follows.

◎…1.0×10¹³Omega or more

○…1.0×10¹²Omega is more than or equal to 1.0 multiplied by 10¹³Ω

X … is less than 1.0X 10¹²Ω

< electrostatic potential of photosensitive resin layer >

As a test substrate, previously treated CZ-8201B was prepared at an etching rate of 0.5 μm/m²A copper-plated substrate having a rectangular planar shape and a size of 150mm × 95mm, and the photosensitive resin composition was formed on the surface of the substrate in the photosensitive resin layer forming step so that the size of the photosensitive resin composition became 80mm × 50mm and the film thickness became about 20 μm, thereby obtaining an evaluation substrate.

The support film of the evaluation substrate obtained above was peeled off (note that the substrate was not in contact therewith) with tweezers within 0.5 seconds. Then, the maximum value of the electrostatic potential was measured on the surface of the resin composition by means of SK-H050 (short distance: 25mm, region: φ 60mm) manufactured by Keyence. This evaluation was repeated 3 times, and the average value was defined as the electrostatic potential. The evaluation criteria are as follows.

… very good below 200kV

O … 200kV or more and less than 250kV

X … 250kV or more

< dielectric breakdown of IC chip >

As a test substrate, a photosensitive resin composition was applied to a WLP of 40mmx40mm in size so that the film thickness on the Cu circuit became about 20 μm, and after drying, exposure was performed under the above exposure conditions with respect to a pattern for opening the pad of the connection terminal. Then, development and curing are performed under predetermined conditions.

Conduction confirmation was performed using the evaluation substrate obtained as described above, and evaluation was performed using the occurrence rate of conduction. Evaluation 100 evaluation subjects were evaluated, and the evaluation criteria are as follows.

Very good: the incidence of poor results is less than 1 percent

O: the incidence of the defects is more than 1 percent and less than 3 percent

And (delta): the incidence of the defects is more than 3 percent and less than 5 percent

X: the incidence of failure is more than 5 percent

< poor peeling >

After the laminated structures of the examples and comparative examples were prepared, the protective film of the dry film prepared in the above was peeled off using TDL-6500L manufactured by Hitachi Plant Mechanics, and the dry film was temporarily bonded to a test substrate formed of a copper-clad laminated sheet. It was confirmed whether or not the protective film was peeled off in a defective manner. The load at peeling was measured as follows: separately, AGS-G100N manufactured by Shimadzu corporation was used to perform a peel test at 180 degrees.

Very good: the load at the time of peeling the protective film was 0.1N/m²Hereinafter, no defective peeling occurred.

O: the load at the time of peeling the protective film exceeds 0.1N/m²But no bad peeling.

X: there was poor peeling.

< adhesion of cured product >

Using CZ-8201B to etchEtching rate of 0.5 μm/m²The photosensitive resin composition was applied to the copper foil treated under the conditions (1) so that the film thickness became about 20 μm, and after drying, the entire surface was exposed under the above exposure conditions. Then, development and curing are performed under predetermined conditions. Thereafter, a thermosetting adhesive Araldite (manufactured by Nichiban corporation) was applied to the surface of the cured coating film, and the cured coating film was bonded to an FR-4 substrate and cured at 80 ℃ for 6 hours. Then, the evaluation substrate was cut at 20mm intervals, and the copper foil was peeled off twice so that the width of the copper foil became 10mm, thereby producing evaluation strips. The evaluation bar was treated at 130 ℃ and 85% for 50 hours, and then subjected to a 90 ℃ peel test using a tensile tester (AGS-G100N, equipment name manufactured by Shimadzu corporation) to evaluate the adhesiveness. The evaluation criteria are as follows.

Very good: 3.0N/cm or more.

O: 2.0N/cm or more and less than 3.0N/cm

And (delta): 1.0N/cm or more and less than 2.0N/cm

X: less than 1.0N/cm

< resolution of cured product >

CZ-8201B in the previous treatment was performed at an etching rate of 0.5 μm/m²The photosensitive resin composition was formed on the copper-plated substrate treated under the conditions (1) so that the film thickness became about 15 μm, and exposure was performed with various opening patterns. Thereafter, development was performed under predetermined conditions, and curing was performed under evaluation conditions.

The aperture diameter of the evaluation substrate obtained as described above was observed to confirm whether or not halo or undercut occurred, and the case where this did not occur at a predetermined aperture diameter was evaluated as a good aperture diameter. The evaluation criteria are as follows.

Good opening diameter was obtained at50 μm ….

O … gave a good opening diameter at 60 μm.

X … did not give a good opening diameter at 60 μm.

< B-HAST Property of cured product >

CZ-8201B in the previous treatment was performed at an etching rate of 0.5 μm/m²Under the condition ofOn the comb-shaped pattern-formed substrate having the processed L/S of 8/8 μm, a photosensitive resin composition was formed so that the Cu upper film thickness became about 15 μm, and full-surface exposure was performed. Then, development and curing are performed under predetermined conditions.

Thereafter, the electrodes were connected, and the B-HAST test was carried out at 130 ℃ and 85% and 3.3V. The evaluation criteria are as follows.

◎：300h pass

○：250h pass

△：200h pass

X: within 200h NG

[ Table 1]

[ Table 2]

*1: the conductive polymer A

*2: the conductive polymer B

*3: the conductive polymer C

*4: the conductive polymer D

*5: PET (polyethylene terephthalate)

*6: PEN (polyethylene naphthalate)

*7: the above carboxyl group-containing resin A

*8: EPICLON N-770 manufactured by DIC corporation, epoxy equivalent 185, and Gardner color number 1.0

*9: EPICLON N-730A manufactured by DIC corporation (2.5-functional epoxy resin containing aromatic (phenol novolac type) skeleton, epoxy equivalent 176, Gardner color number 1.0)

*10: NC-7000L (multifunctional epoxy resin containing aromatic (naphthalene) skeleton, epoxy equivalent 230, Gardner color number >12) manufactured by Nippon Chemicals K.K.)

*11: HP-4032 manufactured by DIC corporation (2-functional epoxy resin containing aromatic (naphthalene) skeleton, epoxy equivalent 142, Gardner color number >12)

*12: OmniradTPO (2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins Co., Ltd

*13: IRGACURE OXE02(1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime) ethanone, manufactured by BASF Japan K.K.)

*14: a silica dispersion obtained by the following production method. Spherical silica particles (SFP-20M, product of Denko chemical industries, Ltd., average particle diameter: 400nm)50g, PMA 48g as a solvent, and a silane coupling agent having a methacryloyl group (KBM-503, product of shin-Etsu chemical Co., Ltd.) 2g were uniformly dispersed.

*15: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Chemicals K.K.

*16: phthalocyanine blue

*17: color phthalein yellow (Chromophdial yellow)

*18: melamine

*19: DICY (dicyandiamide)

From the results shown in tables 1 and 2, the laminated structure of the examples can suppress the generation of static electricity, prevent the IC chip from being broken down, and prevent the occurrence of defective peeling when the protective film is peeled.

Description of the reference numerals

10 Dry film

11 conductive layer

12 support film

13 photosensitive resin layer

14 protective film

Claims (7)

1. A laminated structure is characterized by comprising the following components in sequence: a conductive layer, a support film, a photosensitive resin layer and a protective film,

the surface resistance value of the conductive layer is 1.0 x 10¹⁰Omega or less and the surface resistance value of the support film is 1.0 x 10¹²The content of the carbon dioxide is more than omega,

the photosensitive resin layer includes: a carboxyl group-containing resin, a photopolymerization initiator, a thermosetting component, and an inorganic filler, and the ratio of the residual content of the solvent is less than 5% by mass based on the total amount of the resin layer containing the solvent.

2. The laminated structure body according to claim 1, wherein the thickness of the conductive layer is 2 μm or less.

3. The laminated structure according to claim 1, wherein a gardner color number of a thermosetting component of the photosensitive resin layer is 3 or less.

4. The laminated structure according to claim 1, wherein an electrostatic potential of a surface of the photosensitive resin layer when the support film is peeled from the photosensitive resin layer is 250kV or less.

5. A cured product obtained by curing the photosensitive resin layer of the laminated structure according to any one of claims 1 to 4.

6. A printed wiring board characterized by having the cured product according to claim 5.

7. An electronic component comprising the cured product according to claim 5.

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