WO2020202959A1 - Layered structure body, cured object, printed circuit board and electronic component - Google Patents

Abstract

This layered structure body, wherein the occurrence of static electricity is suppressed and, moreover, parting is prevented, has excellent long-term reliability and comprises an electroconductive layer, a support film, a photosensitive resin layer, and a protective film, in this order. The surface resistance value of the electroconductive layer is 1.0 × 10¹⁰Ω or lower, and the surface resistance value of the support film is 1.0 × 10¹²Ω or higher. The photosensitive resin layer includes a carboxyl group-containing resin, a photopolymerization initiator, a heat-curable component, and an inorganic filler, and the proportion of the solvent residual content is less than 5 % by mass based on the total amount of the resin layer containing the solvent.

Description

Laminated structures, cured products, printed wiring boards and electronic components

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.

Conventionally, a dry film has been used as one of means for forming a protective film or an insulating layer such as a solder resist or an interlayer insulating layer provided on a printed wiring board used in an electronic device or the like. The dry film has a support film (carrier film) and a resin layer obtained by applying a curable resin composition on the support film and drying the support film, and further, the support film in the resin layer. Is marketed as a laminated structure in which a protective film for protecting the opposite surface is laminated. The protective film of the printed wiring board and the insulating layer described above are formed by peeling off the protective film of the dry film, attaching the resin layer to the substrate (hereinafter also referred to as "laminate"), and then performing patterning and curing treatment. Can be done.

After the dry film is attached to a substrate such as a printed wiring board, the static electricity generated when the support film is peeled off may damage the surface of the solder resist or damage the IC chip attached to the printed wiring board. There was a risk. In order to suppress static electricity generated when the support film is peeled off, there is a photosensitive film with a support having a surface resistivity of 1 × 10 ¹³ Ω or less (Patent Document 1).

JP-A-2018-169547

The photosensitive film with a support described in Patent Document 1 has a surface resistance value of 1 × 10 ¹³ Ω or less of the support film by applying an antistatic agent to the surface of the support film or the like. It is said that the low surface resistance value of the support film can suppress the generation of static electricity and is excellent in flexibility.

However, in the photosensitive film with a support described in Patent Document 1, when the protective film is peeled off, a phenomenon called crying separation occurs in which a part of the photosensitive resin layer adheres to the protective film and is peeled off. There was a problem with moisture resistance and, by extension, long-term reliability.

Therefore, an object of the present invention is to have a laminated structure that suppresses the generation of static electricity, prevents crying and has excellent long-term reliability, a cured product obtained by curing the photosensitive resin layer of the laminated structure, and a cured product thereof. It is an object of the present invention to provide a printed wiring board and an electronic component having a cured product thereof or a printed wiring board.

The inventors have repeated research on the crying parting of the laminated structure used as a dry film, and found that the crying parting can be prevented by setting the solvent content to less than 5% by mass. Further, in order to effectively suppress the generation of static electricity, the surface resistance value of the support film containing the antistatic agent is not simply reduced, but the conductive layer formed on the surface of the support film opposite to the resin layer. It was found that it is important to specify the surface resistance value of the above and the surface resistance value of the supporting film within a predetermined range.

Based on the above findings, the laminated structure of the present invention includes a conductive layer, a support film, a photosensitive resin layer, and a protective film in this order.
The surface resistance value of the conductive layer is 1.0 × 10 ¹⁰ Ω or less, and the surface resistance value of the support film is 1.0 × 10 ¹² Ω or more.
The photosensitive resin layer contains 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 5% by mass based on the total amount of the resin layer containing the solvent. It is characterized by being less than.

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

The cured product of the present invention is characterized by being 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.

According to the laminated structure of the present invention, it is possible to suppress the generation of static electricity when the support film is peeled off to prevent scratches on the solder resist and damage to the IC chip, and moreover, crying when the protective film is peeled off. Can be suppressed and long-term reliability can be maintained. Here, crying farewell means that a part of the photosensitive resin layer adheres to the protective film and is peeled off.

It is a schematic sectional view of the dry film of one Embodiment of the laminated structure of this invention.

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

FIG. 1 is a schematic cross-sectional view showing a dry film 10 according to an embodiment of the laminated structure of the present invention. The dry film 10 of FIG. 1 is a film having a structure in which a conductive layer 11, a support film 12, a photosensitive resin layer 13, and a protective film 14 are provided in this order, and at least four layers are laminated. The surface resistance value of the conductive layer 11 is 1.0 × 10 ¹⁰ Ω or less. The surface resistance value of the support film 12 is 1.0 × 10 ¹² Ω or more. Further, the photosensitive resin layer 13 contains 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 5 based on the total amount of the resin layer containing the solvent. Less than% by mass. In addition to this, an uneven cambium may be provided between the support film 12 and the photosensitive resin layer 13.

The laminated structure of the present invention has a support film and a conductive layer, and the conductive layer is laminated on the support film so that the conductive layer has a surface resistance value of 1.0 × 10 ¹⁰ Ω or less and is a support film. By setting the surface resistance value to 1.0 × 10 ¹² Ω or more, the generation of static electricity when the support film is peeled off can be effectively suppressed by the conductive layer having a low surface resistance value. Specifically, the suppression of static electricity can make the electrostatic potential on the surface of the photosensitive resin layer 250 kV when the support film is peeled from the photosensitive resin layer.

Further, by setting the ratio of the residual content of the solvent in the photosensitive resin layer to less than 5% by mass in the total amount of the resin layer, it is possible to prevent crying.
Each layer of the dry film 10 will be described below.

[Conductive layer]
The conductive layer is a layer having a property of increasing conductivity in order to prevent the generation of static electricity when the support film is peeled from the dry film, and can be formed on the surface of the support film made of resin. .. Specifically, an antistatic agent can be used for the conductive layer. Examples of the antistatic agent include a quaternary ammonium salt-type cationic polymer compound, a sulfone group-containing anionic polymer compound, and an ether-type nonionic surfactant. In addition to these antistatic agents, as the conductive layer, one in which a conductive filler made of powder such as graphite, metal or metal oxide, fibers or flakes is dispersed in a thermoplastic resin can be used. Further, a resin composition obtained by mixing a conductive polymer such as polyacetylene or polyaniline with another resin can be used as a conductive layer.

Regardless of the material, the conductive layer needs to have a surface resistance value of 1.0 × 10 ¹⁰ Ω or less. When the surface resistance value is 1.0 × 10 ¹⁰ Ω or less, the conductivity can be further enhanced and the generation of static electricity can be effectively suppressed.
The conductive layer is formed on the side opposite to the photosensitive resin layer with respect to the support film. By forming the conductive layer on the side opposite to the photosensitive resin layer with respect to the support film, 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 are suppressed. Can be done. Further, if the support film, the conductive layer, and the photosensitive resin layer are laminated in this order, the B-HAST property, which indicates the moisture resistance of the photosensitive resin layer, is inferior, and the long-term reliability is not sufficient.

The thickness of the conductive layer is preferably 2 μm or less. When it is 2 μm or less, static electricity can be effectively prevented, and since the thickness of the conductive layer is thin, it is photosensitive by the color depth of the conductive layer and the conductive particles that may be contained in the conductive layer. It is possible to suppress deterioration of the resolution of the sex resin layer. It is preferably 1 μm or less.

[Support film]
The support film has a role of supporting the photosensitive resin layer of the dry film, and is a film to which the photosensitive resin composition is applied when the photosensitive resin layer is formed. Examples of the support film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films and other thermoplastic resins, and surface-treated films. Paper or the like can be used. Among these, a polyester film can be preferably used from the viewpoint of heat resistance, mechanical strength, handleability and the like. The thickness of the support film is not particularly limited, but is appropriately selected in the range of approximately 10 to 150 μm according to 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 ultrathin 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 composed of a photosensitive resin composition containing a carboxyl group-containing photosensitive resin, a photopolymerization initiator, a thermosetting component, and an inorganic filler.

(Carboxylic acid-containing photosensitive resin)
As the carboxyl group-containing photosensitive resin, various conventionally known carboxyl group-containing photosensitive resins having a carboxyl group in the molecule can be used, and in particular, a carboxyl group-containing having an ethylenically unsaturated double bond in the molecule can be used. A photosensitive resin is preferable from the viewpoint of photocurability and resolution. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. When only a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, a compound having an ethylenically unsaturated group in the molecule described later That is, it is necessary to use a photopolymerizable monomer in combination.
Specific examples of the carboxyl group-containing resin include the following compounds (either oligomer or polymer).

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

(2) Carboxylic group-containing photosensitive in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and a dibasic acid anhydride is added to a hydroxyl group existing in a side chain. Sex resin.

(3) A (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. The added carboxyl group-containing photosensitive resin.

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

(5) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing photosensitive urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(6) Carboxy group-containing non-photosensitive material obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid with unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate and isobutylene. Sex resin.

(7) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. Carboxylic group-containing non-photosensitive by multiple addition reaction of diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. Urethane resin.

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin as described later, and the generated primary hydroxyl group is phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride. A carboxyl group-containing non-photosensitive polyester resin to which a dibasic anhydride such as is added.

(9) During the synthesis of the resin according to (5) or (7), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (9). Meta) Acryloylated carboxyl group-containing photosensitive urethane resin.

(10) During the synthesis of the resin according to (5) or (7), one isocyanate group and one or more (meth) acryloyl groups are formed in the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate isomorphic reaction product. A carboxyl group-containing photosensitive urethane resin that is terminally (meth) acrylicized by adding a compound to it.

(11) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (10) above.
In addition, in this specification, (meth) acrylate is a term which collectively refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Since the above-mentioned carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, it can be developed with a dilute alkaline aqueous solution.
The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, alkaline development becomes easy, while when it is 200 mgKOH / g or less, normal resist pattern drawing becomes easy, which is preferable.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the moisture resistance of the coating film after exposure is good, film loss can be suppressed during development, and resolution deterioration can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent. The weight average molecular weight can be measured by GPC.

The blending amount of such a carboxyl group-containing resin is appropriately in the range of 15 to 60% by mass, preferably 20 to 50% by mass, in the entire composition of the photosensitive resin layer. When the blending amount of the carboxyl group-containing resin is within the above range, the film strength does not decrease, and the viscosity of the composition, the coatability, and the like are improved.

These carboxyl group-containing resins can be used without being limited to those listed above, and one type may be used alone or a plurality of types may be mixed and used. Among the carboxyl group-containing resins, a resin having an aromatic ring is preferable because it has a high refractive index and excellent resolvability, and a resin having a novolak structure is not only resolvable but also PCT and It is preferable because it has excellent crack resistance. Among them, the carboxyl group-containing photosensitive resins (1) and (2) are preferable because a solder resist having excellent resolution while satisfying various properties such as PCT resistance can be obtained.

(Photopolymerization initiator)
The photosensitive resin composition for forming the photosensitive resin layer contains a photopolymerization initiator. Examples of the photopolymerization initiator include an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and a titanosen-based photoinitiator. One or more photopolymerization initiators selected from the group consisting of polymerization initiators can be preferably used.

In particular, the above-mentioned oxime ester-based photopolymerization initiator can be added in a small amount and outgas can be suppressed, which is preferable because it is effective in PCT resistance and crack resistance.

Examples of commercially available oxime ester-based photopolymerization initiators include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF Japan, N-1919 and NCI-831 manufactured by Adeka Corporation. Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be preferably used, and specific examples thereof include an oxime ester compound having a carbazole structure represented by the following general formula.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy having 1 to 8 carbon atoms). Group, amino group, alkylamino group having 1 to 8 carbon atoms or dialkylamino group substituted), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, It is substituted with an amino group and an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), and Y and Z are a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and 1 carbon atom, respectively. Alkyl group of 8 to 8, halogen group, phenyl group, phenyl group (alkyl group of 1 to 17 carbon atoms, alkoxy group of 1 to 8 carbon atoms, amino group, alkylamino group having alkyl group of 1 to 8 carbon atoms or Alkyl amino group or dialkyl amino having a naphthyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms), a naphthyl group (substituted by a dialkylamino group). Represents an anthryl group, pyridyl group, benzofuryl group, benzothienyl group), Ar represents a bond or an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene having 1 to 10 carbon atoms. , Thienilen, furylene, 2,5-pyrrole-diyl, 4,4'-stilben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1.)

In particular, in the above general formula, X and Y are methyl groups or ethyl groups, respectively, Z is methyl or phenyl, n is 0, and Ar is a bond or phenylene, naphthylene, thiophene or thienylene. Is preferable.

Moreover, as a preferable carbazole oxime ester compound, a compound represented by the following general formula can also be mentioned.

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms.
R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms.
R ³ may be linked with an oxygen atom or a sulfur atom, may be substituted with a phenyl group, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Represents a good benzyl group.
R ⁴ is a nitro group or a,, X-C (= O ) - represents an acyl group represented.
X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-22007, JP-A-2006-160634, JP-A-2008-09470, JP-A-2008-50967, Examples thereof include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

The blending amount of such an oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass and 0.25 to 3 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferred.
By setting the amount to 0.01 to 5 parts by mass, a solder resist having excellent photocurability and resolution, adhesion and PCT resistance, and chemical resistance such as electroless gold plating resistance can be obtained. be able to.
On the other hand, if it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the solder resist coating film is peeled off, and the coating film characteristics 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 intense, and the deep curability tends to decrease.

Commercially available alkylphenyl photopolymerization initiators include Omnirad 184 manufactured by IGM Resins, DaroCure 1173, Irgacure2959, Omnirad 127 (2-hirodoxy-1- {4- [4- (2-hydroxy-). Examples thereof include α-hydroxyalkylphenone types such as 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one).

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-Molholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-Dimethylaminoacetophenone and the like. Examples of commercially available products include Omnirad (Omnirad) 907, Omnirad (Omnirad) 369, Omnirad (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, and bis (2,6-dimethoxy). Benzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like can be mentioned. Examples of commercially available products include Omnirad TPO manufactured by IGM Resins, Omnirad 819 manufactured by IGM Resins, and the like.

The blending amount of the α-aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, and 1 to 1 to 25 parts by mass. More preferably, it is 20 parts by mass.
By having 0.1 to 25 parts by mass, a solder resist having excellent photocurability and resolution, adhesiveness and PCT resistance, and chemical resistance such as electroless gold plating resistance can be obtained. be able to.
On the other hand, if it is less than 0.1 parts 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 outgas cannot be obtained, light absorption on the solder resist surface becomes intense, and deep curability tends to decrease.

Further, as the photopolymerization initiator, Omnirad 389 manufactured by IGM Resins can also be preferably used. The suitable blending amount of Omnirad 389 is 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

Then, in the case of Omnirad 784 (bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium) and the like. A titanosen-based photopolymerization initiator can also be preferably used. The suitable blending amount of the titanocene-based photopolymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, and the more preferable blending amount is 0.01 to 3 parts by mass. ..
By using a suitable amount of these photopolymerization initiators, the photocurability and resolution are excellent, the adhesion and PCT resistance are improved, and the chemical resistance such as electroless gold plating resistance is also excellent. It can be a solder resist.

On the other hand, if the blending amount is less than the suitable amount, the photocurability on copper is insufficient, the solder resist is peeled off, and the coating film properties such as chemical resistance are deteriorated. On the other hand, if the blending amount exceeds a suitable amount, the effect of reducing outgas cannot be obtained, light absorption on the solder resist surface becomes intense, and deep curability tends to decrease.

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

(Photo-curing auxiliary component)
In addition to the photopolymerization initiator, a photoinitiator aid and a sensitizer can be used in the photosensitive resin composition. Examples of the photopolymerization initiator, photoinitiator aid and sensitizer that can be suitably used for the photosensitive resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds and tertiary amine compounds. , And xantone 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, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

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

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

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl 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. Examples include sulfide.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure, for example, commercially available products include 4,4'-dimethylaminobenzophenone (NissoCure MABP manufactured by Nippon Soda Co., Ltd.). Dialkylaminobenzophenone such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-) Dialkylamino group-containing coumarin compounds such as methylkumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) , 4-Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethyl Examples thereof include 2-ethylhexyl aminobenzoate (Esolol 507 manufactured by Van Dyk) and 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Of these, thioxanthone compounds and tertiary amine compounds are preferable. In particular, it is preferable that a thioxanthone compound is contained from the viewpoint of deep curability. Among them, it is preferable to contain a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

The blending amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

Further, as the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, and ketocoumarins are particularly preferable. ..

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

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

These photopolymerization initiators, photoinitiator aids and sensitizers can be used alone or as a mixture of two or more.
The total amount of such a photopolymerization initiator, photoinitiator aid, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If it exceeds 35 parts by mass, the deep curability tends to decrease due to these light absorptions.

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

(Thermosetting component)
A thermosetting component can be added to the photosensitive resin composition. It was confirmed that the heat resistance was improved by adding the thermosetting component. Examples of the thermosetting component include amino resins such as melamine resin, benzoguanamine resin, melamine derivative and benzoguanamine derivative, blocked isocyanate compound, cyclocarbonate compound, polyfunctional epoxy compound, polyfunctional oxetane compound, episulfide resin, bismaleimide and carbodiimide resin. A known thermosetting resin can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

The thermosetting component having a plurality of cyclic (thio) ether groups in the above-mentioned molecule is a compound having a plurality of one or two kinds of any one or two kinds of cyclic (thio) ether groups having 3, 4, or 5 membered rings in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, That is, an episulfide resin and the like can be mentioned.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as ADEKA's ADEKA Sizer O-130P, ADEKA Sizer O-180A, ADEKA Sizer D-32, and ADEKA Sizer D-55; jER828 and jER834 manufactured by Mitsubishi Chemical Corporation. jER1001, jER1004, EHPE3150 manufactured by Daicel Chemical Industry Co., Ltd., EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 manufactured by DIC, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Co., Ltd. D. E. R. 317, D.I. E. R. 331, D. E. R. 661, D.I. E. R. 664, HUNTSMAN's Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Chemical Industry's Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, etc. (all trade names) Bisphenol A type epoxy resin; YDC-1312, hydroquinone type epoxy resin, YSLV-80XY bisphenol type epoxy resin, YSLV-120TE thioether type epoxy resin (all manufactured by Toto Kasei Co., Ltd.); jERYL903 manufactured by Mitsubishi Chemical Co., Ltd., manufactured by DIC Co., Ltd. EPICLON152, EPICLON165, Epototo YDB-400, YDB-500 manufactured by Toto Kasei Co., Ltd., D.D. E. R. 542, BASF Japan's Araldite 8011, Sumitomo Chemical's Sumi-Epoxy ESB-400, ESB-700, etc. (all trade names) brominated epoxy resins; Mitsubishi Chemical's jER152, jER154, Dow D. Chemical Co., Ltd. E. N. 431, D.I. E. N. 438, EPICLON N-730 manufactured by DIC, EPICLON N-770, EPICLON N-865, Epototo YDCN-701 manufactured by Toto Kasei, YDCN-704, Araldite ECN1235 manufactured by HUNTSMAN, Araldite ECN1235, Araldite ECN1273 , EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd. (all trade names) Novolak type epoxy resin; Biphenol Novolak type epoxy resin such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd .; EPICLON830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YDF-170, YDF- manufactured by Toto Kasei Co., Ltd. Bisphenol F type epoxy resin such as 175, YDF-2004, Araldite XPY306 manufactured by BASF Japan Co., Ltd .; Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Araldite MY720 manufactured by HUNTSMAN, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd., etc. ) Glysidylamine type epoxy resin; Hundant-in type epoxy resin such as Araldite CY-350 (trade name) manufactured by HUNTSMAN; Celoxide 2021 manufactured by Daicel Chemical Industry Co., Ltd., Araldite CY175, CY179 manufactured by HUNTSMAN, etc. (all trade names) ) Oil ring type epoxy resin; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.K. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resins; Mitsubishi Chemical Co., Ltd. YL-6056, YX-4000, YL-6121 (all trade names), etc. Mold or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayakusha, EPX-30 manufactured by ADEKA, EXA-1514 (trade name) manufactured by DIC; manufactured by Mitsubishi Chemical Co., Ltd. Bisphenol A novolak type epoxy resin such as jER157S (trade name); tetraphenylol ethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. and Araldite 163 manufactured by HUNTSMAN (both trade names); manufactured by HUNTSMAN. Heterocyclic epoxy resin such as Araldite PT810 and TEPIC manufactured by Nissan Chemical Industries (both are trade names); Diglycidyl phthalate resin such as Blemmer DGT manufactured by Nippon Yushi Co., Ltd .; Tetraglycidyl xireno such as ZX-1063 manufactured by Toto Kasei Co., Ltd. Iletan resin; Naphthalene group-containing epoxy resin such as ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Co., Ltd .; HP-7200, HP-7200H manufactured by DIC Co., Ltd. Epoxy resin having a dicyclopentadiene skeleton such as; glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd .; further, copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; epoxy-modified polybutadiene Examples include, but are not limited to, rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Toto Kasei Co., Ltd.), and the like. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a bixylenel type epoxy resin, a biphenol type epoxy resin, a biphenol novolac type epoxy resin, a naphthalene type epoxy resin, or a mixture thereof is particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-3-oxythylmethoxy) methyl] ether. Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-3) Oxetane) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetane such as their oligomers or copolymers, as well as oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, etherified products with a resin having a hydroxyl group such as silsesquioxane, and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate can also be mentioned.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, using the same synthesis method, an episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used.

The blending amount of the thermosetting component is preferably 0.6 to 2.5 equivalents with respect to 1 equivalent of the carboxyl groups of the carboxyl group-containing resin. When the blending amount is 0.6 or more, no carboxyl group remains in the solder resist, and heat resistance, alkali resistance, electrical insulation and the like are improved. 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 dry coating film, and the strength of the coating film and the like are improved. More preferably, it is 0.8 to 2.0 equivalents.

Further, examples of other thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol uryl compound, a methylol urea compound and the like. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycol uryl compound and the alkoxymethylated urea compound have the methylol groups of the respective methylol melamine compound, methylol benzoguanamine compound, methylol glycol uryl compound and methylol urea compound. It is obtained by converting to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and may be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration of 0.2% or less, which is friendly to the human body and the environment, is preferable.

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. , 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Siana Mid), Nicarac Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM, (all manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned. Such thermosetting components may be used alone or in combination of two or more.

The thermosetting component may affect the resolution of the photosensitive resin layer when the color is dark. In particular, since the photosensitive resin composition of the photosensitive resin layer has a residual content of the solvent of less than 5% by mass, the color of the photosensitive resin layer is small because the residual content of the solvent is small even if the tearing is good. May become dark and the resolution may not be sufficient. Therefore, it is preferable that the thermosetting component has a Gardner color number of 3 or less as an index of color depth. When the Gardner index is 3 or less, the light transmittance of the thermosetting component is high, and the resolution of the photosensitive resin layer can be improved. It is possible to prevent crying. Here, the Gardner index can be measured in accordance with JIS K6901.

A compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the photosensitive resin composition. Examples of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds and blocked isocyanate compounds. The blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and when heated to a predetermined temperature, the blocking agent dissociates and the isocyanate group is used. Is generated. It was confirmed that the curability and the toughness of the obtained cured product were improved by adding the polyisocyanate compound or the blocked isocyanate compound.

As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is 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, and the like. Examples thereof include m-xylylene diisocyanate and 2,4-tolylen dimer.

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

A specific example of the alicyclic polyisocyanate is bicycloheptane triisocyanate. In addition, the adduct form, burette form, isocyanurate form, etc. of the isocyanate compounds mentioned above can be mentioned.

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

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-parellolactam, γ-butyrolactam and β-propiolactam; Active oxime blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Alcohol-based blocking agents such as ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxim, diacetyl monooxime and cyclohexane oxime. Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid amide-based blocking agents such as acetate amide and benzamide; imides such as succinate imide and maleate imide. Examples thereof include amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine.

The blocked isocyanate compound may be commercially available, for example, Sumijour BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane), Coronate 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, Examples thereof include B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Co., Ltd.) and the like. Sumijour BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used alone or in combination of two or more.

The blending amount of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount 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, it is 2 to 70 parts by mass.

When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such a thermocuring catalyst include imidazole, 2-methylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole. , 1- (2-Cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N Examples thereof include amine compounds such as -dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered) manufactured by San Apro Co., Ltd. Examples thereof include (trademarks) 3503N, U-CAT3502T (trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof). In particular, the present invention is not limited to these, as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or one that promotes a reaction between an epoxy group and / or an oxetaneyl group and a carboxyl group, and may be used alone or in combination of two or more. You may use it. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, preferably as an adhesion imparting agent thereof. A compound that also functions is used in combination with a thermosetting catalyst.

The blending amount of these thermosetting catalysts is usually sufficient, and is preferable with respect to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the carboxyl group-containing resin or molecule, for example. Is 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

(Inorganic filler)
The photosensitive resin composition preferably contains an inorganic filler. Inorganic fillers are used to suppress curing shrinkage of cured products of photosensitive resin compositions and improve properties such as adhesion and hardness. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica soil, molten silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and silicon nitride. Examples include silicon and aluminum nitride.

The average particle size of the inorganic filler is preferably 5 μm or less. The blending 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 may increase, the coatability may decrease, or the cured product of the photosensitive resin composition may become brittle.

(Colorant)
Further, a colorant can be added to the photosensitive resin composition. As the colorant, commonly known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. Specific examples thereof include those with the following color index (CI; issued by The Society of Dyers and Colorists). However, it is preferable that it does not contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, dizuazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and the following are specific examples. Be done.
Monoazo system: 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.
Disazo system: Pigment Red 37, 38, 41.
Monoazolake 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.
Benzimidazolones: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment 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: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.
Anthracinone 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:
There are phthalocyanine-based and anthraquinone-based blue colorants, and pigment-based compounds are classified as Pigment, and specific examples include: 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 dyes, 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 etc. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Green colorant:
Similarly, as the green colorant, there are phthalocyanine type, anthraquinone type, and perylene type, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Yellow colorant:
Examples of the yellow colorant include monoazo type, disazo type, condensed azo type, benzimidazolone type, isoindolinone type, anthraquinone type and the like, and specific examples thereof include the following.
Anthraquinone: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindrinone 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.
Benzimidazolones: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo system: 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.
Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, etc. ..

The colorant as described above can be appropriately blended, but it 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, it is 0.1 to 5 parts by mass.

(Other ingredients)
The photosensitive resin composition may contain a compound having an ethylenically unsaturated group in the molecule as a photosensitive monomer. A compound having an ethylenically unsaturated group in the molecule is photocured by irradiation with active energy rays to insolubilize the photosensitive resin composition in an alkaline aqueous solution or assist in 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. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide. , N-methylol acrylamide, acrylamides such as N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; hexanediol, trimetyl propane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di Polyvalent acrylates such as acrylates and ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropan triglycidyl ether, triglycidyl isocyanurate. Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or Examples thereof include each methacrylate corresponding to the above acrylate.

Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate are added to the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness to the touch.

As the compound having an ethylenically unsaturated group in the molecule as described above, one type may be used alone, or two or more types may be used in combination. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. This is preferable because the linear thermal expansion coefficient of the cured product is lowered and the occurrence of peeling during PCT is reduced.

The amount of the compound having an ethylenically unsaturated group in the molecule as described above is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount is 5 parts by mass or more, the photocurability is improved, and pattern formation becomes easy by alkaline development after irradiation with active energy rays. On the other hand, when it is 100 parts by mass or less, the solubility in a dilute alkaline aqueous solution does not decrease, and the coating film does not become brittle. More preferably, it is 10 to 70 parts by mass.

Further, an elastomer having a functional group can be added to the photosensitive resin composition. By adding an elastomer having a functional group, it can be expected that the coating property is improved and the strength of the coating film is also improved. Examples of elastomers having functional groups include R-45HT, Poly bd HTP-9 (all manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Industry Co., Ltd.), and 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 18 There are 130MA8, Rikon 130MA13, Rikon 130MA20, Rikon 131MA5, Rikon 131MA10, Rikon 131MA17, Rikon 131MA20, Rikon 184MA6, Rikon 156MA17 (all manufactured by Sartmer). Polyester-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, and olefin-based elastomers can be used. Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Furthermore, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, and the like can also be used. The blending amount of these elastomers is preferably in the range of 3 to 124 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. Further, these elastomers may be used alone or in combination of two or more.

A mercapto compound may be added to the photosensitive resin composition if necessary. In particular, it can be expected that the PCT resistance and the B-HAST resistance will be improved by adding the mercapto compound to the photosensitive resin composition for forming the photosensitive resin layer on the side in contact with the base material. It is considered that this is because the adhesion with the base material is improved.

Examples of the mercapto compound include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof, 1-butanethiol, butyl-3-mercaptopropionate, and methyl-3-3. Mercaptopropionate, 2,2- (ethylenedioxy) dietane thiol, ethane thiol, 4-methylbenzene thiol, dodecyl mercaptan, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane thiol , Thioglycerol, 4,4-thiobisbenzenethiol and the like.

Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, TEMPIC (all manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (all manufactured by Showa Denko KK) and the like.

Further, examples of the mercapto compound having a heterocycle include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto-4-ethyl-4. -Butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl- 2-Mercapto-4-butylolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- 4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-Meth) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiazazole, 2-Mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s- Examples thereof include triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet DB) and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet AF).
Among these, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (manufactured by Kawaguchi Chemical Industry Co., Ltd .: trade name Axel M), 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 preferred.

The blending amount of such a mercapto compound is preferably 0.01 part by mass or more and 10.0 parts by mass or less, more preferably 0.05 part by mass or more, with respect to 100 parts by mass of the carboxyl group-containing resin. It is 5 parts by mass or less. When the blending amount of the mercapto compound is 0.01 parts by mass or more, the adhesion to the substrate is improved, while when it is 10.0 parts by mass or less, the photosensitive resin composition is poorly developed and controlled for drying. There is no risk of causing a decrease in width. One of these mercapto compounds may be used alone, or two or more thereof may be used in combination.

Antioxidants such as radical supplements and peroxide decomposing agents can be added to the photosensitive resin composition. In addition to the antioxidant, a known ultraviolet absorber can also be used.

The photosensitive resin composition further comprises, if necessary, a known thermal polymerization inhibitor, adhesion accelerator, fine powder silica, organic bentonite, thickener such as montmorillonite, silicone-based, fluorine-based, polymer-based defoamer, etc. Agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and other known additives can be blended.

In addition, a flame retardant can be added to the photosensitive resin composition. As the flame retardant, commonly known phosphorus compounds such as phosphinates, phosphoric acid ester derivatives, and phosphazene compounds can be used. The preferable phosphorus element concentration is preferably in the range not exceeding 3% in the photosensitive resin composition.

(solvent)
Further, as the photosensitive resin composition, an organic solvent can be used for synthesizing the carboxyl group-containing resin, preparing the composition, or adjusting the viscosity for coating on a base material or a carrier film.
Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum-based solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like In addition to based solvents and the like, N, N-dimethylformamide (DMF), tetrachloroethylene, televisionn oil and the like can be mentioned. In addition, Maruzen Petrochemical Co., Ltd. Swazole 1000, Swazole 1500, Standard Petrochemical Osaka Sales Office Co., Ltd. Solbesso 100, Solvesso 150, Sankyo Chemical Co., Ltd. Solvent # 100, Solvent # 150, Shell Chemicals Japan Co., Ltd. , Idemitsu Kosan Co., Ltd. Ipsol No. 100, Ipsol No. 150 and other organic solvents may be used. As such an organic solvent, one kind may be used alone, or two or more kinds may be used as a mixture.

The residual content of the solvent in the resin layer is preferably less than 5% by mass. When the residual content of the solvent is less than 5% by mass, it is possible to prevent crying. The lower limit of the residual content of the solvent is not particularly limited, but when it is 0.1% by mass or more, the fluidity at the time of laminating is good, and the flatness and the embedding property are better.

The residual content of the solvent in the photosensitive resin layer in the laminated structure used as a dry film is less than 5% by mass depending on the amount of the solvent used at the time of preparing the photosensitive resin composition constituting the photosensitive resin layer. It is possible. However, at the time of producing the dry film, a photosensitive resin composition having a solvent content of 5% by mass or more is prepared, the photosensitive resin composition is applied onto the support film, and then the solvent is heated in a drying furnace. By volatilizing, the residual content of the solvent in the photosensitive resin layer is reduced to less than 5% by mass, so that good workability can be obtained when preparing the photosensitive resin composition, and the residual content of the solvent is set to 5. It is preferable because it can be easily controlled to less than mass%.

The thickness of the photosensitive resin layer of the laminated structure used as a dry film is not particularly limited, and may be, for example, 1 to 200 μm. Since the flatness is more excellent when the thickness is large, for example, a thickness of 30 μm or more, further 50 μm or more, and even 100 μm or more can be preferably used. A plurality of resin layers of the dry film may be superposed to form a resin layer having a thickness of more than 200 μm. In that case, a roll laminator or a vacuum laminator may 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 through a drying step after applying the photosensitive resin composition to the support film.

[Protective film]
The protective film is a surface opposite to the support film of the photosensitive resin layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive resin layer of the laminated structure used as a dry film and improving handleability. It is provided in. As the protective film, for example, a biaxially stretched polypropylene film can be used. By using the biaxially stretched polypropylene film, it is possible to reduce the cooling shrinkage after laminating on the resin layer. The thickness of the protective film is not particularly limited, but is appropriately selected in the range of approximately 10 to 100 μm according to the application. It is preferable that the surface of the protective film on which the resin layer is provided is subjected to a treatment for improving adhesion such as embossing, corona treatment, or slight adhesion treatment, or a mold release treatment.

The laminated structure in which the above-mentioned conductive layer, support film, photosensitive resin layer and protective film are sequentially laminated can be used as a dry film as shown in FIG. The dry film is preferably used for forming a protective film or an insulating layer for electronic components, particularly for forming a permanent protective film for a 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 have been peeled off. It can be preferably used for forming a coverlay of a solder resist layer, an interlayer insulating layer, and a flexible printed wiring board. A wiring board may be formed by bonding wirings using a dry film. It can also be used as a sealing material for semiconductor chips.

Hereinafter, the present invention will be specifically described by showing examples of the present invention together with comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following description, "part" and "%" are all based on mass unless otherwise specified.

<Adjustment of conductive polymer A>
Polyester resin byronal MD16 (manufactured by Toyo Spinning Co., Ltd.) 2 parts, urethane resin H-38 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts, anionic polymer antistatic agent WS134 (manufactured by Shin-Nakamura Chemical Co., Ltd .: containing sulfone group) 0.8 part of acrylic polymer type antistatic agent), 43 parts of water and 43 parts of isopropyl alcohol (hereinafter referred to as IPA) were mixed to obtain conductive polymer A.

<Adjustment of conductive polymer B>
The following formula

35 parts (solid content ratio, the same applies hereinafter) of a quaternary ammonium salt-type cationic polymer compound (manufactured by Nitto Spinning Co., Ltd .; PAS-10L), 50 parts of a copolymerized polyester resin, and a methylolated melamine resin. (Sumitomo Chemical Industry Co., Ltd .; SUMIMALM-40W) 10 parts and epoxy-modified silicone (Shinetsu Chemical Industry Co., Ltd .; PolnMF-18) 5 parts were mixed to obtain a conductive polymer B in a 2 wt% aqueous solution. ..

<Adjustment of conductive polymer C>
Instead of the above-mentioned quaternary ammonium salt type cationic polymer compound of the conductive polymer B, the following formula

Except for the use of a quaternary ammonium salt-type cationic polymer compound (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; Charol DM-283P) containing A sex polymer C was obtained.

<Adjustment of conductive polymer D>
Amidia G-821-60 (iso-butylated melamine resin, solid content 60%) manufactured by DIC Corporation and Acrydic A-405 (acrylic resin for melamine baking, solid content 50%) manufactured by DIC Corporation are solid in mass ratio. The mixture was blended so as to have a minute conversion of 25:75, pre-stirred with a stirrer, and the obtained acrylic melamine resin was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35% by mass. Methyl ethyl ketone is further added to this resin solution so as to have an appropriate solid content concentration according to the thickness of the coating film, and then the average primary particle size is 0.1 μm with a silicone resin (Cymac US-270 manufactured by Toa Synthetic Co., Ltd.). Ag particles were added so that the mass ratio of each of the acrylic melamine resin, the silicone resin, and the Ag particles was 79.7: 0.3: 20, and the mixture was sufficiently stirred at room temperature to add the conductive polymer D. Obtained.

<Adjustment of carboxyl group-containing resin>
A flask equipped with a cooling tube and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, kept at a temperature of 40 ° C. or lower, and added 228 parts of a 25% sodium hydroxide aqueous solution. The reaction was carried out at ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% aqueous phosphoric acid solution while maintaining 40 ° C. or lower. After that, it was allowed to stand and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added to uniformly dissolve the mixture, followed by washing with 500 parts of distilled water three times, and the water, solvent and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
When a part of the obtained methanol solution of the polymethylol compound was dried in a vacuum dryer at room temperature, the solid content was 55.2%.
In a flask equipped with a cooling tube and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and dissolved uniformly at 50 ° C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Then, 8 parts of oxalic acid was added, and the reaction was carried out at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed at 180 ° C. under a reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirrer, 130 parts of Novorak resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, toluene / methyl isobutyl ketone (mass ratio = 2/1). 100 parts were charged, the inside of the system was replaced with nitrogen while stirring, then the temperature was raised by heating, and 45 parts of ethylene oxide was gradually introduced at 150 ° C. and 8 kg / cm ² to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. 3.3 parts of a 36% aqueous hydrochloric acid solution was added to and mixed with this reaction solution to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to have a hydroxyl value of 175 g / eq. An ethylene oxide adduct of novolak resin A was obtained. This was the one in which an average of 1 mol of ethylene oxide was added per equivalent of the phenolic hydroxyl group.
175 parts of ethylene oxide adduct of the obtained novolak resin A, 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 mixed with a stirrer, a thermometer, and an air blowing tube. It was charged into a provided reactor, stirred while blowing air, heated to 115 ° C., and the water produced by the reaction was distilled off as an azeotropic mixture with toluene, reacted for another 4 hours, and then cooled to room temperature. did. The obtained reaction solution was washed with water using a 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 non-volatile content of 68%.
Next, 312 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was charged at 110 ° C. To, 45 parts of tetrahydrophthalic anhydride was added, the mixture was reacted for 4 hours, cooled, and then taken out. The carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 72% and a solid content acid value of 65 mgKOH / g. Hereinafter, the solution of this carboxyl group-containing photosensitive resin will be referred to as carboxyl group-containing resin A.

A laminated structure was created for each of the examples and comparative examples shown in Tables 1 and 2. A photosensitive resin layer was formed on the test substrate using each of the laminated structures as a dry film, and photocured to obtain a cured product. The procedure for producing the photosensitive resin composition, the procedure for producing the laminated structure, the procedure for forming the photosensitive resin layer, and the procedure for curing the photosensitive resin layer in each Example and each comparative example were as follows.

<Procedure for producing photosensitive resin composition>
The various components shown in Tables 1 and 2 were blended in the ratios (parts by mass) shown, premixed with a stirrer, and then dispersed with a bead mill to prepare a photosensitive resin composition. The ratio (parts by mass) in the table is the amount of non-volatile solid content. Further, the dispersion of the above filler was passed through a filter of 10 μm, and then the amount shown in the table was blended in terms of solid content.

<Procedure for manufacturing laminated structure>
A conductive layer was formed on one surface of the support film, and a photosensitive resin composition containing the components shown in Tables 1 and 2 was applied onto the other surface of the support film with a die coater at a speed of 10 m / min. After that, it was heated to 60 to 120 ° C. in a drying furnace to volatilize the solvent in the photosensitive resin layer to form a predetermined photosensitive resin layer. By laminating a protective film on this photosensitive resin layer, a laminated structure used as a dry film was obtained. Further, for some of the comparative examples, a laminated structure having a structure different from that of the examples was obtained.

<Procedure for forming the photosensitive resin layer>
Using the laminated structure obtained in the above procedure as a dry film, the protective film is peeled off, and a vacuum laminator CVP-300 (manufactured by Nikko Materials Co., Ltd.) is used to laminate it on each test substrate described later to form a conductive layer. A laminate of a support film, a photosensitive resin layer, and a test substrate was obtained.

<Procedure for curing the photosensitive resin layer>
The above-mentioned laminate was exposed to a predetermined pattern according to the evaluation items using an ultra-high pressure mercury lamp DI exposure machine DXP-3580 (manufactured by ORC) with a Stoffer 41-step step tablet so that the number of curing steps was 10. .. The support film was peeled off 10 minutes after the exposure, and development was carried out with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for a development time twice the breakpoint (shortest development time). Then, after exposing at 2000 mJ on a UV conveyor (Metal halide lamp manufactured by ORC), the evaluation substrate was obtained by curing at 170 ° C. for 60 minutes in a heat circulation type box furnace.

In each example and each comparative example, the surface resistance value of the conductive layer in the laminated structure used as a dry film, the surface resistance value of the support film, the electrostatic potential of the photosensitive resin layer, the IC insulation destruction property of the photosensitive resin layer, The tearing of the photosensitive resin layer and the adhesion of the photosensitive resin layer were examined and evaluated, and the resolution and B-HAST property of the cured product obtained by curing the photosensitive resin layer were examined and evaluated. The results of these evaluations are shown in Tables 1 and 2. The criteria for the evaluation results in Tables 1 and 2 are as follows.

<Ratio of residual solvent amount in the photosensitive resin layer>
A photosensitive resin layer of a dry film at 70 ° C. for 60 seconds was laminated on a copper foil (1) having a thickness of 35 μm using CVP-300 manufactured by Nikko Material Co., Ltd. Next, the support film was peeled off (2) and dried at 100 ° C. for 30 minutes to completely remove the solvent (3).
The ratio of the residual solvent amount of the photosensitive resin layer was calculated based on the following formula for calculating the residual solvent amount ratio. (Calculation formula for the ratio of residual solvent amount)
Percentage of residual solvent amount (%) = (mass of (2)-mass of (3)) / (mass of (2)-mass of (1)) x 100
Weight of (1): Weight of copper foil (2) Weight: Weight of copper foil and photosensitive resin layer of dry film combined Weight of (3): Weight of copper foil and photosensitive resin layer after drying combined Weight

<Surface resistance value of conductive layer>
The surface resistance value of the material to be measured was measured with R8340 (500V pressurization) manufactured by Advantest. Here, the surface resistance value of the conductive layer was measured after forming the conductive layer on the support film. The evaluation criteria are as follows.
◎… 1.0 × 10 ⁹ Ω or less ○… 1.0 × 10 ⁹ Ω over 1.0 × 10 ¹⁰ Ω or less ×… 1.0 × 10 over ¹⁰ Ω

<Surface resistance value of support film>
The surface resistance value of the material to be measured was measured with R8340 (500V pressurization) manufactured by Advantest. The evaluation criteria are as follows.
◎… 1.0 × 10 ¹³ Ω or more ○… 1.0 × 10 ¹² Ω or more 1.0 × 10 ¹³ Ω or less ×… 1.0 × 10 less than ¹² Ω

<Electrostatic potential of photosensitive resin layer>
As a test substrate, a plated copper substrate having a rectangular planar shape and a size of 150 mm × 95 mm, which was surface-treated with pretreated CZ-8201B under the condition of an etching rate of 0.5 μm / m ² , was prepared, and on the surface of this substrate. The photosensitive resin composition was formed according to the above-mentioned procedure for forming the photosensitive resin layer so as to have a size of 80 mm × 50 mm and a film thickness of about 20 μm to obtain an evaluation substrate.
The support film of the evaluation substrate obtained as described above was peeled off within 0.5 sec using tweezers (be careful not to touch the substrate at that time). Then, the maximum value of the electrostatic potential was measured on the surface of the resin composition using SK-H050 manufactured by KEYENCE (near mode (distance: 25 mm, region: φ60 mm)). This evaluation was repeated 3 times, and the average value was taken as the electrostatic potential. The evaluation criteria are as follows.
◎… Less than 200kV
○… 200 kV or more, less than 250 kV ×… 250 kV or more

<Dielectric breakdown of IC chip>
As a test substrate, a photosensitive resin composition is applied onto a 40 mm x 40 mm size WLP so as to have a film thickness of about 20 μm on a Cu circuit, and after drying, a pattern exposure that opens a pad of a connection terminal is exposed under the above exposure conditions. Was done. Then, development and curing were carried out under predetermined conditions.
Continuity was confirmed on the evaluation substrate obtained as described above, and evaluation was performed based on the occurrence rate of the continuity. The evaluation was carried out for 100 samples, and the evaluation criteria are as follows.
⊚: Defect occurrence rate less than 1% ○: Defect occurrence rate 1% or more and less than 3% Δ: Defect occurrence rate 3% or more and less than 5% ×: Defect occurrence rate 5% or more

<Crying goodbye>
After preparing the laminated structures of each of the above-described Examples and Comparative Examples, the protective film of the dry film produced above is peeled off using TDL-6500L manufactured by Hitachi Plant Mechanics, Ltd., and the laminated structure is made of a copper-clad laminate. A dry film was temporarily attached to the test substrate. When peeling off the protective film, it was confirmed whether there was a crying farewell. The load at the time of peeling was measured by separately performing a peel test at 180 ° using AGS-G100N manufactured by Shimadzu Corporation.
⊚: The load when the protective film was peeled off was 0.1 N / m ² or less, and there was no crying.
◯: Although the load when the protective film was peeled off exceeded 0.1 N / m ² , there was no crying.
×: There is crying farewell.

<Adhesion of cured product>
A photosensitive resin composition is applied to a copper foil treated with CZ-8201B at an etching rate of 0.5 μm / m ² so as to have a film thickness of about 20 μm, dried, and then exposed to the entire surface under the above exposure conditions. Was done. Then, development and curing were carried out under predetermined conditions. Then, a thermosetting adhesive Araldite (manufactured by Nichiban Co., Ltd.) was applied to the surface of the cured coating film, adhered to the FR-4 substrate, and cured at 80 ° C. for 6 hours. Then, the evaluation substrate was cut at intervals of 20 mm, and both sides were peeled off so that the copper foil width became 10 mm width to prepare an evaluation strip. After treating this evaluation strip at 130 ° C. and 85% for 50 hours, a 90 ° peel test was performed using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation) to evaluate the adhesion. The evaluation criteria are as follows.
⊚: 3.0 N / cm or more.
◯: 2.0 N / cm or more and less than 3.0 N / cm Δ: 1.0 N / cm or more and less than 2.0 N / cm ×: less than 1.0 N / cm

<Resolution of cured product>
A photosensitive resin composition was formed on a plated copper substrate treated with the pretreatment CZ-8201B under the condition of an etching rate of 0.5 μm / m ² so as to have a film thickness of about 15 μm, and exposure was performed with various aperture patterns. It was. After that, development was carried out under predetermined conditions and curing was carried out under evaluation conditions.
The opening diameter of the evaluation substrate obtained as described above was observed, it was confirmed whether halation and undercuts were generated, and the one having a predetermined opening diameter without them was regarded as a good opening diameter and evaluated. The evaluation criteria are as follows.
⊚ ... A good opening diameter was obtained at 50 μm.
◯… A good opening diameter was obtained at 60 μm.
X ... A good opening diameter cannot be obtained at 60 μm.

<B-HAST property of cured product>
The photosensitive resin composition was applied to a substrate on which a comb-shaped pattern of L / S = 8/8 μm was formed, which was treated with the pretreatment CZ-8201B under the condition of an etching rate of 0.5 μm / m ² , and the film thickness on Cu was about 15 μm. It was formed so as to be, and the entire surface was exposed. Then, development and curing were carried out under predetermined conditions.
After that, the electrodes were connected and the B-HAST test was carried out under the conditions of 130 ° C., 85% and 3.3 V. The evaluation criteria are as follows.
⊚: 300h pass
◯: 250h pass
Δ: 200h pass
×: NG within 200 hours

* 1: Conductive polymer A described above
* 2: Conductive polymer B described above
* 3: Conductive polymer C described above
* 4: Conductive polymer D described above
* 5: PET (polyethylene terephthalate)
* 6: PEN (polyethylene naphthalate)
* 7: The above-mentioned carboxyl group-containing resin A
* 8: EPICLON N-770 manufactured by DIC Corporation, epoxy equivalent 185, 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 manufactured by Nippon Kayaku Co., Ltd. (polyfunctional epoxy resin containing aromatic (naphthalene) skeleton, epoxy equivalent 230, Gardner color number> 12)
* 11: HP-4032 manufactured by DIC Corporation (bifunctional epoxy resin containing aromatic (naphthalene) skeleton, epoxy equivalent 142, Gardner color number> 12)
* 12: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins.
* 13: Irgacure OXE02 (Etanon, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (o-acetyloxime) manufactured by BASF Japan Ltd.)
* 14: Silica-dispersed product obtained by the following manufacturing method. Uniform dispersion of 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.). I let you.
* 15: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
* 16: Phthalocyanine blue * 17: Chromophthalyellow * 18: Melamine * 19: DICY (dicyandiamide)

From the results shown in Tables 1 and 2 above, the laminated structure of the example can suppress the generation of static electricity and prevent the IC chip from being destroyed, and when the protective film is peeled off, it can be prevented. There was no crying farewell.

10 Dry film 11 Conductive layer 12 Support film 13 Photosensitive resin layer 14 Protective film

Claims (7)

1. A conductive layer, a support film, a photosensitive resin layer, and a protective film are provided in this order.
   The surface resistance value of the conductive layer is 1.0 × 10 ¹⁰ Ω or less, and the surface resistance value of the support film is 1.0 × 10 ¹² Ω or more.
   The photosensitive resin layer contains 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 5% by mass based on the total amount of the resin layer containing the solvent. A laminated structure, characterized in that it is less than.
2. The laminated structure 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 the number of Gardner colors of the thermosetting component of the photosensitive resin layer is 3 or less.
4. The laminated structure according to claim 1, wherein the electrostatic potential of the surface of the photosensitive resin layer when the support film is peeled from the photosensitive resin layer is 250 kV 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 of claim 5.
7. An electronic component having the cured product according to claim 5.

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