JP2019144521A - Photosensitive film laminate and cured product of the same - Google Patents

Abstract

To provide a photosensitive film laminate that does not degrade a working environment even when a photosensitive resin composition forming a photosensitive film contains carbon black.SOLUTION: The photosensitive film laminate comprises a support film and a photosensitive film made of a photosensitive resin composition laminated thereon, in which the photosensitive resin composition comprises at least carbon black and a filler having a charge opposite to that of the carbon black.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive film laminate and a cured product thereof.

  In general, when mounting electronic components on a printed wiring board used in electronic devices, etc., it is necessary to prevent the solder from adhering to unnecessary portions on the circuit pattern formed substrate. A solder resist layer is formed in a region excluding the connection holes.

  Along with the recent trend toward high precision and high density of printed wiring boards due to the miniaturization of electronic devices, the solder resist layer is currently coated with a photosensitive resin composition on a substrate, dried, and patterned by exposure and development. The mainstream is a so-called photo solder resist in which a patterned resin is cured by heating or light irradiation.

  In addition, it has also been proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film without using the liquid photosensitive resin composition as described above. Such a photosensitive film laminate is generally obtained by laminating a photosensitive film formed of a photosensitive resin composition on a support film, and protecting the surface of the photosensitive film as necessary. A film may be attached. In such a photosensitive film laminate, the protective film is peeled off at the time of use and laminated to the wiring board by thermocompression bonding, and the exposure is performed before or after exposure from the support film side, and the support film is peeled off for development. Thus, a patterned solder resist layer can be formed. By using the photosensitive film laminate, it is possible to eliminate the need for a drying step after coating, as well as the surface smoothness and surface hardness of the obtained solder resist layer, compared to wet coating.

  Furthermore, in recent years, from the viewpoint of workability, the photosensitive film tends to be thinned. Along with this, the concealability of the solder resist layer is lowered, and the discoloration of the underlying circuit is visible through the solder resist layer, resulting in a problem of appearance defects. Therefore, in order to improve the concealability of the solder resist layer, it has been demanded to use a black photosensitive film. Moreover, the black photosensitive film was calculated | required also from the viewpoint of design property. Conventionally, carbon black is used as a colorant in the black photosensitive film as described above (for example, Patent Document 1).

JP 2008-257045 A

  However, in a photosensitive film laminate using carbon black, a trace amount of carbon black may remain on the support film when the support film is peeled off. Moreover, although there exists a thing with the protective film provided in the photosensitive film surface, when peeling a protective film and using a photosensitive film, a trace amount carbon black may remain on a protective film similarly. There was a risk that the working environment would be deteriorated by the minute amount of carbon black remaining on the support film and the protective film being scattered or adhering to the surroundings.

  Therefore, the objective of this invention is providing the photosensitive film laminated body which does not deteriorate a working environment, even if carbon black is contained in the photosensitive resin composition which forms a photosensitive film. Another object of the present invention is to provide a cured product formed using the photosensitive film laminate.

  When the photosensitive film containing carbon black has a positive or negative charge of the carbon black to be used, the present inventors have a filler having a negative or positive charge, that is, opposite to the charge of the carbon black. By using a charged filler in combination with carbon black for a photosensitive film, carbon black can be effectively retained in the photosensitive film, and as a result, carbon is removed from the peeled support film and protective film. The knowledge that black does not remain was acquired. The present invention is based on this finding.

  That is, the photosensitive film laminate according to the present invention is a photosensitive film laminate obtained by laminating a support film and a photosensitive film made of a photosensitive resin composition, wherein the photosensitive resin composition contains at least carbon black. And a filler having an electric charge opposite to the electric charge of the carbon black.

  In the aspect of this invention, it is preferable that the compounding quantity of the said carbon black is 0.3-5 mass% in conversion of solid content in the photosensitive resin composition.

  In the aspect of the present invention, the support film preferably has a thickness of 10 to 150 μm.

  In the aspect of this invention, it is preferable that the said support film is a thermoplastic resin film.

  In the aspect of the present invention, the thermoplastic resin film is preferably at least one selected from the group consisting of a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film.

  In the embodiment of the present invention, the support film preferably has an arithmetic average surface roughness Ra of 1000 nm or less.

  In the aspect of this invention, it is preferable to further provide the protective film laminated | stacked on the surface opposite to the said support film of the said photosensitive film.

  A cured product according to another aspect of the present invention is formed using the photosensitive film laminate.

  ADVANTAGE OF THE INVENTION According to this invention, even if carbon black is contained in the photosensitive resin composition which forms a photosensitive film, the photosensitive film laminated body which does not deteriorate a working environment is realizable. Furthermore, according to another form of this invention, the hardened | cured material formed using the said photosensitive film laminated body is realizable.

  The photosensitive film laminated body by this invention is demonstrated. The photosensitive film laminated body by this invention is a photosensitive film laminated body provided with the support film and the photosensitive film in order. In the photosensitive film laminate according to the present invention, a protective film may be further provided on the surface of the photosensitive film opposite to the support film. In the present invention, the “photosensitive film” refers to a film obtained by forming a photosensitive resin composition into a film shape, and other layers such as a support film and a protective film are not laminated. Hereinafter, each component which comprises the photosensitive film laminated body by this invention is demonstrated.

[Support film]
The support film constituting the photosensitive film laminate of the present invention supports a photosensitive film (that is, a layer made of a photosensitive resin composition, hereinafter sometimes abbreviated as “photosensitive resin layer”). Is.

  As a support film, if it is a well-known thing, it can be especially used without a restriction | limiting, For example, the film which consists of a thermoplastic resin can be used conveniently. As the thermoplastic resin film, a film made of a thermoplastic resin such as a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film can be suitably used. When the thermoplastic resin film is used, a filler is added (kneading treatment) to the resin when the film is formed, mat coating (coating treatment), or the film surface is subjected to sandblast treatment. It may be subjected to a blast treatment, or a treatment such as hairline processing or chemical etching. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability, and the like.

  The thermoplastic resin film as described above is preferably a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength.

  Moreover, the mold release process may be given to the surface of the support film. For example, a coating solution prepared by dissolving or dispersing a release agent such as waxes, silicone wax, alkyd resin, urethane resin, melamine resin, or silicone resin in an appropriate solvent can be applied to a roll coating method or a spray. The mold release treatment can be performed by coating and drying on the surface of the support film by a known method such as a coating method such as a coating method, a gravure printing method, or a screen printing method.

  The thickness of the support film is preferably in the range of 10 to 150 μm, more preferably in the range of 10 to 100 μm, and still more preferably in the range of 10 to 50 μm from the viewpoint of handleability. By setting the thickness within the range of 10 to 150 μm, the resolution is further improved.

  The arithmetic average surface roughness Ra of the support film is preferably 1000 nm or less, more preferably 750 nm or less, and further preferably 500 nm or less. The resolution is further improved by setting the arithmetic average surface roughness Ra of the support film to 1000 nm or less. In addition, since the surface area does not become too large, the risk of carbon black desorption is reduced. From the viewpoint of expecting the above effect, in the photosensitive film laminate, the arithmetic average surface roughness Ra of the surface of the support film in contact with the photosensitive film is preferably 1000 nm or less. Further, in the photosensitive film laminate of the present invention, when the protective film described later is not laminated, the surface of the support film that is in contact with the photosensitive film is also in contact with the photosensitive film when the laminate is wound up. In this case, the arithmetic average surface roughness Ra on the surface opposite to the surface in contact with the photosensitive film is preferably 1000 nm or less. In addition, arithmetic mean surface roughness Ra means the value measured with the measuring apparatus based on JISB0601-1994.

  In the present invention, since carbon black does not remain on the peeled support film or protective film, it is possible to prevent a minute amount of carbon black from scattering. In particular, the support film is a film that is cured from the photosensitive film by exposure to form a cured film, and then peeled off from the cured film, and peeling the support film before curing the photosensitive film is Although it is not the usual process of this, it is thought that the carbon black remains on the support film more before the curing than after the photosensitive film is cured. Therefore, if carbon black does not remain on the support film when the support film is peeled off from the photosensitive film, the support film is peeled off after the photosensitive film is cured to form a cured coating in the actual manufacturing process. However, it is considered that no carbon black remains on the support film.

[Photosensitive film]
The photosensitive film which comprises the photosensitive film laminated body of this invention is what was made into the film shape using the photosensitive resin composition, Comprising: The other layer, such as a support film and a protective film, is not laminated | stacked. . The photosensitive film is patterned by exposure and development to become a cured coating provided on the circuit board. The cured film is preferably a solder resist layer. Such a photosensitive film is formed using a photosensitive resin composition, and the photosensitive resin composition can be used without limitation with a conventionally known solder resist ink or the like, but can be preferably used for the photosensitive film according to the present invention. An example of the photosensitive resin composition will be described.

  The photosensitive resin composition constituting the photosensitive film of the present invention contains at least carbon black and a filler other than carbon black. The filler has a negative or positive charge when it has a positive or negative charge of carbon black. That is, in the present invention, a filler having a charge opposite to that of carbon black is used in the photosensitive resin composition in combination with carbon black. As a result of diligent research, the present inventors have found that the photosensitive film contains carbon black, further carbon black, and a filler having a charge opposite to that of the carbon black, thereby peeling the support film. It was found that no carbon black remained. The reason is not necessarily clear, but is considered as follows. When the photosensitive film contains carbon black, the carbon black has either a positive or negative charging potential. Therefore, when the support film or the protective film is peeled off, the electrostatic force is applied to the support film or the protective film. It is thought that black adheres. In the present invention, since the photosensitive film contains a filler having a charge opposite to that of carbon black, carbon black is detached from the photosensitive film by the electrostatic force of the filler and carbon black. It is thought that it can be suppressed. As a result, it is presumed that the transfer of carbon black to the support film or the protective film does not occur, but it is only in the range of estimation and is not necessarily limited to this.

[Carbon black]
As the carbon black used in the present invention, known and conventional carbon blacks can be used as long as they are carbon-based fine particles produced by industrially quality control. Carbon black includes, for example, furnace black, thermal black, channel black, acetylene black and the like. Carbon black may be surface-treated by a known method. Carbon black may be positively or negatively charged. The particle size of carbon black is preferably 3 to 500 nm in diameter.

  Whether the carbon black is positively or negatively charged can be determined by measuring the electric charge. The charge can be measured using a non-contact type electrostatic meter. For example, SK-H050 manufactured by Keyence Corporation can be used. Specifically, it can be measured in a charged potential measurement mode using an electrostatic meter. At this time, the static electricity measuring device is preferably grounded. Although any mode can be selected for the measurement distance, the measurement range, and the measurement accuracy, it is preferable to select the high accuracy mode. It is preferable that the static electricity measuring device adjusts the zero point toward a grounded object. Note that the zero point adjustment is preferably performed for each measurement of each sample. The sample to check the charged state is put in a metal can. As long as the type of metal can is not surface-treated and is conductive, it can be used without particular limitation. Use metal cans on an insulating table. It is preferable that the metal can is placed on the table and then neutralized, and only the sample is touched until the measurement is completed. Samples can be placed in metal cans using a metal bowl. Although the capacity | capacitance of a metal can and a sample amount can use arbitrary things, it is preferable to make it spread over the whole bottom face of a metal can. From the viewpoint of handleability, it is preferable to use a metal can of 20 to 50 ml and measure with a sample amount of 3 to 10 g. The measurement is performed on the surface of the sample. The measurement is preferably performed for about 10 seconds. The measurement chamber at this time is preferably an environment having a temperature of 23 to 26 ° C. and a humidity of 45 to 55%.

  The blending amount of carbon black is preferably 0.3 to 5% by mass, more preferably 0.5 to 3% by mass, and further preferably 1 to 3% by mass in terms of solid content in the photosensitive resin composition. is there. When the blending amount of carbon black is 0.3% by mass or more, the concealability is improved. In the case of 5% by mass or less, the photosensitivity and resolution become better. Further, the carbon black is more likely to remain in the photosensitive film.

[Filler]
In the present invention, as described above, a filler having a charge opposite to that of carbon black is included. Whether the filler is positively or negatively charged can be determined by measuring the charge in the same manner as described above. When carbon black has a positive charge, a filler having a negative charge is used. Conversely, when carbon black has a negative charge, a filler having a positive charge is used. In the present invention, at least carbon black and another filler having a charge opposite to the charge of carbon black may be included, and another filler may be included.

  As the filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, titanium oxide, Neuburg silica clay particles, and talc are preferably used. The filler may be positively or negatively charged as long as it contains at least one filler having a charge opposite to that of carbon black. Moreover, aluminum hydroxide, magnesium hydroxide, boehmite, etc. can be used for the purpose of imparting flame retardancy to the photosensitive film. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all are product grade names) manufactured by Hanse-Chemie . These may be used alone or in combination of two or more. By including the filler, the physical strength of the obtained cured product can be increased.

  The average particle size of the filler is preferably 0.05 to 15 μm, more preferably 0.1 to 5 μm. By setting it in this range, carbon black tends to stay in the photosensitive film more effectively. Further, resolution and electrical characteristics are further improved.

  The blending amount of the filler is preferably 0.05 to 80% by mass, more preferably 0.1 to 75% by mass, and particularly preferably 1 to 70% by mass in terms of solid content in the photosensitive resin composition. . When the blending amount of the filler is 80% by mass or less, the viscosity of the photosensitive resin composition does not become too high, the applicability in forming a photosensitive film is good, and the cured product is not easily brittle. Moreover, when the compounding quantity of a filler is 0.05 mass% or more, carbon black will remain in a photosensitive film more easily.

  In the photosensitive resin composition, the mixing ratio of carbon black and a filler having a charge opposite to that of carbon black is not particularly limited, but by mass, carbon black: filler having a charge opposite to that of carbon black = The ratio is preferably 2:98 to 98: 2. More preferably, it is 3: 97-75: 25, More preferably, it is 4: 96-50: 50. By blending at this ratio, desorption of carbon black is less likely to occur.

  In the present invention, the photosensitive resin composition preferably contains a crosslinking component in addition to the above-described carbon black and filler. Furthermore, it is more preferable that a photopolymerization initiator is included. The crosslinking component is preferably a carboxyl group-containing photosensitive resin or a photosensitive monomer, and further includes a component that is crosslinked by heat when heated. Hereinafter, each component will be described.

[Crosslinking component]
The cross-linking component is not particularly limited as long as it is a cross-linking component, and known and conventional ones can be used. In particular, a carboxyl group-containing photosensitive resin and a photosensitive monomer are preferable, and when further heated, it is preferable to include a component that is crosslinked by heat (hereinafter referred to as a thermal crosslinking component) by improving characteristics such as heat resistance and insulation reliability. .

  The carboxyl group-containing photosensitive resin is a component that is polymerized or cross-linked by light irradiation to be cured, and can be rendered alkali developable by containing a carboxyl group. Moreover, it is preferable to have an ethylenically unsaturated bond in a molecule | numerator other than a carboxyl group from a viewpoint of photocurability and image development resistance. As the ethylenically unsaturated double bond, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.

  Moreover, as the carboxyl group-containing photosensitive resin, it is preferable to use a carboxyl group-containing photosensitive resin obtained by synthesizing a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material or a resin other than an epoxy resin. . Carboxyl group-containing resins obtained by synthesizing resins other than epoxy resin and carboxyl group-containing photosensitive resins that do not use epoxy resin as a starting material have very low halide ion content and deteriorate insulation reliability. As a result, the electrical characteristics are more excellent. Specific examples of the carboxyl group-containing photosensitive resin include the compounds listed below (which may be either oligomers or polymers).

(1) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl group present in the side chain has two bases such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which an acid anhydride is added,
(2) A polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin,
(3) An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like. Polybasic, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated carboxylic acid containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(4) Two or more per molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Reaction obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with the product,
(5) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride,
(6) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminal (meth) acrylated,
(7) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin in which a compound having one isocyanate group and one or more (meth) acryloyl groups is added and terminal (meth) acrylated,
(8) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group. Further, a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule, such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. And (9) a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing photosensitive resin of any one of (1) to (8) described above. Resin,
(10) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. On the other hand, a carboxyl group-containing photosensitive resin obtained by reacting a compound having a cyclic ether group and a (meth) acryloyl group in one molecule such as 3,4-epoxycyclohexyl methacrylate,
Etc. Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Among the above carboxyl group-containing photosensitive resins, as described above, a carboxyl group-containing photosensitive resin obtained by synthesizing a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material or a resin other than an epoxy resin. Can be suitably used. Therefore, among the specific examples of the carboxyl group-containing photosensitive resin described above, any one or more of the carboxyl group-containing photosensitive resins (4) to (7) can be particularly preferably used. It can have characteristics required for a solder resist for a semiconductor package, that is, PCT resistance, HAST resistance, and thermal shock resistance.

  Thus, by not using an epoxy resin as a starting material, the amount of chlorine ion impurities can be suppressed to a very low value, for example, 100 ppm or less. The content of chloride ions in the carboxyl group-containing photosensitive resin suitably used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

  In addition, by not using an epoxy resin as a starting material, a resin containing no hydroxyl group (or a reduced amount of hydroxyl group) can be easily obtained. In general, the presence of hydroxyl groups has excellent characteristics such as improved adhesion due to hydrogen bonding, but it is known to significantly reduce moisture resistance, and a carboxyl group-containing photosensitive resin that does not contain hydroxyl groups. As a result, the moisture resistance can be improved.

  A carboxyl group-containing urethane resin synthesized from an isocyanate compound not using phosgene as a starting material and a raw material not using epihalohydrin and having a chlorine ion impurity amount of 0 to 30 ppm is also preferably used. In such a urethane resin, a resin containing no hydroxyl group can be easily synthesized by combining the equivalents of the hydroxyl group and the isocyanate group.

  In the synthesis of the urethane resin, an epoxy acrylate-modified raw material can also be used as the diol compound. Although chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled. In addition, the carboxyl group-containing photosensitive resin (10) can be suitably used because it contains few chlorine ion impurities.

  Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution is possible.

  The acid value of the carboxyl group-containing photosensitive resin is preferably 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin is 40 mgKOH / g or more, alkali development is improved. Moreover, it can be made easy to draw a favorable resist pattern by making an acid value into 150 mgKOH / g or less. More preferably, it is 50-130 mgKOH / g.

  The weight average molecular weight of the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, tack-free performance and resolution when a photosensitive film is obtained can be improved. Moreover, developability and storage stability can be improved by the weight average molecular weight being 150,000 or less. More preferably, it is 5,000-100,000.

  It is preferable that the compounding quantity of carboxyl group-containing photosensitive resin is 20-60 mass% in conversion of solid content in the photosensitive resin composition. By setting it as 20 mass% or more, the coating-film intensity | strength at the time of setting it as a photosensitive film can be improved. Further, when the content is 60% by mass or less, viscosity becomes appropriate and workability is improved. More preferably, it is 30-50 mass%.

  Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. 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 Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent acrylates such as thyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Polyurethane polyol such as polyester polyol is directly acrylated or urethane acrylate via diisocyanate It can be used by appropriately selecting from at least one selected from acrylates and melamine acrylates and methacrylates corresponding to the acrylates.

  Epoxy acrylate resin obtained by reacting polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and hydroxyl acrylate of the epoxy acrylate resin, hydroxy acrylate such as pentaerythritol triacrylate, and diisocyanate half urethane such as isophorone diisocyanate An epoxy urethane acrylate compound reacted with a compound may be used as the photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the compound which has an ethylenically unsaturated group in the molecule | numerator used as a photosensitive monomer, Preferably it is 0.2-60 mass% in conversion of solid content in a photosensitive resin composition, More preferably, it is 0.00. 2 to 50% by mass. The photocurability of a photocurable resin composition improves by making the compounding quantity of the compound which has an ethylenically unsaturated group into 0.2 mass% or more. Moreover, the coating-film hardness can be improved by making a compounding quantity 60 mass% or less.

  The photosensitive monomer is one or more ethylenically unsaturated groups in the molecule in order to make the composition photocurable, particularly when a carboxyl group-containing non-photosensitive resin having no ethylenically unsaturated double bond is used. This is effective because it is necessary to use a compound having a group (photosensitive monomer) in combination.

  A thermosetting resin etc. are mentioned as a heat-crosslinking component. Examples of thermosetting resins include known and conventional ones such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Can be used. Among these, a preferred thermal crosslinking component is a thermal crosslinking component having at least one of a plurality of cyclic ether groups and a plurality of cyclic thioether groups (hereinafter abbreviated as a cyclic (thio) ether group) in one molecule. is there. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule has either one of the three, four or five-membered cyclic ether groups, or the cyclic thioether group, or a plurality of two types of groups in the molecule. Compound, 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 etc. are mentioned.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 840-S, Epicron 850, Epicron 1050, Epicron 2055, Nippon Steel & Sumikin Chemical Co., Ltd. manufactured by DIC Corporation. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Chemical Industries, Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Co., Ltd., A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC Corporation, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. EPPN-201, EOCN manufactured by Nippon Kayaku Co., Ltd. -1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumitomo Chemical Co., Ltd., Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. ECN-235, ECN-299, etc. (both trade names) novolac type epoxy resins; DIC Corporation Epicron 830, Mitsubishi Chemical Corporation jER807, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDF-170, YDF-175 Bisphenol F type epoxy resins such as YDF-2004 (all trade names); hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Glycidylamine type epoxy resin such as jER604 manufactured by Mitsubishi Chemical Corporation, Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); Daicel Celoxide 2021, etc. (trade name) alicyclic ring Epoxy resin; Mitsubishi Chemical Co., Ltd. of YL-933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy such as xylenol type or biphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd. Resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resin such as jERYL-931 etc. (trade name) manufactured by Mitsubishi Chemical Corporation; Nissan Chemical Industries, Ltd. Heterocyclic epoxy such as TEPIC (trade name) Fat; Diglycidyl phthalate resin such as Blenmer DGT manufactured by Nippon Oil &Fats; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co .; ESN-190, ESN-360, DIC manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, and EXA-4700 manufactured by KK; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC, EXA-4816, and EXA- 4822, EXA-4850 series flexible tough epoxy resin; CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins such as Nippon Oil & Fats Co .; and cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin Including without being limited thereto. These epoxy resins can be used alone or in combination of two or more.

  Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (P-hydroxystyrene), cardo-type bisphenol S, calixarenes, calix resorcin arenes, or the like ethers of 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 is also included.

  Examples of the episulfide resin include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  When the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the solid content Preferably it is 0.3 equivalent or more with respect to 1 equivalent of carboxyl groups of the carboxyl group-containing resin in terms of conversion, more preferably 0.5 to 3.0 equivalents. By making the amount of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule 0.3 equivalent or more, no carboxyl group remains in the cured film, heat resistance, alkali resistance, electrical insulation Etc. will be improved. In addition, when the photosensitive resin composition does not contain a carboxyl group-containing resin, the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is converted into solid content in the photosensitive resin composition. It is preferable that it is 20-60 mass%. By setting it as 20 mass% or more, the coating-film intensity | strength at the time of setting it as a photosensitive film can be improved. Further, when the content is 60% by mass or less, viscosity becomes appropriate and workability is improved. More preferably, it is 30-50 mass%.

  When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to add a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT manufactured by San Apro Co., Ltd. (Registered trademark) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. . In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group may be used alone or in combination. A mixture of seeds or more may be used. Also, 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 and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.

  When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the composition includes a plurality of cyclic (thio) ether groups in terms of solid content. Preferably it is 0.1-20 mass parts with respect to 100 mass parts of thermosetting components which have this, More preferably, it is 0.5-15.0 mass parts.

  Amino resins include amino resins such as melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can 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 which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak 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 (above, manufactured by Sanwa Chemical Co., Ltd.).

  As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the 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, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As an isocyanate compound used in order to synthesize | combine a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  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-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene 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 Ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents and the like.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumika Covestrourethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Tosoh Corporation make, trade name), B-830, B-815, B-846, B-870, B-874, B-882 (above, Mitsui Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Corporation, trade name) Etc. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  In the photosensitive resin composition, a urethanization catalyst may be blended in order to accelerate the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group. As the urethanization catalyst, it is preferable to use a urethanization catalyst selected from at least one of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and amine salts.

[Photopolymerization initiator]
In the present invention, as the photopolymerization initiator used for photopolymerizing the above-described photosensitive resin composition, known ones can be used, and among them, oxime ester-based photopolymerization having an oxime ester group. An initiator, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator are preferred. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of commercially available oxime ester photopolymerization initiators include CGI-325, IRGACURE (registered trademark) OXE01, IRGACURE OXE02, manufactured by BASF Japan Ltd., N-1919, manufactured by ADEKA Corporation, and Adeka Arcles (registered trademark) NCI. -831, TR-PBG-304 manufactured by Changzhou Power Electronics New Materials Co., Ltd.

（式中、Ｘ_１は、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ_１、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０または１の整数である） In addition, a photopolymerization initiator having two oxime ester groups in the molecule can also be preferably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (I). .

(Wherein, _{X 1} is a hydrogen atom, an alkyl group of 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group of 1 to 17 carbon atoms, 1 to 8 carbon atoms An alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Y ₁ and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, carbon, and an amino group, substituted with an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group) An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an 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); An alkylamino group having a alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, or an alkyl group having 1 to 8 carbon atoms. Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene , Thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

In particular, in the above formula, X ₁ and Y ₁ are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene, or thienylene. An ester photopolymerization initiator is preferred.

  Preferred examples of the carbazole oxime ester compound include compounds that can be represented by the following general formula (II).

（式中、Ｒ_３は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ_４は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ_５は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ_６は、ニトロ基、または、Ｘ_２−Ｃ（＝Ｏ）−で表されるアシル基を表す。
Ｘ_２は、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式（ＩＩＩ）で示される構造を表す。）

(Wherein, R ₃ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ₄ represents a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group or alkoxy group having 1 to 4 carbon atoms.
R ₅ may be connected with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ₆ represents a nitro group or an acyl group represented by X ₂ —C (═O) —.
X ₂ represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (III), 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-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

  In the case of using the oxime ester photopolymerization initiator, the blending amount in the photosensitive resin composition is preferably 0.01 to 10% by mass in terms of solid content. By setting it as 0.01 mass% or more, the photocurability on copper becomes more reliable and coating-film characteristics, such as chemical resistance, improve. On the other hand, when the content is 10% by mass or less, halation or the like hardly occurs and the resolution is improved. More preferably, it is 0.05-5 mass%.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned. Commercially available products include Omnirad 907, Omnirad 369, Omnirad 379 manufactured by IGM Resins.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercial products include Omnirad TPO, Omnirad 819 manufactured by IGM Resins, and the like.

  In addition, as a photopolymerization initiator, Yueyang Kimoutain Sci-tech Co. , Ltd., Ltd. JMT-784 manufactured by the company can also be suitably used.

  The blending amount when using a photopolymerization initiator other than the oxime ester photopolymerization initiator is preferably 0.01 to 10% by mass in terms of solid content in the photosensitive resin composition. By setting it as 0.01 mass% or more, the photocurability on copper becomes more reliable and coating-film characteristics, such as chemical resistance, improve. Moreover, by setting it as 10 mass% or less, sufficient reduction effect of outgas is acquired, Furthermore, the light absorption in the cured film surface is suppressed, and the sclerosis | hardenability of a deep part also improves. More preferably, it is 0.05-8 mass%.

  A photoinitiator or sensitizer may be used in combination with the above-described photopolymerization initiator. Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as a photopolymerization initiator in some cases, but are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and they may function as ultraviolet absorbers. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.

  The photosensitive resin composition used for the photosensitive film according to the present invention may contain other components such as a block copolymer, a colorant, an elastomer, and a thermoplastic resin in addition to the components described above.

  The photosensitive resin composition may contain a colorant. As the colorant, known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

  Moreover, an elastomer can be mix | blended with the photosensitive resin composition for the purpose of provision of the softness | flexibility with respect to the hardened | cured material obtained, improvement of the brittleness of hardened | cured material, etc. One type of elastomer may be used alone, or a mixture of two or more types may be used.

  Moreover, a conventionally well-known binder polymer can be used for the purpose of the improvement of the flexibility of the hardened | cured material obtained, and finger touch drying property.

  In addition, the photosensitive resin composition may further contain components such as an adhesion promoter, an antioxidant, and an ultraviolet absorber as necessary. As these, those known in the field of electronic materials can be used. In addition, at least one of defoamers and leveling agents such as silicone, fluorine, and polymer, silane coupling agents such as imidazole, thiazole, and triazole, rust preventives, fluorescent whitening agents, and the like At least one kind of known and commonly used additives such as

  The photosensitive film can be formed by applying the above-described photosensitive resin composition to one surface of the support film and drying it. In consideration of the applicability of the photosensitive resin composition, the photosensitive resin composition is diluted with an organic solvent and adjusted to an appropriate viscosity. A comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, The transfer roll coater, gravure coater, spray coater, etc. are applied to one side of the support film to a uniform thickness, and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to volatilize the organic solvent. A free coating film can be obtained. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, 5-150 micrometers, Preferably it selects suitably in the range of 10-60 micrometers.

  The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. be able to. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  Volatile drying of organic solvents supports hot air circulation drying furnaces, IR furnaces, hot plates, convection ovens, etc. (methods using counter-contact with hot air in the dryer using a steam-heated heat source and nozzle support Can be performed using a method of spraying on the body).

[Protective film]
The photosensitive film laminate according to the present invention is a protective film on the surface opposite to the support film of the photosensitive film for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving the handleability. May be provided. As described later, the photosensitive film laminate including the protective film peels off the protective film when the photosensitive film laminate is used, but the protective film is peeled off in a state where the photosensitive film is not cured. Therefore, in general, carbon black tends to remain in the protective film as compared with the case where the support film is peeled off after the photosensitive film is cured to form a cured film. In the present invention, as described above, since the photosensitive film contains a filler having a charge opposite to that of the carbon black, together with the carbon black, the photosensitive film contains the filler even when the protective film is peeled off. Can effectively keep carbon black.

  As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, but the adhesive force between the protective film and the photosensitive film is different from that of the photosensitive film. It is preferable to select a material that is smaller than the adhesive strength of the material. Moreover, in order to make it easy to peel a protective film at the time of use of a photosensitive film laminated body, you may give a mold release process as mentioned above to the surface which contacts the photosensitive film of a protective film.

  The thickness of the protective film is not particularly limited, but is appropriately selected depending on the intended use within a range of about 10 to 150 μm.

  In the protective film, the arithmetic average surface roughness Ra on the side in contact with the photosensitive film is preferably 1000 nm or less, more preferably 750 nm or less, and further preferably 500 nm or less. By setting it to 1000 nm or less, the surface area does not become too large, so the risk of carbon black desorption is reduced. In addition, arithmetic mean surface roughness Ra means the value measured with the measuring apparatus based on JISB0601-1994.

<Method for producing cured product and printed wiring board>
A cured product is formed using the photosensitive film laminate of the present invention. A method for producing such a cured product and a method for producing a printed wiring board provided with the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. As an example, a method for producing a printed wiring board using a photosensitive film laminate provided with a protective film will be described. First, i) the protective film is peeled off from the above-described photosensitive film laminate to expose the photosensitive film, and ii) the photosensitive film of the photosensitive film laminate is formed on the substrate on which the circuit pattern is formed. Pasted together, iii) exposed from above the support film of the photosensitive film laminate, and iv) peeled off the support film from the photosensitive film laminate and developed, thereby being patterned on the substrate. A printed wiring board is formed by forming a conductive film and v) curing the patterned photosensitive film by light irradiation or heat to form a cured film. In addition, when using the photosensitive film laminated body in which the protective film is not provided, it cannot be overemphasized that the peeling process (i process) of a protective film is unnecessary. Hereinafter, each step will be described.

  First, the protective film is peeled from the photosensitive film laminate to expose the photosensitive film, and the photosensitive film of the photosensitive film laminate is bonded onto the substrate on which the circuit pattern is formed. As a substrate on which a circuit pattern is formed, in addition to a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper Copper grades of all grades (FR-4 etc.) using materials such as epoxy, synthetic fiber epoxy, copper clad laminates for high frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. Laminated plates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

  In order to paste the photosensitive film of the photosensitive film laminate on the circuit board, it is preferable to use a vacuum laminator or the like to bond under pressure and heating. By using such a vacuum laminator, since the photosensitive film adheres to the circuit board, there is no mixing of bubbles, and the hole filling property on the substrate surface is improved. The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120 ° C.

  Next, exposure (irradiation of active energy rays) is performed on the support film of the photosensitive film laminate. By this step, only the exposed photosensitive resin layer is cured. The exposure process is not particularly limited. For example, the exposure process may be selectively performed with active energy rays through a photomask having a desired pattern formed by a contact method (or a non-contact method). A desired pattern may be exposed with an active energy ray.

As an exposure machine used for active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, or the like is mounted, and any apparatus that irradiates ultraviolet rays in a range of 350 to 450 nm may be used. For example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

  After the exposure, the support film is peeled from the photosensitive film laminate. In this step, a support film for confirming whether carbon black remains is obtained. The peeling method of a support film is not specifically limited, There exist the method of peeling using machines, such as an auto peeler using an adhesive tape and an air blow, and the method of peeling with a human hand.

  The development process is not particularly limited, and a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

Next, the patterned photosensitive film is cured by irradiation with active energy rays (light) or heat to form a cured product (cured film). This process is called main curing or additional curing, promotes the polymerization of unreacted monomers in the photosensitive film, and further thermally cures the carboxyl group-containing photosensitive resin and the epoxy resin to leave residual carboxyl. The amount of groups can be reduced. The active energy ray irradiation can be performed in the same manner as the exposure described above, but is preferably performed under a condition stronger than the irradiation energy at the time of exposure. For example, it can be set to 500 to 3000 mJ / cm ² . Moreover, thermosetting can be performed on the heating conditions for about 20 to 90 minutes at 100-200 degreeC.

  The photosensitive film laminate according to the present invention can be suitably used as an insulating material for printed wiring boards, an insulating material for semiconductors, a sealing material for semiconductors, and can be more suitably used for forming a solder resist layer or an interlayer insulating layer, It can be more suitably used for forming a solder resist layer.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples.

<Charging state confirmation method>
First, the earth connection terminal of the static electricity measuring device (SK-H050 manufactured by Keyence Corporation) was grounded to D type. The static electricity measuring device to which the ground connection was made was activated, and “Static Meter” was selected from “MODE”. Next, with the “RANGE” key, “Near”, which is a high-precision mode, was selected. The measurement response time was 0.8 s, and the measurement region was Φ60 mm. Next, the “START” key was pressed to enter the measurement state. The “ZERO” key was pressed with the static electricity meter toward the target grounded. After confirming that the potential was zero, the “STOP” key was pressed and the zero point was adjusted. Next, confirm that the continuity is obtained, place a 30 ml metal can that has not been surface-treated on an insulating base, and blower type ionizer (SJ-F030, manufactured by Keyence Corporation) toward the metal can. For 10 seconds. Using a metal basket, 5 g of carbon black was placed so as to spread over the entire metal can. At this time, only the sample was touched to the metal can. Thereafter, the measurement distance was adjusted to the surface of the carbon black with a laser pointer of a static electricity measuring device, and the “START” key was pressed to measure the charged potential on the surface. After 10 seconds, the “STOP” key was pressed to complete the measurement. The measurement was performed under conditions of a temperature of 25 ° C. and a humidity of 50%, and zero point adjustment was performed for each measurement. The maximum value, minimum value, and absolute value of the obtained charging potential were confirmed. In addition, the measurement was performed 3 times for each sample, and positive / negative was determined by a value obtained by averaging the absolute values of 3 times. When measuring the filler, the same operation was performed to determine whether it was positive or negative.

<Confirmation of the charged state of carbon black>
Carbon black A having an average particle size of 24 nm and carbon black B having an average particle size of 38 nm were prepared, and the charged state of the carbon black was confirmed by the method described above (both carbon black A and carbon black B were powdered) Status). As a result, it was confirmed that carbon black A was positively charged and carbon black B was negatively charged.

<Checking the charged state of the filler>
By the method described above, the charged state of the filler described later was confirmed (both fillers are in powder form). It was confirmed that spherical silica having an average particle diameter of 0.55 μm was negatively charged, titanium oxide A having an average particle diameter of 0.28 μm was positive, and titanium oxide B having an average particle diameter of 0.25 μm was negatively charged.

<Preparation of carboxyl group-containing photosensitive resin>
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 119.4 g of a novolac-type cresol resin (Shornol CRG951, OH equivalent: 119.4, manufactured by Showa Denko KK) and potassium hydroxide 1 .19 g and 119.4 g of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. The resulting novolac cresol resin had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 g of the resulting novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer and a thermometer. And a reactor equipped with an air blowing tube, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 62.3 g of tetrahydrophthalic anhydride is gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a carboxyl group-containing photosensitive resin varnish 1 having an acid value of 88 mgKOH / g and a nonvolatile content of 71%. It was.

<Preparation of photosensitive resin compositions 1-10>
The carboxyl group-containing photosensitive resin varnish 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), which is a photosensitive monomer, as an acrylate compound, and an epoxy, which is a thermosetting component As the resin, bisphenol A type epoxy resin (EPICLON 840-S manufactured by DIC Corporation) and biphenol novolac type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.), IRGACURE OXE02 manufactured by BASF Japan Co., Ltd. as a photopolymerization initiator, Melamine, carbon black A or carbon black B as a thermosetting catalyst, and each component selected from spherical silica, titanium oxide A, and titanium oxide B as fillers in the proportions (parts by mass) shown in Table 1 below. Mix and stir And kneaded with a three-roll mill were preliminarily mixed in, to prepare a photosensitive resin composition 1-10.

[Example 1]
<Preparation of photosensitive film laminate>
The photosensitive resin composition 1 obtained as described above was diluted by adding 300 g of methyl ethyl ketone, and stirred for 15 minutes with a stirrer to obtain a coating solution. The coating solution is applied as a support film on a 25 μm thick polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc., Ra = 0.03 μm), dried at a temperature of 80 ° C. for 15 minutes, and has a thickness of 20 μm. A film was formed. Subsequently, a 15-μm-thick polypropylene film (Alphan MA-411 manufactured by Oji F-Tex Co., Ltd., Ra = 0.4 μm) was bonded as a protective film on the photosensitive film to prepare a photosensitive film laminate.

[Example 2]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 2, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 2. FIG.

[Example 3]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 3, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 3. FIG.

[Example 4]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 4, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 4. FIG.

[Example 5]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 5, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 5. FIG.

[Example 6]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 6, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 6. FIG.

[Example 7]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 7, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 7. FIG.

[Comparative Example 1]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 8, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 8. FIG.

[Comparative Example 2]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 9, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 9. FIG.

[Comparative Example 3]
In Example 1, it replaced with the photosensitive resin composition 1, and except having used the photosensitive resin composition 10, it carried out similarly to Example 1, and obtained the photosensitive film laminated body 10. FIG.

<Production of test substrate>
FR-4 copper-clad laminate (100 mm x 150 mm x 0.8 mmt, double-sided copper foil, copper foil thickness is 18 μm on both sides) The surface is chemically polished with CZ8101 manufactured by MEC Co., Ltd., and the substrate is chemically polished on the surface Then, the exposed surface of the photosensitive film exposed by peeling off the protective film from each photosensitive film laminate obtained as described above was bonded, and then a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) Was used for heat laminating under the conditions of pressure: 0.8 Mpa, 70 ° C., 1 minute, vacuum: 133.3 Pa, and the substrate and the photosensitive film were adhered to obtain a test substrate.

<Evaluation of carbon black residue>
The support film was manually peeled off from the test substrate prepared as described above in about 1 second, and the peeled support film and the protective film peeled off in <Preparation of test substrate> were each cut into approximately 1 × 1 cm squares. Then, Pt was vapor-deposited on the surfaces of the support film and the protective film that were in contact with the photosensitive resin. The surface on which Pt was deposited was observed with an SEM (scanning electron microscope, JSM-7600 manufactured by JEOL Ltd.) to confirm whether carbon black remained on the support film and the protective film. Each film was observed at an arbitrary position at an acceleration voltage of 10 kV and a measurement magnification of 50,000, and evaluated according to the following criteria.
○: × no carbon black particles are detected in the measurement area 1 [mu] m ^2: Measurement area 1 [mu] m results of evaluation of carbon black particles are detected one or more in ² were as shown in Table 2 below.

<Resolution evaluation>
For Examples 1 to 7 in which carbon black did not remain on the support film and the protective film, evaluation of resolution was further performed. After heating and laminating in <Preparation of test substrate>, SRO (solder resist opening) from the polyethylene terephthalate film surface side of the support film through the exposure mask using a parallel light exposure apparatus equipped with a short arc type high-pressure mercury lamp After each exposure using a negative pattern designed to be 200 μm, the support film was peeled off by hand in about 1 second to expose the photosensitive film. In addition, the exposure amount was set to the exposure amount which will become 7 steps | paragraphs when it exposes using Stuffer 41 steps | paragraphs from the support film which touches a photosensitive film. Thereafter, the exposed surface of the exposed photosensitive film was subjected to development for 60 seconds under the conditions of 30 ° C. and a spray pressure of 2 kg / cm ² using a 1 wt% Na ₂ CO ₃ aqueous solution and patterned. Subsequently, after irradiating the photosensitive film patterned with an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, it is heated at 160 ° C. for 60 minutes to be additionally cured to form a cured film, A test substrate having a cured coating formed on the substrate was produced. The opening part with an opening diameter of 200 μm of each test substrate of Examples 1 to 7 was observed by SEM and evaluated according to the following criteria.
○: Halation and undercut do not occur, and a good opening shape is obtained. ×: Halation or undercut occurs, and a favorable opening shape cannot be obtained. Evaluation results are as shown in Table 2 below. .

<Electrical characteristics evaluation>
For Examples 1 to 7 in which carbon black did not remain on the support film and the protective film, electrical characteristics were further evaluated. A test substrate was prepared in the same manner as in the resolution evaluation except that a comb-type electrode pattern of line / space = 100/100 μm was used, and electrical characteristics were evaluated. Evaluation is performed in a high-temperature and high-humidity tank under an atmosphere of a temperature of 130 ° C. and a humidity of 85%, a voltage of 5.5 V is applied, the HAST test in the tank is performed, and the insulation resistance value in the tank when a predetermined time has elapsed is measured. The HAST resistance was evaluated. The judgment criteria are as follows.
◯: Insulation resistance value in the tank is less than 10 ⁶ Ω or short circuit occurs for 100 hours or more.
X: The insulation resistance value in the tank is less than 10 ⁶ Ω or a short circuit occurs in less than 100 hours.
The evaluation results were as shown in Table 2 below.

  As is clear from the above results, the photosensitive film laminate comprising at least carbon black in the photosensitive film and further containing a filler having a charge opposite to that of carbon black is obtained from the evaluation result of the presence or absence of carbon black. Carbon black can be effectively retained in the photosensitive film, and as a result, the carbon black does not remain in the support film and the protective film to be peeled, and in addition to not deteriorating the working environment, other evaluation The results show that the resolution and electrical characteristics are also good.

Claims (8)

In the photosensitive film laminate formed by laminating the support film and the photosensitive film made of the photosensitive resin composition,
A photosensitive film laminate, wherein the photosensitive resin composition comprises at least carbon black and a filler having a charge opposite to that of the carbon black.   The photosensitive film laminated body of Claim 1 whose compounding quantity of the said carbon black is 0.3-5 mass% in conversion of solid content in the photosensitive resin composition.   The photosensitive film laminated body of Claim 1 or 2 whose thickness of the said support film is 10-150 micrometers.   The photosensitive film laminated body as described in any one of Claims 1-3 whose said support film is a thermoplastic resin film.   The photosensitive film laminate according to claim 4, wherein the thermoplastic resin film is at least one selected from the group consisting of a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film.   The photosensitive film laminated body as described in any one of Claims 1-5 whose arithmetic mean surface roughness Ra of the said support film is 1000 nm or less.   The photosensitive film laminated body as described in any one of Claims 1-6 further equipped with the protective film laminated | stacked on the surface opposite to the said support film of the said photosensitive film.   A cured product formed using the photosensitive film laminate according to any one of claims 1 to 7.