TW201841762A - Photosensitive film laminate and cured product formed by using same - Google Patents

Abstract

Provided is a photosensitive film laminate, which has excellent resolution and can improve the yield even in the visual inspection of a cured film. The photosensitive film laminate comprises an inorganic particle-containing layer and a photosensitive film formed by a photosensitive resin composition in order, wherein the inorganic particle-containing layer contains inorganic particles, and the content ratio of the inorganic particles in the thickness direction of the inorganic particle-containing layer is high at the side in contact with the photosensitive film and is low at the side far from the photosensitive film.

Description

Photosensitive film laminate and cured product formed by using same

The present invention relates to a photosensitive film laminate and a cured product formed by using the same.

Generally, in printed wiring boards used in electronic equipment and the like, when mounting electronic components on printed wiring boards, in order to prevent solder from being attached to unnecessary portions, they are attached to substrates with circuit patterns except connection holes. Area forms a solder resist layer.

With the recent increase in precision and density of printed wiring boards caused by the thinness and thinness of electronic devices in recent years, currently, solder resist layers are coated with a photosensitive resin composition on a substrate, dried, and exposed and developed to form a pattern. After the molding, the patterned resin is hardened by heating or light irradiation, so-called formed by a photo solder resist is the mainstream.

It is also proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film instead of the liquid photosensitive resin composition as described above. Such a photosensitive film laminate is generally a photosensitive film formed by a photosensitive resin composition bonded to a supporting film, and a protective film may be bonded to the surface of the photosensitive film as needed. When such a photosensitive film laminate is used, the protective film is peeled off and laminated on the wiring substrate by heat and pressure bonding, and the supporting film is peeled off and developed before exposure or after exposure from the supporting film side. Thereby, a patterned solder resist layer can be formed. By using the photosensitive film laminate, compared with the case of wet coating, a drying step after coating is not required, and the surface smoothness or surface hardness of the obtained solder resist layer is also excellent.

In order to improve the operability during the production of the photosensitive film or the operability of the photosensitive film laminate itself, the support film is required to have a moderate slip. A method in which fine particles are contained in the support film and fine protrusions are formed on the surface of the film is used to satisfy such characteristics (for example, Japanese Patent Application Laid-Open No. 10-128930). In Japanese Patent Application Laid-Open No. 10-128930, by adopting a structure in which fine particles are contained in a supporting film, the resolution during exposure and development is also improved.

On the other hand, the solder resist layer using the above-mentioned photosensitive film laminate is formed as the outermost layer of the substrate and is formed at the final stage of the substrate production step. Therefore, when using devices in the substrate production process, Transporting rollers and the like may damage the cured film of the photosensitive film (for example, Japanese Patent Application Laid-Open No. 2015-206992). This damage is judged to be NG in the visual inspection before the semiconductor mounting step, and the production yield is deteriorated. Especially in recent years, even slight damage without quality problems can cause a reduction in productivity. In addition, with the recent increase in the density of printed wiring boards due to the reduction in weight, thickness, and shortness of electronic devices in recent years, the resolution required for the above characteristics has also been required in the past.

However, when a photosensitive laminate using a support film as disclosed in Japanese Patent Application Laid-Open No. 10-128930 is used as a solder resist, it is difficult to balance both the suppression of the visibility of the damage and the improvement of the resolution. That is, the average particle size of the fine particles contained in the support film is small, so that the damage is not visually recognizable. On the other hand, when the average particle size of the fine particles is large, the minute damage on the surface of the solder resist layer is difficult to be visually recognized. However, scattering occurs due to fine particles during the exposure on the support film side, which deteriorates the resolution, and therefore it is difficult to balance the visibility of damage and the improvement of resolution.

Therefore, an object of the present invention is to provide a photosensitive thin film laminate which is excellent in resolvability and can also improve the yield in the visual inspection of a cured film. Another object of the present invention is to provide a photosensitive film laminate and a cured product formed by using the same.

The present inventors have discovered that in a photosensitive film laminate including a layer containing inorganic particles and a photosensitive film formed of a photosensitive resin composition in this order, The proportion of inorganic particles contained is higher toward the surface side adjacent to the photosensitive film, and lower on the surface side further away from the photosensitive film, and particularly improves the resolution of the solder resist layer after exposure and development. . Furthermore, the present inventors have found that the use of a solder resist formed by using a photosensitive thin film laminate having a specific inorganic particle-containing layer as described above makes it difficult to visually recognize the damage even if the surface is damaged. Yield can be improved in visual inspection. In particular, it has been found that the aforementioned effects are exhibited regardless of the particle size of the inorganic particles. This invention is made based on this knowledge.

[1] The photosensitive film laminate according to the first embodiment of the present invention is a photosensitive film laminate including a layer containing inorganic particles and a photosensitive film formed of a photosensitive resin composition in this order, It is characterized in that the inorganic particle-containing layer contains inorganic particles, and the content ratio of the inorganic particles is higher in the thickness direction of the inorganic particle-containing layer than the side adjacent to the photosensitive film, and is far from the photosensitive film. The side is lower.

[2] The photosensitive film laminate of the second embodiment of the present invention is the photosensitive film laminate of [1], in which the thickness of the layer containing the inorganic particles is T (μm) in the thickness direction, The ratio α of the inorganic particles contained in the inorganic particle-containing layer from the surface on the side adjacent to the photosensitive film to T / 2 (μm), and on the opposite side from the side adjacent to the photosensitive film The ratio β of the inorganic particles contained on the surface up to T / 2 (μm) satisfies the following formula (1): .

[3] The photosensitive film laminate according to the third embodiment of the present invention is a photosensitive film laminate according to [1] or [2], wherein the average primary particle diameter of the inorganic particles is in a range of 0.1 to 10 μm.

[4] The photosensitive film laminate according to the fourth embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [3], wherein the inorganic particles are silicon dioxide.

[5] The photosensitive film laminate according to the fifth embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [4], wherein the layer containing the inorganic particles further contains melamine or melamine It consists of at least one kind of compound.

[6] The photosensitive film laminate according to the sixth embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [5], wherein the photosensitive resin composition contains a filler and a crosslinking component Made.

[7] The photosensitive film laminate according to the seventh embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [6], wherein the photosensitive film and the inorganic particle-containing material are The opposite side of the layer is further provided with a protective film.

[8] The cured product according to the eighth embodiment of the present invention is characterized by being formed using the photosensitive film laminate according to any one of [1] to [7].

According to the present invention, it is possible to realize a photosensitive thin film laminate which is excellent in resolvability and can also improve the yield in the visual inspection of a cured film. In particular, it is effective to use the said photosensitive thin film laminated body when forming a solder resist layer. Furthermore, according to another aspect of this invention, the hardened | cured material formed using the said photosensitive film laminated body can be implemented.

The photosensitive film laminate of the present invention will be described. The photosensitive film laminate of the present invention is a photosensitive film laminate having a layer containing inorganic particles and a photosensitive film in this order, characterized in that the layer containing inorganic particles contains inorganic particles, and the content ratio of the inorganic particles, The side adjacent to the photosensitive film is higher, and the side farther from the photosensitive film is lower. The photosensitive film laminate of the present invention may further include a protective film on the surface of the photosensitive film opposite to the layer containing the inorganic particles. In addition, in the present invention, the "photosensitive film" refers to a person having a photosensitive resin composition having a film shape, and refers to a person in which another layer such as a supporting film or a protective film is not laminated. Hereinafter, each component which comprises the photosensitive film laminated body of this invention is demonstrated.

[Layer containing inorganic particles] (1) The inorganic particle-containing layer constituting the photosensitive film laminate of the present invention refers to a layer containing inorganic particles, which has a photosensitive film (that is, a photosensitive resin composition) for supporting the film described later. The formed layer is hereinafter referred to as a "photosensitive resin layer"), and the surface of the side of the photosensitive film adjacent to the layer containing the inorganic particles during the exposure and development of the photosensitive film will be described later. A character who gives a specific surface shape. The layer containing inorganic particles is not limited to a single layer, and may be laminated into a plurality of layers of two or more layers. When the inorganic particle-containing layer is composed of a plurality of layers, a part of the plurality of layers may include a layer adjacent to the photosensitive film or may be an intermediate layer. At this time, in the present invention, the entire plurality of layers (including those in which the plurality of layers are intermediate layers) are referred to as "layers containing inorganic particles". Furthermore, when the inorganic particle-containing layer is composed of a plurality of layers, it is not necessary to include inorganic particles in all the layers, as long as the content ratio of the inorganic particles on the side adjacent to the photosensitive film in the thickness direction of the inorganic particle-containing layer is included. If the content is higher, the content ratio of the inorganic particles on the far side from the photosensitive film may be lower. By using such a layer containing an inorganic particle as a support layer of a photosensitive film, it is surprisingly excellent in resolving property, and the appearance inspection of a hardened film can also improve the yield.

As a layer containing an inorganic particle, if it is a well-known person, it can use without a restriction | limiting especially, It can use especially suitably as a support film. As the supporting film, for example, a polyester film made of polyethylene terephthalate, polyethylene naphthalate, or the like, a polyimide film, a polyimide film, a polypropylene film, or a polybenzene can be suitably used. A film made of a thermoplastic resin such as an ethylene film. When the thermoplastic resin film is used, a filler may be added to the resin when the film is formed (kneading treatment), or a matte coating (coating treatment) may be performed, and the surface of the film may be subjected to a sandblasting treatment like a sandblasting treatment. Alternatively, it may be a processor that performs hairline processing or chemical etching. Among these, from the viewpoints of heat resistance, mechanical strength, workability, etc., a polyester film is particularly suitably used.

The thermoplastic resin film described above is preferably used for a film extending in one or two axial directions for the purpose of improving strength.

The surface of the layer containing the inorganic particles adjacent to the photosensitive film may be subjected to a release treatment. For example, a coating prepared by dissolving or dispersing a release agent such as wax, polysiloxane wax, alkyd resin, urethane resin, melamine resin, polysiloxane resin in an appropriate solvent can be used. The coating is performed on the surface of the layer containing the inorganic particles by a known method such as a roll coating method, a spray coating method, or a gravure printing method or a screen printing method. deal with.

From the viewpoint of operability, the thickness of the layer containing the inorganic particles is preferably in the range of 10 to 150 μm, more preferably in the range of 10 to 100 μm, and even more preferably in the range of 10 to 50 μm.

As described above, in the photosensitive film laminate of the present invention, as the content ratio of the inorganic particles contained in the inorganic particle-containing layer, the higher the surface side adjacent to the photosensitive film, the farther away from the surface the photosensitive film is. The lower the side. In the present invention, when the thickness of the layer containing inorganic particles is T (μm), the thickness of the layer containing inorganic particles from the surface adjacent to the photosensitive film to T / 2 (μm) in the thickness direction. The ratio α of the inorganic particles contained therein and the ratio β of the inorganic particles contained from the surface on the opposite side of the side adjacent to the photosensitive film to T / 2 (μm), preferably satisfy the following formula (1): . By being an inorganic particle-containing layer that satisfies the above formula (1), it is possible to achieve higher levels of suppression of damage visibility and improvement of resolution. To form a layer containing inorganic particles having such a content ratio of inorganic particles, for example, a resin composition containing inorganic particles may be coated on one surface of a thermoplastic resin film, and the content ratio of inorganic particles may be laminated. A layer containing inorganic particles in two layers, a high layer and a low layer, or when forming the above-mentioned thermoplastic resin film, the inorganic resin in one of the thermoplastic resin compositions is made by a biaxial extrusion molding machine or the like. The content ratio of the particles is high, and the content ratio of the inorganic particles in the other thermoplastic resin composition is low, and coextrusion is performed to form a film.

The average primary particle diameter of the inorganic particles contained in the inorganic particle-containing layer is preferably 0.1 to 10 μm. By being in the above range, it is possible to achieve higher levels of suppression of damage visibility and improvement of resolution. The maximum particle diameter is preferably an upper limit of the film thickness of the layer containing the inorganic particles. In addition, in the present invention, the average primary particle diameter refers to dispersing inorganic particles contained in a layer containing inorganic particles in a solvent by ultrasonic waves, dissolving agglutination, drying to remove the solvent, and then scanning electrons. Using a microscope image, the particle diameters of ten randomly selected inorganic particles were measured and their arithmetic mean values were given.

As the inorganic particles, a conventionally known one can be used, and examples thereof include silicon dioxide, barium sulfate, and titanium oxide, and they may be used alone or in combination of two or more. Among them, silicon dioxide is particularly preferable from the viewpoint of cost or availability.

In addition, when an intermediate layer is included in the layer containing an inorganic particle, the intermediate layer is included, and it is preferable to contain at least any one of melamine and a melamine compound. By laminating a photosensitive film laminate containing at least one of melamine and a melamine compound in a layer containing inorganic particles, even if a substrate or the like on which a photosensitive film laminate is laminated is strongly impacted or pressed, It is also preferable from the viewpoint of suppressing the influence on the surface of the photosensitive film. Furthermore, it is preferable that the melamine and the melamine compound contained in the inorganic particle-containing layer contain a large amount on the side adjacent to the photosensitive film.

As a melamine and a melamine compound, a well-known person can be used. In the present invention, the melamine compound also includes a mixture of the melamine compound and other substances. In addition, the "melamine" in the present invention refers to a resin hardened by the addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde, but also includes the resin The concept of methylol melamine and its alkylated alkylated methylol melamine as the initial reactants of melamine and formaldehyde. Melamine also includes modified melamine such as methylated methylol melamine, propylated methylol melamine, butylated methylol melamine, isobutylated methylol melamine, and the like. It also includes melamine modified products such as melamine (meth) acrylate.

The melamine compound refers to a mixture of the melamine and other resins such as an acrylic resin, an epoxy resin, and an alkyd resin, and examples thereof include acrylic melamine, alkyd melamine, polyester melamine, and epoxy melamine. Among these, in order to obtain more excellent impact resistance, melamine acrylic acid and epoxy melamine are preferred; melamine acrylic acid is more preferred. Furthermore, the melamine acrylic acid herein refers to a mixture of an acrylic resin and a melamine resin, and is a form in which an acrylic resin is hardened with a melamine resin. The epoxy melamine refers to a mixture of an epoxy resin and a melamine resin, and is a form in which an epoxy resin is hardened with a melamine resin. Specific examples of melamine include AMIDIR J-820-60, L-109-65, L-117-60, L-127-60, 13-548, G-821-60, and L-110 manufactured by DIC Corporation. -60G, L-125-60, L-166-60B, L-105-60, U-VAN 20SE60, 20SB, 22R, 125, 132, 62, 60R, 169, etc. manufactured by Mitsui Chemicals Corporation. In addition, an acrylic resin or an epoxy resin can be used by a publicly known person without particular limitation. Specific examples of the acrylic resin include ACRYDIC 54-172-60, A-322, A-405, and A-452 manufactured by DIC Corporation. Specific examples of the epoxy resin include Epomik R301 manufactured by Mitsui Chemicals Co., Ltd. and the like. The content of the melamine resin is preferably 0.1 to 50% by mass, and more preferably 1 to 40% by mass based on the total amount of the acrylic resin or epoxy resin.

<Photosensitive film> The photosensitive film constituting the photosensitive film laminate of the present invention is formed into a film shape using a photosensitive resin composition, and means that a layer containing an inorganic particle or another layer such as a protective film is not laminated. By. The photosensitive film is patterned by exposure and development, and becomes a hardened film provided on a circuit board. The hardened film is preferably a solder resist layer. As the photosensitive resin composition, conventionally known solder resist inks and the like can be used without limitation. An example of the photosensitive resin composition which can be preferably used for the photosensitive film of the present invention will be described below.

In the present invention, the photosensitive resin composition preferably contains a crosslinking component and a filler. More preferably, it further contains a photopolymerization initiator. The crosslinking component is preferably a photosensitive resin or photosensitive monomer containing a carboxyl group, and when further heated, it is preferable to contain a component that is crosslinked by heat. Each component is explained below.

[Crosslinking component] The crosslinking component is not particularly limited as long as it is a component that can be crosslinked, and a publicly known one can be used. Particularly preferred is a photosensitive resin or a photosensitive monomer containing a carboxyl group. In the case of further heating, it is preferred to contain a component that is crosslinked by heat (hereinafter referred to as a thermal crosslinking component).

The photosensitive resin containing a carboxyl group is a component which is hardened by polymerization or crosslinking by light irradiation, and can be alkali developable by containing a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule other than the carboxyl group. The ethylenically unsaturated double bond is preferably one derived from acrylic acid or methacrylic acid or a derivative thereof.

Moreover, it is preferable that the photosensitive resin containing a carboxyl group uses the photosensitive resin containing a carboxyl group without using an epoxy resin as a starting material. The photosensitive resin containing a carboxyl group, which does not use epoxy resin as a starting material, has very low halide ion content, and can suppress deterioration of insulation reliability. Specific examples of the carboxyl group-containing photosensitive resin include the following compounds (either oligomers or polymers).

Examples include: (1) reacting (meth) acrylic acid with a polyfunctional (solid) epoxy resin having two or more functions, and adding phthalic anhydride and tetrahydrophthalic acid to hydroxyl groups present on a side chain; A carboxyl group-containing photosensitive resin obtained from a dibasic acid anhydride such as formic anhydride, hexahydrophthalic anhydride, and the like. (2) A hydroxyl group of (meth) acrylic acid and a bifunctional (solid) epoxy resin is further subjected to epichlorine. A polyfunctional epoxy resin obtained by epoxidation of an alcohol, and a photosensitive resin containing a carboxyl group obtained by adding a dibasic acid anhydride to the generated hydroxyl group, (3) having at least one alcoholic hydroxyl group in one molecule and One phenolic hydroxyl compound and (meth) acrylic acid-containing unsaturated monocarboxylic acid react with an epoxy compound having two or more epoxy groups in one molecule, and react with the obtained reaction product Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., (4) using Monocarboxylic acids containing unsaturated groups such as (meth) acrylic acid, and bisphenol A, bisphenol F, bisphenol S, phenol Varnish-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, and a compound having two or more phenolic hydroxyl groups in one molecule and ethylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting an alkylene oxide such as alkane and propylene oxide with a polybasic acid anhydride; (5) making an unsaturated group-containing monomer The carboxylic acid reacts with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups and a cyclic carbonate compound such as ethyl carbonate and propyl carbonate in one molecule, and generates the obtained reaction. A carboxyl group-containing photosensitive resin obtained by reacting a substance with a polybasic acid anhydride, (6) a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, and a polycarbonate Polyols, Polyether Polyols, Polyester Polyols, Polyolefin Polyols, Acrylic Polyols, Bisphenol A alkylene oxide adduct glycols, Compounds with phenolic and alcoholic hydroxyl groups Wait Carbamate resin containing terminal carboxyl group obtained by addition polymerization reaction of diol compound and acid anhydride reaction, (7) using diisocyanate; dimethylolpropane Carboxyl-containing diol compounds such as acids, dimethylolbutyric acid, and the like; and carboxyl-containing urethane resins obtained by addition polymerization with a diol compound, hydroxyalkane (meth) acrylate is added A compound having one hydroxyl group and one or more (meth) acrylfluorene groups in a molecule such as an ester, a carboxyl group-containing urethane resin that is terminally (meth) acrylated, and (8) a diisocyanate In the synthesis of a carboxyl group-containing diol compound and a carboxyl group-containing urethane resin obtained by addition polymerization with a diol compound, a mole reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added. Compounds having one isocyanate group and one or more (meth) acrylfluorene groups in the molecule, etc., a terminal (meth) acrylated carboxyl group-containing urethane resin, (9) adipic acid, Phthalic acid, hexahydrophthalic acid A dicarboxylic acid such as dicarboxylic acid is reacted with a polyfunctional oxetane resin, and a dibasic acid anhydride is added to the generated primary hydroxyl group, and the polyester resin containing a carboxyl group obtained by the addition is further added ( A carboxyl group containing a compound having one epoxy group and one or more (meth) acrylfluorenyl groups in one molecule such as glycidyl (meth) acrylate and α-methyl glycidyl (meth) acrylate (10) Add a compound having a cyclic ether group and a (meth) acryl group in one molecule to the photosensitive resin containing a carboxyl group in any one of (1) to (9) above. The obtained carboxyl group-containing photosensitive resin, (11) For unsaturated carboxylic acids such as (meth) acrylic acid, styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene, etc. A carboxyl group-containing resin obtained by copolymerizing an unsaturated group-containing compound so that one of the molecules such as 3,4-epoxycyclohexyl methacrylate has a cyclic ether group and a (meth) acrylfluorenyl group. A carboxyl group-containing photosensitive resin and the like obtained by the reaction. Here, (meth) acrylate refers to a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

Among the carboxyl group-containing photosensitive resins, a carboxyl group-containing photosensitive resin that does not use epoxy resin as a starting material or a carboxyl group-containing photosensitive resin obtained from a resin other than a synthetic epoxy resin can be suitably used as described above. Resin. Therefore, among the specific examples of the photosensitive resin containing a carboxyl group, any one or more of the photosensitive resins containing a carboxyl group (4) to (8) and (11) may be suitably used, and (4) to ( 8) Exemplified resin. It can have the characteristics required for solder resist for semiconductor packaging, that is, PCT resistance, HAST resistance, and thermal shock resistance.

In this way, by not using an epoxy resin as a starting material, the amount of chloride ions can be suppressed to a very small amount, for example, 100 ppm or less. The content of chloride ion impurities in the photosensitive resin containing a carboxyl group 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.

Further, 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 a hydroxyl group also has excellent properties such as improved adhesion due to hydrogen bonding, but it is known that the moisture resistance is significantly reduced. By becoming a photosensitive resin containing a carboxyl group that does not contain a hydroxyl group, the resistance can be improved. Wet.

Furthermore, it is also suitable to use a carboxyl group-containing urethane resin synthesized from an isocyanate compound that does not use phosgene as a starting material and a raw material that does not use epihalohydrin, and has a chloride ion content of 0 to 30 ppm. In such a urethane resin, a resin having no hydroxyl group can be easily synthesized by blending the equivalents of a hydroxyl group and an isocyanate group.

When synthesizing a urethane resin, an acrylic epoxy ester modified raw material may be used as the diol compound. Although chloride ion impurities are mixed in, they can be used from the viewpoint of controlling the amount of chloride ion impurities.

Since the photosensitive resin containing a carboxyl group as described above has a large number of carboxyl groups in a skeleton and a polymer side chain, it can be developed with an alkaline aqueous solution.

The acid value of the photosensitive resin containing a carboxyl group is preferably 40 to 150 mgKOH / g. When the acid value of the photosensitive resin containing a carboxyl group is 40 mgKOH / g or more, alkali development becomes favorable. In addition, by setting the acid value to 150 mgKOH / g or less, a normal resist pattern can be easily drawn. More preferably, it is 50 to 130 mgKOH / g.

Although the weight average molecular weight of the photosensitive resin containing a carboxyl group varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, non-stick performance or resolution can be improved. In addition, by setting the weight average molecular weight to 150,000 or less, developability and storage stability can be improved. More preferably, it is 5,000 to 100,000.

The blending amount of the photosensitive resin containing a carboxyl group is preferably 20 to 60% by mass based on the solid content. When it is 20% by mass or more, the coating film strength can be improved. Moreover, when it is 60% by mass or less, the viscosity becomes appropriate and the workability improves. More preferably, it is 30 to 50% by mass.

Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, and carbonates (methyl ) Acrylate, (meth) acrylate epoxy, and the like. Specific examples include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Diacrylates; N, N-dimethyl acrylamide, N-methyl methacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; acrylic N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, and the like; amine alkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and p-hydroxyethyl Polyisocyanates such as polyisocyanates or polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate Esters, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, Polyvalent acrylic acid esters of glycidyl ethers such as trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and the like; Polyols such as polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, polyester polyols, etc. are directly acrylated, or urethane acrylates and melamine acrylics are passed through diisocyanates An ester and at least any one of the respective methacrylates corresponding to the aforementioned acrylate are appropriately selected and used.

An acrylic epoxy resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanate may also be used. An epoxy urethane acrylate compound or the like obtained by reacting a bis-urethane compound of an isocyanate with a hydroxyl group of the acrylic epoxy resin as a photosensitive monomer. Such an acrylic epoxy resin can improve the photo-hardening property without reducing the touch dryness.

When the amount of the compound having an ethylenically unsaturated group in the molecule as a photosensitive monomer is used, when a resin containing a carboxyl group is included in the composition, the solid content is converted to 100 parts by mass of the resin containing a carboxyl group. The ratio is preferably 5 to 100 parts by mass, and more preferably 5 to 70 parts by mass. When the compounding amount of the compound having an ethylenically unsaturated group is 5 parts by mass or more, the photocurability of the photocurable resin composition is improved. In addition, by setting the blending amount to 100 parts by mass or less, the hardness of the coating film can be increased. The carboxyl group-containing resin referred to herein means any of a photosensitive resin containing a carboxyl group and a non-photosensitive resin containing a carboxyl group. That is, when any one of the compositions is blended alone, it means alone, and when it is blended, it means its total (the same applies to the following paragraphs).

In particular, when a non-photosensitive resin containing a carboxyl group having no ethylenically unsaturated double bond is used, since the composition is photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in the molecule (photosensitive Photosensitive monomers), so photosensitive monomers are effective.

Examples of the thermal crosslinking component include a thermosetting resin. As the thermosetting resin, an isocyanate compound, a blocked isocyanate compound, an amine resin, a maleimine compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, Polyfunctional oxetane compounds, episulfide resins, and the like are commonly known. Among these, a particularly preferable thermal cross-linking component is thermal cross-linking having at least any one of a plurality of cyclic ether groups and cyclic thioether groups in one molecule (hereinafter referred to as a cyclic (thio) ether group).联 组合。 Composition. These thermosetting components having a cyclic (thio) ether group are commercially available in many varieties, and various properties can be imparted depending on the structure.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a cyclic ether group having a plurality of 3, 4 or 5 member rings, or any one or two of the cyclic thioether groups For example, a compound having a plurality of epoxy groups in a molecule is a polyfunctional epoxy compound; a compound having a plurality of oxetanyl groups in a molecule is a polyfunctional oxetane compound; a molecule The compound having a plurality of thioether groups is an episulfide resin and the like.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 1050, Epiclon 2055, and Nippon Steel Co., Ltd. Epotohto YD-011, YD-013, YD-127, YD-128 manufactured by Sumitomo Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., and manufactured by Sumitomo Chemical Industry Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all trade names) made of Asahi Kasei Industrial Co., Ltd. ; JERYL903 by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 by DIC, Epotohto YDB-400, YDB-500 by Nippon Steel & Sumitomo Chemical Co., Ltd., DER542 by Dow Chemical Co., Ltd., Sumitomo Chemical Brominated epoxy resins such as Sumiepoxy ESB-400, ESB-700 manufactured by Industrial Co., Ltd., and AER711, AER714, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd .; Mitsubishi Chemical Corporation has JER152, jER154, DEN431, DEN438, Epiclon N-730, Epiclon N-770, Epiclon N-865, Nippon Steel & Sumitomo Chemical Co., Ltd. Epotohto YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, manufactured by Sumitomo Chemical Industry Co., Ltd. Sumiepoxy ESCN-195X, ESCN-220, ARECEN-235, ECN-299, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. (both trade names) novolac-type epoxy resins; Epiclon 830 manufactured by DIC Corporation, Mitsubishi Chemical Bisphenol F-type epoxy resins such as jER807 manufactured by Nippon Steel Co., Ltd., and Epotohto YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; Nippon Steel & Sumitomo Chemical Co., Ltd. Hydrogenated bisphenol A epoxy resin made by Epotohto ST-2004, ST-2007, ST-3000 (trade name), etc .; JER604 made by Mitsubishi Chemical Corporation; manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Epotohto YH-434, Sumitomo Chemical Industries, Ltd. Glycidylamine type epoxy resins such as Sumiepoxy ELM-120 (both trade names) manufactured by the company limited; alicyclic epoxy resins such as Celloxide 2021P (trade name) manufactured by Daicel Corporation; Mitsubishi Chemical Corporation YL-933 made by Dow Chemical, TEN, EPPN-501, EPPN-502 made by The Dow Chemical Company (all are trade names) trihydroxyphenylmethane type epoxy resin; YL-6056 made by Mitsubishi Chemical Corporation, YX-4000, YL-6121 (both are trade names), bixylenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., and Asahi Denka Chemical Industry Co., Ltd. Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by EPX-30 and DIC Corporation; bisphenol A novolac epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation Resins; jERYL-931 and other (trade names) tetraphenol-based ethane-type epoxy resins made by Mitsubishi Chemical Corporation; TEPIC and other (trade names) heterocyclic epoxy resins made by Nissan Chemical Industry Co., Ltd .; Phthalic acid such as Blemmer DGT made by Japan Oil Corporation Glycidyl ester resin; Tetraglycidyl xylenol ethane resin such as ZX-1063 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; ESN-190, ESN-360, and DIC Limited by Nippon Steel & Sumitomo Chemical Co., Ltd. Naphthyl-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by the company; HP-7200, HP-7200H, etc. manufactured by DIC Corporation with dicyclopentadiene skeleton, EXA -4816, EXA-4822, EXA-4850 series of soft and strong epoxy resin; CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resins manufactured by Japan Oil & Fat Co., Ltd .; Copolymerized epoxy resin and the like of hexylmaleimide and glycidyl methacrylate, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, and bis [(3-ethyl-3-oxetane Alkylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl Methyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) acrylate, methyl (3-ethyl-3-oxetan) Butyl) methyl ester, (3-methyl-3-oxetanyl) methacrylate, (3-ethyl-3-oxetanyl) methacrylate, or the Polyfunctional oxetanes such as oligomers or copolymers, oxetanol and novolac resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarene , Ethers of resins having a hydroxyl group, such as calorcinol aromatics or silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

Examples of the episulfide resin include YL7000 (bisphenol A episulfide resin) manufactured by Mitsubishi Chemical Corporation. In addition, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolak epoxy resin is replaced with a sulfur atom by a similar synthetic method can also be used.

When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a solid component The conversion is preferably in the range of 0.3 to 2.5 equivalents, and more preferably in the range of 0.5 to 2.0 equivalents with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. By setting the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule to 0.3 equivalent or more, the carboxyl group is not left in the hardened film, and heat resistance, alkali resistance, and electrical insulation properties are improved. . In addition, when the molecular weight is 2.5 equivalents or less, a cyclic (thio) ether group having a low molecular weight does not remain in the dry coating film, and the strength of the cured film is improved.

When a thermosetting component having a plurality of cyclic (thio) ether groups in a molecule is used, a thermosetting catalyst is preferably blended. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanide. Imidazole derivatives such as ethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4- (Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc. Amine compounds; hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate and the like; phosphorus compounds such as triphenylphosphine and the like. Examples of marketers include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-made by San-Apro Co., Ltd. -CAT (registered trademark) 3503N, U-CAT3502T (both trade names of dimethylamine-blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic hydrazone compounds and their salts) Wait. It is not particularly limited to these, as long as it is a thermosetting catalyst of epoxy resin or oxetane compound, or it can promote the reaction of at least one of epoxy group and oxetanyl group with carboxyl group. It can be used alone or as a mixture of two or more. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used. 2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isotricyanic acid adduct, 2,4-diamino-6-formaldehyde S-triazine derivatives such as propylene ethoxyethyl-S-triazine / isocyanuric acid adducts, etc., are preferably compounds and heat which also function as adhesiveness imparting agents. The hardening catalyst is used in combination.

When the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the blending amount of the thermosetting catalyst is calculated based on the solid content, relative to the molecule having a plurality of cyclic (sulfur) groups. The amount of the thermosetting component of the ether group is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass.

Examples of the amine-based resin include amine-based resins such as melamine derivatives and benzoguanamine derivatives. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, and a methylol urea compound. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated acetylene urea compound, and the alkoxymethylated urea compound can be obtained by changing the respective hydroxyl groups. A methyl melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, and a methylol urea compound are converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl. Particularly preferred is a melamine derivative that is mild to humans or the environment with a concentration of formalin of 0.2% or less.

Commercial products of amine resins include Cymel 300, same 301, same 303, same 370, same 325, same 327, same 701, same 266, same 267, same 238, same 1141, same 272, and 202, Same as 1156, Same as 1158, Same as 1123, Same as 1170, Same as 1174, Same as UFR65, Same as 300 (above, made by Mitsui Cyanamid Co., Ltd.), Nikalac Mx-750, Same as Mx-032, Same as Mx-270, Same as Mx-280 , Same Mx-290, same Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM , Same as Mw-750LM, (above, made by Sanwa Chemical Co., Ltd.) and so on.

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, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and o-diene Toluene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylenebis (cyclo Hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include dicycloheptane triisocyanate. Examples of the adducts, biuret and isotricyanate of the isocyanate compounds mentioned above are also listed.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is not activated for a while. When heated to a specific temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, biuret type, and adduct type. Examples of the isocyanate compound used to synthesize the blocked isocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valprolactam, and γ-butyrolactam And β-propiolactam endogenous capping agents; active methylene-based end capping agents such as ethyl acetate and ethyl acetone; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, ethylene glycol Alcohol-based capping agents such as butyl alkylate, diacetone alcohol, methyl lactate, and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, diethylfluorenyl monooxime, cyclohexyl Oxime-based capping agents such as alkoxime; thiol-based capping agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl mercaptan, and ethyl mercaptan; acetamide Acid benzylamine-based end-capping agents such as benzamidine; acetonitrile succinate and maleimide-based imine based terminals; dimethyltoluidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agent; imidazole, 2-ethylimidazole, etc. Azole-based capping agent; imine-based capping agent such as methyleneimine and propyleneimine.

The blocked isocyanate compound may also be commercially available, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, and Desmotherm 2170. Desmotherm 2265 (above, manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Japan Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B-846, B-870, B-874, B-882 (above, manufactured by Mitsui Takeda Chemical Co., Ltd., trade names), TPA-B80E, 17B-60PX, E402-B80T ( Above, manufactured by Asahi Kasei Chemical Co., Ltd., trade name). In addition, Sumidur BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a capping agent.

In order to promote the hardening reaction between the hydroxyl group or the carboxyl group and the isocyanate group, a urethane-forming catalyst may be added to the photosensitive resin composition. The urethane catalyst is preferably an amino formic acid selected from at least one of a tin-based catalyst, a metal chloride, a metal acetone acetone salt, a metal sulfate salt, an amine compound, and an amine salt. Esterification catalyst.

Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds. Examples of the metal chloride include chlorides of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include cobalt (III) chloride, nickel (II) chloride, and chloride. Iron (III), etc. Examples of the metal acetoacetone salt include acetoacetone salts of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as cobalt acetoacetone, nickel acetoacetone, and acetone. Iron acetone etc. Furthermore, examples of the metal sulfate include sulfates of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, and bis (2-dimethylaminoethyl) ether. , N, N, N ', N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinyl di Ethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N '-(2-hydroxyethyl) -N, N, N'-trimethylphosphonium bis (2-aminoethyl) ) Ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N '-(2-hydroxyethyl) ethyl Diamine, N- (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N "-tetramethyldiethylenetriamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl ) Piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanolamine, 2-aminoquinine ring, 3-amine Quinine ring, 4-aminoquinine ring, 2-quinol, 3-quinol, 4-quinol, 1- (2'-hydroxypropyl) imidazole, 1- (2'-hydroxy Propyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'- Ethyl) -2-methylimidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- (3'-aminopropyl) ) -2-methylimidazole, 1- (3'-hydroxypropyl) imidazole, 1- (3'-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl- N '-(2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N', N'-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl -N ', N'-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N', N'-bis (2-hydroxyethyl) amine, N, N- At least any one of dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine, and benzoguanamine, and the like.

Examples of the amine salt include organic acid salt-based amine salts such as DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

[Filler] As the filler, well-known and commonly used inorganic or organic fillers can be used. Particularly preferred are barium sulfate, spherical silica, titanium oxide, Newcastle silica particles and talc. Further, for the purpose of imparting flame resistance, aluminum hydroxide, magnesium hydroxide, gibbsite, or the like may be used. Furthermore, it can also be used in a compound of one or more ethylenically unsaturated groups, or NANOCRYL (trade name) manufactured by Hanse-Chemie Co., Ltd., where nano silica is dispersed in the polyfunctional epoxy resin. XP 0396, XP 0596 , XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names), or NANOPOX (trade name) manufactured by Hanse-Chemie Corporation XP 0516, XP 0525, XP 0314 ( (Both product grade names). These may be used alone or in combination of two or more. By including a filler, the physical strength etc. of the hardened | cured material obtained can be improved.

When the resin containing a carboxyl group is contained in the composition, the blending amount of the filler is, in terms of solid content, preferably 500 parts by mass or less, and more preferably 0.1 to 300 parts by mass relative to 100 parts by mass of the resin containing a carboxyl group. And particularly good for 0.1 to 150 parts by mass. When the blending amount of the filler is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition does not become too high, the printability is good, and the cured product is not easily brittle.

[Photopolymerization initiator] 中 In the present invention, known photopolymerization initiators for photopolymerizing the above-mentioned photosensitive resin containing a carboxyl group can be used. Among them, an oxime ester system having an oxime ester group is particularly used for photopolymerization. Initiators, α-aminoacetophenone-based photopolymerization initiators, and fluorenylphosphine oxide-based photopolymerization initiators are preferred. The photopolymerization initiator may be used singly or in combination of two or more kinds.

The commercially available oxime ester-based photopolymerization initiators include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, ADEKA Corporation N-1919, Adeka Arkls (registered trademark) manufactured by BASF JAPAN. Trademark) NCI-831, etc.

In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (I) can be used. (Wherein X ₁ represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (via an alkyl group having 1 to 17 carbon atoms and 1 to 8 carbon atoms) Alkoxy, amine, alkylamino or dialkylamino substituted with an alkyl group having 1 to 8 carbon atoms), naphthyl (using an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms) (Alkoxy, amine, alkylamino or dialkylamino substituted with an alkyl group having 1 to 8 carbons), Y ₁ and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbons, and carbon Alkoxy, halo, phenyl, and phenyl groups with 1 to 8 carbon atoms (via alkyl groups with 1 to 17 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, amine groups, and alkyl groups with 1 to 8 carbon atoms Substituted with alkylamino or dialkylamino), naphthyl (via an alkyl group with 1 to 17 carbon atoms, alkoxy group with 1 to 8 carbon atoms, amine group, and an alkyl group with 1 to 8 carbon atoms Alkylamino or dialkylamino substituted), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylidene, vinylidene, vinylidene Biphenyl, pyridyl, naphthyl, thiophene, anthracenyl, thienyl, furfuryl, 2,5-pyrrole-diyl, 4,4'-stilbyl-diyl, 4,2 '-Styrene-diyl, n is 0 Integers 1).

In the above formula, X ₁ and Y ₁ are methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthyl, thiophene, or thiophene oxime ester. Department of photopolymerization initiator.

Preferable carbazoxime ester compounds include compounds which can be represented by the following general formula (II).

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R ₄ represents an alkyl group having 1 to 4 carbon atoms. An alkyl group, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by an alkyl group or alkoxy group having 1 to 4 carbon atoms. R ₅ means that it may be bonded via an oxygen atom or a sulfur atom and may be A benzyl group substituted by a phenyl substituted alkyl group having 1 to 20 carbon atoms and an alkoxy group substituted with 1 to 4 carbon atoms. R ₆ represents a nitro group or a fluorenyl group represented by X ₂ -C (= O)-. X ₂ represents an aryl group, a thienyl group, a morpholinyl group, a phenylthio group, or a structure represented by the following formula (III) which may be substituted with an alkyl group having 1 to 4 carbon atoms;

Other examples include Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, Japanese Patent Laid-Open No. 2008-094770, and Japan The carbazoxime ester compounds described in Japanese Patent Application Publication No. 2008-509967, Japanese Patent Application Publication No. 2009-040762, and Japanese Patent Application Publication No. 2011-80036.

When the oxime ester-based photopolymerization initiator is used, when a resin containing a carboxyl group is included in the composition, it is preferably 0.01 to 5 mass based on 100 parts by mass of the resin containing a carboxyl group. Serving. When it is 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film properties such as chemical resistance are improved. Moreover, when it is 5 parts by mass or less, the light absorption on the surface of the coating film is suppressed, and the hardenability at the deep part tends to be improved. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of resin containing a carboxyl group.

α-aminoacetophenone-based photopolymerization initiator, and specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylacetone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -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 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.

A fluorenylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzyl) (Fluorenyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Omnirad TPO, Omnirad 819, and the like manufactured by IGM Resins.

As the photopolymerization initiator, JMT-784 manufactured by Yueyang Kimoutain Sci-tech Co., Ltd. can also be suitably used.

When a photopolymerization initiator other than the oxime ester-based photopolymerization initiator is used, when a resin containing a carboxyl group is contained in the composition, the solid content is converted to 100 parts by mass of the resin containing a carboxyl group. It is preferably 0.01 to 15 parts by mass. When it is 0.01 parts by mass or more, the photocurability on copper becomes more reliable, and the coating film properties such as chemical resistance are improved. Moreover, when it is 15 parts by mass or less, a sufficient effect of reducing outgassing can be obtained, light absorption on the surface of the cured film is further suppressed, and hardenability in the deep portion is also improved. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of resin containing a carboxyl group.

A photoinitiator or a sensitizer may be used in combination with the photopolymerization initiator. Photoinitiators or sensitizers include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds Wait. These compounds may be used as a photopolymerization initiator, but they are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone and the like. Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone. Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Wait. Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Further, examples of the benzophenone compound include benzophenone, 4-benzylfluorenyldiphenyl sulfide, 4-benzylfluorenyl-4'-methyldiphenylsulfide, and 4-benzene Formamyl-4'-ethyldiphenylsulfide, 4-benzyl-4'-propyldiphenylsulfide, and the like.

Examples of tertiary amine compounds include ethanolamine compounds and compounds having a dialkylaminobenzene structure. Examples of commercially available products include 4,4'-dimethylaminobenzophenone (Nisso, manufactured by Soda Co., Ltd., Japan). Cure (registered trademark) (MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Industry Co., Ltd.), and 7- (diethyl Diamino group) 4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthetics) Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Japanese version) Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl ester (Esolol 507, manufactured by Van Dyk), and the like. A tertiary amine compound, preferably a compound having a dialkylaminobenzene structure. Among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin with a maximum absorption wavelength of 350 to 450nm Particularly preferred are vegetal compounds and ketocoumarins.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. Since the coumarin compound containing a dialkylamine group has a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, it is of course a light-colored, colorless and transparent photosensitive resin composition, and a coloring pigment can be used to reflect the coloring pigment. Color-sensitive photosensitive film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

Among these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by containing a thioxanthone compound, deep hardenability can be improved.

When a carboxyl group-containing resin is included in the composition, the total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is, in terms of solid content, more preferably 100 parts by mass of the carboxyl group-containing resin. 35 parts by mass or less. By being 35 parts by mass or less, such light absorption is suppressed, and the hardenability at the deep portion is also improved.

In addition, these photopolymerization initiators, photostarters, and sensitizers may have low sensitivity depending on the specific wavelength due to absorption of specific wavelengths, and function as ultraviolet absorbers. However, these are not only used for the purpose of improving the sensitivity of the composition. It can absorb light of specific wavelength according to the need, improve the light reactivity of the surface, make the line shape and opening of the resist become vertical, tapered, reverse tapered, and improve the processing precision of line width or opening diameter.

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

The photosensitive resin composition may suitably contain a block copolymer. A block copolymer refers to a copolymer of two or more polymers having different properties and linked by a covalent bond to form a long-chain molecular structure. It is preferably a solid in a range of 20 ° C to 30 ° C. As long as it is solid within this range, it can be solid at temperatures outside this range. Since the above-mentioned temperature range is solid, the adhesiveness is excellent when it becomes a photosensitive film or when it is applied to a layer containing inorganic particles and temporarily dried.

The block copolymer is preferably an XYX or XYX 'type block copolymer. Among XYX or XYX'-type block copolymers, Y in the center is a soft block, and the glass transition point Tg is low, preferably less than 0 ° C. Both outer X or X 'are hard blocks, and Tg is high, preferably A polymer unit having a temperature of 0 ° C or higher is preferred. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Among the XYX or XYX 'type block copolymers, it is more preferable that the copolymers are formed by polymer units having a Tg of X or X' being 50 ° C or higher, and polymer units having a Tg of Y or lower than -20 ° C. Paragraph copolymer. Among the XYX or XYX 'type block copolymers, X or X' is preferably one having high compatibility with a carboxyl group-containing resin, and Y is preferably one having low compatibility with a carboxyl group-containing resin. In this way, it can be considered that by becoming a block copolymer in which the blocks at both ends are compatible with the matrix, and the block at the center is incompatible with the matrix, it is easy to show a specific structure in the matrix.

The block copolymer is not limited to the XYX or XYX 'type, and may be used without particular limitation as long as the hard block and soft block components each have at least one type.

As the X or X ′ component, polymethyl methacrylate (PMMA), polystyrene (PS), and the like are preferable, and as the Y component, poly n-butyl acrylate (PBA) and polybutadiene ( PB) and so on. In addition, a resin having a carboxyl group such as a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy group-containing unit, an N-substituted acrylamide unit, or the like may be introduced into a part of the X or X 'component A hydrophilic unit with excellent compatibility further improves compatibility. The present inventors have found that the block copolymer obtained in this way has particularly good compatibility with the carboxyl group-containing resin described above. Surprisingly, it can improve the resistance to cold and heat shock, and more surprisingly, an elastomer is added. On the other hand, the glass transition temperature (Tg) tends to decrease. On the other hand, in the case where the block copolymer is added, the Tg does not decrease.

Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application No. 2005-515281 and Japanese Patent Application No. 2007-516326. Examples of commercially available block copolymers include acrylic triblock copolymers produced by living polymerization by Arkema. Examples include SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and further MAM N type or MAM A type treated with carboxylic acid or hydrophilic group. Examples of the SBM type include E41, E40, E21, E20, etc., examples of the MAM type include M51, M52, M53, M22, etc., examples of the MAM N type include 52N, 22N, and types of the MAM A type include SM4032XM10. In addition, Kurarity manufactured by Kuraray Co., Ltd. is a block copolymer derived from methyl methacrylate and butyl acrylate.

The block copolymer is preferably a ternary block copolymer or more. In order to obtain the effect of the present invention, it is more preferable that the molecular structure synthesized by the living polymerization method is a precisely controlled block copolymer. This is considered to be because the molecular weight distribution of the block copolymer synthesized by the living polymerization method is narrow, and the unit characteristics of each block become clear. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, and more preferably 2.0 or less.

The weight average molecular weight of the block copolymer is generally from 20,000 to 400,000, and more preferably from 30,000 to 300,000. When the weight-average molecular weight is less than 20,000, the intended effects of toughness and flexibility are not obtained, and the adhesiveness is also poor. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition becomes high, and printability and developability are significantly deteriorated.

When the blending amount of the block copolymer includes a resin containing a carboxyl group in the composition, it is preferably 1 to 50 parts by mass, more preferably 5 to 100 parts by mass of the resin containing a carboxyl group. ~ 35 parts by mass. The effect is expected to be 1 part by mass or more, and 50 parts by mass or less is good in developability or coatability as a photocurable resin composition.

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

Red colorants are monoazo, diazo, azo lake, benzimidazolone, hydrazone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include those with a color index (CI; issued by The Society of Dyers and Colourists) as follows.

Monoazo-based red colorants include 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, etc. Examples of the disazo red colorant include Pigment Red 37, 38, and 41. Examples of the monoazo lake-based red colorant include 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, and so on. Examples of the benzimidazolone red colorant include Pigment Red 171, 175, 176, 185, and 208. Examples of the actinic red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. The diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of the condensed azo-based red colorant include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of the anthraquinone-based red colorants include Pigment Red 168, 177, and 216, Solvent Red 149, 150, 52, and 207. Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, and 209.

Blue colorants are phthalocyanine and anthraquinone. Pigments include compounds classified as pigments. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. For example, anthraquinone-based yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. Isoindolinone-based yellow colorants include Pigment Yellow 110, 109, 139, 179, 185, and the like. Examples of the condensed azo-based yellow colorant include Pigment Yellow 93, 94, 95, 128, 155, 166, 180, and the like. Examples of benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of the monoazo yellow colorant include 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, etc. Examples of the disazo yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and so on.

In addition, you can add purple, orange, brown, black, white and other coloring agents. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32; Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CIPigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61 , 63, 64, 71, 73; Pigment Brown 23, 25; titanium oxide, carbon black, etc.

The blending amount of the colorant is not particularly limited. When a resin containing a carboxyl group is contained in the composition, it is preferably 10 parts by mass or less, more preferably 0.1, based on 100 parts by mass of the resin containing a carboxyl group. ~ 7 parts by mass. However, the blending amount of the white colorant such as titanium oxide is in terms of solid content, and is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, more based on 100 parts by mass of the carboxyl group-containing resin. It is preferably 3 to 80 parts by mass.

In addition, an elastomer can be blended into the photosensitive resin composition for the purpose of imparting flexibility to the obtained cured product, improving the brittleness of the cured product, and the like. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester polyurethane elastomers, polyamide elastomers, polyester elastomers, and acrylic elastomers. Body, olefin-based elastomer. In addition, a resin obtained by modifying a part or all of epoxy groups of epoxy resins having various skeletons with both terminal carboxylic acid-modified butadiene-acrylonitrile rubbers and the like can also be used. Furthermore, a polybutadiene-based elastomer containing an epoxy group, a polybutadiene-based elastomer containing acrylic, a polybutadiene-based elastomer containing a hydroxyl group, and isoprene containing a hydroxyl group can also be used. Department of elastomers and so on. The elastomer may be used singly or as a mixture of two or more kinds.

Moreover, conventionally well-known adhesive polymers can be used for the purpose of improving the flexibility and touch-drying property of the obtained hardened | cured material. The binder polymer is preferably a cellulose-based, polyester-based, or phenoxy resin-based polymer. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman. The polyester polymer is preferably Vylon manufactured by Toyobo Co., Ltd. In the series, the phenoxy resin-based polymer is preferably a phenoxy resin of bisphenol A, bisphenol F, and hydrogenated compounds thereof.

When a carboxyl group-containing resin is contained in the composition, the blending amount of the binder polymer is, in terms of solid content, preferably 50 parts by mass or less, more preferably 1 to 100 parts by mass of the carboxyl group-containing resin. 30 parts by mass, and particularly preferably 5 to 30 parts by mass. When the blending amount of the binder polymer is 50 parts by mass or less, the alkali-developability of the photosensitive resin composition is more excellent, and the development time can be lengthened.

Moreover, the photosensitive resin composition can further mix components, such as an adhesion promoter, an antioxidant, an ultraviolet absorber, as needed. These can be used in well-known fields in the field of electronic materials. In addition, it is possible to blend well-known and commonly used thickening agents such as fine powdered silica, hydrotalcite, organic bentonite, montmorillonite, etc .; polyfoam-based, fluorine-based, polymer-based antifoaming agents and leveling agents. At least any one of them; at least any one of well-known and commonly used additives such as imidazole-based, thiazole-based, triazole-based silane coupling agents, and rust inhibitors and fluorescent brighteners.

The photosensitive film can be formed by coating the photosensitive resin composition on one side of a layer containing inorganic particles and drying the photosensitive resin composition. Considering the applicability of the photosensitive resin composition, the photosensitive resin composition can be diluted with an organic solvent and adjusted to a suitable viscosity. The notch wheel applicator, doctor blade applicator, lip applicator, and rod coating can be used. A cloth applicator, squeeze applicator, reverse applicator, transfer roll applicator, gravure applicator, spray applicator, etc. are applied to one side of the layer containing the inorganic particles to a uniform thickness. Dry at 50 ~ 130 ℃ for 1 ~ 30 minutes to volatilize the organic solvent, and obtain a non-stick coating film. The coating film thickness is not particularly limited. Generally speaking, it is appropriately selected in a range of 5 to 150 μm, preferably 10 to 60 μm, based on the film thickness after drying.

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, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Kisangsu, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Propylene glycol butyl ether acetate and other esters; alcohols, propanol, ethylene glycol, propylene glycol and other alcohols; aliphatic hydrocarbons such as octane, decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvents Petroleum solvents such as petroleum brain. Such organic solvents may be used alone or as a mixture of two or more.

Volatile drying of organic solvents, such as hot air circulation drying furnace, IR furnace, heating plate, convection oven, etc. Support blowing method).

[Protective film] The photosensitive film laminate of the present invention can provide a protective film on the surface of the photosensitive film opposite to the intermediate layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving the operability.

The protective film can be, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. It is preferred that the adhesion force between the protective film and the photosensitive film is less than that of the layer containing inorganic particles and A material for the adhesion of photosensitive films. When the photosensitive film laminate is used, in order to facilitate peeling of the protective film, the surface of the protective film adjacent to the photosensitive film may be subjected to the release treatment as described above.

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

<The manufacturing method of a hardened | cured material and a printed wiring board> 硬化 A hardened | cured material is formed using the photosensitive film laminated body of this invention. A method for forming the cured product and a method for producing a printed wiring board including the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. A method of manufacturing a printed wiring board using a photosensitive film laminate having a protective film will be described as an example. First, i) the protective film is peeled from the photosensitive film laminate to expose the photosensitive film, ii) the photosensitive film of the photosensitive film laminate is bonded to the substrate on which the circuit pattern is formed, and iii ) Exposure is performed on the layer containing inorganic particles of the aforementioned photosensitive film laminate, iv) the layer containing inorganic particles is peeled off from the aforementioned photosensitive film laminate, and development is performed to form patterned photosensitive on the substrate (V) The aforementioned patterned photosensitive film is cured by light irradiation or heat to form a cured film; thereby forming a printed wiring board. In addition, when a photosensitive film laminate without a protective film is used, the peeling step (i step) of the protective film is of course not required. Each step is described below.

First, the protective film is peeled off from the photosensitive film laminate, the photosensitive film is exposed, and the photosensitive film of the photosensitive film laminate is bonded to a substrate on which a circuit pattern is formed. Examples of the substrate on which the circuit pattern is formed include a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance. In addition, the use of paper phenol, epoxy paper, glass cloth epoxy resin, glass polyimide, Glass cloth / non-woven epoxy resin, glass cloth / epoxy paper, synthetic fiber epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene ether / cyanate, etc. The materials are copper-clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer boards, etc.

If the photosensitive film of the photosensitive film laminate is to be bonded to a circuit board, it is preferable to use a vacuum laminator or the like, and to bond them under pressure and heating. By using such a vacuum laminator, the photosensitive film is closely adhered to the circuit substrate, so that no bubbles are mixed in, and the hole filling property to the substrate surface is also improved. The pressing conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120 ° C.

Next, exposure is performed on the layer containing the inorganic particles of the photosensitive film laminate (irradiation with active energy rays). With this step, only the exposed photosensitive resin layer is hardened. The exposure step is not particularly limited. For example, the contact (or non-contact) method can be used to selectively expose the active energy rays by forming a photomask with a desired pattern. It is desired that the pattern is exposed with active energy rays.

The exposure machine used for active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, etc., which irradiates ultraviolet rays in the range of 350 to 450 nm. Further, a direct drawing device (such as from a computer The CAD data is a laser direct imaging device that directly depicts the image with a laser). As long as the laser light source of the direct scan machine uses laser light with a maximum wavelength in the range of 350 to 410 nm, gas lasers and solid lasers can be used. Although the amount of exposure used to form an image varies depending on the film thickness, etc., it can generally be in the range of 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

After the exposure, the layer containing the inorganic particles is peeled off from the photosensitive film laminate and developed, so that a patterned photosensitive film is formed on the substrate. When the layer containing inorganic particles is peeled off, the surface of the photosensitive film hardened by exposure is given the form of the surface of the layer containing inorganic particles. In addition, as long as the characteristics are not impaired, the layer containing the inorganic particles may be peeled off from the photosensitive film laminate before exposure, and the exposed photosensitive film may be exposed and developed.

The developing step is not particularly limited, and a dipping method, a spray method, a spray method, a brush method, or the like can be used. As the developing solution, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines 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 step is called formal hardening or additional hardening, which can promote the polymerization of unreacted monomers in the photosensitive film, and then thermally harden the photosensitive resin containing carboxyl group and epoxy resin to reduce the amount of remaining carboxyl group. The active energy ray irradiation can be performed in the same manner as the above-mentioned exposure, but it is preferably performed under conditions that are stronger than the irradiation energy during exposure. For example, it may be 500 to 3000 mJ / cm ² . In addition, heat curing can be performed under heating conditions of 100 to 200 ° C. for about 20 to 90 minutes. It is to be noted that the hardening is preferably performed after the light hardening. By performing light hardening first, the resin flow is also suppressed during heat hardening, and it is possible to maintain the surface given the shape.

The photosensitive film laminate of the present invention can be suitably used as a printed wiring board, can be more suitably used for the formation of a solder resist layer, and can be particularly suitably used for the formation of a solder resist layer for IC packaging. Examples

Examples are given next to explain the present invention in more detail, but the present invention is not limited to these examples.

<Preparation of carboxyl group-containing photosensitive resin> A novolac-type cresol resin (Shonol CRG951 manufactured by Showa Denko Corporation, OH equivalent: 119.4) 119.4 g, 1.19 g of potassium hydroxide, and 119.4 g of toluene. The nitrogen in the system was replaced while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. Propane reaction solution. The obtained novolac-type cresol resin was obtained by adding an average of 1.08 mole alkylene oxide per equivalent of phenolic hydroxyl group.

293.0 g of the alkylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were fed into a container equipped with a stirrer, a thermometer, and an air blowing tube. In the reactor, air was blown in at a rate of 10 ml / minute, and the reaction was carried out at 110 ° C. for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene, and 12.6 g of water was distilled off. After that, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% sodium hydroxide aqueous solution, followed by washing with water. Thereafter, toluene was replaced with 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown in at a rate of 10 ml / minute while stirring. While slowly adding 62.3 g of tetrahydrophthalic anhydride and reacting at 95 to 101 ° C. for 6 hours, a photosensitive resin paint 1 containing a carboxyl group with an acid value of 88 mgKOH / g as a non-volatile component and 71% was obtained.

<Preparation of photosensitive resin composition> The photosensitive resin containing a carboxyl group obtained as described above is painted 1. Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a photosensitive monomer of an acrylate compound. KAYARAD DPHA), bisphenol A epoxy resin (EPICLON840-S, manufactured by DIC Corporation) as a thermosetting epoxy resin, and biphenol novolak epoxy resin (NC-made by Nippon Kayaku Co., Ltd.) 3000H), as a photopolymerization initiator, Omnirad TPO manufactured by IGM Resins, or IRGACURE OXE02 manufactured by BASF JAPAN, barium sulfate as a filler (B-30 manufactured by Sakai Chemical Industry Co., Ltd.), and / or spherical silica ( Admafine SO-E2, manufactured by Admatechs Co., Ltd.), melamine as a thermosetting catalyst, carbon black M-50 manufactured by Mitsubishi Chemical Co., Ltd., dioxazine violet CIPigment Violet 23, CIPigment Yellow 147, Each component selected in CIPigment Blue 15: 3 and CIPigment Red 177, and diethylene glycol monoethyl ether acetate as an organic solvent are used in a ratio (mass ratio) shown in Table 1 below. ) Blended in a mixer after preliminary mixing, kneading with a triple roll mill to prepare a photosensitive resin composition 1 and 2.

＜ Production of layer 1 containing inorganic particles ＞ Amidir G-821-60 (iso-butylated melamine resin, solid content 60%) manufactured by DIC Corporation and ACRYDIC A-405 (for melamine roasting) manufactured by DIC Corporation (Acrylic resin, solid content 50%), blended in a mass ratio of 25:75 in terms of solid content, blended with a stirrer, and the obtained acrylic melamine resin was diluted with methyl ethyl ketone to adjust the solid content concentration. 35 mass% resin solution. According to the thickness of the coating film, methyl ethyl ketone was further added to the resin solution to an appropriate solid content concentration, and then a polysiloxane resin (SYMACUS-270 manufactured by Toa Synthesis Co., Ltd.) was added and the average primary particle diameter was 0.1 μm of silicon dioxide, so that each mass ratio of acrylic melamine resin, polysiloxane resin and silicon dioxide becomes 59.7: 0.3: 40, and fully stirred at room temperature to obtain a uniform coating solution. This coating solution was applied to one side of a polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm by a gravure roll method, and dried at 130 ° C. for 20 seconds. An intermediate layer is formed on the polyethylene terephthalate film, and the inorganic particle-containing layer 1 is produced by a combination of the polyethylene terephthalate film and the intermediate layer. The thickness of the entire inorganic particle-containing layer was 28 μm.

<Production of Inorganic Particle-containing Layer 2> In the production of Inorganic Particle-containing Layer 1, except that silicon dioxide having an average primary particle diameter of 1 μm is used, and the entire thickness of the inorganic particle-containing layer is 30 μm, it is the same as above A layer 2 containing inorganic particles is produced in situ.

<Production of layer 3 containing inorganic particles> 制作 In the production of layer 1 containing inorganic particles, in addition to using silica with an average primary particle size of 10 μm to remove particles of 15 μm or more by classification, the inorganic particle-containing layer is used. The entire thickness was 43 μm, and the layer 3 containing the inorganic particles was prepared in the same manner as described above.

<Production of Inorganic Particle-Containing Layer 4> (1) Polyethylene terephthalate and polyethylene terephthalate containing 1.0% by mass of silicon dioxide having an average primary particle diameter of 1 µm were dried at 170 ° C, respectively. Next, the two were fed to a two-axis extruder, melted at 290 ° C, and coextruded from a T die to form a film to obtain an unstretched film. The obtained unstretched film was biaxially stretched to obtain a layer 4 containing inorganic particles having a thickness of 25 μm.

<Confirmation of Inorganic Particle Dispersion State of Inorganic Particle-Containing Layer> For the inorganic particle-containing layers 1 to 4 obtained as described above, the content ratio of the inorganic particles in the thickness direction was evaluated as follows. First, the inorganic particle-containing layer prepared as described above was cut to a size of about 1 × 1 cm square. Next, Pt is vapor-deposited on the front and back surfaces of the layer containing the inorganic particles, so that the interface of the layer containing the inorganic particles can be identified during observation. Thereafter, the resin was embedded by cold-embedding resin (No. 105 manufactured by Marumoto Struers Co., Ltd.) to prepare samples, and SiC abrasive paper (manufactured by Marumoto Struers Co., Ltd.) and a grinder (HERZOG Japan Co., Ltd.) were used. FORCIPOL-2V), grinding the cross section of the layer containing inorganic particles. Furthermore, using a polishing cloth (MD-Cloths Chem, manufactured by Marumoto Struers Co., Ltd.) and a polishing agent (DP-Spray P, 3 μm and 1 μm, manufactured by Marumoto Struers Co., Ltd.), the cross section of the layer containing inorganic particles was ground to JISB0601 : 2001 arithmetic mean thickness Ra <0.01 μm. Finally, Pt was evaporated on the polished observation surface to prepare a sample for confirming the dispersed state of the inorganic particles.

Next, the observation method of a sample is demonstrated. The observation of the sample was performed with an SEM (scanning electron microscope, JSM-7600F, manufactured by Japan Electronics Co., Ltd.) equipped with an EDS (energy dispersive X-ray spectroscope, JFD-2300, manufactured by Japan Electronics Co., Ltd.). The SEM was observed with an acceleration voltage of 20 kV, a measurement magnification of 2000 times, and a COMPO image (reflected electron composition image). First, the SEM was operated to confirm the dispersed state of the inorganic particle-containing layer between Pt vapor deposition on the front and back surfaces, and an image of the inorganic particle-containing layer was read. In EDS, start continuous analysis and specify the analysis area. The analysis area is set on the read image, from the surface of the layer containing the inorganic particles to a region of 0 to 50% in the thickness direction (that is, the area from the surface to T / 2 when the thickness of the cross section is T). Whole surface. After that, start elemental analysis and collect the spectrum. After the spectrum is collected, a qualitative analysis is selected to confirm the components of the inorganic particles contained in the layer containing the inorganic particles. Further, a quantitative analysis is selected to obtain the content of the inorganic particles contained in the inorganic particle-containing layer as a mass% value. Similarly, an elemental analysis is also performed on a region from 50 to 100% of the thickness direction from the surface of the layer containing the inorganic particles (that is, a region from T / 2 to T when the thickness of the cross section is T). Qualitative and quantitative. Finally, the content of the inorganic particles in the two observed regions is compared to determine the surface with a higher content of inorganic particles in the layer containing the inorganic particles.

Example 1 <Production of photosensitive film laminate> 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above, diluted, and stirred with a stirrer for 15 minutes to obtain a coating solution. The coating liquid was applied on the surface containing the inorganic particles in the layer 1 containing a higher proportion of inorganic particles, and dried at 80 ° C for 15 minutes. The layer containing the inorganic particles was used as a support film, and a thickness of 20 μm was formed thereon. Photosensitive film. Next, a 18 μm-thick polypropylene film (OPP-FOA manufactured by Futaura Chemical Co., Ltd.) was bonded to the photosensitive film to prepare a photosensitive film laminate. In this case, when the thickness of the layer 1 containing the inorganic particles is T (μm), the surface of the layer containing the inorganic particles on the side adjacent to the photosensitive film in the thickness direction is up to T / 2 (μm). The ratio α of the inorganic particles and the ratio β of the inorganic particles contained in the surface on the opposite side to the side adjacent to the photosensitive film up to T / 2 (μm) satisfy α> β.

＜ Production of test substrate ＞ FRThe surface of FR-4 copper-clad laminate (100mm × 150mm × 0.8mmt, both sides of copper foil, and thickness of both sides of copper foil are both 18μm) was chemically polished with CZ8101 manufactured by MEC Co., Ltd. The chemically polished surface was bonded to the exposed surface of the photosensitive film from which the polypropylene film was peeled from the photosensitive film laminate obtained as described above, and then a vacuum laminator (MVLP manufactured by Meiki Seisakusho Co., Ltd.) was used. -500) Heating and laminating under the conditions of pressure: 0.8Mpa, 70 ° C, 1 minute, and vacuum: 133.3Pa, so that the substrate and the photosensitive film are in close contact.

Next, using a parallel light exposure device equipped with a short-arc high-pressure mercury lamp, through the exposure mask, from the side of the polyethylene terephthalate film containing a layer containing inorganic particles, the visual recognition of the damage described later and the resistance For the drop evaluation of the hammer, uniform exposure was performed, and for the resolution evaluation, exposure was performed using a negative pattern designed as SRO 80 μm, and then the layer containing inorganic particles was peeled off to expose the photosensitive film. It should be noted that the exposure amount is a 7-segment exposure amount when a 41-segment Stouffer is used for the layer containing the inorganic particles adjacent to the photosensitive film. Then, the exposed surface of the exposed photosensitive film was developed using a 1% by weight Na ₂ CO ₃ aqueous solution at 30 ° C. and a spray pressure of 2 kg / cm ² for 60 seconds to perform patterning. Next, in a UV conveyor belt furnace equipped with a high-pressure mercury lamp, the patterned photosensitive film was irradiated with an exposure amount of 1 J / cm ² , and then heated at 160 ° C. for 60 minutes to perform additional hardening to form a hardened film, and produced it on a substrate. A test substrate 1 having a cured film formed thereon.

Example 2 中 In Example 1, a test substrate 2 was produced in the same manner as in Example 1 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

Example 3 中 In Example 1, a test substrate 3 was produced in the same manner as in Example 1, except that the layer 2 containing inorganic particles was used instead of the layer 1 containing inorganic particles.

Example 4: In Example 3, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 4 was produced in the same manner as in Example 3.

Example 5 中 In Example 1, a test substrate 5 was produced in the same manner as in Example 1 except that the layer 3 containing inorganic particles was used instead of the layer 1 containing inorganic particles.

Example 6: In Example 5, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 6 was produced in the same manner as in Example 5.

Example 7 中 In Example 1, a test substrate 7 was produced in the same manner as in Example 1 except that the layer 4 containing inorganic particles was used instead of the layer 1 containing inorganic particles.

Example 8: In Example 7, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 8 was produced in the same manner as in Example 7.

Comparative Example 1 In Example 1, a test was made in the same manner as in Example 1 except that the surface on which the coating liquid was applied to the layer 1 containing the inorganic particles was the opposite side (the surface with a lower proportion of inorganic particles). Substrate 9.

Comparative Example 2 In Comparative Example 1, a test substrate 10 was produced in the same manner as in Comparative Example 1 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

Comparative Example 3 中 In Example 3, a test was made in the same manner as in Example 3 except that the surface on which the coating liquid was applied to the layer 2 containing the inorganic particles was the opposite surface (the surface with a lower content of inorganic particles). Substrate 11.

Comparative Example 4: In Comparative Example 3, a test substrate 12 was produced in the same manner as in Comparative Example 3, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

Comparative Example 5: In Example 5, a test was made in the same manner as in Example 5 except that the surface on which the coating liquid was applied to the layer 3 containing the inorganic particles was the opposite surface (the surface with a lower content of inorganic particles). Substrate 13.

Comparative Example 6 In Comparative Example 5, a test substrate 14 was produced in the same manner as in Comparative Example 5 except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

Comparative Example 7 In Example 7, the test was made in the same manner as in Example 7 except that the surface on which the coating liquid was applied to the layer 4 containing the inorganic particles was the opposite surface (the surface with a lower proportion of inorganic particles). Substrate 15.

Comparative Example 8: In Comparative Example 7, except that the photosensitive resin composition 2 was used instead of the photosensitive resin composition 1, a test substrate 16 was produced in the same manner as in Comparative Example 7.

<Resolution Evaluation> 性 The openings having an opening diameter of 80 μm of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 8 produced as described above were observed with a SEM (scanning electron microscope), and evaluated by the following criteria. ○: Vignette and undercut were not generated, and a good opening shape was obtained. ×: Vignette or undercut was generated, and a good opening shape was not obtained. The evaluation results are shown in Table 2 below.

<Evaluation of visual recognition of damage> (1) As a method for easily confirming the improvement of the yield in the visual inspection of the hardened film, the visual recognition of damage is evaluated as follows. On the surface of the hardened film of the exposed areas of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 8 produced as described above, a pencil lead having a hardness of 2H was pressed at an angle of 45 ° and a load of 4.9 N was applied. , Move 1cm at a speed of 1mm for 1 second, and change the location 3 times. The visual recognition of the damage on the surface of the hardened film was evaluated visually. The evaluation criteria are as follows. ：: No damage was observed on the surface of the hardened film in the exposed area three times. ○: Damage was confirmed on the surface of the hardened film in the exposed area 3 times. ×: 3 times on the surface of the hardened film in the exposed area. It was confirmed that the damage evaluation results are shown in Table 2 below.

It is also apparent from the evaluation results shown in Table 2 that by using the inorganic particles contained in the layer containing the inorganic particles, the closer the content ratio of the inorganic particles to the surface side adjacent to the photosensitive film, the higher the distance from the photosensitive film. The lower the far surface side, the thinner the photosensitive film laminate containing the inorganic particle-containing layer (Examples 1 to 8) is, the better the resolution can be achieved. In addition, it was found that the visibility of the damage was also suppressed, and the yield was improved in the visual inspection of the hardened film.

<Evaluation of drop resistance under test hammer> Among photosensitive film laminates which are excellent in resolvability and can also improve the yield on the appearance inspection of the hardened film, at least any one of melamine and melamine compounds contained in the layer containing inorganic particles Examples 1 to 6 were prepared, and the drop resistance of the hammer was further evaluated. Each of the test substrates of Examples 1 to 6 produced in the production of the aforementioned test substrate was placed on concrete, and a ball made of brass having a diameter of 30 mm and a weight of 120 g as a test hammer was perpendicular to the layer containing inorganic particles. The direction of the surface was dropped from a height of 30 cm on the surface of the layer containing inorganic particles of each of the aforementioned test substrates. The cavity formed by the falling weight of the exposed surface of the photosensitive film was visually evaluated. The drop of the measuring hammer was performed on each of the test substrates of Examples 1 to 6 by 10 pieces each. The evaluation criteria are as follows. In addition, each test substrate was subjected to this test and evaluation 5 minutes after the heating lamination in the above-mentioned <Preparation of a test substrate>. The test and evaluation were performed under a test environment of 23 ° C and a relative humidity of 50%. ○: No cavity was confirmed on the surface of the 10 exposed photosensitive films ×: A cavity was confirmed on more than 10 of the exposed surfaces of the photosensitive film Evaluation results, all of Examples 1 to 6 were ○.

It can be seen that an inorganic particle-containing layer containing an inorganic particle and a photosensitive film laminate of a photosensitive film formed of a photosensitive resin composition are sequentially provided. Among the inorganic particle-containing layer, The content ratio is higher on the side adjacent to the photosensitive film, and lower on the surface side farther from the photosensitive film. Furthermore, in the layer containing inorganic particles, the photosensitive property contains at least one of melamine and a melamine compound. The thin film laminate (Examples 1 to 6) has excellent resolvability, and the yield can be improved by visual inspection of the hardened film. In addition, the drop resistance of the test hammer is also good, that is, even if a photosensitive film is laminated The strong impact or pressing when the substrates of the laminate are overlapped can also suppress the impact on the surface.

Claims (8)

A photosensitive film laminate comprising a layer containing inorganic particles and a photosensitive film formed from a photosensitive resin composition in this order, characterized in that the layer containing inorganic particles is described above. It is formed by containing inorganic particles. 含有 The content ratio of the inorganic particles is higher in the thickness direction of the inorganic particle-containing layer than on the side adjacent to the photosensitive film and on the side farther from the photosensitive film. The photosensitive film laminate according to claim 1, wherein when the thickness of the inorganic particle-containing layer is T (μm), in the thickness direction, the surface of the inorganic particle-containing layer from the side adjacent to the photosensitive film Proportion α of inorganic particles contained from T / 2 (μm) and ratio of inorganic particles contained from the surface on the opposite side of the side adjacent to the photosensitive film to T / 2 (μm) β, which satisfies the following formula (1): . The photosensitive thin film laminate of claim 1 or 2, wherein the average primary particle diameter of the inorganic particles is in a range of 0.1 to 10 μm. The photosensitive film laminate of claim 1 or 2, wherein the inorganic particles are silicon dioxide. The photosensitive film laminate according to claim 1 or 2, wherein the layer containing the inorganic particles further contains at least one of melamine or a melamine compound. The photosensitive film laminate according to claim 1 or 2, wherein the photosensitive resin composition contains a filler and a crosslinking component. The photosensitive film laminate according to claim 1 or 2, further comprising a protective film laminated on the surface of the photosensitive film opposite to the layer containing the inorganic particles. A cured product formed by using the photosensitive thin film laminate according to any one of claims 1 to 7.