TW201839514A - Photosensitive film photosensitive film laminate and cured product formed by using same - Google Patents

Abstract

Provided is a photosensitive film excellent in adhesion to a die attachment material and capable of improving yield even in an external inspection of a cured film. To this end, in the photosensitive film which is formed of a photosensitive resin composition and comprises a side having a concave part on a surface, the number of the concave part per 1mm2 unit square area of the surface is 3.0*10<SP>2</SP> or more.

Description

Photosensitive film, photosensitive film laminate, and cured product formed by using these

The present invention relates to a photosensitive film, 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 increase in precision and density of printed wiring boards caused by the thinness and thinness of electronic equipment in recent years, currently, the solder resist layer is formed by coating a photosensitive resin composition on a substrate and exposing and developing the pattern. The formation of a patterned resin that is formally hardened by heating or light irradiation is so-called formed by a light solder resist.

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. By using a photosensitive film laminate, a drying step after coating can be eliminated as compared with the case of wet coating. The surface smoothness and surface hardness are also excellent.

The substrate on which the solder resist is formed is subjected to a semiconductor assembly step. Among them, the solder resist used in the wire bonding specification is a semiconductor mounted on a solid crystal material and connected by wire bonding. Here, in terms of the solder resist, the surface smoothness or the adhesion to the solid crystal material becomes a very important factor. In recent years, due to the thinning of the substrate, a very high specification accuracy has been required among various materials used. From this point of view, the solder resist also uses the thin film laminate as described above, and requires surface uniformity. Similarly, the solid-state material on which a semiconductor is mounted also requires uniform thickness and thin film thickness of the material. For example, Japanese Patent Application Laid-Open No. 2016-069625 proposes a dry film laminate corresponding to a thin film substrate. However, it has been very difficult to improve the accuracy of the aforementioned specifications and to ensure the adhesion between the solder resist and the solid-state material.

On the other hand, solder resist is used in the outermost layer of the substrate and is formed at the final stage of the substrate manufacturing process. Therefore, when using devices or substrates in the substrate manufacturing process, damage may occur (for example, Japanese special (Publication No. 2015-206992). This damage is judged to be NG in the visual inspection before the semiconductor mounting step, and the production yield may be deteriorated. Especially in recent years, minor damage without quality problems has also caused the decrease in productivity, so it is one of the important requirements and requires new improvement methods.

Therefore, an object of the present invention is to provide a photosensitive film that is excellent in adhesion to a solid-state material 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 including a photosensitive film and a cured product formed by using the same.

The inventors have found that this time, when forming a layer formed using a photosensitive thin film laminate, especially a solder resist layer, especially when applied to a substrate for IC packaging, a solid crystal material formation step after IC chip assembly is performed. The reason for the poor adhesion to the solder resist layer is the surface morphology of the solder resist layer. In addition, the present inventors have found that by using a photosensitive film having a surface having a specific cavity on the surface, a moderate cavity can be imparted to the surface of the solder resist layer. As a result, it can be improved with respect to the solid crystal material. Closeness. Furthermore, the present inventors have obtained the following insight: The use of the solder resist layer formed by the photosensitive film having a surface with a specific cavity as described above, even if the surface is damaged, the damage is not easily visually recognized, so it is used for appearance inspection Medium can improve yield. This invention is made based on this knowledge.

[1] The photosensitive film according to the first embodiment of the present invention is characterized in that the photosensitive film is provided with a surface having a cavity on the surface and formed of a photosensitive resin composition, and the unit area of the surface is The number of cavities of 1 mm ² is 3.0 × 10 ² or more.

[2] The photosensitive film according to the second embodiment of the present invention is the photosensitive film according to [1], wherein the number of the cavities per 1 mm ² per unit area of the aforementioned surface is 2.0 × 10 ⁴ or less.

[3] The photosensitive film according to the third embodiment of the present invention is a photosensitive film such as [1] or [2], wherein the arithmetic average surface roughness Ra of the aforementioned surface is 0.05 μm or more.

[4] The photosensitive film according to the fourth embodiment of the present invention is the photosensitive film according to any one of [1] to [3], wherein the photosensitive resin composition contains a filler and a crosslinking component.

[5] The photosensitive film laminate according to the fifth embodiment of the present invention is characterized by being formed by laminating a supporting film with a photosensitive film according to any one of [1] to [4].

[6] The photosensitive film laminate according to the sixth embodiment of the present invention is the photosensitive film laminate as described in [5], wherein the photosensitive film laminate has a surface having a cavity on the surface and is formed of a photosensitive resin composition. In the resulting photosensitive film, a support film is laminated on the surface side having the cavity on the surface. [7] A hardened material according to a seventh embodiment of the present invention, which is characterized by using the photosensitive film according to any one of [1] to [4] or the photosensitive film laminate according to [5] or [6]. form.

According to the present invention, it is possible to realize a photosensitive film having excellent adhesiveness with a solid crystal material, and also improving the yield rate in the visual inspection of the cured film. In addition, according to a preferred aspect of the present invention, it is possible to realize the formation of a photosensitive pattern, particularly a photosensitive film that is excellent in suppressing the edge collapse of the pattern. It is especially effective when using a photosensitive film for formation of a solder resist layer.

The photosensitive film of this invention is demonstrated. The photosensitive film refers to a person who makes the photosensitive resin composition into a film shape and is not laminated with another layer such as a support film or a protective film. In the present invention, in consideration of workability or ease of forming the surface of the photosensitive film into a specific form as described later, a support film may be provided on one side of the photosensitive film, and prevention of the photosensitive film may be considered. The surface is covered with dust, etc., and the operability of the photosensitive film laminate, and a protective film may be further provided on the side opposite to the support film. Hereinafter, the photosensitive film of the present invention and other layers optionally provided will be described.

<Photosensitive film> The photosensitive film of the present invention is characterized by having a surface having a cavity on the surface and being formed of a photosensitive resin composition, and the number of the cavity per unit area of the surface is 1 mm ² It is 3.0 × 10 ² or more. The number of cavities per 1 mm ² per unit area is measured in three dimensions with the z-axis as the height direction, and the unevenness on the surface of the target photosensitive film is measured three-dimensionally, and the maximum and minimum values of the obtained z-value aggregate are obtained. A Zs value of 0.2 μm lower than the average value calculated from the maximum and minimum values is used as a threshold, a region having a z value below the threshold is used as a region of the cavity, and a unit area of 1 mm ² is counted. Calculated value of the number of cavity areas present. For example, in the aforementioned three-dimensional measurement of the height z using the surface of the photosensitive film as the xy axis plane, when the maximum and minimum values of the obtained z-value aggregate are 3.00 μm and 1.00 μm, respectively, the average value is 2.00 μm. , 1.80 μm, which is 0.2 μm lower than it, is the Zs value, which is the “threshold value”. A set of continuous cavities on the xy axis plane with a value lower than the threshold value of 1.80 μm is taken as one cavity region, and the number of cavities can be determined by counting the number of cavity regions existing in a spot shape in the measurement plane. A more detailed measurement procedure is described later.

In the present invention, the use of a photosensitive film having a surface having a number of cavities per unit area of 1 mm ² of 3.0 × 10 ² or more calculated as described above can improve the adhesion to the solid crystal material. In addition, when a solder resist layer or the like is formed using a photosensitive film having such a specific surface morphology, the yield can be improved in an external inspection such as inspecting the solder resist layer for surface damage or the like. The reason for such an unexpected effect is not necessarily clear, but it is presumed that by forming recesses in the surface of the photosensitive film and making the recesses a proper number, a moderate continuous surface is formed on the surface of the photosensitive film, even if The small damage is formed in the area where the continuous surface and the cavity are mixed, and the reflection of the damage is eased by the cavity, so that the damage is difficult to be observed. On the other hand, it is speculated that the anchoring effect caused by the cavity will rapidly increase the bonding force with the solid crystal material. However, it is only an estimated range, and it is not necessarily limited to this.

The number of the cavities per 1 mm ² of the surface area of the photosensitive film is preferably 4.0 × 10 ² or more, and more preferably 5.0 × 10 ² or more. There is no particular upper limit for the number of cavities per 1 mm ² per unit area, as long as such a surface can be formed. However, the number of cavities per unit area is 2.0 × 10 ⁴ or less. In the appearance inspection of the cured film, the yield can be improved, and in addition, the formation of the photosensitive pattern of the solder resist layer can be obtained, and the excellent effect of suppressing the edge collapse of the pattern can be obtained. The number of cavities per 1 mm ² per unit area is more preferably 1.5 × 10 ⁴ or less, and still more preferably 1.0 × 10 ⁴ or less. Here, the edge collapse of the pattern means, for example, that when a SRO (solder resist opening) is formed using a photosensitive film, after exposure and development, the resin component contained in the photosensitive film located on the edge of the opening collapses. Phenomenon coming out of the opening. In the present invention, it has been found that by forming a photosensitive film having a specific surface morphology as described above, it is expected that the edge collapse of a pattern can be suppressed in the field.

In addition, from the viewpoint of the balance between the adhesion with the solid-state material and the improvement in yield in the visual inspection, the arithmetic average surface roughness Ra of the surface of the photosensitive film having a cavity is preferably 0.05 μm or more, It is more preferably 0.06 μm or more, and still more preferably 0.07 μm or more. When the upper limit is set, it is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 1.0 μm or less.

In addition, the cavity on the surface of the photosensitive film may be uniform or non-uniform, but from the viewpoint of the balance between the adhesion with the solid-state material and the improvement of the yield during appearance inspection, it is preferably non-uniform. The depth of the cavity is preferably 0.2 μm or more.

From the viewpoint of the foregoing balance, the arithmetic average surface roughness Ra of the surface of the photosensitive film having a specific cavity is preferably 0.05 μm or more, more preferably 0.06 μm or more, and still more preferably 0.07 μm or more. When the upper limit is set, it is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 1.0 μm or less.

In the present invention, the above-mentioned "number of cavities per 1 mm ² per unit area" and "arithmetic average surface roughness Ra" mean values measured by a measuring device according to JIS B0601-1994. Hereinafter, a specific measurement method will be described. The number of concave cavities per unit area of 1 mm ² and the arithmetic average surface roughness Ra can be measured using a shape measurement laser microscope (for example, VK-X100 manufactured by Keyence Corporation). The shape measuring laser microscope (same as VK-X100) body (control part) and VK observation application (VK-H1VX manufactured by Keyence Co., Ltd.) were started, and the measured sample was placed on an xy stage. The lens rotator of the rotating microscope section (VK-X110 manufactured by Keyence Co., Ltd.) selects an objective lens with a magnification of 10 times, and uses the image observation mode of the VK observation application (same as VK-H1VX) to roughly adjust the focus and brightness. Operate the xy stage to adjust the approximate center of the sample surface to the center of the screen. Replace the objective lens with 10x magnification to 100x magnification, and use the autofocus function of the image observation mode of the VK observation application (same as VK-H1VX) to focus on the sample surface. Select the simple mode of the shape measurement tag of the VK observation application (same as VK-H1VX), press the measurement start button, and measure the surface shape of the sample to obtain the surface image file. Start the VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.), display the obtained surface image file, and then perform slope correction.

In the measurement of "the number of cavities per 1 mm ² per unit area", the observation measurement range (area) in the measurement of the surface shape of the sample was 15073 μm ² . For example, you can use a parsing application (same as VK-H1XA). Select [Volume ･ Area] from the measurement analysis menu on the display screen to display the [Volume ･ Area] window. Select [Height] from the [Display image] box in the [Volume / Area] window, and then press the [Threshold] button to display the [Threshold area setting dialog] box. Calculate the displayed value of the [Upper Limit] box and the value of the [Lower Limit] box and divide by 2 to get the value Ave. (μm), and subtract this Ave. (μm) from the 0.2 μm Zs value (μm) or less. The part is "cavity". The value in the [Lower Limit] box is not changed. Enter the Zs value (μm) in the [Upper Limit] box. After pressing the OK button, count the number of parts C (number) in the image display area that has changed to the ROI drawing color From the number C (number), the value of the number D (number / mm ² ) (D = C × 66.34) per 1 mm ² per unit area is calculated. In addition, the number of parts that change to the color of the ROI drawing color described above is 0.5 because those that are interrupted at the boundary of the video display area and cannot be recognized as one.

In the measurement of "arithmetic average surface roughness Ra", the objective lens was switched to 50 times, and the observation measurement range (horizontal) in the measurement of the surface shape of the sample was 270 μm. The line thickness window is displayed. After selecting JIS B0601-1994 in the parameter setting area, select the horizontal line by the measurement line button, display the horizontal line at any place in the surface image, and press the OK button to obtain the value of the arithmetic average surface roughness Ra ₁ . Further, horizontal lines are displayed at the four different locations in the surface image, and the values of the respective arithmetic average surface roughnesses Ra ₁ are obtained. Calculate the average _{Raave. Of the} five values obtained, and use this value as the arithmetic average surface roughness Ra value of the sample surface. In addition, when measuring the photosensitive film in the photosensitive film laminate, after the support film is peeled off to expose the surface of the photosensitive film, the "number of cavities per 1 mm ² per unit area" and " Measurement of arithmetic average surface roughness Ra ".

In order to make the surface morphology of the photosensitive film into the above-mentioned range of the specific number of cavities per unit area of 1 mm ² and the specific arithmetic average surface roughness Ra, a well-known and commonly used method can be applied, and among them, such a surface is formed From the viewpoint of ease of form, it is particularly preferable to form a photosensitive film using a support film as described later. That is, in the case of a photosensitive thin film laminated body formed by the photosensitive thin film lamination support film of the present invention, the photosensitive thin film laminate includes a surface having the above-mentioned specific number of cavities, and a specific arithmetic average surface roughness Ra as desired. The surface of the photosensitive film is preferably a surface adjacent to the support film. The photosensitive film is preferably used for forming a solder resist layer.

A photosensitive film having a surface of 3.0 × 10 ² or more cavities per 1 mm ² of the above unit area, and more preferably a photosensitive film having an arithmetic average surface roughness Ra of the surface of 0.05 μm or more It is patterned by exposure and development to become a hardened film provided on a circuit board. The cured film is preferably a solder resist layer. Such a photosensitive film can be formed using a photosensitive resin composition, and the photosensitive resin composition can be used without limitation with a conventionally known solder resist ink. The following describes the sensitivity of the photosensitive film that can be preferably used in the present invention. An example of a resin composition.

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, and when further heated, it is preferable 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, etc. (2) The 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) has 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 Hydroxy group, a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., (4) using Unsaturated monocarboxylic acids such as (meth) acrylic acid, and bisphenol A, bis Phenol F, bisphenol S, novolac-type phenol resin, poly-p-hydroxystyrene, naphthol and aldehyde condensation products, dihydroxynaphthalene and aldehyde condensation products, etc. have more than two phenols in one molecule The hydroxy-containing compound reacts with a reaction product obtained by reacting an alkylene oxide such as ethylene oxide and propylene oxide, and a carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride. A reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a compound having two or more phenolic hydroxyl groups and cyclic carbonate compounds such as ethyl carbonate and propyl carbonate in one molecule A photosensitive resin containing a carboxyl group obtained by reacting the obtained reaction product with a polybasic acid anhydride, and (6) reacting an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, etc. Diisocyanate compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adducts, and phenols Sex A urethane resin terminal obtained by addition polymerization reaction of a diol compound such as a hydroxyl group, an alcoholic hydroxyl compound, and the like, and a terminal carboxyl group-containing urethane resin obtained by further reacting an acid anhydride with (7) in Diisocyanate; carboxyl-containing diol compounds such as dimethylolpropionic acid, dimethylolbutanoic acid; and carboxyl-containing urethane resins obtained by addition polymerization with diol compounds Add a compound with one hydroxy group and one or more (meth) acrylfluorenyl groups in the molecule such as hydroxyalkyl (meth) acrylate, and a terminal (meth) acrylated carboxyl group-containing urethane Resin, (8) In the synthesis of a diisocyanate, a diol compound containing a carboxyl group, and a carboxyl group-containing urethane resin obtained by addition polymerization with a diol compound, isophorone diisocyanate and pentaerythritol are added. Compounds with one isocyanate group and one or more (meth) acryl fluorene groups in molecules such as moire reactants such as triacrylates, and terminal (meth) acrylated carboxyl group-containing urethane resins , (9) Dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid and the like are reacted with a polyfunctional oxetane resin, and a dibasic acid anhydride is added to the generated primary hydroxyl group, and then Glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like are further added to the carboxyl group-containing polyester resin obtained by the addition described above. A carboxyl group-containing photosensitive resin made of more than one (meth) acrylfluorenyl compound. (10) Add 1 to the carboxyl group-containing photosensitive resin in any one of (1) to (9) above. A carboxyl group-containing photosensitive resin obtained from a compound having a cyclic ether group and a (meth) acrylfluorene group in the molecule, (11) For unsaturated carboxylic acids such as (meth) acrylic acid, styrene, and α -A carboxyl group-containing resin obtained by copolymerizing an unsaturated group-containing compound such as methylstyrene, a lower alkyl (meth) acrylate, isobutylene, etc., to make one of 3,4-epoxycyclohexyl methacrylate, etc. A carboxyl group-containing compound obtained by reacting a compound having a cyclic ether group with a (meth) acryl group in the molecule Photosensitive resin and the like. 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 hydroxyl groups also has excellent characteristics such as improved adhesion caused by hydrogen bonding, but it is known that the moisture resistance will be 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 one of each of the methacrylates corresponding to the above-mentioned 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 Corporation, DER317, DER331, DER661, DER664, manufactured by The Dow Chemical Company, Sumiepoxy, manufactured by Sumitomo Chemical Industry Co., Ltd. ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all trade names) made by Asahi Kasei Industrial Co., Ltd. JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Epotohto YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Corporation, DER542 manufactured 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 Limited by jER152, jER154, Dow Chemical Co., DEN431, DEN438, DIC Corporation Epiclon N-730, Epiclon N-770, Epiclon N-865, Nippon Steel & Sumitomo Corporation Epotohto YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumiepoxy manufactured by Sumitomo Chemical Industry Co., Ltd. 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 Corporation Bisphenol F-type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., and Epotohto YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Nippon Steel & Sumitomo Metal Co., Ltd .; manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. Epotohto ST-2004, ST-2007, ST-3000 (brand name) and other hydrogenated bisphenol A epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation; Epotohto YH-434 manufactured by Nippon Steel & Sumikin Corporation Sumiepo, manufactured by Sumitomo Chemical Industries, Ltd. Glycidylamine type epoxy resins such as xy ELM-120, etc. (both trade names); alicyclic epoxy resins, such as Celloxide 2021, etc., manufactured by Daicel Corporation; YL- manufactured by Mitsubishi Chemical Corporation 933, TEN, EPPN-501, EPPN-502, etc. (all trade names) made of Dow Chemical Company, trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, Mitsubishi Chemical Corporation, YL-6121 (both trade names) bixylenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd. and EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd. And bisphenol S epoxy resins such as EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Tetraphenol-based ethane type epoxy resins such as jERYL-931 (trade name) manufactured by a joint-stock company; Heterocyclic epoxy resins such as TEPIC (trade name) manufactured by Nissan Chemical Industry Co., Ltd .; Japan Grease Co., Ltd. Diglycidyl phthalate resins such as Blemmer DGT made by the company; Tetraglycidyl xylenol ethane resins such as ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd .; ESN-190, ESN-360, HP-4032, EXA, manufactured by DIC Co., Ltd. -4750, EXA-4700 and other naphthyl-containing epoxy resins; HP-7200, HP-7200H and other dicyclopentadiene skeleton epoxy resins manufactured by DIC Corporation, EXA-4816, EXA-4822, EXA-4850 series of soft and strong epoxy resin; CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resins made by Japan Oil Co., Ltd .; Cyclohexylmaleimide and Copolymerized epoxy resin and the like of 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 as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or one that can promote the reaction of an epoxy group and / or an oxetanyl group with a carboxyl group, may be alone Alternatively, two or more kinds may be used in combination. 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 Carbamate Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Tosoh Corporation, trade name), B-830, B- 815, B-846, B-870, B-874, B-882 (above, made by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemical Co., Ltd. Company system, trade name) etc. 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 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 is a photosensitive film or when it is applied to a support film 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 respective unit characteristics 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 terms of solid content, it is preferably in a range of 1 to 50 parts by mass relative to 100 parts by mass of the resin containing a carboxyl group. It is 5 to 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 the supporting film and drying it. 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. Cloth spreader, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater are applied on one side of the support film to a uniform thickness, usually at a temperature of 50 to 130 ° C Dry for 1 to 30 minutes to volatilize the organic solvent to obtain a non-sticky 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 and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cyperidine, methyl cyperidine, butyl cyperone Sulfur, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, and other glycols 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 butane Esters such as ethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane, decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent petroleum brain, etc. Petroleum solvents. 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).

[Photosensitive film laminate] 的 A photosensitive film laminate according to another embodiment of the present invention refers to a film in which a support film is laminated on any of the above-mentioned photosensitive films. The photosensitive film laminate of the present invention is preferably formed by further laminating a protective film. The details are described below.

[Supporting film] The supporting film supports the above-mentioned photosensitive film (that is, a layer made of a photosensitive resin composition, hereinafter referred to as a "photosensitive resin layer"), and is included in the photosensitive film. During exposure and development, the surface of the side of the photosensitive film adjacent to the support film is given a character with a specific surface shape. In the present invention, it is preferred to use a support film having a number of protrusions per unit area of 1 mm ² per surface area of the surface adjacent to the photosensitive film of 3.0 × 10 ² or more. Furthermore, it is more preferable to use a support film having an arithmetic average surface roughness Ra´ of the surface on the side adjacent to the photosensitive film of 0.05 μm or more. By using a support film having such a surface morphology, it is easy to form a photosensitive film having a surface area of 3.0 × 10 ² or more per 1 mm ² of the cavity, and it is easy to form an arithmetic average surface having a thickness of 0.05 μm or more. Photographic film of coarseness Ra. That is, by providing a specific surface morphology of the support film to the surface of the photosensitive film, it is easy to form the adhesiveness of the hardened film and the solid crystal material that can be formed later, and the yield can be improved in appearance inspection. A photosensitive film is effective from a viewpoint. The number of protrusions per unit area of 1 mm ² on the surface of the support film is more preferably 4.0 × 10 ² or more, and still more preferably 5.0 × 10 ² or more. When the upper limit is set, it is preferably 2.0 × 10 ⁴ or less, more preferably 1.5 × 10 ⁴ or less, and still more preferably 1.0 × 10 ⁴ or less. Moreover, the protrusions on the surface of the support film may be uniform or non-uniform, and preferably non-uniform.

The range of the arithmetic mean surface roughness Ra 'of the supporting film is more preferably 0.06 μm or more, and particularly preferably 0.07 μm or more. When the upper limit is set, it is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 1.0 μm or less. Here, the number of protrusions per 1 mm ² per unit area of the surface of the support film refers to the z-axis as the height direction, and the three-dimensional measurement of the unevenness on the surface of the support film is performed to determine the aggregate of the obtained z value. The maximum and minimum values are based on a Zs´ value that is 0.2 μm higher than the average value calculated from the maximum and minimum values, and the area with a z value above the threshold is the area of the protrusion. The value is calculated by counting the number of protrusion regions existing in a unit area of 1 mm ² . The meaning of the arithmetic average surface roughness Ra´ is as described in the aforementioned [photosensitive film]. The specific measurement method is as described above. Moreover, the number of protrusions per 1 mm ² per unit area of the surface of the support film does not necessarily match the number of cavities per 1 mm ² per unit area of the surface of the photosensitive film. Similarly, the arithmetic of the surface of the support film The surface roughness Ra´ is not necessarily the same as the arithmetic surface roughness Ra of the surface of the photosensitive film, but by appropriately adjusting the surface morphology of the support film, the number of cavities per 1 mm ² per unit area of the surface of the photosensitive film can be adjusted. And the arithmetic surface roughness Ra is within a specific range as described above.

The support film can be used without particular limitation as long as it has a surface shape as described above. For example, a polyester film made of polyethylene terephthalate, polyethylene naphthalate, or the like can be suitably used. Polyimide film, polyimide film, polypropylene film, polystyrene film and other thermoplastic resin films, among these, from the standpoint of heat resistance, mechanical strength, handling, etc. In other words, polyester film is particularly suitable. The support film may be a single layer, or two or more layers may be laminated.

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.

For a support film having a surface area of 3.0 × 10 ² or more per unit area of 1 mm ² as described above, and an arithmetic average surface roughness Ra´ of 0.05 μm or more, when using a thermoplastic resin film, In this case, it is possible to add a filler (kneading treatment) or matte coating (coating treatment) to the resin when the film is formed into a film, or to perform a sandblasting treatment such as a sandblasting treatment on the film surface, or a hairline ) Processing or chemical etching to make the surface into a specific form as described above. For example, when adding a filler to the resin, the number of protrusions per 1 mm ² per unit area or the arithmetic average surface roughness Ra´ can be controlled by adjusting the particle diameter or amount of the filler. Further, when the surface of the support film coating treatment, may be adjusted by the type or amount of coating agent, or to control the number of arithmetic average surface area per unit of 1mm ² projecting portion thickness Ra'. Further, when the blasting process, the process conditions can be adjusted by blasting pressure or blasting material, etc., or to control the number of arithmetic average surface area per unit of 1mm ² projecting portion thickness Ra'. A commercially available thermoplastic resin film having such a surface roughness can also be used. For example, CM-25 manufactured by Unitika Co., Ltd., G50 manufactured by Kimoto Co., Ltd., and the like are not limited thereto.

The surface of the support film on which the photosensitive resin layer is provided 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 liquid is coated and dried on the surface of the support film by a known method such as a roll coating method, a spray coating method, or a gravure printing method, a screen printing method, or the like to perform a mold release treatment.

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

In addition, the photosensitive thin film laminate of the present invention is apt to exhibit the effect of the present invention that is excellent in adhesion with a solid crystal material and improves the yield in appearance inspection. A support film is laminated on the surface side of the film having a cavity on the surface side.

[Protective film] 感光 The photosensitive film laminate of the present invention can provide a protective film on the surface of the photosensitive resin layer opposite to the support film in order to prevent dust and the like from adhering to the surface of the photosensitive resin layer and to improve operability. .

The protective film can be, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or a surface-treated paper. The adhesive force between the selected protective film and the photosensitive resin layer is preferably smaller than that of the supporting film and the photosensitive property. Adhesive material for resin layer. When the photosensitive film laminate is used, in order to easily peel off the protective film, the surface of the protective film adjacent to the photosensitive resin layer may be subjected to the above-mentioned release treatment.

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 The hardened | cured material is formed using the photosensitive film or 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 support film of the aforementioned photosensitive film laminate, iv) the support film is peeled off from the aforementioned photosensitive film laminate, and development is performed to form a patterned photosensitive film on the substrate, v) The patterned photosensitive film is hardened by light irradiation or heat to form a hardened 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 to expose the photosensitive resin layer, and the photosensitive resin layer 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, even if the surface of the circuit substrate has irregularities, the photosensitive resin composition layer will be closely adhered to the circuit substrate, so that no bubbles are mixed in, and the hole filling property of the concave portion on 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 support film of the photosensitive thin 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 support film is peeled off from the photosensitive film laminate to perform development, and a patterned photosensitive film is formed on the substrate. When peeling a support film, the surface of the photosensitive film hardened | cured by exposure is given the form of the surface of a support film. In addition, as long as the characteristics are not impaired, the supporting film may be peeled 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.

As described above, a moderate unevenness can be imparted to the surface of the cured product. As a result, the adhesiveness with the solid crystal material is improved, and the yield in appearance inspection is also improved. The solid crystal material can be used by well-known and customary persons, and is not particularly limited. Therefore, 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 is particularly suitably used for the formation of a solder resist layer for IC packaging. [Example]

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.

[Table 1]

<Production of Photosensitive Film Laminate> Example 1 Sandblasting was performed on one side of a polyethylene terephthalate film (Diafoil R310 manufactured by Mitsubishi Chemical Corporation) to form uneven protrusions on the film surface. Supporting film with a thickness of 16 μm. As the film-like surface of the support obtained by measuring the number of 1mm per unit area and an arithmetic mean surface roughness of the projecting portion Ra' ^2, the number per unit area of the surface of the projecting portion ² per 1mm of 8.0 × 10 ² th 2. The arithmetic average surface roughness Ra´ is 0.13μm.

The number of protrusions per unit area of 1 mm ² and the arithmetic mean surface roughness Ra´ were measured using a shape measurement laser microscope (VK-X100 manufactured by Keyence Corporation). After starting the shape measurement laser microscope (same as VK-X100) body (control part) and VK observation application (VK-H1VX manufactured by Keyence Co., Ltd.), the measured sample (support film) is provided with the aforementioned support film. The surface of the protruding part is an upper part and is placed on the xy stage. The lens rotator of the rotating microscope section (VK-X110 manufactured by Keyence Co., Ltd.) selects an objective lens with a magnification of 10 times, and uses the image observation mode of the VK observation application (same as VK-H1VX) to roughly adjust the focus and brightness. Operate the xy stage and adjust so that the approximate center of the sample surface comes to the center of the screen. Change the objective lens with 10x magnification to 100x magnification, and use the autofocus function of the image observation mode of the VK observation application (same as VK-H1VX) to focus on the sample surface. Select the simple mode of the shape measurement tag of the VK observation application (same as VK-H1VX), and press the measurement start button to measure the surface shape of the sample to obtain the surface image file. Start the VK analysis application (VK-H1XA manufactured by Keyence Co., Ltd.), display the obtained surface image file, and then perform slope correction.

In the measurement of “the number of protrusions per 1 mm ² per unit area”, the observation measurement range (area) in the measurement of the surface shape of the sample was 15073 μm ² . An analysis application (VK-H1XA, manufactured by Keyence Corporation) is used. Select [Volume ･ Area] from the measurement analysis menu on the display screen to display the [Volume ･ Area] window, select [Height] from the [DisplayImage] box in the [Volume ･ Area] window, and press the [Threshold] button. The [Threshold Area Setting Dialog] box is displayed. Calculate the value of the [Upper Limit] box and the value of the [Lower Limit] box and divide by the value Ave. (μm), and add the Ave. (μm) to the part with a Zs´ value (μm) or more of 0.2μm As "protruding part". The value of the [Lower Limit] box is unchanged. Enter the Zs´ value (μm) in the [Upper Limit] box. After pressing the OK button, count the number of parts C (a ), From the number C (number), calculate the number D (number / mm ² ) per 1 mm ² per unit area (D = C × 66.34). In addition, the number of parts that change to the color of the ROI drawing color described above is 0.5 because they are discontinued in the video display area and cannot be recognized as one.

In the measurement of "arithmetic average surface roughness Ra", the objective lens was switched to 50 times, and the observation measurement range (horizontal) in the measurement of the surface shape of the sample was 270 µm. The line thickness window is displayed. After selecting JIS B0601-1994 in the parameter setting area, select the horizontal line by the measurement line button to display the horizontal line at any place in the surface image. Press the OK button to obtain the arithmetic average surface roughness Ra´ of the surface. Value. The horizontal lines are further displayed at the four different locations in the surface image to obtain the value of the arithmetic average surface roughness Ra´. Calculate the average of the five values obtained as the arithmetic mean surface roughness Ra´ of the sample surface.

Next, 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 liquid. The coating solution was coated on the surface subjected to the sandblasting treatment of the support film, and dried at a temperature of 80 ° C. for 15 minutes to form a photosensitive film having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (OPP-FOA manufactured by Futaura Chemical Co., Ltd.) was bonded to the photosensitive film to produce a photosensitive film laminate composed of three layers.

＜ Production of test substrate ＞ 表面 The surface of the substrate (500mm × 600mm × 0.4mmt) on which the circuit is formed is chemically polished with CZ8101 manufactured by MEC Co., Ltd., and the chemically polished surface of the substrate is bonded with the photosensitive film obtained as described above. The laminated body peeled the polypropylene film and exposed the exposed surface of the photosensitive film. Then, using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho), the pressure was 0.8 Mpa, 70 ° C, 1 minute, and the degree of vacuum: The lamination was carried out under the condition of 133.3 Pa so that the substrate and the photosensitive film were in close contact.

Next, a parallel light exposure device equipped with a short-arc high-pressure mercury lamp was used to pass through the exposure mask on the polyethylene terephthalate film adjacent to the photosensitive film to visualize the damage and the relationship with the solid crystal material. In terms of adhesiveness, uniform exposure is performed, and in terms of edge collapse of the pattern, exposure is performed using a negative pattern designed to be SRO80 μm, and then the polyethylene terephthalate film is peeled off to expose the photosensitive film. It should be noted that the exposure amount is a 7-segment exposure amount when a Stouffer 41-segment exposure is performed on a polyethylene terephthalate film 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 further harden 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 In Example 1, a support film with a thickness of 125 μm was formed on the surface of the film by applying a coating treatment to one side of a polyethylene terephthalate film (Gimoto Co., Ltd. 50), instead of a support film with a thickness of 16 μm on a surface with a surface area of 1 mm ² per unit area on a single surface of 8.0 × 10 ^{2 and} an arithmetic average surface roughness Ra´ of 0.13 μm, The test substrate 3 was produced in the same manner as in Example 1. The number of protrusions per 1 mm ² per unit area of the surface and the arithmetic average surface roughness Ra´ were measured in the same manner as described above, and the number of protrusions per 1 mm ² per unit area of the surface was measured. It is 1.3 × 10 ³ , and the arithmetic average surface roughness Ra´ is 0.19 μm.

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 In Example 1, a support film having a thickness of 25 μm with uneven protrusions formed on the surface of the film was coated on one side of a polyethylene terephthalate film (CM-Co., Ltd., CM- 25), instead of a support film with a thickness of 16 μm on a surface with a surface area of 1 mm ² per unit area on a single surface of 8.0 × 10 ^{2 and} an arithmetic average surface roughness Ra´ of 0.13 μm, A test substrate 5 was produced in the same manner as in Example 1. The number of protrusions per 1 mm ² per unit area of the surface and the arithmetic average surface roughness Ra´ were measured in the same manner as described above, and the number of protrusions per 1 mm ² per unit area of the surface was measured. It is 4.5 × 10 ³ , and the arithmetic average surface roughness Ra´ is 0.48 μm.

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 In Example 1, a support film having a thickness of 25 μm with uneven protrusions was formed on the surface of the film by sandblasting one side of a polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.). In place of a support film with a thickness of 16 μm on a surface with a surface area of 1 mm ² per unit area on a single surface of 8.0 × 10 ^{2 and} an arithmetic average surface roughness Ra´ of 0.13 μm, the system is in addition to Example 1 produced a test substrate 7 in the same manner. After measuring the number of protrusions per 1 mm ² per unit area and the arithmetic average surface roughness Ra´ of the surface subjected to the sandblasting treatment of the supporting film in the same manner as above, the number of protrusions per 1 mm ² per unit area of the surface is 1.7 × 10 ⁴ pieces, the arithmetic average surface roughness Ra´ is 5.00 μm.

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 polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used as a supporting film, instead of the number of protrusions per 1 mm ² per unit area having a surface on one side. A test substrate 9 was produced in the same manner as in Example 1 except that the number of support films was 8.0 × 10 ² and the thickness was 16 μm on the surface having an arithmetic average surface roughness Ra of 0.13 μm. And the rear surface of the support film was measured in the same manner of the number per unit area of 1mm and an arithmetic mean surface roughness of the projecting portion of each Ra' ^2, the number per unit area of 1mm ² of the surface of each projecting portion is 0, the arithmetic average surface The thickness Ra´ is 0.02 μm.

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.

<Evaluation of visual recognition of damage> The hardened film surface of the exposed area of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 2 produced as described above, a pencil core with a hardness of 2H was applied at an angle of 45 ° with a load Press in the state of 4.9N, move 1cm at a speed of 1mm for 1 second, and change the position 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. After the damage was confirmed, the test and evaluation were performed based on the above-mentioned content within 5 minutes after each test substrate was produced. The evaluation results are shown in Table 2 below.

＜ Production of solid crystal materials ＞ 80 parts of ginseng hydroxyphenylmethane type epoxy resin (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) as epoxy resin, bisphenol F type epoxy resin (Nippon Kayaku Co., Ltd. 15 parts of RE-303S-L manufactured by the company, 5 parts of flexible epoxy resin (YX7105 manufactured by Mitsubishi Chemical Corporation), and 50 parts of methyl ethyl ketone were added and heated and melted to obtain resin paint A. 150 parts of the obtained resin paint A, 3 parts of imidazole compound (2E4MZ manufactured by Shikoku Chemical Industry Co., Ltd.) as a hardening catalyst, and fused silica (FB-3SDX manufactured by Denka Corporation) as a filler were added 150 Parts, 1 part of a silane coupling agent (KBE-402, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), preliminarily mixed with a blender, and kneaded with a 3-roll mill to obtain a resin paint B. The obtained resin paint B was applied to a substrate film and dried at a temperature of 80 ° C. for 15 minutes to produce a solid crystal material having a thickness of 45 μm.

＜ Evaluation of Adhesiveness to Solid-Crystal Materials ＞ Cut the solid-crystal materials prepared as above to a specific size (5mm in height × 5mm in width × 0.045mm in thickness) and attach them to a silicon wafer (5mm in length × 5mm in width) at 70 ° C. × thickness 0.725 mm, oxide film coating), using a thermocompression tester, on the surface of the hardened film of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 2, silicon wafers, solid crystal materials, and hardened films They were crimped in this order (crimping conditions: 260 ° C, 10 seconds, 1.0 MPa). Then, it was heated at 175 ° C for 120 minutes to completely harden the solid crystal material. After that, it was left in a constant temperature and humidity device (PR-2KP, manufactured by ESPEC Co., Ltd.) for 85 hours at 85 ° C and a relative humidity of 85%. After that, it was taken out using an adhesive force measuring device (Nordson Advanced Technology Co., Ltd., universal bonding). Strength tester 4000Plus), the temperature of the stage on which the sample was set was 260 ° C, and the adhesive force was measured under conditions of a tool height of 0.05 mm from the substrate and a tool speed of 0.05 mm / sec. Ten test pieces were produced each, and the evaluation reference system was as follows. ○: Ten test pieces have a bonding force of 3 MPa or more ×: Among the ten test pieces, there is one or more test pieces with a bonding force of less than 3 MPa, and it is based on the foregoing within 5 minutes after the production of each test substrate Testing and evaluation. The measurement results are shown in Table 2 below.

<Measurement of the number of cavities per unit area of the photosensitive film surface per 1 mm ² and the arithmetic average surface roughness Ra> The surface of the substrate (150 mm × 95 mm × 0.8 mmt) on which the circuit is formed is made by MEC Co., Ltd. CZ8101 Chemical polishing. The chemically polished surface of the substrate was bonded to the photosensitive film (140mm × 90mm) exposed by peeling the polypropylene film from each photosensitive film laminate used in Examples 1 to 8 and Comparative Examples 1 to 2. The exposed surface was then laminated using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) under the conditions of pressure: 0.8Mpa, 70 ° C, 1 minute, and vacuum: 133.3Pa to make the substrate and photosensitivity. The film is tight. After that, the polyethylene terephthalate film was peeled from the substrate at 90 ° to expose the photosensitive film. After exposure, the number of cavities per 1 mm ² per unit area of the surface of the photosensitive film and the arithmetic average surface roughness Ra were measured within 5 minutes as follows.

The number of cavities per 1 mm ² per unit area of the surface of the photosensitive film is the same as that used to measure the number of protrusions per 1 mm ² per unit area of the surface of the support film, so as to expose the photosensitivity by bonding The measurement was performed in the same manner as described above except that the substrate of the film (with the photosensitive film surface as the upper part) was used as a sample instead of the support film. In the measurement of "the number of cavities per unit area of 1 mm ² " on the surface of the photosensitive film, the observation measurement range (area) in the measurement of the surface shape of the sample was set to 15073 μm ² . Use parsing application (same as VK-H1XA). Select [Volume ･ Area] from the measurement analysis menu on the display screen to display the [Volume ･ Area] window, select [Height] from the [DisplayImage] box in the [Volume ･ Area] window, and press the [Threshold] button. The [Threshold Area Setting Dialog] box is displayed. Calculate the value of the [Upper Limit] box and the value of the [Lower Limit] box and divide by the value Ave. (μm) to subtract the value of 0.2 μm from the Ave. (μm) and less than Zs (μm). As a "cavity." The value in the [Lower Limit] box is not changed. Enter the value of Zs (μm) in the [Upper Limit] box. After pressing the OK button, count the number of parts C in the boundary portion of the image display area that becomes the color of the ROI drawing color. (Number), from the number C (number), calculate the number D (number / mm ² ) per 1 mm ² per unit area (D = C × 66.34). In addition, the number of parts that change to the color of the ROI drawing color described above is 0.5 because they are discontinued in the video display area and cannot be recognized as one. In addition, the "arithmetic average surface roughness Ra" on the surface of the photosensitive film is based on the substrate (with the photosensitive film surface as the upper part) of the photosensitive film exposed after lamination as a sample to replace the supporting film. The measurement was performed in the same manner as described above. The “number of cavities per unit area of 1 mm ² ” and “arithmetic average surface roughness Ra” of the surface of each photosensitive film measured are shown in Table 2. Moreover, in all the examples, the identified cavities were uneven.

<Edge collapse of pattern> Using each test substrate prepared as described above, the edges of 10 openings were observed with a scanning electron microscope (SEM) at 1000 times. The evaluation criteria are as follows. ：: The edges of the 10 openings are all well-formed ○: Although the openings are tapered, no resin component contained in the photosensitive film emerged from the upper edges of the openings ×: Yu The evaluation results of the resin component contained in the photosensitive film from one or more openings appearing in the upper part of the edge are shown in Table 2 below.

Claims (7)

A photosensitive film comprising a surface having a cavity on the surface and formed of a photosensitive resin composition, wherein the number of the cavity per unit area of the surface is 1 mm ² 3.0 × 10 ² or more. For example, the photosensitive film of claim 1, wherein the number of cavities per 1 mm ² per unit area of the aforementioned surface is 2.0 × 10 ⁴ or less. The photosensitive film according to claim 1 or 2, wherein the arithmetic mean surface roughness Ra of the aforementioned surface is 0.05 μm or more. The photosensitive film according to claim 1 or 2, wherein the photosensitive resin composition contains a filler and a crosslinking component. A photosensitive film laminate, which is formed by laminating a supporting film with a photosensitive film according to any one of claims 1 to 4. For example, the photosensitive film laminate according to claim 5, wherein the photosensitive film laminate having a surface having a cavity on the surface and formed of a photosensitive resin composition is laminated on the side of the surface having the cavity on the surface. Made of support film. A cured product formed by using the photosensitive film according to any one of claims 1 to 4 or the photosensitive film laminate according to claim 5 or 6.