JP6175205B1 - Photosensitive film, photosensitive film laminate, and cured product formed using the same - Google Patents

Abstract

Provided is a photosensitive film that has excellent adhesion to a die attach material and can improve the yield even in the appearance inspection of a cured film. Moreover, the photosensitive film laminated body provided with a photosensitive film and the hardened | cured material formed using it are provided. A photosensitive film comprising a surface having depressions on a surface where the number of depressions per unit area of 1 mm 2 of the surface is 3.0 × 10 2 or more and formed of a photosensitive resin composition. [Selection figure] None

Description

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

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

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

  In addition, it has also been proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film without using the liquid photosensitive resin composition as described above. By using the photosensitive film laminate, a drying step after coating can be made unnecessary as compared with wet coating. Moreover, it is excellent also in surface smoothness and surface hardness.

  The substrate on which the solder resist is formed proceeds to the semiconductor mounting process. Among them, the solder resist used for the wire bonding specification has a semiconductor mounted by a die attach material and is connected by wire bonding. Here, as a solder resist, surface smoothness and adhesion to a die attach material are very important factors. In recent years, due to the reduction in the thickness of the substrate, there has been a demand for an extremely high specification accuracy improvement in various materials used. From such a viewpoint, the above-described film laminate is also used as the solder resist, and surface uniformity is required. Similarly, a die attach material for mounting a semiconductor is required to have a uniform film thickness and a thin film. For example, Patent Document 1 proposes a dry film laminate corresponding to a thin film substrate. However, it is extremely difficult to achieve both the above-described improvement in spec accuracy and the adhesion between the solder resist and the die attach material.

  On the other hand, the solder resist is used for the outermost layer of the substrate and is formed at the final stage of the substrate manufacturing process, so if the device is damaged during use of the equipment or transport tools during the substrate manufacturing process (For example, Patent Document 2). This scratch may be judged as NG in the appearance inspection before the semiconductor mounting process, and the production yield may deteriorate. In particular, in recent years, even small scratches that do not cause a problem in quality cause a drop in productivity, which is one of the important requirements, and a new improvement method is required.

Japanese Patent Application Laid-Open No. 2006-069625 JP2015-206992A

  Accordingly, an object of the present invention is to provide a photosensitive film that has excellent adhesion to a die attach material and can improve the yield even in the appearance 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 using the same.

  In the process of forming a die attach material after mounting an IC chip, the present inventors have recently applied a layer formed using a photosensitive film laminate, particularly a solder resist layer, particularly to an IC package substrate. It was found that the cause of poor adhesion to the solder resist layer is the surface form of the solder resist layer. And by using a photosensitive film having a surface having a specific depression on the surface, the present inventors can impart an appropriate depression to the surface of the solder resist layer, and as a result, adherence to the die attach material. The knowledge that it can be improved is obtained. Furthermore, the present inventors have a solder resist layer formed by using a photosensitive film having a surface having a specific depression as described above, and it is difficult to visually recognize the scratch even when the surface is scratched. It was found that the yield can be improved in the inspection. The present invention is based on this finding.

That is, the photosensitive film according to the present invention has a surface having depressions on the surface and is formed of a photosensitive resin composition, and the number of depressions per unit area 1 mm ^{2 of the} surface is 3.0 ×. 10 ² or more.
It is characterized by.

In the aspect of the present invention, the number of depressions per 1 mm ^{2 of the} surface area is preferably 2.0 × 10 ⁴ or less.

  In the embodiment of the present invention, the arithmetic average surface roughness Ra of the surface is preferably 0.05 μm or more.

  In the aspect of the present invention, the photosensitive resin composition preferably includes a filler and a crosslinking component.

  The photosensitive film laminate according to another aspect of the present invention is characterized in that a support film is laminated on the photosensitive film.

  In the aspect of this invention, it is preferable that the photosensitive film formed by the photosensitive resin composition is provided with the surface which has a dent on the surface, and a support film is laminated | stacked on the surface side which has a dent on the said surface. .

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

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive film which is excellent in adhesiveness with a die attach material and can improve a yield also in the external appearance test | inspection of a cured film is realizable. Moreover, according to the preferable aspect of this invention, the photosensitive film excellent in formation of the photosensitive pattern, especially suppression of the collapse of a pattern is realizable. This is particularly effective when a photosensitive film is used for forming the solder resist layer.

  The photosensitive film according to the present invention will be described. The photosensitive film is a film obtained by forming a photosensitive resin composition into a film shape, and other layers such as a support film and a protective film are not laminated. Further, in the present invention, in consideration of workability and ease of forming the surface of the photosensitive film into a predetermined form as described later, a support film may be provided on one surface of the photosensitive film. In addition, in addition to preventing dust and the like from adhering to the surface of the photosensitive film, a protective film is further provided on the surface opposite to the support film in consideration of the handleability of the photosensitive film laminate. It may be. Hereinafter, the photosensitive film according to the present invention and other layers optionally provided will be described.

<Photosensitive film>
The photosensitive film according to the present invention has a surface having a depression on the surface and is formed of a photosensitive resin composition. The number of depressions per unit area of 1 mm ^{2 on the} surface is 3.0 × 10 ^2. It is characterized by being more than one. The number of depressions per unit area of 1 mm ² is determined by three-dimensionally measuring the unevenness of the surface of the target photosensitive film with the z-axis as the height direction, and the maximum value and minimum value of the aggregate of the obtained z values. The Zs value that is 0.2 μm lower than the average value calculated from the maximum value and the minimum value is used as a threshold value, a region having a z value equal to or lower than the threshold value is set as a hollow region, and the unit area is 1 mm ² . It shall mean a value calculated by counting the number of depression regions present. For example, in the three-dimensional measurement in which the height z is measured with the surface of the photosensitive film as the xy axis surface as described above, the maximum value and the minimum value of the aggregate of the obtained z values are 3.00 μm and 1.00 μm, respectively. In this case, the average value is 2.00 μm, and 1.80 μm lower by 0.2 μm is the Zs value, that is, the “threshold value”. A set on the xy-axis plane that is continuous at a value lower than the threshold value 1.80 μm is defined as one depression area, and the number of depressions is determined by counting the number of depression areas scattered in the measurement surface. Can be determined. A more detailed measurement procedure will be described later.

In the present invention, a die attach material is used by using a photosensitive film having a surface such that the number of depressions per unit area 1 mm ² calculated as described above is 3.0 × 10 ² or more. It can improve the adhesiveness. In addition, when a solder resist layer or the like is formed using a photosensitive film having such a specific surface form, the yield can be improved in an appearance inspection for inspecting the presence or absence of surface scratches or the like of the solder resist layer. . The reason for such an unexpected effect is not necessarily clear, but by forming depressions on the surface of the photosensitive film and making the depressions in an appropriate number, the surface of the photosensitive film is moderately continuous. Even if a surface is formed and a minute scratch is formed in a region where the continuous surface and the depression are mixed, it is assumed that the reflection of the wound is relaxed by the depression and the scratch becomes difficult to see. On the other hand, it is surmised that the adhesive force with the die attach material is drastically improved by the anchor effect by the depression. However, this is only an estimation area, and not necessarily limited to this.

The number of depressions per 1 mm ² of unit area on the photosensitive film surface is preferably 4.0 × 10 ² or more, and more preferably 5.0 × 10 ² or more. The number of depressions per unit area of 1 mm ² is not particularly limited as long as such a surface can be formed, but by setting it to 2.0 × 10 ⁴ or less, the adhesion to the die attach material is excellent. In addition to improving the yield even in the appearance inspection of the cured coating, it is possible to obtain an excellent effect that the formation of the photosensitive pattern of the solder resist layer, particularly the collapse of the pattern can be suppressed. The number of depressions per unit area 1 mm ² is more preferably 1.5 × 10 ⁴ or less, and further preferably 1.0 × 10 ⁴ or less. Here, the collapse of the pattern means that, for example, when a SRO (solder resist opening) is formed using a photosensitive film, the resin content contained in the photosensitive film on the opening of the opening after exposure and development is It means a phenomenon that collapses and protrudes inside the opening. In the present invention, it was found that pattern collapse can be suppressed unexpectedly by using a photosensitive film having a specific surface form as described above.

  Further, from the viewpoint of the balance between adhesion to the die attach material and the yield improvement in the appearance inspection, the arithmetic average surface roughness Ra of the surface having the depression on the surface of the photosensitive film is preferably 0.05 μm or more. It is more preferably 0.06 μm or more, and further preferably 0.07 μm or more. Moreover, when providing an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometers or less.

  In addition, the depression on the surface of the photosensitive film may be uniform or non-uniform, but is preferably non-uniform from the viewpoint of adhesion to the die attach material and a balance of yield improvement in appearance inspection. Furthermore, the depth of the recess is preferably 0.2 μm or more.

  Further, from the viewpoint of the balance described above, the arithmetic average surface roughness Ra of the surface having the predetermined depression of the photosensitive film is preferably 0.05 μm or more, more preferably 0.06 μm or more, and 0.07 μm. More preferably, it is the above. Moreover, when providing an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometers or less.

In the present invention, the above-mentioned “number of depressions per unit area 1 mm ² ” and “arithmetic average surface roughness Ra” mean values measured by a measuring device based on JIS B0601-1994. Hereinafter, a specific measurement method will be described. The number of depressions per unit area 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). After the shape measurement laser microscope (VK-X100) main body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Corporation) are activated, a sample to be measured is placed on the xy stage. Turn the lens revolver of the microscope unit (Keyence VK-X110) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (VK-H1VX). . The xy stage is operated and adjusted so that the approximate center of the sample surface is at the center of the screen. The objective lens with a magnification of 10 times is changed to a magnification of 100 times, and the surface of the sample is focused with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). By selecting the simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) and pressing the measurement start button, the surface shape of the sample can be measured to obtain a surface image file. After starting the VK analysis application (VK-H1XA manufactured by Keyence Corporation) and displaying the obtained surface image file, tilt correction is performed.

In the measurement of “the number of depressions per 1 mm ^{2 of} unit area”, the observation measurement range (area) in the measurement of the surface shape of the sample is 15073 μm ² . For example, an analysis application (same VK-H1XA) can be used. Select [Volume / Area] from the measurement analysis menu on the display screen to display the [Volume / Area] window. After selecting [Height] from the [Display Image] box in the [Volume / Area] window, the [Threshold] button is pressed to display the [Threshold Area Setting Dialog] box. A value obtained by adding the value of the displayed [Upper limit] box and the value of the [Lower limit] box and dividing the result by 2 Ave. (Μm) was calculated and its Ave. A portion having a Zs value (μm) or less obtained by subtracting 0.2 μm from (μm) is defined as a “dent”. The value in the [Lower limit] box is not changed, and the number C () of the portion changed to the color of the ROI drawing color in the image display area after inputting the Zs value (μm) in the [Upper limit] box and pressing the OK button. counting number), from the number C (number), the number D (number ^/ mm 2 per unit area ^{1mm 2) (D = C ×} 66.34) a value was calculated. Of the portions that have changed to the ROI drawing color, those that are cut off at the boundary of the image display area and cannot be recognized as one are counted as 0.5.

In the measurement of “arithmetic average surface roughness Ra”, the objective lens is switched to 50 times, and the observation measurement range (horizontal) in the measurement of the surface shape of the sample is 270 μm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. Then, the numerical value of the arithmetic average surface roughness Ra ₁ is obtained. Further, horizontal lines are displayed at four different positions in the surface image, and numerical values of the respective arithmetic average surface roughness Ra ₁ are obtained. The average value Ra _ave. This value is taken as the arithmetic average surface roughness Ra value of the sample surface. When measuring the photosensitive film in the photosensitive film laminate, after peeling the support film and exposing the photosensitive film surface, within 5 minutes, “the number of depressions per 1 mm ^{2 of} unit area” and “ “Arithmetic mean surface roughness Ra” is measured.

In order to make the surface form of the photosensitive film within the range of the specific number of depressions per unit area 1 mm ² and the specific arithmetic average surface roughness Ra, known and commonly used techniques can be applied. From the viewpoint of easy formation in such a surface form, it is preferable to form a photosensitive film using a support film as described later. That is, in the case of a photosensitive film laminate in which a support film is laminated on the photosensitive film of the present invention, the photosensitive film has a surface having the above-mentioned specific number of depressions, and a specific arithmetic average surface roughness Ra as desired. It is preferable that the surface of the photosensitive film to be in contact with the support film. The photosensitive film is preferably used for forming a solder resist layer.

The photosensitive film provided with the surface whose number of depressions per unit area of 1 mm ² is 3.0 × 10 ² or more, which is a more preferred embodiment, and further the arithmetic average surface roughness Ra of the surface is 0.05 μm. The photosensitive film as described above is patterned by exposure and development to become a cured film provided on the 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 use a conventionally known solder resist ink or the like without limitation. An example of a photosensitive resin composition that can be preferably used will be described.

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

[Crosslinking component]
The cross-linking component is not particularly limited as long as it is a cross-linking component, and known and conventional ones can be used. In particular, a carboxyl group-containing photosensitive resin or a photosensitive monomer is preferable, and when it is further heated, it preferably includes a component that is cross-linked by heat (hereinafter, a thermal cross-linking component).

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

  Further, as the carboxyl group-containing photosensitive resin, it is preferable to use a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material. A carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material has a very low halide ion content and can suppress deterioration in insulation reliability. Specific examples of the carboxyl group-containing photosensitive resin include the compounds listed below (which may be either oligomers or polymers).

(1) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl group present in the side chain has two bases such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which an acid anhydride is added,
(2) A polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin,
(3) An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like. Polybasic, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated carboxylic acid containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride,
(4) Two or more per molecule such as bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes Reaction obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with the product,
(5) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride,
(6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group,
(7) During synthesis of a carboxyl group-containing urethane resin by a polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminal (meth) acrylated,
(8) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin in which a compound having one isocyanate group and one or more (meth) acryloyl groups is added and terminal (meth) acrylated,
(9) Carboxy group-containing photosensitivity obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. resin,
(10) A carboxyl group obtained by reacting a difunctional acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a polyfunctional oxetane resin as described later and adding a dibasic acid anhydride to the resulting primary hydroxyl group A carboxyl group formed by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule, such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate, to the containing polyester resin A compound having a cyclic ether group and a (meth) acryloyl group in one molecule was added to the photosensitive resin containing (11) and the carboxyl group-containing photosensitive resin of any one of (1) to (10) described above. Examples thereof include a carboxyl group-containing photosensitive resin. Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Among the above-described carboxyl group-containing photosensitive resins, as described above, a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material can be suitably used. Therefore, among the specific examples of the carboxyl group-containing photosensitive resin described above, any one or more of the carboxyl group-containing photosensitive resins (4) to (8) can be particularly preferably used.

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

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

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

  In the synthesis of the urethane resin, an epoxy acrylate-modified raw material can also be used as the diol compound. Although chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.

  From such a viewpoint, for example, in order to obtain a photosensitive resin composition having more excellent PCT resistance, HAST resistance, and thermal shock resistance as a solder resist for semiconductor packages, the above-described carboxyl group-containing photosensitive resin (4) to Any one or more of the carboxyl group-containing photosensitive resins of (8) can be more suitably used.

  Further, as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule with respect to the carboxyl group-containing photosensitive resin (9) obtained by copolymerization with the unsaturated group-containing compound shown above, 3, 4 -Since the alicyclic epoxy is used also for the carboxyl group-containing photosensitive resin which reacted with epoxy cyclohexyl methyl methacrylate, there are few chlorine ion impurities and it can use it suitably.

  Moreover, in order for the adhesiveness with a molding material to improve more by using together the carboxyl group containing photosensitive resin in any one or more of said (4)-(8), and the carboxyl group containing photosensitive resin of said (9). ,preferable.

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

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

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

  It is preferable that the compounding quantity of carboxyl group-containing photosensitive resin is 20-60 mass% in all compositions in conversion of solid content. Coating strength can be improved by setting it as 20 mass% or more. Further, when the content is 60% by mass or less, viscosity becomes appropriate and workability is improved. More preferably, it is 30-50 mass%.

  Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent acrylates such as thyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Polyurethane polyol such as polyester polyol is directly acrylated or urethane acrylate via diisocyanate It can be used by appropriately selecting from at least one selected from acrylates and melamine acrylates and methacrylates corresponding to the acrylates.

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

  The compounding amount of the compound having an ethylenically unsaturated group in the molecule used as the photosensitive monomer is preferably relative to 100 parts by mass of the carboxyl group-containing resin in terms of solid content when the composition contains the carboxyl group-containing resin. Is 5 to 100 parts by mass, more preferably 5 to 70 parts by mass. By making the compounding quantity of the compound which has an ethylenically unsaturated group 5 mass parts or more, the photocurability of a photocurable resin composition improves. Moreover, the coating-film hardness can be improved by making a compounding quantity into 100 mass parts or less. Here, the carboxyl group-containing resin includes both a carboxyl group-containing photosensitive resin and a carboxyl group non-photosensitive resin. That is, when it is blended alone in the composition, it means alone, and when both are blended, it means the total (the same applies in the following paragraphs).

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

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

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule has either one of the three, four or five-membered cyclic ether groups, or the cyclic thioether group, or a plurality of two types of groups in the molecule. Compound, for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule That is, an episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 840-S, Epicron 850, Epicron 1050, Epicron 2055, and Epoto YD manufactured by Tohto Kasei Co., Ltd. -011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000H, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., A.C. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; glycidylamine type epoxy resin such as jER604, Etototo YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both trade names); Celoxide 2021 manufactured by Daicel Chemical Industries Co., Ltd. ) Cycloaliphatic epoxy resin; YL-933 manufactured by Mitsubishi Chemical Corporation, T.W. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation; TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (trade name) ) Heterocyclic epoxy resin; diglycidyl phthalate such as Bremer DGT manufactured by NOF Corporation Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton such as HP-7200, HP-7200H, etc. manufactured by DIC, EXA-4816, EXA-4822, EXA-4850 series flexible tough epoxy resin; Examples include, but are not limited to, glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M; and a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. These epoxy resins can be used alone or in combination of two or more.

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

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

  When the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, the solid content Preferably it is 0.3-2.5 equivalent with respect to 1 equivalent of carboxyl groups of carboxyl group containing resin in conversion, More preferably, it is the range used as 0.5-2.0 equivalent. By making the amount of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule 0.3 equivalent or more, no carboxyl group remains in the cured film, heat resistance, alkali resistance, electrical insulation Etc. improve. Moreover, by setting it as 2.5 equivalent or less, the low molecular weight cyclic (thio) ether group does not remain in the dry coating film, and the strength and the like of the cured coating film are improved.

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

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

  Amino resins include amino resins such as melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarak Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM (made by Sanwa Chemical Co., Ltd.) and the like.

  As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

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

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

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents and the like.

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

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

  Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds. The metal chloride is a metal chloride selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al. For example, cobalt chloride, nickel chloride, ferric chloride, etc. Is mentioned. The metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al. For example, cobalt acetylacetonate, nickel acetylacetonate, iron Examples include acetylacetonate. Furthermore, the metal sulfate is a metal sulfate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N ′-( 2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N ′ -(2-hydroxyethyl) ethylenediamine, 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-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1- ( 2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole 1- (2′-hydroxyethyl) -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-dimethylaminoethyl-N ′, N ′ -At least 1 sort (s) of bis (2-hydroxypropyl) amine, melamine, and benzoguanamine etc. are mentioned.

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

[Filler]
As the filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, titanium oxide, Neuburg silica clay particles, and talc are preferably used. Further, for the purpose of imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, boehmite and the like can also be used. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all are product grade names) manufactured by Hanse-Chemie . These may be used alone or in combination of two or more. By including the filler, the physical strength of the obtained cured product can be increased.

  When the filler contains a carboxyl group-containing resin in the composition, it is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Particularly preferred is 0.1 to 150 parts by mass. When the compounding quantity of a filler is 500 mass parts or less, the viscosity of a photocurable thermosetting resin composition does not become high too much, printability is good, and hardened | cured material does not become weak easily.

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

  As oxime ester photopolymerization initiators, commercially available products include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, manufactured by BASF Japan, N-1919, Adeka Arcles (registered trademark) NCI, manufactured by ADEKA. -831 etc. are mentioned.

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

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), Represents an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, a C 1-17 alkyl group, and a carbon number 1 Alkoxy group having ˜8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Substituted with a mino group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene , Thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

  In particular, the oxime ester system in which X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene in the above formula Photoinitiators are preferred.

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

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。
Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

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

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

  When the oxime ester photopolymerization initiator is used, the compounding amount includes 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content when the composition contains a carboxyl group-containing resin. It is preferable that By setting it as 0.01 mass part or more, photocurability on copper becomes more reliable and coating-film characteristics, such as chemical resistance, improve. Moreover, the light absorption in the coating-film surface is suppressed by setting it as 5 mass parts or less, and there exists a tendency for the sclerosis | hardenability of a deep part to improve. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of carboxyl group-containing resin.

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

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Irgacure TPO and Irgacure 819 manufactured by BASF Japan.

  Further, as a photopolymerization initiator, Irgacure 389 and Irgacure 784 manufactured by BASF Japan can also be suitably used.

  When the photopolymerization initiator other than the oxime ester photopolymerization initiator is used, when the composition contains a carboxyl group-containing resin, the blending amount is 0. It is preferable that it is 01-15 mass parts. By setting it as 0.01 mass part or more, photocurability on copper becomes more reliable and coating-film characteristics, such as chemical resistance, improve. Moreover, by setting it as 15 mass parts or less, sufficient reduction effect of an outgas is acquired, Furthermore, the light absorption in the cured film surface is suppressed, and the sclerosis | hardenability of a deep part improves. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of carboxyl group-containing resin.

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

  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, 1,1-dichloroacetophenone, and the like. Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like. Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal. Furthermore, examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. Can be mentioned.

  Examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nissoure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.), 4,4 Dialkylaminobenzophenone such as' -diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-di Tylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk). As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

  As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm and is in the ultraviolet region, so it is less colored and uses not only a colorless and transparent photosensitive resin composition but also a colored pigment, which reflects the color of the colored pigment itself. A colored photosensitive film can be obtained. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by including a thioxanthone compound, it is possible to improve deep curability.

  The total amount of the photopolymerization initiator, photoinitiator auxiliary, and sensitizer is 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content when the composition contains a carboxyl group-containing resin. It is preferable. By setting it as 35 mass parts or less, these light absorption is suppressed and the sclerosis | hardenability of a deep part is also improved.

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

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

  A block copolymer can be suitably mix | blended with the above-mentioned photosensitive resin composition. The block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain. What is solid in the range of 20 degreeC-30 degreeC is preferable. Any solid may be used within this range, and it may be solid even at a temperature outside this range. Since it is solid in the above temperature range, it is excellent in tackiness when it is used as 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. Of the XYX or XYX ′ type block copolymers, the central B is a soft block and has a low glass transition point Tg, preferably less than 0 ° C., and both outer sides A to X ′ are hard blocks and have a high Tg. Preferably, those composed of polymer units at 0 ° C. or higher are preferred. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

  Among the XYX or XYX ′ type block copolymers, there is further provided a block copolymer wherein X to X ′ are composed of polymer units having a Tg of 50 ° C. or more and Y is a polymer unit having a Tg of −20 ° C. or less. preferable. Of the XYX or XYX ′ type block copolymers, X to X ′ are preferably those having high compatibility with the carboxyl group-containing resin, and Y is preferably having low compatibility with the carboxyl group-containing resin. Thus, it is considered that a specific structure in the matrix can be easily shown by using a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.

  The block copolymer is not limited to XYX or XYX ′ type, and can be used without particular limitation as long as it has at least one hard block and one soft block component.

  The X to X 'component is preferably polymethyl methacrylate (PMMA), polystyrene (PS) or the like, and the B component is preferably poly n-butyl acrylate (PBA) or polybutadiene (PB). Further, a hydrophilic unit excellent in compatibility with the carboxyl group-containing resin represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, or the like as a part of the X to X ′ components. It becomes possible to introduce and further improve the compatibility. The inventors of the present invention have particularly good compatibility with the carboxyl group-containing resin described above, and surprisingly, the thermal shock resistance can be improved. Furthermore, surprisingly, it has been found that the glass transition temperature (Tg) tends to decrease when the elastomer is added, whereas the Tg tends not to decrease when the block copolymer is added.

  Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application Nos. 2005-515281 and 2007-516326. Examples of commercially available block copolymers include acrylic triblock copolymers manufactured using living polymerization manufactured by Arkema. SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and MAM N type treated with carboxylic acid modification or hydrophilic group modification. And MAM A type. Examples of SBM types include E41, E40, E21, E20, MAM types include M51, M52, M53, M22, etc., MAM N types include 52N, 22N, and MAM A types include SM4032XM10. It is done. The clarity produced by Kuraray is also a block copolymer derived from methyl methacrylate and butyl acrylate.

  The block copolymer is preferably a ternary or more block copolymer, and more preferably a block copolymer having a precisely controlled molecular structure synthesized by a living polymerization method in order to obtain the effects of the present invention. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified. The molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.

  The block copolymer preferably has a weight average molecular weight in the range of 20,000 to 400,000, more preferably 30,000 to 300,000. When the weight average molecular weight is less than 20,000, the intended effects of toughness and flexibility cannot be obtained, and the tackiness is inferior. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition is increased, and the printability and developability are significantly deteriorated.

  When the composition contains a carboxyl group-containing resin, the blend amount of the block copolymer is preferably in the range of 1 to 50 parts by mass, more preferably 5 to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. -35 parts by mass. The effect can be expected when the amount is 1 part by mass or more, and when the amount is 50 parts by mass or less, the developability and applicability of the photocurable resin composition are improved.

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

Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Indexes (CI; Issued by The Society of Dyersand Colors) are listed.

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

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

  Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the anthraquinone yellow colorant include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like. Examples of the isoindolinone-based yellow colorant include Pigment Yellow 110, 109, 139, 179, 185, and the like. Examples of the condensed azo yellow colorant include Pigment Yellow 93, 94, 95, 128, 155, 166, 180, and the like. Examples of the benzimidazolone yellow colorant include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like. 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, and 183. 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 the like. Is mentioned.

  In addition, colorants such as purple, orange, brown, black, and white may be added. 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, C.I. I. Pigment 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, Examples thereof include carbon black.

  The blending amount of the colorant is not particularly limited, but when the carboxyl group-containing resin is included in the composition, it is preferably 10 parts by mass or less, more preferably 0 with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. .1 to 7 parts by mass. However, the blending amount of the white colorant such as titanium oxide is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and more preferably 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Is 3-80 parts by mass.

  Moreover, an elastomer can be mix | blended with the photosensitive resin composition for the purpose of provision of the softness | flexibility with respect to the hardened | cured material obtained, improvement of the brittleness of hardened | cured material, etc. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers. In addition, resins in which some or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. One type of elastomer may be used alone, or a mixture of two or more types may be used.

  Moreover, a conventionally well-known binder polymer can be used for the purpose of the improvement of the flexibility of the hardened | cured material obtained, and finger touch drying property. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo Co., Ltd., and a phenoxy resin-based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.

  When the carboxyl group-containing resin is included in the composition, the blending amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Especially preferably, it is 5-30 mass parts. When the blending amount of the binder polymer is 50 parts by mass or less, the photosensitive resin composition is excellent in alkali developability, and the usable potable time for development becomes long.

  In addition, the photosensitive resin composition may further contain components such as an adhesion promoter, an antioxidant, and an ultraviolet absorber as necessary. As these, those known in the field of electronic materials can be used. Further, known and commonly used thickeners such as fine silica, hydrotalcite, organic bentonite, montmorillonite, at least one of defoamers and leveling agents such as silicone, fluorine, and polymer, imidazole, and thiazole At least one of known and commonly used additives such as a silane coupling agent such as a triazole or triazole, a rust inhibitor, and a fluorescent brightening agent can be blended.

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

  The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. be able to. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate , Propylene glycol ethyl ether acetate, propylene glycol butyl ether Esters such as cetate; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha is there. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

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

[Photosensitive film laminate]
The photosensitive film laminated body which is another embodiment of this invention says that the support film is laminated | stacked on one of said photosensitive films. Moreover, it is preferable that the photosensitive film laminated body of this invention is further laminated | stacked with a protective film. Details will be described below.

[Support film]
The support film supports the above-described photosensitive film (that is, a layer made of a photosensitive resin composition, hereinafter may be abbreviated as “photosensitive resin layer”), and at the time of exposure and development of the photosensitive film, It has a role which molds a predetermined surface form on the surface of the conductive film in contact with the support film. In the present invention, it is preferable to use a support film in which the number of protrusions per unit area of 1 mm ² on the surface side in contact with the photosensitive film is 3.0 × 10 ² or more. Moreover, it is more preferable to use a support film having an arithmetic average surface roughness Ra ′ of 0.05 μm or more on the surface side in contact with the photosensitive film. By using a support film having such a surface form, it becomes easier to form a photosensitive film in which the number of depressions per 1 mm ² of the surface area is 3.0 × 10 ² or more, and It becomes easy to form a photosensitive film having an arithmetic average surface roughness Ra of 0.05 μm or more. That is, by forming a predetermined surface form of the support film on the surface of the photosensitive film, it is possible to improve the adhesion between the cured film to be formed later and the die attach material. This is effective in that it is easy to form a photosensitive film capable of improving the resistance. The number of protrusions in a unit area of 1 mm ^{2 on the} surface of the support film is more preferably 4.0 × 10 ² or more, and further preferably 5.0 × 10 ² or more. Moreover, when providing an upper limit, 2.0 * 10 < ⁴ > or less is preferable, 1.5 * 10 < ⁴ > or less is more preferable, and 1.0 * 10 < ⁴ > or less is further more preferable. Moreover, although the protrusion part on the surface of a support film may be uniform or nonuniform, it is preferable that it is nonuniform.

The range of the arithmetic average surface roughness Ra ′ of the support film is more preferably 0.06 μm or more, and particularly preferably 0.07 μm or more. Moreover, when providing an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometers or less. Here, the number of protrusions per unit area 1 mm ^{2 on} the surface of the support film is a set of z values obtained by three-dimensionally measuring the unevenness of the surface of the target support film with the z axis as the height direction. The maximum value and the minimum value of the body are obtained, the Zs ′ value 0.2 μm higher than the average value calculated from the maximum value and the minimum value is set as a threshold value, and a region having a z value greater than the threshold value is projected And a value calculated by counting the number of protrusion regions present in a unit area of 1 mm ² . Further, the meaning of the arithmetic average surface roughness Ra ′ is as described in the above-mentioned “Photosensitive film”. The specific measurement method is as described above. It should be noted that the number of protrusions per unit area 1 mm ^{2 on the} surface of the support film and the number of depressions per unit area 1 mm ^{2 on the} surface of the photosensitive film do not necessarily coincide with each other. The surface roughness Ra ′ and the arithmetic surface roughness Ra of the photosensitive film surface do not necessarily coincide, but by appropriately adjusting the surface form of the support film, the depression per unit area 1 mm ² of the photosensitive film surface The number and the arithmetic surface roughness Ra can be set within the specific ranges as described above.

  The support film can be used without particular limitation as long as it has the above surface form. For example, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyimide film, polyamideimide film, polypropylene film, polystyrene A film made of a thermoplastic resin such as a film can be preferably used. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability, and the like. The support film may be a single layer, or two or more layers may be laminated.

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

As a support film in which the number of protrusions per 1 mm ^{2 of the} surface area as described above is 3.0 × 10 ² or more, and the arithmetic average surface roughness Ra ′ is 0.05 μm or more, When a thermoplastic resin film is used, a filler is added (kneading treatment) to the resin during film formation, mat coating (coating treatment), or blasting treatment such as sandblasting is performed on the film surface. Or the surface can be brought into the predetermined form as described above by hairline processing, chemical etching, or the like. For example, when a filler is added to the resin, the number of protrusions per unit area of 1 mm ² and the arithmetic average surface roughness Ra ′ can be controlled by adjusting the particle size and addition amount of the filler. When the surface of the support film is coated, the number of protrusions per unit area 1 mm ² and the arithmetic average surface roughness Ra ′ can be controlled by adjusting the type and amount of the coating agent. When blasting, the number of protrusions per unit area 1 mm ² and the arithmetic average surface roughness Ra ′ can be controlled by adjusting processing conditions such as blasting material and blast pressure. As the thermoplastic resin film having such a surface roughness, commercially available ones may be used, and examples thereof include Unit-25 Corporation CM-25, Kimoto Corporation G50, etc., but are not limited thereto. is not.

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

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

  In addition, the photosensitive film laminate according to the present invention has excellent adhesion to a die attach material, and further has an appearance, wherein a support film is laminated on the surface side having a depression on the surface of any of the above photosensitive films. This is preferable in that the effect of the present invention of improving the yield in inspection is easily achieved.

[Protective film]
The photosensitive film laminate according to the present invention has a surface opposite to the support film of the photosensitive resin layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive resin layer and improving the handleability. A protective film may be provided.

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

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

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

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

  In order to paste the photosensitive film of the photosensitive film laminate on the circuit board, it is preferable to use a vacuum laminator or the like to bond under pressure and heating. By using such a vacuum laminator, even if the circuit board surface has irregularities, the photosensitive resin composition layer adheres to the circuit board, so there is no mixing of bubbles, and filling of the recesses on the substrate surface is possible. Will also improve. The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120 ° C.

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

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

  After the exposure, the support film is peeled off from the photosensitive film laminate and developed to form a patterned photosensitive film on the substrate. When the support film is peeled off, the form of the support film surface is formed on the surface of the exposed and cured photosensitive film.

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

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

  As described above, an appropriate uneven state can be imparted to the surface of the cured product. As a result, the adhesion with the die attach material is improved and the yield in the appearance inspection is also improved. A well-known and conventional material can be used as the die attach material, and is not particularly limited. Therefore, the photosensitive film laminate according to the present invention can be suitably used particularly for forming a solder resist layer for IC packages.

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

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

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

<Preparation of photosensitive resin composition>
The carboxyl group-containing photosensitive resin varnish 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) which is a photosensitive monomer as an acrylate compound, and an epoxy resin which is a thermosetting component Bisphenol A type epoxy resin (EPICLON 840-S manufactured by DIC) and biphenol novolak type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.), IRGACURE TPO manufactured by BASF Japan Co., Ltd. or IRGACURE manufactured by BASF Japan Co., Ltd. OXE02, barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.) and / or spherical silica (Admafine SO-E2 manufactured by Admatechs) as a filler, melamine as a thermosetting catalyst, and Mitsubishi Chemical as a colorant Gaksha carbon black M-50, dioxazine violet C.I. I. Pigment Violet 23, C.I. I. Pigment Yellow 147, C.I. I. Pigment Blue 15: 3 and C.I. I. Each component selected from Pigment Red 177 and diethylene glycol monoethyl ether acetate as an organic solvent are blended in the proportions (parts by mass) shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. Photosensitive resin compositions 1 and 2 were prepared.

<Preparation of photosensitive film laminate>
A support film having a thickness of 16 μm was prepared by sandblasting one side of a polyethylene terephthalate film (Diafoil R310 manufactured by Mitsubishi Plastics, Inc.) to form a non-uniform protrusion on the film surface. The number of protrusions per unit area 1 mm ^{2 on} the surface of the obtained support film and the measurement of the arithmetic average surface roughness Ra ′ were measured as follows. The number of protrusions per unit area 1 mm ^{2 of the} surface Was 8.0 × 10 ² pieces, and the arithmetic average surface roughness Ra ′ was 0.13 μm.

A shape measurement laser microscope (VK-X100 manufactured by Keyence Corporation) was used for the measurement of the number of protrusions per unit area of 1 mm ² and the arithmetic average surface roughness Ra ′. After starting the shape measurement laser microscope (VK-X100) main body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Corporation), the sample (support film) to be measured on the xy stage is described above. The surface of the support film having the protruding portion was placed on top. Turn the lens revolver of the microscope (Keyence VK-X110) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (VK-H1VX). . The xy stage was operated and adjusted so that the approximate center of the sample surface was at the center of the screen. The objective lens with a magnification of 10 times was changed to a magnification of 100 times, and the surface of the sample was focused with the autofocus function in the image observation mode of the VK observation application (same VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) was selected, the measurement start button was pressed, the surface shape of the sample was measured, and a surface image file was obtained. After starting the VK analysis application (VK-H1XA made by Keyence Corporation) and displaying the obtained surface image file, inclination correction was performed.

In the measurement of “number of protrusions per unit area of 1 mm ² ”, the observation measurement range (area) in the measurement of the surface shape of the sample was 15073 μm ² . An analysis application (Keyence VK-H1XA) was used. 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, Press the [Threshold] button to display the [Threshold area setting dialog] box. A value obtained by adding the value in the [upper limit] box and the value in the [lower limit] box and dividing the result by 2 Ave. (Μm) was calculated and its Ave. A portion having a Zs ′ value (μm) or more obtained by adding 0.2 μm to (μm) was defined as a “projection”. The value in the [Lower limit] box is not changed, and the number C of places where the color changes to the ROI drawing color in the image display area after inputting the Zs' value (μm) in the [Upper limit] box and pressing the OK button. (number) counting, from the number C (number) was calculated unit area 1 mm ² number per D (number ^{/ mm 2) (D = C} × 66.34). Of the portions that changed to the ROI drawing color, those that were cut off in the image display area and could not be recognized as one were counted as 0.5.

  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. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. The numerical value of the arithmetic average surface roughness Ra ′ of the surface was obtained. Furthermore, horizontal lines were displayed at four different locations in the surface image, and the numerical value of the arithmetic average surface roughness Ra ′ was obtained. The average value of the obtained five numerical values was calculated and used as the arithmetic average surface roughness Ra ′ value of the sample surface.

  Subsequently, 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above for dilution, and the mixture was stirred for 15 minutes with a stirrer to obtain a coating solution. The coating solution was applied to the surface of the support film that had been kneaded 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 Futamura Co., Ltd.) was bonded onto the photosensitive film to prepare a photosensitive film laminate composed of three layers.

<Production of test substrate>
Circuit-formed substrate (500 mm × 600 mm × 0.4 mmt) surface is chemically polished with CZ8101 manufactured by Mec Co., Ltd., and the photosensitive film laminate obtained as described above is formed on the chemically polished surface of the substrate. The exposed surface of the photosensitive film that was exposed by peeling the polypropylene film from the body was bonded together, and then the degree of pressure was 0.8 Mpa, 70 ° C., 1 minute using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho). Then, the laminate was heated and laminated under the condition of a degree of vacuum of 133.3 Pa to adhere the substrate and the photosensitive film.

Next, using a parallel light exposure device equipped with a short arc type high-pressure mercury lamp, solid exposure was performed for the visibility of scratches and the adhesion to the die attach material from the polyethylene terephthalate film in contact with the photosensitive film through the exposure mask. The pattern collapse was exposed using a negative pattern designed to be SRO 80 μm, and then the polyethylene terephthalate film was peeled off to expose the photosensitive film. In addition, the exposure amount was taken as the exposure amount which will become 7 steps | paragraphs, when exposing using the Stuffer 41 step | paragraph from the polyethylene terephthalate film which touches a photosensitive film. Thereafter, the exposed surface of the exposed photosensitive film was developed and patterned using a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. and a spray pressure of 2 kg / cm ² for 60 seconds. Then, after irradiating the photosensitive film patterned with an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, it is heated at 160 ° C. for 60 minutes to be additionally cured to form a cured film, A test substrate 1 having a cured coating formed on the substrate was produced.

Example 2
A test substrate 2 was produced in the same manner as in Example 1 except that the photosensitive resin composition 2 was used in place of the photosensitive resin composition 1 in Example 1.

Example 3
In Example 1, the number of protrusions per unit area of 1 mm ² of the surface is 8.0 × 10 ² , and the support having a thickness of 16 μm having an arithmetic average surface roughness Ra ′ of 0.13 μm on one side. Example, except that instead of the film, a support film (G-50, manufactured by Kimoto Co., Ltd.) having a thickness of 125 μm in which a non-uniform protrusion was formed on one surface of the polyethylene terephthalate film was coated. In the same manner as in Example 1, a test substrate 3 was produced. When the number of protrusions per unit area 1 mm ^{2 of the} surface subjected to the coating treatment of the support film and the measurement of the arithmetic average surface roughness Ra ′ were measured in the same manner as described above, the protrusions per unit area 1 mm ^{2 of the} surface Was 1.3 × 10 ³ and the arithmetic average surface roughness Ra ′ was 0.48 μm.

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

Example 5
In Example 1, the number of protrusions per unit area of 1 mm ² of the surface is 8.0 × 10 ² , and the support having a thickness of 16 μm having an arithmetic average surface roughness Ra ′ of 0.13 μm on one side. Example, except that instead of the film, a support film (CM-25 manufactured by Unitika Co., Ltd.) having a thickness of 25 μm in which a non-uniform protrusion was formed on one surface of the polyethylene terephthalate film was coated. In the same manner as in Example 1, a test substrate 5 was produced. When the number of protrusions per unit area 1 mm ^{2 of the} surface subjected to the coating treatment of the support film and the measurement of the arithmetic average surface roughness Ra ′ were measured in the same manner as described above, the protrusions per unit area 1 mm ^{2 of the} surface Was 4.5 × 10 ³ and the arithmetic average surface roughness Ra ′ was 0.19 μm.

Example 6
A test substrate 6 was produced in the same manner as in Example 5 except that the photosensitive resin composition 2 was used in place of the photosensitive resin composition 1 in Example 5.

Example 7
In Example 1, the number of protrusions per unit area of 1 mm ² of the surface is 8.0 × 10 ² , and the support having a thickness of 16 μm having an arithmetic average surface roughness Ra ′ of 0.13 μm on one side. Example 1 except that instead of the film, sandblast treatment was performed on one side of a polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.) and a support film having a thickness of 25 μm formed with uneven protrusions on the film surface was used. Similarly, a test substrate 7 was produced. When the number of protrusions per unit area 1 mm ^{2 of the} surface of the support film subjected to sandblasting and the measurement of the arithmetic average surface roughness Ra ′ were measured in the same manner as described above, the protrusions per unit area 1 mm ^{2 of the} surface Was 1.7 × 10 ⁴ and the arithmetic average surface roughness Ra ′ was 5.00 μm.

Example 8
A test substrate 8 was produced in the same manner as in Example 7 except that the photosensitive resin composition 2 was used in place of the photosensitive resin composition 1 in Example 7.

Comparative Example 1
In Example 1, the number of protrusions per unit area of 1 mm ² of the surface is 8.0 × 10 ² , and the support having a thickness of 16 μm having an arithmetic average surface roughness Ra ′ of 0.13 μm on one side. A test substrate 9 was produced in the same manner as in Example 1 except that a polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used as the support film instead of the film. When the number of protrusions per unit area 1 mm ^{2 on} the surface of the support film and the arithmetic average surface roughness Ra ′ were measured in the same manner as described above, the number of protrusions per unit area 1 mm ^{2 of the} surface was 0. The arithmetic average surface roughness Ra ′ was 0.20 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.

<Scratch visibility evaluation>
A pencil core having a hardness of 2H is applied to the surface of the cured film in the exposed areas of the test substrates of Examples 1 to 8 and Comparative Examples 1 and 2 prepared as described above at an angle of 45 ° and a load of 4.9 N. In this state, the film was pressed at a speed of 1 mm per second, and the visibility of scratches on the surface of the cured film was visually evaluated. The evaluation criteria were as follows.
○: No scratches are confirmed on the surface of the cured film in the exposed area. ×: Scratches are confirmed on the surface of the cured film in the exposed area. And evaluated. The evaluation results were as shown in Table 2 below.

<Production of die attach material>
As an epoxy resin, 80 parts of trishydroxyphenylmethane type epoxy resin (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), 15 parts of bisphenol F type epoxy resin (RE-303S-L manufactured by Nippon Kayaku Co., Ltd.), and a flexible epoxy resin 50 parts of methyl ethyl ketone was added to 5 parts (Mitsubishi Chemical Corporation YX7105), and the mixture was heated and melted to obtain Resin Varnish A. For 150 parts of the obtained resin varnish A, 3 parts of an imidazole compound (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) as a curing catalyst, 150 parts of fused silica (FB-3SDX, manufactured by Denka), a silane coupling agent (Shin-Etsu Silicone) 1 part of KBE-402) was added, premixed with a stirrer, and kneaded with a three-roll mill to obtain resin varnish B. The obtained resin varnish B was applied to a substrate film and dried at a temperature of 80 ° C. for 15 minutes to produce a die attach material having a thickness of 45 μm.

<Adhesion evaluation with die attach material>
The die attach material produced as described above is cut out to a predetermined size (vertical 5 mm × horizontal 5 mm × thickness 0.045 mm) and formed into a silicon chip (vertical 5 mm × horizontal 5 mm × thickness 0.725 mm, oxide film coating). Affixed at 70 ° C. and crimped to the surface of the cured film of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 and 2 in the order of silicon chip, die attach material, and cured film using a thermocompression tester. (Pressing condition: 260 ° C., 10 seconds, 1.0 MPa). Next, the die attach material was completely cured by heating at 175 ° C. for 120 minutes. Then, it is left for 72 hours in a constant temperature and humidity chamber (PR-2KP manufactured by Espec Co., Ltd.) at 85 ° C. and 85% relative humidity, and after taking out, an adhesive force measuring device (manufactured by Nordson Advanced Technology Co., Ltd., universal bond tester 4000 Plus). The temperature of the stage on which the sample was set was 260 ° C., and the adhesive force was measured under the 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 prepared, and the evaluation criteria were as follows.
○: Adhesive strength is 3 MPa or more for all 10 test pieces. ×: One or more test pieces having an adhesive strength of less than 3 MPa are generated in 10 test pieces. Based on the test and evaluation. The measurement results were as shown in Table 2 below.

<Measurement of the number of depressions per unit area 1 mm ² of the surface of the photosensitive film and the arithmetic average surface roughness Ra>
The substrate (150 mm × 95 mm × 0.8 mmt) on which the circuit was formed was chemically polished with CZ8101 manufactured by Mec Co., Ltd., and the surfaces of the substrate subjected to chemical polishing were subjected to Examples 1-8 and Comparative Examples 1-2. The exposed surface of the photosensitive film (140 mm × 90 mm) exposed by peeling the polypropylene film from each of the used photosensitive film laminates was bonded together, and then a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho) was used. The substrate and the photosensitive film were brought into close contact with each other by heating lamination under conditions of a pressure of 0.8 Mpa, 70 ° C., 1 minute, and a vacuum of 133.3 Pa. Thereafter, the polyethylene terephthalate film was peeled off at 90 ° from the substrate to expose the photosensitive film. Within 5 minutes after exposure, the number of depressions per unit area 1 mm ^{2 on the} surface of the photosensitive film and the arithmetic average surface roughness Ra were measured as follows.

The number of depressions per unit area 1 mm ^{2 on the} surface of the photosensitive film is the same as the measurement of the number of protrusions per unit area 1 mm ^{2 on the} surface of the support film. The measurement was performed in the same manner as described above except that the substrate was bonded to the film (the photosensitive film surface was on the top). In the measurement of the “number of depressions 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 15073 μm ² . An analysis application (VK-H1XA) was used. 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, Press the [Threshold] button to display the [Threshold area setting dialog] box. A value obtained by adding the value in the [upper limit] box and the value in the [lower limit] box and dividing the result by 2 Ave. (Μm) was calculated and its Ave. A portion having a value Zs (μm) or less obtained by subtracting 0.2 μm from (μm) was defined as a “dent”. Do not change the value in the [Lower limit] box, enter the value of Zs (μm) in the [Upper limit] box, press the OK button, and then change the ROI drawing color at the border of the image display area. counted number C (number), from the number C (number) was calculated unit area 1 mm ² number per D (number ^{/ mm 2) (D = C} × 66.34). Of the portions that changed to the ROI drawing color, those that were cut off in the image display area and could not be recognized as one were counted as 0.5. In addition, the “arithmetic average surface roughness Ra” of the photosensitive film surface is the same as that described above except that the sample is replaced with a support film and the exposed photosensitive film is bonded to the substrate (the photosensitive film surface is at the top). The measurement was performed in the same manner as above. “Measured number of depressions per 1 mm ^{2 of} unit area” and “arithmetic average surface roughness Ra” of the surface of each photosensitive film were as shown in Table 2. In any of the examples, the confirmed depression was non-uniform.

<Pattern collapse>
Using each test substrate produced as described above, the wrinkles of 10 openings were observed with a 1000 × scanning electron microscope (SEM). The evaluation criteria were as follows.
：: All of the 10 openings have good formation of wrinkles. ○: The opening has a tapered shape, but the protrusion of the resin contained in the photosensitive film on the top of the wrinkles is 10 pieces. Not observed in any of the openings X: The protrusion of the resin contained in the photosensitive film on the top of the ridge is observed in one or more openings. The evaluation results are as shown in Table 2 below. It was.

Claims (4)

A photosensitive film laminate in which a support film is laminated on a photosensitive film,
The photosensitive film is provided with a surface having a depression in the surface, Ri Na is formed by a photosensitive resin composition, the number of depressions of the unit area 1 mm ² per said surface 3.0 × 10 ² or more, 2 0.0 × 10 ⁴ or less ,
The photosensitive said support film on the side having a recess on the surface of the film, wherein Rukoto such are stacked, photosensitive film laminate. The photosensitive film laminated body of Claim 1 whose arithmetic mean surface roughness Ra of the said surface is 0.05 micrometer or more. The photosensitive film laminated body of Claim 1 or 2 in which the said photosensitive resin composition comprises a filler and a crosslinking component. Hardened | cured material formed using the photosensitive film laminated body as described in any one of Claims 1-3 .