KR102158945B1 - Photosensitive film, photosensitive film laminate and cured product formed by using same - Google Patents

Abstract

It provides a photosensitive film which is excellent in adhesion to a die attach material and can improve yield even in visual inspection of a cured film. Provided with a surface having a concave portion on the surface and, in the photosensitive film formed of formed of a photosensitive resin composition, characterized in that the number per unit area of the concave portion 1mm ² of the surface with more than 3.0 × 10 ^2.

Description

A photosensitive film, a photosensitive film laminate, and a cured product formed by using them {PHOTOSENSITIVE FILM, PHOTOSENSITIVE FILM LAMINATE AND CURED PRODUCT FORMED BY USING SAME}

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

In general, in printed wiring boards used in electronic devices, etc., when mounting electronic components on the printed wiring board, in order to prevent solder from adhering to unnecessary portions, a solder resist layer is provided in the area except for the connection holes on the substrate on which the circuit pattern is formed. Is formed.

Along with the high precision and high density of printed wiring boards due to light, thin and short reduction in electronic devices in recent years, the current solder resist layer is a patterned resin after applying a photosensitive resin composition to a substrate and forming a pattern by exposure and development. The mainstream is that which is formed by a so-called photo solder resist which is cured by heating or irradiation with light.

Further, it is also proposed to form a solder resist layer using a so-called photosensitive film laminate provided with a photosensitive film without using the liquid photosensitive resin composition as described above. By using the photosensitive film layered product, compared with the case of wet coating, the drying process after application|coating can be made unnecessary. In addition, surface smoothness and surface hardness are also excellent.

The substrate on which the solder resist has been formed proceeds to a semiconductor mounting process. Among them, in the solder resist used in the wire bonding specification, a semiconductor is mounted by a die attach material and connected by wire bonding. Here, as a solder resist, surface smoothness and adhesion with a die attach material are very important factors. In recent years, according to the thinning of the substrate, a very high degree of specification accuracy is required for various materials used. From this point of view, the film laminate as described above is also used for the solder resist, and surface uniformity is required. Similarly, for die attach materials on which semiconductors are mounted, uniform film thickness of the material and thinner are required. For example, in Japanese Patent Application Laid-Open No. 2016-069625, a dry film laminate corresponding to a thin film substrate is proposed. However, it was very difficult to achieve both the above-described improvement of the specification accuracy and the adhesion between the solder resist and the die attach material.

On the other hand, since the solder resist is used for the outermost layer of the substrate and is formed in the final stage of the substrate manufacturing process, scratches may occur during the substrate manufacturing process due to the use of equipment or transfer tools (e.g., Japanese Patent Publication No. 2015-206992). These scratches are judged as NG in the visual inspection before the semiconductor mounting step, and the production yield may deteriorate. In particular, in recent years, even a small scratch without a quality problem causes a decrease in productivity, so it is one of the important requirements, and a new improvement method is required.

Accordingly, it is an object of the present invention to provide a photosensitive film that is excellent in adhesion to a die attach material and can improve yield even in visual inspection of a cured film. Further, another object of the present invention is to provide a photosensitive film laminate provided with a photosensitive film and a cured product formed using the photosensitive film laminate.

The inventors of the present invention have pointed out that in the case of forming a layer formed using a photosensitive film laminate, especially a solder resist layer, especially when applied to a substrate for an IC package, in the die attach material forming process after IC chip mounting, the solder resist It was found that the cause of the poor adhesion to the layer lies in the shape of the surface of the solder resist layer. In addition, the present inventors believe that by using a photosensitive film having a surface having a specific concave portion on the surface, an appropriate concave portion can be provided on the surface of the solder resist layer, and as a result, the adhesion to the die attach material can be improved. Gained knowledge. In addition, the present inventors believe that the solder resist layer formed by using a photosensitive film having a surface having a specific concave portion as described above becomes difficult to visually recognize the scratch even when the surface is scratched, so that the yield can be improved in the appearance inspection. I got the knowledge that I can. The present invention is based on this knowledge.

[1] The photosensitive film according to the first embodiment of the present invention has a surface having a concave portion on its surface and is formed of a photosensitive resin composition, wherein the number of concave portions per unit area of the surface 1 mm ² Is characterized in that 3.0×10 ² or more.

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

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

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

[5] A photosensitive film laminate according to a fifth embodiment of the present invention is characterized in that a support film is laminated on the photosensitive film in any one of [1] to [4].

[6] A photosensitive film laminate according to a sixth embodiment of the present invention has a surface having a concave portion on its surface, and is supported on the side of a surface having a concave portion on the surface in a photosensitive film formed of a photosensitive resin composition It is the photosensitive film laminate of [6] obtained by laminating films.

[7] The cured product according to the seventh embodiment of the present invention is characterized in that it is formed using the photosensitive film of any one of [1] to [4], or the photosensitive film laminate of [5] or [6]. Is to do.

Advantageous Effects of Invention According to the present invention, it is possible to realize a photosensitive film which is excellent in adhesion to a die attach material and can improve yield even in visual inspection of a cured film. Further, according to a preferred embodiment of the present invention, a photosensitive film excellent in formation of a photosensitive pattern, particularly suppression of furrow collapse of the pattern can be realized. It is particularly effective when a photosensitive film is used for formation of a solder resist layer.

The photosensitive film according to the present invention will be described. The photosensitive film has a photosensitive resin composition in the form of a film, and it means that no other layers such as a support film or a protective film are laminated. Further, in the present invention, in consideration of workability and easiness in forming the surface of the photosensitive film into a predetermined shape to be described later, a support film may be provided on one side of the photosensitive film, and the surface of the photosensitive film While preventing the etc. from adhering, in consideration of the handling property of the photosensitive film laminate, a protective film may be further provided on the surface opposite to the support film. 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 concave portion on its surface, is formed of a photosensitive resin composition, and the number of concave portions per 1 mm ² of the surface is 3.0×10 ² or more. . The number of concave portions per unit area of 1 mm ² is three-dimensionally measured by three-dimensionally measuring the unevenness of the surface of the target photosensitive film with the z-axis as the height direction, obtaining the maximum and minimum values of the aggregates of the obtained z values, and calculated from the maximum and minimum values. A Zs value that is 0.2 μm lower than the average value is used as the threshold value, and the area having a z value less than the threshold value is used as the concave area, and the value is calculated by counting the number of concave areas in a unit area of 1 mm ² . 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 plane, when the maximum and minimum values of the aggregates of the obtained z values are 3.00 μm and 1.00 μm, respectively, the average value becomes 2.00 μm. , 1.80 µm, which is 0.2 µm lower than this, becomes the Zs value, that is, the "threshold value". The number of concave portions can be determined by counting the number of concave portions scattered in the measurement surface by making the set of the xy-axis plane continuous with a value lower than the threshold value of 1.80 mu m as one concave area. A more detailed measurement procedure will be described later.

In the present invention, by using a photosensitive film having a surface in which the number of concave portions per unit area 1 mm ² calculated as described above is 3.0×10 ² or more, it is possible to improve adhesion to the die attach material. In addition, when a solder resist layer or the like is formed by using a photosensitive film having such a specific surface shape, the yield can be improved in visual inspection to check the presence or absence of surface scratches of the solder resist layer. The reason for this unexpected effect is not necessarily clear, but by forming concave portions on the surface of the photosensitive film and making the concave portions an appropriate number, an appropriate continuous surface is formed on the surface of the photosensitive film, and the continuous surface and the concave portion are mixed. Even if a small flaw is formed in the region, it is speculated that the reflection of the flaw is alleviated by the concave portion and the flaw is difficult to see. On the other hand, it is speculated that the adhesion to the die attaching member is dramatically improved by the anchor effect due to the concave portion. However, it is the area of speculation to the last, and not necessarily.

The number of concave portions per unit area of 1 mm ² on the surface of the photosensitive film is preferably 4.0×10 ² or more, more preferably 5.0×10 ² or more. The number of concave portions 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, it has excellent adhesion to the die attaching material, and the yield is also improved in visual inspection of the cured film. In addition to the point that can be improved, it is possible to obtain an excellent effect of suppressing the formation of a photosensitive pattern of the solder resist layer, particularly the collapse of the furrows of the pattern. The number of concave portions per unit area of 1 mm ² is more preferably 1.5×10 ⁴ or less, and still more preferably 1.0×10 ⁴ or less. Here, the furrow collapse of the pattern is, for example, in the case of forming SRO (solder resist openings) using a photosensitive film, after exposure and development, the resin content contained in the photosensitive film on the furrow of the opening collapses and the inside of the opening It means a phenomenon that is pushed out by. In the present invention, it was found that by setting it as a photosensitive film having a specific surface shape as described above, it is possible to suppress unexpected collapse of the furrow of the pattern.

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

Further, the concave portion on the surface of the photosensitive film may be uniform or non-uniform, but from the viewpoint of the balance of improving the adhesion to the die attaching material and the yield in the appearance inspection, it is preferably non-uniform. Further, it is preferable that the depth of the concave portion is 0.2 µm or more.

In addition, from the viewpoint of the balance described above, the arithmetic mean surface roughness Ra of the surface having a predetermined concave portion of the photosensitive film is preferably 0.05 µm or more, more preferably 0.06 µm or more, and even more preferably 0.07 µm or more. Further, when setting the upper limit, it is preferably 5.0 µm or less, more preferably 3.0 µm or less, and still more preferably 1.0 µm or less.

In the present invention, the "number of concave portions per unit area of 1 mm ² " and "arithmetic average surface roughness Ra" mean values measured by a measuring apparatus conforming to JIS B0601-1994. Hereinafter, a specific measurement method will be described. The number of concave portions per unit area of 1 mm ² and the arithmetic mean surface roughness Ra can be measured using a shape measuring laser microscope (eg, VK-X100 manufactured by Keyence Corporation). After starting the shape measurement laser microscope (the VK-X100) body (control unit) and the VK observation application (VK-H1VX manufactured by Keyence Corporation), the sample to be measured is loaded on the xy stage. Turn the lens revolver of the microscope unit (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10 times, and adjust the focus and brightness approximately in the image observation mode of the VK observation application (VK-H1VX). By operating the xy stage, adjust so that the almost 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 autofocus function of the image observation mode of the VK observation application (VK-H1VX) is used to focus on the surface of the sample. The simple mode of the shape measurement tab of the VK observation application (VK-H1VX) is selected, the measurement start button is pressed, the surface shape of the sample is measured, and a surface image file can be obtained. A VK analysis application (VK-H1XA manufactured by Keyence Corporation) is started, the obtained surface image file is displayed, and then tilt correction is performed.

In the measurement of "the number of concave portions per unit area 1 mm ² ", the observed measurement range (area) in the measurement of the surface shape of the sample is 15073 μm ² . For example, an analysis application (VK-H1XA) can be used. Select [Volume·Area] from the measurement analysis menu on the display screen and display the [Volume·Area] window. After selecting [Height] from the [Display image] box in the [Volume·Area] window, press the [Threshold] button to display the [Threshold Area Setting Dialog] box. Divided by 2 by adding the value of the displayed [Upper Limit] box and the value of the [Lower Limit] box to calculate Ave.(µm), and subtract 0.2µm from the Ave.(µm) to calculate the Zs value (µm) or less. The concave part”. Without changing the value of the [Lower Limit] box, enter the Zs value (µm) in the [Upper Limit] box, press the OK button, and then the number of places in the image display area that change to the color of the ROI drawing color C (pcs) the counting, and with a number of from C (dog), the unit area value of the calculated number of 1mm ² D (dog / mm ²⁾ per (D = C × 66.34). It is to be noted that, among the locations that have changed to the color of the ROI drawing color, those which are cut off at the boundary of the image display area and cannot be recognized as one are counted as 0.5.

Moreover, in the measurement of "arithmetic mean surface roughness Ra", the objective lens is switched 50 times, and the observation measurement range (horizontal) in the measurement of the surface shape of a sample is 270 micrometers. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line at an arbitrary place in the surface image, and press the OK button to determine the arithmetic average surface. The value of the illuminance Ra ₁ is obtained. Further, horizontal lines are displayed at four other places in the surface image, and numerical values of the respective arithmetic mean surface roughness Ra ₁ are obtained. The average value of the five values obtained Ra _ave. Is calculated, and these values are taken as the arithmetic mean surface roughness Ra value of the sample surface. In addition, when measuring the photosensitive film in the photosensitive film laminate, after peeling the supporting film to expose the surface of the photosensitive film, measurement of ``the number of concave parts per unit area 1 mm <sup>2</sup> '' and ``arithmetic average surface roughness Ra'' within 5 minutes Let's do.

In order to make the surface shape of the photosensitive film into the range of the specific number of concave portions per unit area 1 mm ² and the specific arithmetic average surface roughness Ra, a known and common method can be applied, but among them, forming in such a surface shape It is preferable to form a photosensitive film using the supporting film mentioned later from a viewpoint of the easiness of thing. That is, in the case of a photosensitive film laminate formed by laminating a support film on the photosensitive film of the present invention, the surface of the photosensitive film having a surface having a specific number of concave portions and, if desired, a specific arithmetic average surface roughness Ra, is the support film It is preferably a surface in contact with. Further, it is preferable that the photosensitive film is for forming a solder resist layer.

The above-described photosensitive film having a surface having a number of concave portions of 3.0×10 ² or more per 1 mm ² of unit area, and in a more preferred embodiment, a photosensitive film having an arithmetic average surface roughness Ra of 0.05 μm or more of the surface is exposed and developed. As a result, it is patterned and becomes a cured film provided on a circuit board. As a cured film, it is preferable that it is a solder resist layer. Such a photosensitive film can be formed using a photosensitive resin composition, and the photosensitive resin composition can be used without limitation, such as a conventionally known solder resist ink, but hereinafter, a photosensitive resin composition that can be preferably used for the photosensitive film according to the present invention An example of will be described.

In the present invention, it is preferable that the photosensitive resin composition contains a crosslinking component and a filler. Moreover, it is more preferable to contain a photoinitiator. The crosslinking component is preferably a carboxyl group-containing photosensitive resin or a photosensitive monomer, and when further heated, it is preferable to include a component that is crosslinked by heat. Hereinafter, each component is demonstrated.

[Crosslinking ingredients]

The crosslinking component is not particularly limited as long as it is a component to be crosslinked, and a known and commonly used one can be used. Particularly, a carboxyl group-containing photosensitive resin or a photosensitive monomer is preferable, and when further heated, it is preferable to include a component that is crosslinked by heat (hereinafter, a thermal crosslinking component).

The carboxyl group-containing photosensitive resin is a component that is polymerized or crosslinked by light irradiation to be cured, and can be made alkali developable by including a carboxyl group. Moreover, it is preferable to have an ethylenically unsaturated bond in a molecule other than a carboxyl group from a viewpoint of photocurability and development resistance. As the ethylenically unsaturated double bond, those derived from acrylic acid or 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 in which no epoxy resin is used as a starting material. The carboxyl group-containing photosensitive resin in which an epoxy resin is not used as a starting material has a very small halide ion content, so that deterioration of insulation reliability can be suppressed. As a specific example of a carboxyl group-containing photosensitive resin, the compound (all oligomer or polymer may be sufficient) enumerated below is mentioned.

(1) Dibasic acid anhydrides such as phthalic anhydride, tetrahydro phthalic anhydride, and hexahydro phthalic anhydride are added to the hydroxyl group present in the side chain by reacting (meth)acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin. Carboxyl group-containing photosensitive resin,

(2) The hydroxyl group of a bifunctional (solid) epoxy resin is further epoxidized with epichlorohydrin, and (meth)acrylic acid is reacted with a carboxyl group obtained by adding a dibasic acid anhydride to the resulting hydroxyl group. Photosensitive resin,

(3) Reaction of an epoxy compound having two or more epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with respect to the alcoholic hydroxyl group of the reaction product obtained by

(4) In one molecule of bisphenol A, bisphenol F, bisphenol S, novolak-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. In the reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide or propylene oxide, a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid is reacted to the reaction product obtained. Carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride,

(5) Polybasic acid in the reaction product obtained by reacting 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 and propylene carbonate, and a monocarboxylic acid containing an unsaturated group. Carboxyl group-containing photosensitive resin obtained by reacting an anhydride,

(6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenols A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the terminal of a urethane resin by polyaddition reaction of a diol compound such as a compound having an A-based alkylene oxide adduct diol, a phenolic hydroxyl group and an alcoholic hydroxyl group,

(7) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, hydroxyalkyl (meth)acrylate, etc. A carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule to form a terminal (meth)acrylate,

(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., 1 in the molecule. A carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth)acryloyl groups to obtain a terminal (meth)acrylate,

(9) To a carboxyl group-containing polyester resin in which a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid is reacted with a polyfunctional oxetane resin, and dibasic acid anhydride is added to the generated primary hydroxyl group, In addition, carboxyl group-containing photosensitivity obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate Suzy,

(10) a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth)acryloyl group in one molecule to the photosensitive resin containing a carboxyl group in any of the above (1) to (9),

(11) About a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene, A photosensitive resin containing a carboxyl group in which a compound having a cyclic ether group and a (meth)acryloyl group is reacted in one molecule such as 3,4-epoxycyclohexyl methacrylate, etc. are mentioned. In addition, (meth)acrylate herein is a term generically referring to acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions below.

Among the above-described carboxyl group-containing photosensitive resins, as described above, a carboxyl group-containing photosensitive resin obtained by synthesizing a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material or a resin other than an epoxy resin can be suitably used. Therefore, among the specific examples of the above-described carboxyl group-containing photosensitive resin, any one or more carboxyl group-containing photosensitive resins of (4) to (8) and (11) can be suitably used, as illustrated in (4) to (8). Resins can be used particularly suitably. It can have properties required for a solder resist for a semiconductor package, that is, PCT resistance, HAST resistance, and cold heat shock resistance.

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

Further, by not using the epoxy resin as a starting material, a resin containing no hydroxyl group (or the amount of hydroxyl group reduced) can be easily obtained. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but is known to significantly lower moisture resistance, and it is possible to improve moisture resistance by using a photosensitive resin containing a carboxyl group that does not contain a hydroxyl group. It becomes.

Further, a carboxyl group-containing urethane resin synthesized from an isocyanate compound not using phosgene as a starting material and a 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, by matching the equivalent of a hydroxyl group and an isocyanate group, a resin containing no hydroxyl group can be easily synthesized.

In addition, when synthesizing a urethane resin, an epoxy acrylate modified raw material may be used as a diol compound. Although the chlorine ion impurity enters, it can be used in that the amount of the chlorine ion impurity can be controlled.

Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chains of the backbone/polymer, it can be developed with an aqueous alkali solution.

It is preferable that the acid value of the carboxyl group-containing photosensitive resin is 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing photosensitive resin is 40 mgKOH/g or more, the alkali phenomenon is improved. Further, 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 differs depending on the resin skeleton, but is generally preferably 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, the dry-to-touch performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, developability and storage stability can be improved. More preferably, it is 5,000-100,000.

It is preferable that the blending amount of the carboxyl group-containing photosensitive resin is 20 to 60 mass% in the total composition in terms of solid content. By setting it as 20 mass% or more, the coating film strength can be improved. Moreover, by setting it as 60 mass% or less, viscosity becomes moderate and workability improves. More preferably, it is 30-50 mass %.

As a compound used as a photosensitive monomer, for example, commonly 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; Glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, etc. Polyhydric acrylates; Polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, or urethane acrylate through diisocyanate, and It can be appropriately selected and used from at least any one of each of the methacrylates corresponding to the acrylate.

Epoxy acrylate resin in which acrylic acid is reacted with polyfunctional epoxy resin such as cresol novolak type epoxy resin, or hydroxyacrylate such as pentaerythritol triacrylate and isophorone in the hydroxyl group of the epoxy acrylate resin An epoxy urethane acrylate compound obtained by reacting a half urethane compound of diisocyanate such as diisocyanate, etc., may be used as the photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating dry to touch.

The compounding amount of the compound having an ethylenically unsaturated group in the molecule used as the photosensitive monomer is preferably 5 to 100 parts by mass, more preferably 5 to 100 parts by mass, more preferably, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content, when a carboxyl group-containing resin is included in the composition. The ratio is 5 to 70 parts by mass. When the compounding amount of the compound having an ethylenically unsaturated group is 5 parts by mass or more, the photocurability of the photocurable resin composition is improved. In addition, coating film hardness can be improved by making the compounding amount 100 parts by mass or less. The carboxyl group-containing resin referred to herein includes any of a carboxyl group-containing photosensitive resin and a carboxyl group non-photosensitive resin. That is, when any one of the compositions is blended alone, the sum is used alone, and if all are blended, the sum is referred to (same in the subsequent paragraphs).

As the photosensitive monomer, especially when using a non-photosensitive resin containing a carboxyl group that does not have an ethylenically unsaturated double bond, it is necessary to use a compound (photosensitive monomer) having at least one ethylenically unsaturated group in the molecule in order to make the composition photocurable. Because, it is valid.

As a thermal crosslinking component, a thermosetting resin etc. are mentioned. As the thermosetting resin, known such as isocyanate compound, block isocyanate compound, amino resin, maleimide compound, benzoxazine resin, carbodiimide resin, cyclocarbonate compound, polyfunctional epoxy compound, polyfunctional oxetane compound, episulfide resin, etc. You can use something of tolerance. 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 these cyclic (thio) ether groups, and various properties can be imparted depending on their structure.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of groups of either or two types of a 3, 4 or 5 membered cyclic ether group or a cyclic thioether group in the molecule, for example Compounds having a plurality of epoxy groups, i.e., 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, episulfide resin, etc. Can be mentioned.

As a polyfunctional epoxy compound, for example, Mitsubishi Chemical Corporation jER828, jER834, jER1001, jER1004, DIC Corporation Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 1050, Epiclon 2055, Epotto YD-011, YD-013, YD-127, YD-128 manufactured by Shinnittetsu Sumikin Co., Ltd., DER317, DER331, DER661, DER664, and Sumitomo manufactured by Dow Chemical Of Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Gaku High School Co., Ltd., AER330, AER331, AER661, AER664 manufactured by Asahi Kasei Kogyo Co., Ltd. (all brand names) Bisphenol A type epoxy resin; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 manufactured by DIC Corporation, Epiclon 165 manufactured by DIC Corporation, Epotto YDB-400 manufactured by Shinnittetsu Sumikin Corporation, YDB-500 manufactured by Dow Chemical, and DER542 manufactured by Dow Chemical Corporation. , Sumitomo Chemical Co., Ltd. Sumiepoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd. AER711, AER714, etc. (all brand names) of brominated epoxy resins; JER152, jER154 manufactured by Mitsubishi Chemical Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical, and Epiclon N-730 manufactured by DIC Corporation, Epiclone N-770, Epiclon N-865, and Shinnittetsu Sumikin Epotto YDCN-701, YDCN-704 manufactured by Nippon Kayaku Corporation, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, Sumitomo manufactured by Nippon Kayaku Corporation Novolac-type epoxy resins such as Sumiepoxy ESCN-195X, ESCN-220, manufactured by Kagaku Kogyo Kogyo, AERECN-235, ECN-299 manufactured by Asahi Kasei Kogyo, etc. (all are brand names); Bisphenol F type of Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Epotto YDF-170, YDF-175, YDF-2004 manufactured by Shinnittetsu Sumikin Corporation (all brand names) Epoxy resin; Hydrogenated bisphenol A type epoxy resins, such as Epototo ST-2004, ST-2007, and ST-3000 (brand name) manufactured by Shinnittetsu Sumikin Co., Ltd.; Glycidylamines such as jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epotto YH-434 manufactured by Shinnittetsu Sumikin Corporation, and Sumitomo Chemical Co., Ltd. Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Type epoxy resin; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Co., Ltd. (brand name); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.E.N. manufactured by Dow Chemical, EPPN-501, and EPPN-502 (all are brand names); Bixylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000, and YL-6121 (all brand names) manufactured by Mitsubishi Chemical Co., Ltd., or mixtures thereof; Bisphenol S-type epoxy resins such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Asahi Tenka Kogyo Co., Ltd., and EXA-1514 (brand name) by DIC Co., Ltd.; Bisphenol A novolac type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Co., Ltd.; Tetraphenylolethane type epoxy resins such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd.; Heterocyclic epoxy resins such as TEPIC (brand name) manufactured by Nissan Chemical Industry Co., Ltd.; Diglycidylphthalate resins such as Blemmer DGT manufactured by Nippon Yushi Co., Ltd.; Tetraglycidyl xylenoylethane resin, such as ZX-1063 manufactured by Shinnittetsu Sumikin Co., Ltd.; Naphthalene group-containing epoxy resins, such as ESN-190, ESN-360, and DIC Corporation HP-4032, EXA-4750, EXA-4700 manufactured by Shinnittetsu Chemical Co., Ltd.; Epoxy resins having dicyclopentadiene skeletons, such as HP-7200 and HP-7200H manufactured by DIC Corporation, and flexible tough epoxy resins of the EXA-4816, EXA-4822, and EXA-4850 series; Glycidyl methacrylate copolymerized epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; Further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate may be mentioned, but the present invention is not limited thereto. These epoxy resins can be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, and 1,4-bis[( 3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methylacrylic Rate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate and their In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calix resorcinarenes or silsesquioxane Etherified products with resins having a hydroxyl group such as the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. are also mentioned.

Examples of the episulfide resin include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like. Further, by using the same synthesis method, an episulfide resin in which the oxygen atom of the epoxy group of the novolac type epoxy resin is substituted with a sulfur atom can also be used.

The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin in terms of solid content when the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. , Preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents. When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is 0.3 equivalent or more, no carboxyl groups remain in the cured film, and heat resistance, alkali resistance, electrical insulation, and the like are improved. Moreover, by setting it as 2.5 equivalent or less, the cyclic (thio) ether group of a low molecular weight does not remain in a dry coating film, and strength etc. of a cured film are improved.

In the case of using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to blend a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole , Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid dihydrazide, and sebacic acid dihydrazide; Phosphorus compounds, such as triphenylphosphine, etc. are mentioned. In addition, as commercially available ones, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., manufactured by San Apro U-CAT (registered trademark) 3503N, U-CAT3502T (all trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof), etc. are mentioned. . In particular, it is not limited to these, and may be used alone or in combination of two or more, as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group. none. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid S-triazine derivatives such as adducts may also be used, and compounds which also function as adhesive imparting agents are preferably used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is based on 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule in terms of solid content when the composition contains a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. , Preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound. In addition, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound, and alkoxymethylated urea compound are each methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound, and methylolurea compound. It is obtained by converting the methylol group of to an alkoxymethyl group. The kind of this alkoxymethyl group is not particularly limited, and may be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, or a butoxymethyl group. In particular, a melamine derivative having a formalin concentration of 0.2% or less, which is friendly to the human body or the environment, is preferable.

Commercially available products of amino resins include, for example, Cymel 300, B 301, B 303, B 370, B 325, B 327, B 701, B 266, B 267, B 238, B 1141, B 272, B 202, B 1156, East 1158, East 1123, East 1170, East 1174, East UFR65, East 300 (above, manufactured by Mitsui Cyanamide Co., Ltd.), Nikalak Mx-750, East Mx-032, East Mx-270, East Mx -280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw -100LM, copper Mw-750LM (above, manufactured by Sanwa Chemical Co., Ltd.), etc. are mentioned.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is used, for example. As specific examples of the aromatic polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylenediisocyanate 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. As a specific example of the alicyclic polyisocyanate, bicycloheptane triisocyanate is mentioned. And the adduct body, the biuret body, and the isocyanurate body of the isocyanate compound illustrated above are 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 is temporarily inactivated. When heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, an isocyanurate type, a burette type, an adduct type, etc. are mentioned. As an isocyanate compound used for synthesizing a block isocyanate compound, an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate is mentioned, for example. As a specific example of an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate, the compound illustrated above can be mentioned.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; Active methylene-based 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, glycol Alcohol-based blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide-based blocking agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; And imine-based blocking agents such as methyleneimine and propyleneimine.

The block isocyanate compound may be commercially available, for example, Sumdul BL-3175, BL-4165, BL-1100, BL-1265, Death module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Death Mosam 2170, Desmosam 2265 (above, manufactured by Sumitomo Bayer Urethane Corporation, brand name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Tosoh Corporation, brand name), B-830, B-815 , B-846, B-870, B-874, B-882 (above, manufactured by Mitsui Tageda Chemical Co., Ltd., brand name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals Corporation) Shikigaisha make, brand name), etc. are mentioned. In addition, Sumdule BL-3175 and BL-4265 are obtained by using methylethyloxime as a blocking agent.

In the photosensitive resin composition, a urethanization catalyst may be blended in order to accelerate the curing reaction of 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 a tin catalyst, a metal chloride, a metal acetylacetonate salt, a metal sulfate, an amine compound, and an amine salt.

Examples of the tin catalyst include organic tin compounds such as Stanus octoate and dibutyltin dilaurate, and inorganic tin compounds. Further, as the metal chloride, it is a metal chloride selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include cobalt chloride, nickel chloride, ferric chloride, and the like. have. In addition, the metal acetylacetonate salt is an acetylacetonate salt of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. For example, cobalt acetylacetonate, nickel acetylacetonate, iron And acetylacetonate. Moreover, as a metal sulfate, it is a sulfate of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and, for example, copper sulfate etc. are mentioned.

As an amine compound, for example, 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, dimorpholinodiethylether, N-methylimidazole, dimethylamino Pyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethylbis(2-aminoethyl)ether, N,N-dimethylhexanolamine, N,N-dimethylaminoethoxy Ethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetri Amine, N-(2-hydroxypropyl)-N,N',N",N"-tetramethyldiethylenetriamine, N,N,N'-trimethyl-N'-(2-hydroxyethyl)propane Diamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis(N,N-dimethylaminopropyl)amine, bis(N,N-dimethylaminopropyl)isopropanolamine, 2-aminoquinuclidine , 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidinol, 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'-hydroxy Propyl) 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 At least any one of',N'-bis(2-hydroxyethyl)amine, N,N-dimethylaminoethyl-N',N'-bis(2-hydroxypropyl)amine, melamine and benzoguanamine, etc. Can be mentioned.

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

[filler]

As the filler, a well-known and commonly used inorganic or organic filler can be used. In particular, barium sulfate, spherical silica, titanium oxide, Neuburg silica 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. In addition, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768 manufactured by Hanse-Chemie in which a compound having one or more ethylenically unsaturated groups or nanosilica is dispersed in the polyfunctional epoxy resin. , XP 0953, XP 0954, XP 1045 (all product grade names), or Hanse-Chemie's NANOPOX (brand name) XP 0516, XP 0525, XP 0314 (all product grade names) can also be used. These may be used alone or in combination of two or more. By including the filler, the physical strength of the resulting cured product can be increased.

The blending amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 based on 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 ~150 parts by mass. When the blending amount of the filler is 500 parts by mass or less, the viscosity of the photocurable thermosetting resin composition is not too high, the printability is good, and the cured product is hardly embrittled.

[Photopolymerization initiator]

In the present invention, as the photopolymerization initiator used to photopolymerize the carboxyl group-containing photosensitive resin, a known photopolymerization initiator may be used, but among them, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, An acylphosphine oxide-based photopolymerization initiator is preferred. Photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more types.

As a commercially available oxime ester type photoinitiator, CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, Adeka N-1919 manufactured by Adeka Corporation, and Adeka Acles (registered trademark) ) NCI-831, etc. are mentioned.

Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (I) is mentioned.

(In the formula, X ₁ 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, an amino group, 1 to carbon number) Substituted by an alkylamino group or dialkylamino group having an alkyl group of 8), 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 di Represents a substituted alkylamino group), Y ₁ and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, Substituted by 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 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) , Substituted by an alkylamino group or dialkylamino group having an alkyl group of 1 to 8 carbon atoms), 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 '-Represents styrene-diyl, n is an integer of 0 or 1)

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

As a preferable carbazole oxime ester compound, a compound which can be represented by the following general formula (II) is also mentioned.

(In the formula, R ₃ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

R ₄ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or alkoxy group having 1 to 4 carbon atoms.

R ₅ represents a benzyl group which may be connected with an oxygen atom or a sulfur atom and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group.

R ₆ represents a nitro group or an acyl group represented by X ₂ -C(=O)-.

X ₂ represents an aryl group, thienyl group, morpholino group, thiophenyl group, or a structure represented by the following formula (III) which may be substituted with an alkyl group having 1 to 4 carbon atoms.)

In addition, Japanese Patent Application Publication No. 2004-359639, Japanese Patent Application Publication No. 2005-097141, Japanese Patent Application Publication No. 2005-220097, Japanese Patent Application Publication No. 2006-160634, Japanese Patent Application Publication No. 2008-094770 The carbazole oxime ester compounds described in Japanese Patent Publication No. 2008-509967, Japanese Patent Publication No. 2009-040762, Japanese Patent Application Publication No. 2011-80036, and the like are mentioned.

When the oxime ester photopolymerization initiator is used, the blending amount is preferably 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 a carboxyl group-containing resin is included in the composition. By setting it as 0.01 mass part or more, photocurability on copper becomes more reliable, and coating film characteristics, such as chemical resistance, are improved. Moreover, by setting it as 5 mass parts or less, light absorption on the surface of a coating film is suppressed, and there exists a tendency for hardening of a core part to also improve. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of carboxyl group-containing resins.

As an α-aminoacetophenone-based photoinitiator, 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, etc. are mentioned. As a commercial item, Omnirad (Omniard) 907, Omnirad (Omniard) 369, Omnirad (Omniard) 379, etc. manufactured by IGM Resins are mentioned.

As an acylphosphine oxide-based photoinitiator, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dime) Oxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and the like. As a commercial item, IGM Resins' Omnirad (Omniard) TPO, Omnirad (Omniard) 819, etc. are mentioned.

In addition, as a photoinitiator, Yueyang Kimoutain Sci-tech Co., Ltd. The manufactured JMT-784 can also be used suitably.

When a photopolymerization initiator other than an oxime ester photopolymerization initiator is used, the blending amount is preferably 0.01 to 15 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. By setting it as 0.01 mass part or more, photocurability on copper becomes more reliable, and coating film characteristics, such as chemical resistance, are improved. Further, by setting it as 15 parts by mass or less, a sufficient effect of reducing outgas is obtained, light absorption on the surface of the cured film is suppressed, and the curability of the core is improved. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of carboxyl group-containing resins.

In combination with the above photoinitiator, a photoinitiation aid or a sensitizer may be used. Examples of the photoinitiation aid or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds and xanthone compounds. Although these compounds can be used as a photoinitiator in some cases, it is preferable to use it in combination with a photoinitiator. Moreover, a photoinitiation aid or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned, for example. In addition, as an acetophenone compound, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. are mentioned, for example. have. Moreover, as an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinone, etc. are mentioned, for example. In addition, as a thioxanthone compound, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-diisopropyl thioxanthone, etc. are mentioned, for example. I can. Moreover, as a ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned, for example. In addition, as a benzophenone compound, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl -4'-propyl diphenyl sulfide, etc. are mentioned.

As a tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, as a commercial product, 4,4'-dimethylaminobenzophenone (Nissocure (registered trademark) manufactured by Nippon Soda Corporation. ) MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and other dialkylaminobenzophenone, 7-(diethylamino)-4-methyl-2H-1- Dialkylamino group-containing coumarin compounds such as benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 4-dimethylaminobenzoate ethyl (Kayacure (registered trademark) manufactured by Nippon Kayaku Co., Ltd.) EPA ), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid (n-butoxy)ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid Soami ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk), etc. are mentioned. 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 desirable.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Since the dialkylamino group-containing coumarin compound is in the ultraviolet region with a maximum absorption wavelength of 350 to 410 nm, there is little coloration, and as well as a colorless and transparent photosensitive resin composition, a colored photosensitive film that reflects the color of the colored pigment itself by using a color pigment. It becomes possible to get In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect with respect to laser light having a wavelength of 400 to 410 nm.

Among these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by containing a thioxanthone compound, it is possible to improve the deep curing properties.

When a carboxyl group-containing resin is included in the composition, the total amount of the photoinitiator, photoinitiation aid, and sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. By setting it as 35 parts by mass or less, their light absorption is suppressed, and the curability of the core is also improved.

Further, since these photoinitiators, photoinitiation aids, and sensitizers absorb specific wavelengths, in some cases, sensitivity is lowered and may function as an ultraviolet absorber. However, they are not used solely for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, the photoreactivity of the surface is improved, and the line shape and opening of the resist are changed into vertical, tapered, and inverse tapered shapes, and the processing precision of the line width and opening diameter is improved. I can.

In addition to the above components, 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. Hereinafter, these components are also described.

A block copolymer can be suitably blended into the above photosensitive resin composition. The block copolymer refers to a copolymer having a molecular structure in which two or more types of polymers having different properties are linked by covalent bonds to form a long chain. It is preferably a solid in the range of 20°C to 30°C. Solid may be sufficient within this range, and solid may also be sufficient at a temperature outside this range. By being solid in the said temperature range, it is excellent in adhesiveness when it is set as a photosensitive film, or when it is applied to a support film and pre-dried.

The block copolymer is preferably an XYX or XYX' type block copolymer. In the XYX or XYX' type block copolymer, Y in the center is a soft block and the glass transition point Tg is low, preferably less than 0°C, and both outer sides X to X'are hard blocks and Tg is high, preferably It is preferably composed of a polymer unit of 0°C or higher. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

Further, among the XYX or XYX' type block copolymers, a block copolymer containing a polymer unit having a Tg of 50°C or higher for X to X'and a polymer unit having a Tg of Y of -20°C or lower is more preferable. In addition, in the XYX or XYX' type block copolymer, it is preferable that X to X'have high compatibility with a carboxyl group-containing resin, and that Y has low compatibility with a carboxyl group-containing resin. In this way, it is considered that by making the blocks at both ends compatible with the matrix and the central block as a block copolymer incompatible with the matrix, it is easy to exhibit a specific structure in the matrix.

In addition, the block copolymer may be used without particular limitation as long as it has at least one or more hard block and soft block components, as well as XYX or XYX' type.

As the X to X'component, polymethyl methacrylate (PMMA), polystyrene (PS) and the like are preferred, and as the Y component, polyn-butyl acrylate (PBA), polybutadiene (PB) and the like are preferred. In addition, a hydrophilic unit having excellent 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, and the like is introduced into some of the components X to X'. It becomes possible to improve the compatibility. The inventors of the present invention believe that the block copolymer thus obtained has particularly good compatibility with the above-described carboxyl group-containing resin, and surprisingly, can improve cold and heat shock resistance, and more surprisingly, the product to which the elastomer is added is advantageous. It was found that the transition temperature (Tg) tends to decrease, whereas the material to which the block copolymer is added tends to not decrease Tg.

As a method for producing the block copolymer, the method described in Japanese Patent Application No. 2005-515281 and Japanese Patent Application No. 2007-516326 can be mentioned, for example. As a commercial item of the block copolymer, an acrylic triblock copolymer manufactured using living polymerization manufactured by Arkema Corporation is mentioned. SBM type represented by polystyrene-polybutadiene-polymethylmethacrylate, MAM type represented by polymethylmethacrylate-polybutylacrylate-polymethylmethacrylate, and MAM N treated with carboxylic acid modification or hydrophilic group modification Type or MAM A type. SBM types include E41, E40, E21, E20, etc., MAM types include M51, M52, M53, M22, etc., MAM N types include 52N, 22N, and MAM A types include SM4032XM10. . In addition, Kuraray Co., Ltd. is a block copolymerization derived from methyl methacrylate and butyl acrylate.

As the block copolymer, a block copolymer of three or more members is preferable, and a block copolymer synthesized by a living polymerization method in which the molecular structure is precisely controlled is more preferable for obtaining 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 become clear. The molecular weight distribution of the block copolymer to be used is preferably 2.5 or less, and more preferably 2.0 or less.

The weight average molecular weight of the block copolymer is generally in the range of 20,000 to 400,000, and further preferably 30,000 to 300,000. When the weight average molecular weight is less than 20,000, the target toughness and the effect of flexibility are not obtained, and the adhesiveness is also poor. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition increases, and printability and developability are remarkably deteriorated.

When the blending amount of the block copolymer contains a carboxyl group-containing resin in the composition, the range is preferably 1 to 50 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. The effect can be expected in 1 part by mass or more, and developability and coatability become favorable as a photocurable resin composition in 50 parts by mass or less.

A colorant may be contained in the photosensitive resin composition. As the colorant, known colorants such as red, blue, green, and sulfur can be used, and any of a pigment, a dye, and a dye may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

Examples of the red colorant include monoazo-based, disazo-based, azolake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridone-based, and the like. For example, the same color index (CI; published by The Society of Dyers and Colorists) number is assigned.

As a monoazo-based red colorant, 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. Moreover, Pigment Red 37, 38, 41, etc. are mentioned as a disazo type red colorant. In addition, as a monoazo lake-based red colorant, 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. In addition, Pigment Red 171, 175, 176, 185, 208, etc. are mentioned as a benzimidazolone-based red colorant. Further, examples of the perylene-based red colorant include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, and the like. Moreover, Pigment Red 254, 255, 264, 270, 272, etc. are mentioned as a diketopyrrolopyrrole type red colorant. Moreover, Pigment Red 220, 144, 166, 214, 220, 221, 242, etc. are mentioned as a condensed azo red colorant. Moreover, as an anthraquinone type red colorant, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207, etc. are mentioned. Moreover, Pigment Red 122, 202, 206, 207, 209, etc. are mentioned as a quinacridone type red colorant.

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

Examples of the yellow colorant include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. For example, as an anthraquinone-based yellow colorant, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. are mentioned. Pigment Yellow 110, 109, 139, 179, 185, etc. are mentioned as an isoindolinone type yellow colorant. Pigment Yellow 93, 94, 95, 128, 155, 166, 180, etc. are mentioned as a condensed azo yellow colorant. As a benzimidazolone yellow colorant, Pigment Yellow 120, 151, 154, 156, 175, 181, etc. are mentioned. In addition, as a monoazo yellow colorant, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104 , 105, 111, 116, 167, 168, 169, 182, 183, etc. are mentioned. In addition, as the disazo yellow colorant, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. Can be lifted.

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, CI 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 And carbon black.

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

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

In addition, a commonly known binder polymer can be used for the purpose of improving the flexibility and dryness to touch of the resulting cured product. As the binder polymer, a cellulose-based, polyester-based, or phenoxy resin-based polymer is preferable. Cellulose-based polymers include Eastman's cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series. As a polyester polymer, Toyobo Corporation's Byron series, and a phenoxy resin polymer are bisphenol A, Phenoxy resins of bisphenol F and their hydrogenated compounds are preferred.

The blending amount of the binder polymer, when the composition contains a carboxyl group-containing resin, is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, particularly preferably, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is 5 to 30 parts by mass. When the blending amount of the binder polymer is 50 parts by mass or less, the alkali developability of the photosensitive resin composition is more excellent, and the developable pot life becomes longer.

In addition, components such as an adhesion promoter, an antioxidant, and an ultraviolet absorber can be further added to the photosensitive resin composition as necessary. These can use known objects in the field of electronic materials. In addition, at least one of known and common thickeners such as finely divided silica, hydrotalcite, organic bentonite, and montmorillonite, antifoaming agents such as silicone, fluorine, and polymeric, and leveling agents, and silanes such as imidazole, thiazole, and triazole At least any one of known and common additives such as coupling agents, rust inhibitors, and optical brighteners can be blended.

The photosensitive film can be formed by applying the above-described photosensitive resin composition to one side of a 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, and comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, It is applied to one side of the supporting film with a spray coater or the like to have a uniform thickness, and is usually dried at a temperature of 50 to 130°C for 1 to 30 minutes to volatilize an organic solvent to obtain a touch-drying coating film. Although there is no restriction|limiting in particular about the coating film thickness, In general, it is a film thickness after drying, and it is suitably selected from 5 to 150 micrometers, Preferably it is 10 to 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, and petroleum solvents. More specifically, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as; Esters such as ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; 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. These organic solvents may be used individually by 1 type, and may be used as a mixture of 2 or more types.

Volatilization drying of the organic solvent is a method of countercurrent contacting the hot air in the dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of the air heating method by steam, and from a nozzle to a support body. Spraying method) can be used.

[Photosensitive film laminate]

The photosensitive film layered product which is another embodiment of the present invention means that a support film is laminated on any of the above photosensitive films. In addition, it is preferable that the photosensitive film layered product of the present invention is formed by laminating a protective film further. Hereinafter, details will be described.

[Support film]

The supporting film supports the above-described photosensitive film (i.e., a layer containing a photosensitive resin composition, hereinafter may be abbreviated as ``photosensitive resin layer''), and at the time of exposure and development of the photosensitive film, a photosensitive film It has a role of shaping a predetermined surface shape on the surface of the side in contact with the supporting film. In the present invention, it is preferable to use a supporting 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. Further, it is more preferable to use a supporting film having an arithmetic mean surface roughness Ra' of 0.05 µm or more on the surface of the surface in contact with the photosensitive film. By using a supporting film having such a surface shape, it becomes easy to form a photosensitive film having a number of concave portions of 3.0×10 ² or more per unit area of the surface of 1 mm ² , and furthermore, a photosensitive film having an arithmetic average surface roughness Ra of 0.05 μm or more is obtained. It becomes easy to form. That is, by shaping a predetermined surface shape of the support film on the surface of the photosensitive film, it is possible to improve the adhesion between the later formed cured film and the die attach material, and furthermore, a photosensitive film capable of improving the yield in appearance inspection. It is effective in that it becomes easy to form. 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 still more preferably 5.0×10 ² or more. In addition, when setting an upper limit, 2.0×10 ⁴ or less are preferable, 1.5×10 ⁴ or less are more preferable, and 1.0×10 ⁴ or less are still more preferable. Further, the protrusions on the surface of the support film may be uniform or non-uniform, but non-uniform ones are preferable.

Moreover, it is more preferable that it is 0.06 micrometers or more, and, as for the range of the arithmetic mean surface roughness Ra' of a support film, it is especially preferable that it is 0.07 micrometers or more. Further, when setting the upper limit, it is preferably 5.0 µm or less, more preferably 3.0 µm or less, and still more preferably 1.0 µm or less. Here, the number of protrusions per unit area of 1 mm ² of the surface of the support film is three-dimensional measurement of the surface irregularities of the target support film with the z-axis as the height direction, and the maximum and minimum values of the aggregates of the obtained z-values are obtained, and the maximum value A value calculated by counting the number of protrusion regions present in a unit area of 1 mm ² is taken as the Zs' value 0.2 μm higher than the average value calculated from the minimum value and the threshold value, and the region having a z value equal to or greater than the threshold value is used as the protrusion region. I shall say. In addition, what is meant by the arithmetic mean surface roughness Ra' is as described in the above-described [photosensitive film]. The specific measurement method is as described above. In addition, the number of protrusions per 1 mm ² of the surface of the supporting film and the number of concave portions per 1 mm ² of the surface of the photosensitive film do not necessarily coincide, and also, the arithmetic surface roughness of the surface of the supporting film Ra' and the photosensitive film The surface arithmetic surface roughness Ra of the surface is not necessarily identical, but by appropriately adjusting the surface shape of the supporting film, the number of concave portions per unit area of 1 mm ^{2 of the} surface of the photosensitive film and arithmetic surface roughness Ra are set within a specific range as described above. I can.

As the supporting film, it can be used without particular limitation as long as it has the above-described surface shape. For example, polyester film such as polyethylene terephthalate or polyethylene naphthalate, polyimide film, polyamideimide film, polypropylene film, polystyrene film A film containing a thermoplastic resin such as a thermoplastic resin can be suitably used, but among these, a polyester film can be suitably used from the viewpoints of heat resistance, mechanical strength, and handling properties. A single layer may be sufficient as a support film, and two or more layers may be laminated|stacked.

In addition, as for the thermoplastic resin film as described above, for the purpose of improving strength, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction.

As described above, the number of protrusions per 1 mm ² of the surface is 3.0×10 ² or more, and further, as a support film having an arithmetic average surface roughness Ra′ of 0.05 μm or more, when a thermoplastic resin film is used, the film can be formed. Add a filler (kneading treatment), matte coating (coating treatment) to the resin at the time, blast treatment such as sand blast treatment on the film surface, or hairline treatment or chemical etching, the surface as described above. It can be done in the same predetermined form. For example, in the case of adding a filler to the resin, the number of protrusions per unit area of 1 mm ² and the arithmetic mean surface roughness Ra' can be controlled by adjusting the particle diameter or amount of the filler. Further, in the case of coating the surface of the supporting film, the number of protrusions per unit area 1 mm ² and the arithmetic average surface roughness Ra' can be controlled by adjusting the type or amount of the coating agent. In addition, in the case of blasting, the number of protrusions per unit area of 1 mm ² and the arithmetic mean surface roughness Ra' can be controlled by adjusting treatment conditions such as blasting material and blasting pressure. As the thermoplastic resin film having such a surface roughness, a commercially available one may be used, and examples thereof include CM-25, manufactured by Unityka Corporation, G50 manufactured by Kimoto Corporation, and the like, but are not limited thereto.

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

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

In addition, in the photosensitive film laminate according to the present invention, a support film is laminated on the surface side having a concave portion on the surface of any of the photosensitive films, which has excellent adhesion to the die attach material, and also improves the yield in appearance inspection. It is preferable from the viewpoint that it becomes easy to exhibit the effect of the present invention.

[Protective film]

The photosensitive film laminate according to the present invention is provided with a protective film on the opposite side of the support film of the photosensitive resin layer for the purpose of improving handling properties while preventing the adhesion of dust or the like on the surface of the photosensitive resin layer. It may be installed.

As the protective film, for example, a polyester film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, but the adhesion between the protective film and the photosensitive resin layer is determined by the support film and photosensitive It is preferable to select a material that becomes smaller than the adhesive force with the resin layer. In addition, in order to facilitate peeling of the protective film in use of the photosensitive film laminate, the above-described release treatment may be performed on the surface of the protective film in contact with the photosensitive resin layer.

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

<Method of manufacturing cured product and printed wiring board>

A cured product is formed using the photosensitive film or photosensitive film laminate of the present invention. A method of forming such a cured product and a method of manufacturing a printed wiring board including the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. As an example, a method of manufacturing a printed wiring board using a photosensitive film laminate with a protective film will be described. First, i) peeling the protective film from the photosensitive film laminate to expose the photosensitive film, ii) bonding the photosensitive film of the photosensitive film laminate to the substrate on which the circuit pattern is formed, and iii) the photosensitive film By performing exposure on the support film of the film laminate, iv) peeling the support film from the photosensitive film laminate and performing development, thereby forming a patterned photosensitive film on the substrate, v) forming the patterned photosensitive film A printed wiring board is formed by curing by light irradiation or heat to form a cured film. In addition, in the case of using a photosensitive film laminate without a protective film, it goes without saying that the peeling step (i step) of the protective film is unnecessary. Hereinafter, each process is demonstrated.

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 on the substrate on which the circuit pattern was formed. In addition to printed circuit boards and flexible printed circuit boards with circuit patterns formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Materials such as copper clad laminates for high-frequency circuits using polyethylene·polyphenylene ether, polyphenylene oxide·cyanate ester, etc. are used, and copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, A glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned.

In order to bond the photosensitive film of the photosensitive film laminate on a circuit board, it is preferable to bond under pressure and heating using a vacuum laminator or the like. By using such a vacuum laminator, even if there are irregularities on the surface of the circuit board, since the photosensitive resin composition layer is in close contact with the circuit board, there is no mixing of air bubbles, and the hole filling property of the concave portion on the surface of the board is also improved. The pressurizing condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120°C.

Next, exposure (irradiation with active energy rays) is performed from the support film of the photosensitive film laminate. By this process, only the exposed photosensitive resin layer is cured. The exposure process is not particularly limited, for example, by a contact type (or non-contact type), it may be selectively exposed with an active energy ray through a photomask having a desired pattern, but a desired pattern can be directly obtained by a drawing device. You may expose it with an active energy ray.

As an exposure machine used for active energy ray irradiation, a high-pressure mercury lamp lamp, ultra-high pressure mercury lamp lamp, metal halide lamp, etc. may be mounted, and an apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm may be used, and a direct drawing device (for example, from a computer A laser direct imaging device that draws an image with a laser directly from the CAD data of As the laser light source of the direct writing machine, any of a gas laser and a solid-state laser may be used as long as a laser light having a maximum wavelength in the range of 350 to 410 nm is used. Light exposure for image formation film varies, depending upon the thickness, but in general may be set within 20 ~ 800mJ / cm ^2, preferably in the range of 20 ~ 600mJ / cm ^2.

After exposure, the support film is peeled from the photosensitive film laminate and developed to form a patterned photosensitive film on the substrate. When the support film is peeled off, the shape of the surface of the support film is shaped on the surface of the photosensitive film exposed and cured. Further, as long as the properties are not impaired, the supporting film may be peeled off from the photosensitive film laminate before exposure, and the exposed photosensitive film may be exposed and developed.

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

Next, the patterned photosensitive film is cured by irradiation with active energy rays (light) or heat to form a cured product (cured film). This step is called main curing or further curing, and promotes polymerization of the unreacted monomer in the photosensitive film, and further, thermally cures the carboxyl group-containing photosensitive resin and the epoxy resin, thereby reducing the amount of remaining carboxyl groups. The active energy ray irradiation can be performed in the same manner as the above-described exposure, but is preferably performed under conditions stronger than the irradiation energy at the time of exposure. For example, it can be 500-3000mJ/cm ² . In addition, thermal curing can be performed under heating conditions of about 20 to 90 minutes at 100 to 200°C. In addition, it is preferable to perform thermal curing after making this curing photocure. By performing photocuring first, flow of the resin is suppressed even at the time of heat curing, and the molded surface may be maintained.

In this way, it is possible to impart an appropriate uneven state to the surface of the cured product. As a result, the adhesion to the die attaching material is improved, and the yield in the visual inspection is also improved. As the die attaching material, a known and common one can be used, and it is not particularly limited. Therefore, the photosensitive film laminate according to the present invention can be suitably used for a printed wiring board, and can be used more suitably for forming a solder resist layer, and in particular, can be suitably used for forming a solder resist layer for an IC package. have.

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

<Preparation of carboxyl group-containing photosensitive resin>

In an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device, a novolac cresol resin (Shonol CRG951 manufactured by Showa Denko Corporation, OH equivalent: 119.4) 119.4 g, and potassium hydroxide 1.19 g And 119.4 g of toluene were added, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 g of propylene oxide was gradually added dropwise, followed by reaction 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 potassium hydroxide was neutralized by adding and mixing 1.56 g of 89% phosphoric acid to the reaction solution. The propylene oxide reaction of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. I got a solution. The obtained novolac-type cresol resin had an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

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

<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.) as a photosensitive monomer as an acrylate compound, and bisphenol A-type as an epoxy resin as a thermosetting component. Epoxy resin (EPICLON840-S manufactured by DIC Corporation) and biphenol novolac-type epoxy resin (NC-3000H manufactured by Nippon Kayaku Corporation) and Omnirad manufactured by IGM Resins as a photoinitiator (Omnirad) TPO or BASF Japan IRGACURE OXE02 manufactured by Co., Ltd., as a filler, barium sulfate (B-30 manufactured by Kagaku Kogyo Co., Ltd.) and/or spherical silica (Admafine SO-E2 manufactured by Admatex, Inc.), and as a thermal curing catalyst Melamine and as a colorant, carbon black M-50 manufactured by Mitsubishi Chemical Co., Ltd., Dioxazine Violet CI Pigment Violet 23, C.I. Pigment Yellow 147, C.I. Pigment Blue 15:3 and C.I. Each component selected from Pigment Red 177 and diethylene glycol monoethyl ether acetate as an organic solvent were blended in the ratio (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.

<Production of photosensitive film laminate>

Example 1

One side of a polyethylene terephthalate film (diafoil R310 manufactured by Mitsubishi Chemical Co., Ltd.) was subjected to a sand blast treatment to prepare a support film having a thickness of 16 μm in which non-uniform protrusions were formed on the film surface. The number of protrusions per unit area of the surface of the obtained supporting film 1 mm ² and the arithmetic mean surface roughness Ra' were measured as follows, as a result, the number of protrusions per unit area of the surface 1 mm ² was 8.0×10 ² , The arithmetic mean surface roughness Ra' was 0.13 µm.

For the measurement of the number of protrusions per unit area of 1 mm ² and the arithmetic mean surface roughness Ra', a shape measuring laser microscope (VK-X100 manufactured by Keyence Corporation) was used. After starting the shape measurement laser microscope (the VK-X100) main body (control unit), and the VK observation application (VK-H1VX manufactured by Keyence Corporation), a sample (supporting film) to be measured on the xy stage was placed on the support film. The surface with the protrusion was put on top. The lens revolver of the microscope unit (VK-X110 manufactured by Keyence Corporation) was turned to select an objective lens with a magnification of 10 times, and in the image observation mode of the VK observation application (VK-H1VX), the focus and brightness were approximately adjusted. By operating the xy stage, it was adjusted so that the almost central portion of the sample surface was in the center of the screen. An objective lens with a magnification of 10 times was changed to a magnification of 100 times, and a focus was placed on the surface of the sample with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (VK-H1VX) was selected, the measurement start button was pressed, and the surface shape of the sample was measured to obtain a surface image file. After starting up the VK analysis application (VK-H1XA manufactured by Keyence Corporation), displaying the obtained surface image file, tilt correction was performed.

In the measurement of "the number of protrusions per unit area 1 mm ² ", the observation measurement range (area) in the measurement of the surface shape of the sample was set to 15073 μm ² . An analysis application (VK-H1XA manufactured by Keyence Corporation) was used. Select [Volume·Area] from the measurement analysis menu on the display screen, display the [Volume·Area] window, select [Height] from the [Display image] box in the [Volume·Area] window, and then select [Threshold] By pressing the button, the [Threshold Area Setting Dialog] box is displayed. Divided by 2 by adding the value of the [Upper Limit] box and the value of the [Lower Limit] box, calculate Ave.(㎛), and add 0.2㎛ to the Ave. ". Without changing the value of the [Lower Limit] box, enter the Zs' value (µm) in the [Upper Limit] box, press the OK button, and then the number of points that have changed to the color of the ROI drawing color in the image display area C ( ) the count, was calculated from the number C (one), the number of unit area of 1mm ² D (dog / mm ² each) (D = C × 66.34) . In addition, among the places that changed to the color of the ROI drawing color, those which were cut off in the image display area and could not be recognized as one were counted as 0.5.

Moreover, in the measurement of "arithmetic mean surface roughness Ra", the objective lens was switched 50 times, and the observation measurement range (horizontal) in the measurement of the surface shape of a sample was 270 micrometers. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select a horizontal line from the measurement line button, display a horizontal line at an arbitrary place in the surface image, and press the OK button to calculate the surface. The value of the average surface roughness Ra' was obtained. Further, horizontal lines were displayed at four other places in the surface image to obtain a numerical value of the arithmetic mean surface roughness Ra'. The average value of the obtained five numerical values was calculated, and it was set 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, diluted, and stirred for 15 minutes with a stirrer to obtain a coating solution. The coating liquid was applied to the surface of the above-described support film subjected to the sand blast treatment, and dried at 80° C. for 15 minutes to form a photosensitive film having a thickness of 20 μm. Subsequently, on the photosensitive film, a polypropylene film (OPP-FOA manufactured by Futamura Chemical Co., Ltd.) having a thickness of 18 µm was bonded to each other to prepare a photosensitive film laminate comprising three layers.

<Preparation of test board>

The surface of the circuit-formed substrate (500 mm × 600 mm × 0.4 mmt) was chemically polished using CZ8101 manufactured by McC. Co., Ltd., and the polypropylene film was peeled from the photosensitive film laminate obtained as above on the chemically polished surface of the substrate. The exposed surface of the exposed photosensitive film was bonded, and then heated under the conditions of a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho) at a pressure of 0.8 MPa, 70° C., 1 minute, and a vacuum degree of 133.3 Pa. By laminating, the substrate and the photosensitive film were brought into close contact with each other.

Next, using a parallel light exposure apparatus equipped with a short arc type high pressure mercury lamp, through an exposure mask, solid exposure was performed for the visibility of scratches and adhesion to the die attach material from the polyethylene terephthalate film in contact with the photosensitive film. Regarding the collapse of the furrows, after each exposure was performed using a negative pattern designed to be 80 μm SRO, the polyethylene terephthalate film was peeled to expose the photosensitive film. In addition, the exposure amount was made into the exposure amount which becomes 7 steps when exposed using 41 steps of Stouffer on the polyethylene terephthalate film in contact with the photosensitive film. Then, with respect to the exposed surface of the exposed photosensitive film, development was performed for 60 seconds under the conditions of 30 degreeC and spray pressure 2 kg/cm ² using 1 weight% Na ₂ CO ₃ aqueous solution, and it patterned. Subsequently, after irradiating the patterned photosensitive film at an exposure dose of 1 J/cm ² in a UV conveyor furnace equipped with a high-pressure mercury lamp, it was heated at 160° C. for 60 minutes to further cure to form a cured film, and a cured film was formed on the substrate. Substrate 1 was prepared.

Example 2

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

Example 3

In Example 1, the number of protrusions per unit area of the surface 1 mm ² was 8.0 × 10 ² and the arithmetic mean surface roughness Ra' was 0.13 μm, instead of a 16 μm thick support film having a surface on one side, polyethylene tere A test substrate in the same manner as in Example 1, except that a coating treatment was performed on one side of the phthalate film and a 125 µm thick support film (G-50 manufactured by Kimoto Co., Ltd.) was used, in which non-uniform protrusions were formed on the film surface. 3 was produced. As a result of measuring the number of protrusions per unit area 1 mm ² of the supporting film coated surface and the arithmetic mean surface roughness Ra′ in the same manner as above, the number of protrusions per unit area of the surface 1 mm ² is 1.3 × 10 ³ , and the arithmetic average surface roughness Ra' was 0.19 µm.

Example 4

In Example 3, in place of the photosensitive resin composition 1, except having used the photosensitive resin composition 2, it carried out similarly to Example 3, and produced the test board 4.

Example 5

In Example 1, the number of protrusions per unit area of the surface 1 mm ² was 8.0 × 10 ² and the arithmetic mean surface roughness Ra' was 0.13 μm, instead of a 16 μm thick support film having a surface on one side, polyethylene tere A test substrate in the same manner as in Example 1, except that a support film having a thickness of 25 μm (CM-25, manufactured by Unitika Corporation) was coated on one side of the phthalate film to form uneven protrusions on the film surface. 5 was produced. As a result of measuring the number of protrusions per unit area 1 mm ² of the supporting film coated surface and the arithmetic mean surface roughness Ra′ in the same manner as above, the number of protrusions per unit area of the surface 1 mm ² is 4.5×10 ³ , and the arithmetic average surface roughness Ra' was 0.48 µm.

Example 6

In Example 5, in place of the photosensitive resin composition 1, except having used the photosensitive resin composition 2, it carried out similarly to Example 5, and produced the test board 6.

Example 7

In Example 1, the number of protrusions per unit area of the surface 1 mm ² was 8.0 × 10 ² and the arithmetic mean surface roughness Ra' was 0.13 μm, instead of a 16 μm thick support film having a surface on one side, polyethylene tere Test substrate 7 in the same manner as in Example 1, except that a support film having a thickness of 25 µm in which a phthalate film (E5041 manufactured by Toyobo Co., Ltd.) was subjected to a sand blast treatment to form a non-uniform protrusion on the film surface. Was produced. As a result of measuring the number of protrusions per unit area 1 mm ² of the support film sandblasted surface and the arithmetic mean surface roughness Ra′ in the same manner as above, the number of protrusions per unit area 1 mm ^{2 of the} surface was 1.7× It was 10 ⁴ pieces, and the arithmetic average surface roughness Ra' was 5.00 micrometer.

Example 8

In Example 7, instead of the photosensitive resin composition 1, except having used the photosensitive resin composition 2, it carried out similarly to Example 7, and produced the test board 8.

Comparative Example 1

In Example 1, the number of protrusions per unit area of the surface of 1 mm ² was 8.0×10 ² and the arithmetic average surface roughness Ra′ was 0.13 μm, instead of a 16 μm thick support film having a surface on one side, with a thickness of 25 A test substrate 9 was produced in the same manner as in Example 1, except that a µm polyethylene terephthalate film (E5041 manufactured by Toyobo Corporation) was used as the supporting film. As a result of measuring the number of protrusions per 1 mm ² surface unit area of the supporting film and the arithmetic average surface roughness Ra' as described above, the number of protrusions per 1 mm ² surface unit area is 0, and the arithmetic average surface roughness Ra' was 0.02 μm.

Comparative Example 2

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

<Evaluation of visibility of scratches>

On the surface of the cured film in the exposed area of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 2 prepared as described above, a pencil lead having a hardness of 2H, an angle of 45°, and a load of 4.9N were applied. It was pressed and moved 1 cm at a speed of 1 mm for 1 second, and the location was changed to perform a total of 3 times. The visibility of the scratch on the surface of the cured film was visually evaluated. The evaluation criteria were as follows.

(Double-circle): scratches are not observed all three times on the surface of the cured film in the exposure area

○: scratches are confirmed once or twice on the surface of the cured film in the exposure area

×: scratches are all confirmed three times on the surface of the cured film in the exposure region

In addition, after preparing each test board, tests and evaluations were performed based on the above contents within 5 minutes. 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.), and 15 parts bisphenol F-type epoxy resin (RE-303S-L manufactured by Nippon Kayaku Corp.), To 5 parts of a flexible epoxy resin (YX7105 manufactured by Mitsubishi Chemical Co., Ltd.), 50 parts of methyl ethyl ketone was added and heated and melted to obtain a resin varnish A. With respect to 150 parts of the obtained resin varnish A, 3 parts of an imidazole compound (2E4MZ manufactured by Shikoku Chemical Industries, Ltd.) as a curing catalyst, 150 parts of fused silica (FB-3SDX manufactured by Denka Corporation) as a filler, and a silane coupling agent (Shinetsu Chemical Co., Ltd. KBE-402) 1 part was added and premixed with a stirrer, and then kneaded in a three roll mill to obtain a resin varnish B. The obtained resin varnish B was applied to a base film and dried at 80° C. for 15 minutes to prepare a 45 µm-thick die attach material.

<Evaluation of adhesion to die attach material>

The die attach material prepared as described above was cut into a predetermined size (5 mm long × 5 mm wide × 0.045 mm thick), and attached to a silicon chip (5 mm long × 5 mm wide × 0.725 mm thick, oxide film coating) at 70°C. , Using a thermocompression testing machine, on the surface of the cured film of each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 2, a silicon chip, a die attach material, and a cured film were pressed in the order (compression conditions: 260°C , For 10 seconds, 1.0 MPa). Subsequently, the die attach material was completely cured by heating at 175° C. for 120 minutes. After that, it is left to stand for 72 hours in a thermo-hygrostat (PR-2KP manufactured by SPEC Co., Ltd.) at 85°C and 85% relative humidity, and after taking out, an adhesion measurement device (manufactured by Nodoson Advanced Technology Co., Ltd., universal type) Bond tester 4000Plus) was used, the temperature of the stage for setting the sample was set to 260°C, and the adhesion 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. Each of ten test pieces was produced, and evaluation criteria were made as follows.

○: The adhesive strength of all 10 test pieces is 3 MPa or more

×: Among 10 test pieces, one or more test pieces having an adhesive force of less than 3 MPa were generated

In addition, after preparing each test board, tests and evaluations were performed based on the above contents within 5 minutes. The measurement results are as shown in Table 2 below.

<Measurement of the number of concave portions per 1 mm ² of surface unit area of the photosensitive film and the arithmetic mean surface roughness Ra>

The surface of the circuit-formed substrate (150 mm × 95 mm × 0.8 mmt) was chemically polished by CZ8101 manufactured by Mack Corporation, and on the chemically polished surface of the substrate, each photosensitive used in Examples 1 to 8 and Comparative Examples 1 to 2 Peeling the polypropylene film from the film laminate to bond the exposed surface of the exposed photosensitive film (140 mm × 90 mm), and then, using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho), pressurization degree: 0.8 MPa , 70° C., 1 minute, vacuum degree: 133.3 Pa was heated and laminated to make the substrate and the photosensitive film in close contact. Thereafter, the polyethylene terephthalate film was peeled from the substrate at 90° to expose the photosensitive film. After exposure, within 5 minutes, the number of concave portions per unit area of 1 mm ^{2 on the} surface of the photosensitive film and the arithmetic average surface roughness Ra were measured as follows.

The number of concave portions per unit area of 1 mm ² of the surface of the photosensitive film was measured using the same apparatus as the number of protrusions per unit area of 1 mm ² of the surface of the supporting film, and the sample was replaced with the supporting film, and the exposed photosensitive film was bonded ( Measurement was carried out in the same manner as above except that the photosensitive film surface was set as the upper part). In the measurement of "the number of concave portions per unit area of 1 mm ² " on the surface of the photosensitive film, the observation measurement range (area) in the measurement of the surface shape of the sample was set to 15073 μm ² . An analysis application (VK-H1XA) was used. Select [Volume·Area] from the measurement analysis menu on the display screen, display the [Volume·Area] window, select [Height] from the [Display image] box in the [Volume·Area] window, and then select [Threshold] By pressing the button, the [Threshold Area Setting Dialog] box is displayed. Divided by 2 by adding the value of the [Upper Limit] box and the value of the [Lower Limit] box to calculate Ave.(㎛), and subtracting 0.2㎛ from the Ave.(㎛) value Zs(㎛) or less is "concave. Negative”. The number of points changed to the color of the ROI drawing color at the border of the image display area after entering the value of Zs (㎛) in the [Upper limit] box without changing the value of the [Lower Limit] box and pressing the OK button. (dogs) for counting, was calculated from the number C (one), the number of unit area of 1mm ² D (dog / mm ²⁾ per (D = C × 66.34). In addition, among the locations that changed to the color of 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 surface of the photosensitive film was measured in the same manner as above except that the sample was replaced with a supporting film and a substrate to which the exposed photosensitive film was bonded (with the photosensitive film surface as the upper part). Done. The "number of concave parts per unit area 1 mm ² " and "arithmetic average surface roughness Ra" of the measured surface of each photosensitive film were as shown in Table 2. In addition, in any of the examples, the identified recesses were uneven.

<The collapse of the furrow of the pattern>

Each test substrate prepared as described above was used, and the furrows of 10 openings were observed with a scanning electron microscope (SEM) of 1000 times. Evaluation criteria were carried out in this way.

◎: All 10 openings have good furrow formation

○: Although the opening is tapered, the resin powder contained in the photosensitive film on the upper part of the furrow is not pushed out of any of the ten openings.

X: Extrusion of the resin powder contained in the photosensitive film on the upper part of the furrow is observed in one or more openings.

The evaluation results are as shown in Table 2 below.

Claims (7)

It is a photosensitive film for forming a solder resist layer, has a surface having a concave portion on its surface, is formed by a photosensitive resin composition, and the number of concave portions per 1 mm ² of the surface is 3.0×10 ² or more. Photosensitive film. The photosensitive film according to claim 1, wherein the number of recesses per 1 mm ² of the surface is 2.0×10 ⁴ or less. The photosensitive film according to claim 1 or 2, wherein the surface has an arithmetic mean surface roughness Ra of 0.05 µm or more. The photosensitive film according to claim 1 or 2, wherein the photosensitive resin composition contains a filler and a crosslinking component. A photosensitive film laminate, characterized in that a support film is laminated on the photosensitive film according to claim 1 or 2. The photosensitive film laminate according to claim 5, wherein in the photosensitive film formed of a photosensitive resin composition having a surface having a concave portion on its surface, a support film is laminated on the side having a concave portion on the surface. A cured product formed using the photosensitive film according to claim 1 or 2, or a photosensitive film laminate obtained by laminating a support film on the photosensitive film.