TWI776613B - Photosensitive film laminate and cured product formed using the same - Google Patents

Abstract

Provides edge collapse that is not easy to generate patterns, even if the substrate on which the photosensitive film laminate is laminated, etc. are strongly impacted or pressed, the influence on the surface of the photosensitive film can be suppressed, and the appearance of the cured film can be inspected. It can also improve the yield of photosensitive film laminates. A photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition in this order, characterized in that the photosensitive film has a surface with a concave-convex surface, and the concave-convex surface is The unevenness average interval Sm is 5 μm or more and less than 90 μm.

Description

Photosensitive film laminate and cured product formed using the same

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

In general, in a printed wiring board used in electronic equipment and the like, in order to prevent solder from adhering to unnecessary parts when mounting electronic components on the printed wiring board, other than the connection holes on the substrate on which the circuit pattern is formed area to form a solder resist layer.

With the high precision and high density of printed wiring boards caused by the reduction of light, thin, and short electronic equipment in recent years, the solder resist layer is currently coated with a photosensitive resin composition on the substrate, and exposed and developed to form a pattern. , the so-called photo-solder resist is the mainstream, which is to harden the resin on which the pattern is formed by heating or light irradiation.

Moreover, instead of using the above-mentioned liquid photosensitive resin composition, it is also proposed to use a so-called photosensitive film laminate provided with a photosensitive film to form a solder resist layer. Such a photosensitive film laminate is generally bonded to a photosensitive film formed by a photosensitive resin composition on a support film, and a protective film may be bonded to the surface of the photosensitive film as needed. Such a photosensitive film laminate can be formed by peeling off the protective film during use and laminating it on a wiring board by thermocompression bonding, before exposing it or exposing it from the support film side, and then peeling off the support film and developing it. The patterned solder resist layer. By using the photosensitive film laminate, a high-definition pattern can be formed. Moreover, compared with the case of wet coating, a drying step after coating may not be required. The surface state of the coating film is mostly smooth, but in recent years, the surface is not smooth. For example, in the pamphlet of International Patent Publication No. 2015/163455, it is also proposed to transfer the surface morphology of the roughened support film to form a coating film.

However, when a pattern is formed using a photosensitive film, especially when SRO (solder resist opening) is formed, after exposure and development, the resin component contained in the photosensitive film located at the edge of the opening may be collapsed, resulting in the formation of the opening. The phenomenon of inner protrusion, that is, the collapse of the edge of the pattern, still has room for improvement.

In addition, in the step of forming the solder resist layer on the wiring board as described above, after laminating the photosensitive film laminate on the wiring board, there is a possibility that the laminated wiring board may be attached to the wiring board until the next step. When the sequence overlaps and is temporarily stored. In this case, the surface of the photosensitive film laminate provided on the wiring board may be damaged due to the impact when the wiring boards to which the photosensitive film laminate is bonded, or the weight of the wiring board when superimposed. In particular, due to the influence of the recent thinning of photosensitive film laminates, not only the support film but also the surface of the photosensitive film laminated on the support film may be damaged due to impact at the time of stacking or pressing of its own weight, and improvement is required. .

On the other hand, the solder resist layer using the above-mentioned photosensitive film laminate is formed as the outermost layer of the substrate, and is formed in the final stage of the substrate manufacturing process, so when using devices in the substrate manufacturing process, it may be due to There is a possibility that the cured film of the photosensitive film may be damaged by means of conveyance and the like (for example, Japanese Patent Application Laid-Open No. 2015-206992). This damage is judged as NG in the visual inspection before the semiconductor mounting step, and there is a possibility that the production yield may deteriorate. In particular, in recent years, even a small damage that does not have a problem in quality has become a cause of a decrease in productivity, so it is one of the important requirements, and a new improvement method is required.

Therefore, the object of the present invention is to provide edge collapse that is less likely to cause patterns, and to suppress the influence on the surface of the photosensitive film even when the substrates on which the photosensitive film laminate is laminated are strongly impacted or pressed. Furthermore, the photosensitive thin-film laminate which can improve the yield also in the visual inspection of a cured film. Moreover, the other objective of this invention is to provide the hardened|cured material formed using the said photosensitive film laminated body.

The inventors of the present invention have found that, in the case of a layer formed using a photosensitive film laminate, especially in the case of a solder resist layer, when the surface is damaged, the visual recognition is easy or difficult, and the average distance from the unevenness of the solder resist layer is related. also. The inventors of the present invention have found that, in a photosensitive film having a surface having irregularities on the surface, by using the photosensitive film having a specific average interval between irregularities on the surface, an appropriate irregularity can be imparted to the surface of the solder resist layer. As a result, the edge of the pattern is not easily collapsed, and even if the surface is damaged, the damage is not easily recognized visually, so the yield can be improved during the appearance inspection. In addition, it was found that damage to the surface of the photosensitive film due to impact or pressing when stacking substrates on which the photosensitive film laminate is laminated is not only caused by the impact resistance of the photosensitive film itself, but also caused by the photosensitive film laminate. The overall layer composition is significantly related. Furthermore, the inventors of the present invention have obtained the knowledge that, as a laminate in which an intermediate layer is provided between a support film and a photosensitive film having an uneven surface, even if the substrate on which the photosensitive film laminate is to be laminated is formed. Strong impact or pressing during the overlapping can also suppress the influence on the surface of the photosensitive film. The present invention is based on this knowledge.

[1] The photosensitive film laminate according to the first embodiment of the present invention is a photosensitive film laminate including a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition in this order, It is characterized by The said photosensitive film has the surface which has the uneven|corrugated surface, and the uneven|corrugated average interval Sm of the said uneven surface is 5 micrometers or more and less than 90 micrometers.

[2] The photosensitive film laminate according to the second embodiment of the present invention is the photosensitive film laminate according to [1], which has a surface having an uneven surface and is formed of a photosensitive resin composition In the photosensitive film of , the arithmetic mean surface roughness Ra of the uneven surface is 0.05 μm or more.

[3] The photosensitive film laminate according to the third embodiment of the present invention is the photosensitive film laminate according to [1] or [2], wherein the photosensitive resin composition contains a filler and a crosslinking component.

[4] The photosensitive film laminate according to the fourth embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [3], which has a surface having uneven surfaces and is exposed to In the photosensitive film formed from the resin composition, an intermediate layer is laminated on the surface side having the uneven surface.

[5] The photosensitive film laminate according to the fifth embodiment of the present invention is the photosensitive film laminate according to any one of [1] to [4], wherein the thickness of the intermediate layer is 0.1 μm or more and 10 μm the following.

[6] The cured product according to the sixth embodiment of the present invention is characterized by being formed using the photosensitive film laminate according to any one of [1] to [5].

According to the present invention, the photosensitive film has a surface with a specific average interval of unevenness, so that the edge of the pattern is not easily collapsed, and the appearance inspection of the cured film is also improved. Lamination of photosensitive film laminates in which an intermediate layer is provided between photosensitive films with uneven surfaces can be realized even by strong shocks or pressing when superimposing substrates on which the photosensitive film laminates are laminated. The photosensitive film laminate affected by the surface of the photosensitive film. The photosensitive film of the present invention is particularly effective when used for forming a solder resist layer. Moreover, according to this invention, it is effective from the viewpoint that the above-mentioned effect is exhibited even if a support film is a thin film. Further, according to another aspect of the present invention, a cured product formed using the above-mentioned photosensitive film laminate can be realized.

The photosensitive film laminate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive film laminate of the present invention. The photosensitive film laminate 1 of the present invention has a structure in which a support film 10, an intermediate layer 20, and a photosensitive film 30 formed of a photosensitive resin composition are sequentially laminated. Here, the photosensitive film in the present invention refers to a film-shaped photosensitive resin composition without laminating other layers such as a support film or a protective film. Moreover, in this invention, in addition to the above-mentioned structure, another thin film etc. may be provided. For example, in order to prevent dust and the like from adhering to the surface of the photosensitive film, and considering the handleability of the photosensitive film laminate, as shown in FIG. A protective film 40 is further provided on the side opposite to 20 . Hereinafter, each constituent element constituting the thin film laminate of the present invention will be described.

[Photosensitive film laminate] The photosensitive film laminate of the present invention refers to a photosensitive film in which an intermediate layer and a support film are laminated. In addition, the photosensitive film laminate of the present invention is preferably formed by further laminating a protective film. Details are explained below.

[Support film] The support film in the photosensitive film laminate of the present invention supports the above-mentioned photosensitive film, and has a specific surface morphology to the surface of the photosensitive film on the side adjacent to the support film during exposure and development of the photosensitive film. role player.

The support film in the photosensitive film laminate of the present invention can be used without particular limitation as long as it is a known one. For example, polyesters made of polyethylene terephthalate, polyethylene naphthalate, etc. can be suitably used Films made of thermoplastic resins such as films, polyimide films, polyimide films, polypropylene films, and polystyrene films. In addition, when the aforementioned thermoplastic resin film is used, a filler can be added to the resin when the film is formed (kneading treatment), or a matte coating (coating treatment) can be carried out, and the film surface can be subjected to sandblasting treatment such as sandblasting treatment. Alternatively, it may be processed by hairline processing or chemical etching. Among these, from the viewpoints of heat resistance, mechanical strength, handleability, and the like, polyester films are particularly suitably used. The support film may be a single layer, or two or more layers may be laminated.

In addition, the thermoplastic resin film as described above is preferably used for a film extending in a uniaxial direction or a biaxial direction for the purpose of increasing the strength.

The thickness of the support film is not particularly limited, but may be appropriately selected in the range of about 10 μm or more and 150 μm or less depending on the application.

In addition, a support film in which an intermediate layer described later is provided on the support film by coating, that is, a support film integrated with the intermediate layer can also be used. For example, CM-25 by Unitika Co., Ltd., G50 by Kimoto Co., Ltd., etc. are mentioned.

[middle layer] The photosensitive film laminate of the present invention is characterized by having an intermediate layer between the support film and the photosensitive film having an uneven surface. As a result of diligent research by the present inventors, it has been found that by providing an intermediate layer between the support film and the photosensitive film having an uneven surface, the surface of the photosensitive film is not affected by a strong impact. The reason for this is not necessarily clear, but it is presumed that the interlayer protects the uneven surface of the laminated photosensitive film from strong impact, and as a result, does not affect the surface state of the photosensitive film, but this is only an estimated range. Not necessarily limited to this.

The thickness of the intermediate layer is preferably in the range of 0.1 μm or more and 10 μm or less, and more preferably in the range of 1 μm or more and 8 μm or less. By setting the thickness of the intermediate layer to be 0.1 μm or more, it is possible to further suppress damage due to strong impact or pressing when stacking substrates or the like. Moreover, since it is 10 micrometers or less, light transmittance becomes favorable, and it becomes easy to form a finer pattern.

The intermediate layer preferably contains a resin component. For example, acrylic resin, epoxy resin, alkyd resin, melamine, or a mixture of these resins can be mentioned. Among these, acrylic melamine which is a mixture of acrylic resin and melamine, or epoxy melamine which is a mixture of epoxy resin and melamine is particularly preferable from the viewpoint of impact resistance. Furthermore, in the present invention, "melamine" refers to a resin cured by addition condensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde, but it also includes The concept of methylol melamine which is the initial reactant of melamine and formaldehyde and the alkylated methylol melamine of its alkylate. In addition, the acrylic melamine here means the form which hardened acrylic resin with melamine. As these resins, well-known and conventional ones can be used without particular limitation.

It is preferable that the intermediate layer further contains a polysiloxane-based resin as a resin component in the intermediate layer. In the photosensitive film laminate of the present invention, when the photosensitive film is cured to form a cured film, the support film and the intermediate layer must be peeled off from the photosensitive film (cured film). Since the intermediate layer contains a polysiloxane-based resin, The support film and the intermediate layer can be easily peeled off from the photosensitive film, and the adhesion between the support film and the intermediate layer can be maintained. As the polysiloxane-based resin, it can be used without particular limitation.

In addition, the intermediate layer may appropriately contain fillers, curing accelerators, additives, antistatic agents, and the like as components other than resins. A well-known filler can be used without particular limitation, for example, silica, calcium carbonate, etc. are mentioned. Of these, silica is particularly preferred. The average particle size of the filler is not particularly limited, but is preferably 1.0 μm or more and 5.5 μm or less; more preferably 2.0 μm or more and 4.5 μm or less; and still more preferably 2.0 μm or more and 3.0 μm or less. In addition, as the antistatic agent, a conventionally known antistatic agent can be used, and among these, a cationic surfactant mainly composed of a quaternary ammonium salt represented by the following general formula (I) can be suitably used. By containing the cationic surfactant represented by the following formula in the intermediate layer, damage to the surface of the photosensitive film due to impact or pressing can be further suppressed.

(式中，R表示碳原子數8以上之烷基，R₁ 表示碳原子數8以下之烷基，R₂ 表示碳原子數8以下之伸烷基)。

(In the formula, R represents an alkyl group having 8 or more carbon atoms, R ₁ represents an alkyl group having 8 or less carbon atoms, and R ₂ represents an alkylene group having 8 or less carbon atoms).

(式中，R表示碳原子數8以上之烷基)。Among the cationic surfactants of the above formula (I), those represented by the following general formula (II) can be used particularly preferably.

(in the formula, R represents an alkyl group having 8 or more carbon atoms).

In this invention, it is preferable to use the intermediate layer which the uneven|corrugated average interval Sm' of the surface of the surface adjacent to the photosensitive film is 5 micrometers or more and less than 90 micrometers. Moreover, it is more preferable to use the intermediate layer whose arithmetic mean surface roughness Ra' of the surface of the surface side adjoining the photosensitive film is 0.05 micrometer or more. By using the intermediate layer having such a surface morphology, it is easy to form a photosensitive film having an average interval Sm of unevenness of 5 μm or more and less than 90 μm, and further to easily form a photosensitive film having an arithmetic mean surface roughness Ra of 0.05 μm or more. That is, by imparting the specific surface morphology of the intermediate layer to the surface of the photosensitive film, it is effective in that it is easy to form a photosensitive film that can improve the yield in the edge collapse of the pattern or the appearance inspection. The average interval Sm' of the unevenness of the intermediate layer is preferably not less than 6 μm and not more than 85 μm; more preferably not less than 7 μm and not more than 80 μm. In addition, the range of the arithmetic mean surface roughness Ra' of the intermediate layer is more preferably 0.06 μm or more, and particularly preferably 0.07 μm or more. Moreover, when setting an upper limit, 5.0 micrometers or less are preferable, 3.0 micrometers or less are more preferable, and 1.0 micrometers or less are still more preferable. Here, the meaning of each of the unevenness average interval Sm' and the arithmetic mean surface roughness Ra' or the specific measurement method thereof are as described in the later-mentioned [photosensitive film]. Furthermore, the average interval Sm' of the concavities and convexities of the intermediate layer, the average interval Sm' of the concavities and convexities of the photosensitive film, the arithmetic surface roughness Ra' of the intermediate layer and the arithmetic surface roughness Ra of the photosensitive film are not necessarily the same, but can be adjusted by appropriate methods. It is adjusted so that the uneven|corrugated average interval Sm and the arithmetic surface roughness Ra of the photosensitive film may fall within the above-mentioned specific range.

Any method of adjusting the intermediate layer having the above-mentioned unevenness average interval Sm' and arithmetic mean surface roughness Ra' may be used. For example, when a filler is added to the resin, the particle size or addition amount of the filler can be adjusted. , but not limited to the foregoing.

<Photosensitive film> The photosensitive film that constitutes the photosensitive film laminate of the present invention has a surface having an uneven surface and is formed of a photosensitive resin composition, and is characterized in that the unevenness on the surface has an average interval of Sm It is 5 μm or more and less than 90 μm. First, the mean interval Sm of the unevenness on the surface will be described with reference to the following formula. The average interval Sm of the unevenness on the surface, as shown in Figure 3, is based on the thickness curve, and only the reference length l(L) is extracted in the direction of the average line, and the corresponding value of a wave crest and its adjacent wave trough is obtained. The sum of the lengths of the average lines (Sm ₁ , Sm ₂ , ･･･Sm _i , Sm _n ) represents the average value. That is, the mean interval Sm of the unevenness on the surface can be calculated by the following formula.

In the present invention, when a solder resist layer or the like is formed using a photosensitive film having a specific surface morphology in which the unevenness average interval Sm is within the above-mentioned range, the yield can be improved in the visual inspection for inspecting the presence or absence of surface damage of the solder resist layer. Further, the photosensitive pattern formation of the solder resist layer can be obtained, especially the unexpectedly excellent effect of suppressing the edge collapse of the pattern can be obtained. The unevenness average interval Sm is preferably 6 μm or more and 85 μm or less, and more preferably 7 μm or more and 80 μm or less.

In addition, from the viewpoint of the balance between the edge collapse of the pattern and the improvement of the yield in the visual inspection, the arithmetic mean surface roughness Ra of the surface having the uneven surface of the photosensitive film is preferably 0.05 μm or more, more preferably 0.06 μm or more, and more preferably 0.07 μm or more. Moreover, when setting an upper limit, 5.0 micrometers or less are preferable, 3.0 micrometers or less are more preferable, and 1.0 micrometers or less are still more preferable.

In the present invention, the above-mentioned "average interval of unevenness Sm" and "arithmetic mean surface roughness Ra" mean values measured by a measuring apparatus according to JIS B0601-1994. Hereinafter, a specific measurement method will be described. The unevenness average interval Sm and the arithmetic mean surface roughness Ra can be measured using a shape measuring laser microscope (for example, VK-X100 manufactured by Keyence Co., Ltd.). After starting the shape measuring laser microscope (same as VK-X100) main body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Corporation), the measured sample (photosensitive film) was placed on the x-y stage. ). Rotate the lens rotator of the microscope section (VK-X110 manufactured by Keyence Co., Ltd.), select an objective lens with a magnification of 10 times, and use the image observation mode of the VK observation application (same as VK-H1VX) to roughly adjust the focus and brightness. Operate the x-y stage and adjust so that the part of the sample surface to be measured comes to the center of the screen. Replace the objective lens with a magnification of 10 times to a magnification of 50 times, and use the autofocus function of the image observation mode of the VK observation application (same as VK-H1VX) to focus on the surface of the sample. Select the simple mode of the shape measurement tab (tag) of the VK observation application (same as VK-H1VX), press the measurement start button, and perform the surface shape measurement of the sample, and the surface image file can be obtained. Start the VK analysis application (VK-H1XA manufactured by Keyence Corporation) to display the obtained surface image file, and then perform slope correction. In addition, the observation measurement range (horizontal) in the measurement of the surface shape of a sample was 270 micrometers. Display the line thickness window. After selecting JIS B0601-1994 in the parameter setting area, select the horizontal line with the measuring line button, and display the horizontal line at any place in the surface image. Press the OK button to obtain the average interval Sm of unevenness and the arithmetic average surface thickness. The value of Ra. Further, horizontal lines are displayed at four different positions in the surface image, and the values of the mean interval Sm of the concavities and convexities and the arithmetic mean surface roughness Ra of each are obtained. The average value of the obtained 5 values was calculated respectively, and used as the average interval Sm of the unevenness on the surface of the sample and the arithmetic average surface roughness Ra value. In addition, in the measurement of the said uneven|corrugated average interval Sm and the arithmetic mean surface roughness Ra, the photosensitive film of the state before the hardening process, such as exposure, was used as a measurement sample. As in the present invention, when the photosensitive film laminates the intermediate layer and the support film as a laminate, a measurement sample of the state in which the intermediate layer and the support film are peeled off before a curing step such as exposure is used. In this case, after peeling off the intermediate layer and the support film to expose the photosensitive film, the measurement of the "average interval Sm of unevenness" and the "arithmetic average surface roughness Ra" of the sample surface was performed within 5 minutes.

In order to make the surface morphology of the photosensitive film within the range of the above-mentioned specific unevenness average interval Sm and arithmetic mean surface roughness Ra, well-known and conventional methods can be applied, and among them, from the viewpoint of the ease of forming such a surface morphology, it is particularly preferred. In order to form a photosensitive film using the intermediate layer as described above. That is, the surface which has the uneven|corrugated surface located in the range of the said specific uneven|corrugated average interval Sm or arithmetic mean surface roughness Ra, is preferably the surface adjacent to the intermediate layer.

The photosensitive film provided with the uneven|corrugated surface which has the above-mentioned specific uneven|corrugated average interval Sm and arithmetic mean surface roughness Ra is patterned by exposure and development, and becomes a cured film provided on a circuit board. The cured coating is preferably a solder resist layer. Such a photosensitive film can be formed using a photosensitive resin composition, and the photosensitive resin composition can be used without limitation with conventionally known solder resist inks and the like. The following describes the photosensitivity of the photosensitive film that can be preferably used in the present invention. An example of a resin composition.

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

[Crosslinking ingredients] The crosslinking component is not particularly limited as long as it is a component capable of crosslinking, and a well-known and conventional one can be used. In particular, it is a photosensitive resin or photosensitive monomer containing a carboxyl group. When further heated, it contains a component that is cross-linked by heat (hereinafter referred to as a thermal cross-linking component), in order to improve properties such as heat resistance and insulation reliability. better.

The photosensitive resin containing a carboxyl group is a component which hardens|cures by photoirradiation polymerization or crosslinking, and can become alkali developable by containing a carboxyl group. Moreover, it is preferable to have an ethylenically unsaturated bond in a molecule|numerator other than a carboxyl group from a viewpoint of photocurability or development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof.

In addition, as the carboxyl group-containing photosensitive resin, it is preferable to use a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material, or a carboxyl group-containing resin obtained by synthesizing resins other than epoxy resins. Carboxyl group-containing photosensitive resins that do not use epoxy resins as starting materials or carboxyl group-containing resins obtained by synthesizing resins other than epoxy resins have a very low halide ion content and can suppress deterioration of insulation reliability. , the electrical characteristics are better. As a specific example of the photosensitive resin containing a carboxyl group, the compound (either an oligomer or a polymer may be sufficient) as enumerated below is mentioned.

Examples include (1) reacting (meth)acrylic acid with a bifunctional or higher polyfunctional (solid) epoxy resin, and adding phthalic anhydride and tetrahydrophthalic acid to the hydroxyl group present in the side chain Carboxyl group-containing photosensitive resins obtained from dibasic acid anhydrides such as formic anhydride and hexahydrophthalic anhydride, (2) The (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group The resulting photosensitive resin containing carboxyl groups, (3) Compounds having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, unsaturated group-containing monocarboxylic acids such as (meth)acrylic acid, and two or more rings in one molecule Oxygen-based epoxy compound reaction, and to the alcoholic hydroxyl group of the obtained reaction product, polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. The photosensitive resin containing carboxyl group obtained by the reaction, (4) Using unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and using bisphenol A, bisphenol F, bisphenol S, novolak type phenol resin, poly-p-hydroxystyrene, naphthol Reaction with compounds having two or more phenolic hydroxyl groups in one molecule, such as condensates of aldehydes, condensates of dihydroxynaphthalene and aldehydes, and alkylene oxides such as ethylene oxide and propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting the product and reacting the obtained reaction product with a polybasic acid anhydride, (5) A reaction obtained by reacting a monocarboxylic acid containing an unsaturated group with a compound having two or more phenolic hydroxyl groups in one molecule and a cyclic carbonate compound such as ethylidene carbonate and propylidene carbonate A carboxyl group-containing photosensitive resin obtained by reacting the product and reacting the obtained reaction product with a polybasic acid anhydride, (6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, and polyester-based polyols , Polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, compounds with phenolic hydroxyl groups and alcoholic hydroxyl groups and other diol compounds obtained by addition polymerization. A urethane resin containing a terminal carboxyl group obtained by reacting an acid anhydride at the end of a formate resin, (7) Diisocyanates; carboxyl-containing diol compounds such as dimethylol propionic acid, dimethylol butyric acid, etc.; carboxyl-containing urethanes obtained by addition polymerization with diol compounds In the synthesis of resins, compounds having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylates, are added, and amines containing carboxyl groups that are terminally (meth)acrylated carbamate resin, (8) Add isophorone diisocyanate and pentaerythritol triacrylic acid to synthesis of diisocyanate, carboxyl group-containing diol compound, and carboxyl group-containing urethane resin obtained by addition polymerization of diisocyanate and diol compound Compounds having one isocyanate group and one or more (meth)acryloyl groups in the molecule such as molar reactants such as esters, urethane resins containing carboxyl groups that are terminally (meth)acrylated, (9) The dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc. is reacted with the polyfunctional oxetane resin, and a dibasic acid anhydride is added to the generated primary hydroxyl group, and then To the carboxyl group-containing polyester resin obtained by the above-mentioned addition, glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. are further added to have one epoxy group and one epoxy group in one molecule. A carboxyl group-containing photosensitive resin composed of a compound having at least one (meth)acryloyl group, (10) A carboxyl group-containing compound obtained by adding a compound having a cyclic ether group and a (meth)acryloyl group in one molecule to the carboxyl group-containing photosensitive resin according to any one of the above (1) to (9) photosensitive resin, (11) For a compound obtained by copolymerizing 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 The carboxyl group-containing resin is obtained by reacting a compound having a cyclic ether group and a (meth)acryloyl group in one molecule, such as 3,4-epoxycyclohexyl methacrylate, with a carboxyl group-containing photosensitivity. resin, etc. In addition, here, (meth)acrylate is a term collectively referring to an acrylate, a methacrylate, and a mixture of these, and the following other similar expressions are also the same.

Among the above-mentioned carboxyl group-containing photosensitive resins, carboxyl group-containing photosensitive resins that do not use epoxy resins as starting materials as described above, or carboxyl group-containing photosensitive resins obtained by synthesizing resins other than epoxy resins can be suitably used. resin. Therefore, among the specific examples of the above-mentioned carboxyl group-containing photosensitive resin, any one or more of the carboxyl group-containing photosensitive resins (4) to (8) and (11) can be suitably used, and especially (4) to ( 8) The exemplified resins. It can have the required properties of solder resists for semiconductor packaging, that is, PCT resistance, HAST resistance, and thermal shock resistance.

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

In addition, by not using epoxy resin as a starting material, or by synthesizing resin other than epoxy resin, a resin containing no hydroxyl group (or reducing the amount of hydroxyl group) can be easily obtained. In general, the presence of hydroxyl groups also has excellent characteristics such as improved adhesion due to hydrogen bonds, but it is known that moisture resistance is significantly reduced. wetness.

Furthermore, it is also suitable to use a carboxyl group-containing urethane resin synthesized from an isocyanate compound that does not use phosgene as a starting material and a raw material that does not use an epihalohydrin, and has a chloride ion impurity content of 0 to 30 ppm. In such a urethane resin, by blending the equivalent of a hydroxyl group and an isocyanate group, a hydroxyl group-free resin can be easily synthesized.

Moreover, when synthesizing a urethane resin, an epoxy acrylate modified raw material can also be used as a diol compound. Although a chloride ion impurity may be mixed, it can be used from the viewpoint that the amount of chloride ion impurity can be controlled.

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

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

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

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

Compounds used as photosensitive monomers include, for example, commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates. ) acrylate, (meth)acrylate epoxy ester, etc. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol can be mentioned. Diacrylates; acrylamides such as N,N-dimethylacrylamide, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc.; acrylic acid N, Amino alkyl acrylates such as N-dimethylaminoethyl ester, N,N-dimethylaminopropyl acrylate, etc.; Hexanediol, Trimethylolpropane, Pentaerythritol, Dipentaerythritol, Ps-hydroxyethyl Polyhydric acrylates such as polyols such as isocyanurate or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; acrylic phenoxy Esters, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, Polyvalent acrylates of glycidyl ethers such as trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.; not limited to the above, polyether polyols, polycarbonate diols, hydroxyl-terminated Polyols such as polybutadiene, polyester polyol, etc. are directly acrylated, or acrylates and melamine acrylates that pass through diisocyanate and urethane acrylate, and each methyl ester corresponding to the aforementioned acrylates Any one of the base acrylates can be appropriately selected and used from at least one of them.

Acrylic epoxy ester resins obtained by reacting acrylic acid with polyfunctional epoxy resins such as cresol novolak epoxy resins, or hydroxy acrylates such as pentaerythritol triacrylate and isophorone diisocyanates can also be used. The epoxy urethane acrylate compound etc. which the hemiurethane compound of the diisocyanate and the hydroxyl group of this acrylic epoxy ester resin reacted are used as a photosensitive monomer. Such epoxy acrylate resins can improve photocurability without reducing dryness to the touch.

The compounding amount of a compound having an ethylenically unsaturated group in the molecule used as a photosensitive monomer, when a carboxyl group-containing resin is included in the composition, in terms of solid content, relative to 100 parts by mass of the carboxyl group-containing resin, Preferably it is 5-100 mass parts, More preferably, it is a ratio of 5-70 mass parts. By making the compounding quantity of the compound which has an ethylenically unsaturated group 5 mass parts or more, the photocurability of a photocurable resin composition improves. Moreover, by making a compounding quantity into 100 mass parts or less, the hardness of a coating film can be improved. The carboxyl group-containing resin referred to here refers to any one including a carboxyl group-containing photosensitive resin and a carboxyl group non-photosensitive resin. That is, when any one of the components is blended alone, it means alone, and when both are blended, it means the total (in this specification, the same definition is used below).

In particular, when a carboxyl group-containing non-photosensitive resin that does not have an ethylenically unsaturated double bond is used, since the composition is photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in the molecule in combination (photosensitive resin). photosensitive monomer), so the photosensitive monomer is effective.

A thermosetting resin etc. are mentioned as a thermal crosslinking component. Thermosetting resins, isocyanate compounds, blocked isocyanate compounds, amine resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, polyfunctional epoxy compounds, Well-known conventional ones such as polyfunctional oxetane compounds and episulfide resins. Among these, particularly preferable thermal crosslinking components are those having at least one of a plurality of cyclic ether groups and a plurality of cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in one molecule. Thermal crosslinking ingredients. These thermosetting components having a cyclic (thio)ether group are commercially available in many types, and various properties can be imparted according to their structures.

A thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, which is a cyclic ether group having a plurality of 3-, 4- or 5-membered rings in the molecule, or either or both of the cyclic thioether groups For example, a compound having a plurality of epoxy groups in the molecule, namely a polyfunctional epoxy compound; a compound having a plurality of oxetanyl groups in the molecule, namely a polyfunctional oxetane compound; a molecule Compounds having a plurality of thioether groups are also episulfide resins and the like.

Examples of polyfunctional epoxy compounds include jER828, jER834, jER1001, jER1004, manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 840-S, Epiclon 850, Epiclon 1050, Epiclon 2055, Nippon Steel Corporation, manufactured by DIC Corporation. Epotohto YD-011, YD-013, YD-127, YD-128 manufactured by Sumitomo Metal Corporation, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by The Dow Chemical Company, Sumiepoxy manufactured by Sumitomo Chemical Co., Ltd. ESA-011, ESA-014, ELA-115, ELA-128, A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664, etc. (all trade names) manufactured by Asahi Kasei Industry Co., Ltd.; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Epotohto YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Metal Corporation, D.E.R.542 manufactured by Dow Chemical Co., Ltd., Sumitomo Chemical Sumiepoxy ESB-400 and ESB-700 manufactured by Kogyo Co., Ltd., A.E.R.711 and A.E.R.714 manufactured by Asahi Kasei Industries Co., Ltd. (all are trade names) brominated epoxy resins; jER152, manufactured by Mitsubishi Chemical Corporation, jER154, D.E.N.431, D.E.N.438 manufactured by The Dow Chemical Company, Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by DIC Corporation, Epotohto YDCN-701, YDCN manufactured by Nippon Steel & Sumitomo Metal Corporation -704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H, manufactured by Nippon Kayaku Co., Ltd., Sumiepoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd. 220. A.E.R.ECN-235, ECN-299, etc. (all trade names) made by Asahi Kasei Industry Co., Ltd. are novolak-type epoxy resins; Epiclon 830 made by DIC Co., Ltd., jER807 made by Mitsubishi Chemical Co., Ltd., new Epotohto YDF-170, YDF-175, YDF-2004, etc. (all trade names) manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. are bisphenol F epoxy resins; Epotohto ST-2004, manufactured by Nippon Steel & Sumitomo Metal Hydrogenated bisphenol A epoxy resins such as ST-2007, ST-3000 (trade name), etc.; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epotohto YH-434 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., Sumitomo Chemical Industry Co., Ltd. Glycidylamine-type epoxy resins such as Sumiepoxy ELM-120 manufactured by the company (all trade names); alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Co., Ltd. (trade names); Mitsubishi Chemical Corporation YL-933, T.E.N., EPPN-501, EPPN-502 made by Dow Chemical Company (all are trade names) of trihydroxyphenylmethane type epoxy resin; YL-6056, YX made by Mitsubishi Chemical Co., Ltd. -4000, YL-6121 (all trade names) and other bixylenol type or biphenol type epoxy resins or mixtures of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., manufactured by Asahi Denka Industry Bisphenol S type epoxy resin such as EPX-30, EXA-1514 (trade name) manufactured by DIC Co., Ltd.; Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation ; Tetraphenol ethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Co., Ltd.; Heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Industry Co., Ltd.; Japan Diglycidyl phthalate resin such as Blemmer DGT manufactured by Oil & Fats Co., Ltd.; Tetraglycidyl xylenol ethane resin such as ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.; Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700 manufactured by DIC Co., Ltd. and other epoxy resins containing naphthyl groups; HP-7200, HP-7200H, etc. manufactured by DIC Co., Ltd. Dicyclopentadiene skeleton epoxy resin, EXA-4816, EXA-4822, EXA-4850 series soft and tough epoxy resin; Nippon Oil Co., Ltd. CP-50S, CP-50M and other methacrylic acid shrinkage Glyceryl ester copolymerized epoxy resin; there are also copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, etc., but not limited to these. These epoxy resins can be used alone or in combination of two or more.

Examples of polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetane) Alkylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl) Ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl acrylate) Butyl) methyl ester, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or the Polyfunctional oxetanes such as oligomers or copolymers, as well as oxetanols and novolac resins, poly(p-hydroxystyrene), Cardo-type bisphenols, calixarenes , calix resorcinol aromatic hydrocarbons or silsesquioxane and other ethers of resins with hydroxyl groups, etc. Another example is a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, and the like.

As the episulfide resin, for example, YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Co., Ltd., etc. may be mentioned. Moreover, episulfide resin etc. which replace the oxygen atom of the epoxy group of the novolak-type epoxy resin with a sulfur atom by the same synthesis method can also be used.

When a thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is contained in the composition, the blending amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is calculated as solid content In conversion, it is preferably in the range of 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents, relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. By making the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule to be 0.3 equivalent or more, the carboxyl group does not remain in the cured film, and the heat resistance, alkali resistance, electrical insulation, etc. are improved. . Moreover, by setting it as 2.5 equivalents or less, the low molecular weight cyclic (thio)ether group does not remain in a dry coating film, and the intensity|strength etc. of a cured coating film can be improved.

When using a thermosetting component having a plurality of cyclic (thio)ether groups in the molecule, it is preferable to blend a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives of ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; dicyanodiamine, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Amine compounds; hydrazine compounds such as dihydrazine adipic acid, dihydrazine sebacate, etc.; phosphorus compounds such as triphenylphosphine, etc. In addition, for example, commercially available ones include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U by San-Apro Co., Ltd. -CAT (registered trademark) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts) Wait. It is not particularly limited to these, as long as it is a thermosetting catalyst of epoxy resin or oxetane compound, or it can promote the reaction of epoxy group and/or oxetane group with carboxyl group, it can be used alone Or you may mix and use 2 or more types. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2 ,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as acryloyloxyethyl-S-triazine/isocyanuric acid adducts, preferably compounds that function as adhesion imparting agents, and heat A hardening catalyst is used in combination.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is contained in the composition, the blending amount of the thermosetting catalyst is calculated in terms of solid content relative to that having a plurality of cyclic (sulfur) groups in the molecule. It is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of thermosetting components of an ether group, More preferably, it is 0.5-15.0 mass parts.

Examples of the amine-based resin include amine-based resins such as melamine derivatives and benzoguanamine derivatives. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol acetylene carbamide compounds, and methylol urea compounds. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated acetylene carbamide compound and the alkoxymethylated urea compound can be prepared by combining the respective hydroxyl groups. A methylmelamine compound, a methylol benzoguanamine compound, a methylol acetylene carbamide compound, and a methylol urea compound are obtained by converting methylol groups into alkoxymethyl groups. The type of the alkoxymethyl group is not particularly limited, for example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like can be used. Particularly preferred is a melamine derivative with a formalin concentration of less than 0.2% that is mild to the human body or the environment.

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

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate can be used. Specific examples of aromatic polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-diisocyanate Toluene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclomethylene diisocyanate) hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. And the adduct body of the isocyanate compound mentioned above, a biuret body, and an isocyanurate body are mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a specific temperature, the blocking agent dissociates to generate isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. The isocyanate compound which can react with a blocking agent, an isocyanurate type, a biuret type, an adduct type, etc. are mentioned. Examples of the isocyanate compound used to synthesize the blocked isocyanate compound include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates include the compounds exemplified above.

Examples of isocyanate blocking agents include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valerolactam, and γ-butyrolactone Lactamide-based end-capping agents such as β-propiolactamide; active methylene-based end-capping agents such as ethyl acetate and acetone; 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, glycerol Alcohol-based end-capping agents such as butyl alkyd, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, diacetoxymonoxime, cyclohexane Oxime-based end-capping agents such as alkyl oximes; thiol-based end-capping agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol, etc.; amide acetate , acid amide end-capping agents such as benzyl amine; imide end-capping agents such as succinic acid imide and maleic acid imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based end-capping agents; imidazole-based end-capping agents such as imidazole and 2-ethylimidazole; imine-based end-capping agents such as methyleneimine and propylene imine, etc.

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

In order to promote the hardening reaction of a hydroxyl group or a carboxyl group and an isocyanate group, a urethane-forming catalyst may also be blended in the photosensitive resin composition. As a urethane catalyst, it is preferable to use urethane selected from at least one of tin-based catalysts, metal chlorides, metal acetylacetonates, metal sulfates, amine compounds and amine salts Esterification catalyst.

Examples of the tin-based catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds. In addition, the metal chlorides include chlorides of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as cobalt(III) chloride, nickel(II) chloride, chloride Iron(III) etc. In addition, the metal acetylacetonate includes acetylacetonate of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, such as cobalt acetylacetonate, nickel acetylacetonate, acetylacetonate Iron acetone, etc. Further, metal sulfates include metal sulfates selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, such as copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether , N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylethanolamine, dimorpholino Ethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethylｰbis(2-aminoethyl) ) ether, N,N-dimethylhexanolamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethyl Diamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetriamine, N-(2-hydroxypropyl)-N,N',N", N"-tetramethyldiethylenetriamine, N,N,N'-trimethyl-N'-(2-hydroxyethyl)propanediamine, N-methyl-N'-(2-hydroxyethyl) ) piperazine, bis(N,N-dimethylaminopropyl)amine, bis(N,N-dimethylaminopropyl)isopropanolamine, 2-aminoquinuclidine, 3-amine Quinuclidine, 4-aminoquinuclidine, 2-quinuclidine, 3-quinuclidine, 4-quinuclidine, 1-(2'-hydroxypropyl)imidazole, 1-(2'-hydroxyl propyl)-2-methylimidazole, 1-(2'-hydroxyethyl)imidazole, 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxypropyl)- 2-methylimidazole, 1-(3'-aminopropyl)imidazole, 1-(3'-aminopropyl)-2-methylimidazole, 1-(3'-hydroxypropyl)imidazole, 1 -(3'-hydroxypropyl)-2-methylimidazole, N,N-dimethylaminopropyl-N'-(2-hydroxyethyl)amine, N,N-dimethylaminopropyl base-N',N'-bis(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N',N'-bis(2-hydroxypropyl)amine, N,N- Dimethylaminoethyl-N',N'-bis(2-hydroxyethyl)amine, N,N-dimethylaminoethyl-N',N'-bis(2-hydroxypropyl) At least one of amine, melamine, and benzoguanamine, and the like.

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

[filler] As the filler, well-known and conventional inorganic or organic fillers can be used, and barium sulfate, spherical silica, Newcastle silica particles and talc are particularly preferably used. In addition, aluminum hydroxide, magnesium hydroxide, diaspore or the like may be used for the purpose of imparting flame retardancy. Furthermore, NANOCRYL (trade name) XP 0396 and XP 0596 manufactured by Hanse-Chemie Co., Ltd. in which nano-silicon dioxide is dispersed in a compound having one or more ethylenically unsaturated groups or the aforementioned polyfunctional epoxy resin can also be used , XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), or NANOPOX (trade name) XP 0516, XP 0525, XP 0314 ( Both are product grade names). These may be used alone or in admixture of two or more. By containing a filler, the physical strength etc. of the obtained hardened|cured material can be improved.

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

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

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

(式中，X₁ 表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、苯基、苯基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、萘基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)，Y₁ 、Z係分別表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、鹵基、苯基、苯基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、萘基(經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具備碳數1~8之烷基的烷基胺基或二烷基胺基取代)、蒽基、吡啶基、苯并呋喃基、苯并噻吩基，Ar表示碳數1~10之伸烷基、伸乙烯基、伸苯基、伸聯苯基、伸吡啶基、伸萘基、噻吩、伸蒽基、伸噻吩基、伸呋喃基、2,5-吡咯-二基、4,4’-二苯乙烯-二基、4,2’-苯乙烯-二基，n為0或1之整數)。Moreover, the photopolymerization initiator which has two oxime ester groups in a molecule|numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented by following general formula (III) is mentioned.

(in the formula, X ₁ represents a hydrogen atom, an alkyl group with 1 to 17 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, a phenyl group, a phenyl group (through an alkyl group with 1 to 17 carbon atoms, an alkyl group with 1 to 8 carbon atoms) alkoxy group, amine group, alkylamino group or dialkylamine group with an alkyl group of 1-8 carbon atoms), naphthyl (substituted by an alkyl group with a carbon number of 1-17, an alkyl group with a carbon number of 1-8 alkoxy group, amino group, alkylamino group with alkyl group of 1-8 carbon atoms or dialkylamine group substituted), Y ₁ and Z represent hydrogen atom, alkyl group of carbon number 1-17, carbon atom respectively Alkoxy group with 1~8 carbon number, halogen group, phenyl group, phenyl group (through alkyl group with carbon number 1~17, alkoxy group with carbon number 1~8, amine group, alkyl group with carbon number 1~8 substituted alkylamine or dialkylamine), naphthyl (substituted with an alkyl group having 1 to 17 carbon atoms, an alkoxy group having a carbon number of 1 to 8, an amino group, an alkyl group having an alkyl group of 1 to 8 carbon atoms) Alkylamino or dialkylamino substituted), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents alkylene, vinylidene, phenylene, alkene with carbon number 1~10 Biphenyl, pyridyl, naphthylene, thiophene, anthracenyl, thienyl, furanyl, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2 '-styrene-diyl, n is an integer of 0 or 1).

In the above formula, X ₁ and Y ₁ are respectively methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or oxime ester of thienyl It is a photopolymerization initiator.

Preferred carbazole oxime ester compounds include compounds represented by the following general formula (IV).

(式中，R¹ 表示碳原子數1~4之烷基，或可經硝基、鹵素原子或碳原子數1~4之烷基取代之苯基。 R² 表示碳原子數1~4之烷基、碳原子數1~4之烷氧基，或可經碳原子數1~4之烷基或烷氧基取代之苯基。 R³ 表示可經能夠以氧原子或硫原子連結且可經苯基取代之碳原子數1~20之烷基、碳原子數1~4之烷氧基取代的苄基。 R⁴ 表示硝基或X-C(=O)-表示之醯基。 X表示可經碳原子數1~4之烷基取代之芳基、噻吩基、嗎啉基、苯硫基，或下述式(V)表示之構造)。

(In the formula, R ¹ represents an alkyl group with 1 to 4 carbon atoms, or a phenyl group that can be substituted by a nitro group, a halogen atom or an alkyl group with 1 to 4 carbon atoms. R ² represents a carbon number of 1 to 4. An alkyl group, an alkoxy group having 1 to ⁴ carbon atoms, or a phenyl group that may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms. Alkyl group with 1 to 20 carbon atoms substituted by phenyl, benzyl group substituted with alkoxy group with 1 to 4 carbon atoms. R ⁴ represents nitro or acyl group represented by XC(=O)-. X represents possible An aryl group, a thienyl group, a morpholinyl group, a phenylthio group substituted with an alkyl group having 1 to 4 carbon atoms, or a structure represented by the following formula (V)).

Others include JP 2004-359639 A, JP 2005-097141 A, JP 2005-220097 A, JP 2006-160634 A, JP 2005-220097 A Carbazole oxime ester compounds described in Japanese Patent Publication No. 2008-094770, Japanese Patent Publication No. 2008-509967, Japanese Patent Publication No. 2009-040762, and Japanese Patent Publication No. 2011-80036.

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

α-Aminoacetophenone-based photopolymerization initiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2- Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) ) methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc. Commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins.

Acylphosphine oxide-based photopolymerization initiators include, specifically, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl) Acryloyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins.

When using a photopolymerization initiator other than the oxime ester-based photopolymerization initiator, when the composition contains a carboxyl group-containing resin, it is calculated in terms of solid content relative to 100 parts by mass of the carboxyl group-containing resin. Preferably it is 0.01-15 mass parts. By setting it as 0.01 mass part or more, the photocurability on copper becomes more reliable, and the coating film characteristics, such as chemical resistance, will improve. Moreover, by setting it as 15 mass parts or less, the sufficient reduction effect of outgas can be acquired, the light absorption on the surface of a hardened film is suppressed further, and the hardenability of a deep part is also improved. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of carboxyl group-containing resins.

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

A photoinitiator aid or a sensitizer may also be used in combination with the above-mentioned photopolymerization initiator. Examples of photoinitiator aids or sensitizers include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthine compounds Wait. These compounds may also be used as a photopolymerization initiator, but it is preferably used together with a photopolymerization initiator. In addition, a photoinitiator 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, the acetophenone compound, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,2-dimethoxy-2-phenylacetophenone, 1-Dichloroacetophenone, etc. Moreover, as an anthraquinone compound, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. are mentioned, for example. Moreover, as a thioxanthone compound, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chlorothioxanthone, 2, 4- diisopropyl thioxanthone, for example, can be mentioned Wait. Moreover, as a ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned, for example. Further, examples of the benzophenone compound include benzophenone, 4-benzyl diphenyl sulfide, 4-benzyl-4'-methyl diphenyl sulfide, 4-benzene Formyl-4'-ethyl diphenyl sulfide, 4-benzyl-4'-propyl diphenyl sulfide, etc.

The tertiary amine compound includes, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, and for example, a commercially available product includes 4,4'-dimethylaminobenzophenone (Nisso, manufactured by Nippon Soda Co., Ltd.). Dialkylaminobenzophenone such as Cure (registered trademark) MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Industry Co., Ltd.), 7-(diethylaminobenzophenone) amino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) etc. containing dialkylamine Coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthetics Corporation) Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Nippon Chemical Co., Ltd.) Kayacure DMBI (manufactured by Pharma Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk Co., Ltd.), and the like. 3rd-grade amine compounds, preferably compounds with dialkylaminobenzene structure, especially dialkylaminobenzophenone compounds, coumarin containing dialkylamino groups with a maximum absorption wavelength of 350~450nm Vegan compounds and ketocoumarins are particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. Coumarin compounds containing dialkylamine groups, since the maximum absorption wavelength is in the ultraviolet region of 350 to 410 nm, are naturally colorless, colorless and transparent photosensitive resin compositions, and coloring pigments can be used to obtain coloring pigments. Pigmented photosensitive film of its own color. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect to laser light with a wavelength of 400-410 nm.

Among these, a thioxanthone compound and a tertiary amine compound are preferable. In particular, by containing a thioxanthone compound, deep sclerosis can be improved.

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

Furthermore, these photopolymerization initiators, photoinitiator assistants, and sensitizers may have lower sensitivity in some cases because they absorb specific wavelengths, and function as ultraviolet absorbers. However, these are used not only for the purpose of improving the sensitivity of the composition. It can absorb light of a specific wavelength as required, improve the photoreactivity of the surface, make the line shape and opening of the resist into vertical, tapered, and reverse tapered shapes, and improve the processing accuracy of line width or opening diameter.

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

In the above-mentioned photosensitive resin composition, a block copolymer can be suitably blended. A block copolymer refers to a copolymer in which two or more polymers with different properties are linked by covalent bonds to form a long-chain molecular structure. Preferably, it is a solid in the range of 20 degreeC - 30 degreeC. As long as it is solid within this range, the temperature outside this range may also be solid. Since it is solid in the said temperature range, when it becomes a photosensitive film or it coats a support film and it is temporarily dried, it is excellent in adhesiveness.

The block copolymer is preferably an XYX or XYX' type block copolymer. Among XYX or XYX' type block copolymers, Y in the center is a soft block, the glass transition point Tg is low, preferably less than 0°C, and the two outer sides X or X' are hard blocks, and the Tg is high, preferably It is preferable that it is constituted by a polymer unit of 0°C or higher. The glass transition point Tg is determined by differential scanning calorimetry (DSC).

In addition, among the XYX or XYX' type block copolymers, it is more preferable that the Tg of X or X' is a polymer unit of 50°C or higher, and the Tg of Y is A block copolymer made of polymer units below -20°C. In addition, in the XYX or XYX' type block copolymer, X or X' is preferably one having high compatibility with the carboxyl group-containing resin, and Y is preferably one having low compatibility with the carboxyl group-containing resin. In this way, it is considered that a specific structure is easily exhibited in the matrix by the block copolymer in which the blocks at both ends are compatible with the matrix and the blocks in the center are incompatible with the matrix.

In addition, the block copolymer can be used without particular limitation as long as there are at least one type of hard block and at least one soft block component in addition to the XYX or XYX' type.

As the X or X' component, polymethyl methacrylate (PMMA), polystyrene (PS), etc. are preferred, and as the Y component, poly-n-butyl acrylate (PBA), polybutadiene ( PB) etc. In addition, the above-mentioned carboxyl group-containing resin represented by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy group-containing unit, an N-substituted acrylamide unit, etc. can be introduced into a part of the X or X' component. The hydrophilic unit with excellent compatibility further improves compatibility. The present inventors have found that the block copolymer obtained in this way has particularly good compatibility with the above-mentioned carboxyl group-containing resin, and surprisingly, the thermal shock resistance can be improved, and more surprisingly, an elastomer is added , the glass transition temperature (Tg) tends to decrease, whereas the Tg does not tend to decrease in the case where the above-mentioned block copolymer is added.

As a manufacturing method of a 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 a block copolymer, the acrylic triblock copolymer manufactured using the living polymerization by Arkema company is mentioned. SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate, MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, and further MAM N type or MAM A type treated with carboxylic acid modification or hydrophilic group modification. The SBM type includes E41, E40, E21, E20, etc., the MAM type includes M51, M52, M53, M22, etc., the MAM N type includes 52N, 22N, and the MAM A type includes SM4032XM10. Further, Kurarity manufactured by Kuraray Co., Ltd. is also a block copolymer derived from methyl methacrylate and butyl acrylate.

The block copolymer is preferably a block copolymer having three or more members, and in order to obtain the effects of the present invention, it is more preferably a block copolymer whose molecular structure is precisely controlled by a living polymerization method. This is considered to be because the molecular weight distribution of the block copolymer synthesized by the living polymerization method is narrow, and the characteristics of the respective units become clear. The molecular weight distribution of the block copolymer to be used is preferably 2.5 or less, more preferably 2.0 or less.

The weight average molecular weight of the block copolymer is generally 20,000-400,000, more preferably in the range of 30,000-300,000. When the weight average molecular weight is less than 20,000, the desired effects of toughness and flexibility cannot be obtained, and the adhesiveness is also poor. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity of the photocurable resin composition becomes high, and the printability and developability deteriorate remarkably.

The blending amount of the block copolymer, when a resin containing a carboxyl group is included in the composition, is preferably in the range of 1 to 50 parts by mass, more preferably 100 parts by mass of the resin containing a carboxyl group, in terms of solid content. 5 to 35 parts by mass. 1 mass part or more can expect the effect, and 50 mass parts or less becomes favorable as a photocurable resin composition developability and coatability.

The photosensitive resin composition may contain a colorant. As the colorant, known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferable that no halogen is contained.

The red colorants are monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. etc., specifically, those with the following color index (C.I.; issued by The Society of Dyers and Colourists) number are mentioned.

Monoazo-based red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, etc. Moreover, Pigment Red 37, 38, 41 etc. are mentioned as a disazo red coloring agent. Moreover, 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, etc. Moreover, Pigment Red 171, 175, 176, 185, 208 etc. are mentioned as a benzimidazolone type red coloring agent. Moreover, as a perylene-based red colorant, Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, etc. are mentioned. Moreover, Pigment Red 254, 255, 264, 270, 272 etc. are mentioned as a diketopyrrolopyrrole type red coloring agent. Moreover, Pigment Red 220, 144, 166, 214, 220, 221, 242 etc. are mentioned as a condensed azo type red coloring agent. Moreover, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207 etc. are mentioned as an anthraquinone type red coloring agent. Moreover, Pigment Red 122, 202, 206, 207, 209 etc. are mentioned as a quinacridone type red coloring agent.

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

Yellow colorants include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, and the like, for example, anthraquinone-based yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. Pigment Yellow 110, 109, 139, 179, 185 etc. are mentioned as an isoindolinone type yellow coloring agent. Pigment Yellow 93, 94, 95, 128, 155, 166, 180 etc. are mentioned as a condensed azo type yellow coloring agent. Pigment Yellow 120, 151, 154, 156, 175, 181 etc. are mentioned as a benzimidazolone type yellow coloring agent. Moreover, as the 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. Moreover, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 et al.

Other colorants such as purple, orange, brown, black, and white can also be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32; Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61 , 63, 64, 71, 73; PigmentBrown 23, 25; Titanium oxide, carbon black, etc.

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

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

Moreover, for the purpose of improving the flexibility and dryness to the touch of the obtained cured product, a conventionally known binder polymer can be used. The binder polymer is preferably a cellulose-based, polyester-based, or phenoxy resin-based polymer. The cellulose-based polymer includes cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Corporation, and the polyester-based polymer is preferably Vylon manufactured by Toyobo Co., Ltd. In the series, the phenoxy resin-based polymer is preferably a phenoxy resin of bisphenol A, bisphenol F and their hydrogenated compounds.

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

Moreover, components, such as an adhesion promoter, an antioxidant, an ultraviolet absorber, may be further blended in the photosensitive resin composition as needed. These can be used as known in the field of electronic materials. In addition, well-known and commonly used tackifiers such as micropowder silica, hydrotalcite, organic bentonite, and montmorillonite can be blended; At least any one; silane coupling agents such as imidazole-based, thiazole-based, triazole-based, etc.; at least any one of known and customary additives such as rust inhibitors, optical brighteners, and the like.

The photosensitive film can be formed by apply|coating the said photosensitive resin composition to one side of a support film, and drying it. Considering the coatability of the photosensitive resin composition, the photosensitive resin composition can be diluted with an organic solvent and adjusted to an appropriate viscosity. Spreader, extrusion coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., are applied to one side of the support film to a uniform thickness, usually at a temperature of 50~130℃ Dry for 1 to 30 minutes to volatilize the organic solvent to obtain a non-sticky coating film. The coating film thickness is not particularly limited. Generally speaking, it is appropriately selected in the range of 5 to 150 μm, preferably 10 to 60 μm, in terms of the film thickness after drying.

The organic solvent that can be used is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Gycerol, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , esters of propylene glycol butyl ether acetate, etc.; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, hydrogenated naphtha, solvents Petroleum solvents such as naphtha, etc. Such an organic solvent may be used alone or as a mixture of two or more.

For the volatilization and drying of organic solvents, hot air circulation drying furnaces, IR furnaces, hot plates, convection ovens, etc. can be used (the method of using a steam-based air heating method with a heat source to make the hot air in the dryer countercurrent contact and the nozzles support blowing method).

[protective film] In the photosensitive film laminate of the present invention, a protective film can be provided on the surface of the photosensitive film opposite to the intermediate layer for the purpose of preventing dust and the like from adhering to the surface of the photosensitive film and improving handleability.

For example, the protective film can use polyester film, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. It is preferable to select the protective film and the photosensitive film to have a smaller adhesive force than the support film and the photosensitive film. material for adhesion. Moreover, when using a photosensitive film laminate, in order to peel a protective film easily, you may give the above-mentioned mold release process to the surface adjacent to the photosensitive film of a protective film.

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

<Manufacturing method of cured product and printed wiring board> A cured product is formed using the photosensitive film or the photosensitive film laminate of the present invention. A method of forming the cured product and a method of producing a printed wiring board provided with the cured product (cured film) on the board on which the circuit pattern is formed will be described. The method of manufacturing a printed wiring board using the photosensitive film laminated body provided with a protective film is demonstrated as an example. It is by first i) peeling off the protective film from the photosensitive film laminate to expose the photosensitive film, ii) attaching the photosensitive film of the photosensitive film laminate on the substrate on which the circuit pattern is formed, iii) ) exposure is performed on the support film of the photosensitive film laminate, iv) the support film is peeled off from the photosensitive film laminate, and developed to form a patterned photosensitive film on the substrate, v) the The patterned photosensitive film is cured by light irradiation or heat to form a cured film; and a printed wiring board is formed. In addition, when using the photosensitive thin-film laminated body which is not provided with the protective film as shown in FIG. 1, the peeling process (i-step) of the protective film is of course unnecessary. Hereinafter, each step will be described.

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

In order to bond the photosensitive film of the photosensitive film laminate on the circuit board, it is preferable to use a vacuum laminator or the like, and to bond under pressure and heating. By using such a vacuum laminator, even if the surface of the circuit board has irregularities, the photosensitive film adheres to the circuit board, so that no air bubbles are mixed in, and the hole filling property of the concave portion on the surface of the board is also improved. The pressure conditions are preferably about 0.1 to 2.0 MPa, and the heating conditions are preferably 40 to 120°C.

Next, exposure (irradiation of active energy rays) is performed on the support film of the photosensitive thin film laminate. In this step, the exposed photosensitive film is hardened. The exposure step is not particularly limited. For example, it can be selectively exposed to active energy rays through a photomask forming a desired pattern by contact (or non-contact), or it can be exposed by a direct drawing device. The desired pattern is exposed to active energy rays.

The exposure machine used for active energy ray irradiation may be a device equipped with a high-pressure mercury-vapor lamp, ultra-high-pressure mercury-vapor lamp, metal halide lamp, etc. to irradiate ultraviolet rays in the range of 350 to 450 nm, and a direct drawing device (for example, according to a computer) can also be used. A laser direct imaging device that draws images directly from the CAD data). As long as the laser light source of the direct-drawing machine uses the laser light with the maximum wavelength of 350~410nm, both gas laser and solid-state laser can be used. Although the exposure amount for forming an image varies depending on the film thickness, etc., it is generally within the range of 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

After exposure, the support film and the intermediate layer are peeled off from the photosensitive film laminate and developed, thereby forming a patterned photosensitive film on the substrate. After peeling off the support film and the intermediate layer, the surface of the photosensitive film hardened by exposure is given the shape of the surface of the intermediate layer. In addition, as long as it is a range which does not impair the characteristics, the support film and the intermediate layer may be peeled off from the photosensitive film laminate before exposure, and the exposed photosensitive film may be exposed and developed.

The development step is not particularly limited, and a dipping method, a shower method, a spray method, a brush method, or the like can be used. Moreover, as a developing solution, alkali aqueous solutions, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc., can be used.

Next, the patterned photosensitive film is cured by active energy ray (light) irradiation or heat to form a cured product (cured film). This step is called main hardening or additional hardening, which can promote the polymerization of unreacted monomers in the photosensitive film, and further thermally harden the photosensitive resin and epoxy resin containing carboxyl groups, thereby reducing the amount of residual carboxyl groups. The active energy ray irradiation can be carried out in the same manner as the above-mentioned exposure, but it is preferably carried out under a condition with a stronger irradiation energy than the irradiation energy at the time of exposure. For example, it may be 500 to 3000 mJ/cm ² . In addition, thermal hardening can be performed under heating conditions of about 100 to 200° C. for 20 to 90 minutes. In addition, it is preferable to carry out thermal hardening after photohardening as for main hardening. By performing photocuring first, the flow of the resin during heat curing is also suppressed, and it is possible to maintain the morphological surface.

In the above-described manner, an appropriate unevenness state can be imparted to the surface of the cured product. As a result, the edge collapse of the pattern is improved, and the yield in the visual inspection is also improved. Therefore, the photosensitive film laminate of the present invention can be suitably used as a printed wiring board, can be suitably used for the formation of a solder resist layer, and can be suitably used for the formation of a solder resist layer for IC packaging in particular. [Example]

Next, examples are given to describe the present invention in more detail, 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 introduction device, an alkylene oxide introduction device, and a stirring device, a novolak-type cresol resin (Shonol CRG951, manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4) 119.4 g, 1.19 g of potassium hydroxide, and 119.4 g of toluene, while stirring, the nitrogen in the system was substituted, and the temperature was heated. Next, 63.8 g of propylene oxide was gradually dropped, and the reaction was carried out at 125 to 132° C. and 0 to 4.8 kg/cm ² for 16 hours. Then, it was cooled to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution, and potassium hydroxide was neutralized to obtain an epoxy resin of a novolak-type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g/eq. propane reaction solution. The obtained novolak-type cresol resin had an average addition of 1.08 moles of alkylene oxide per 1 equivalent of phenolic hydroxyl groups.

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 mixer equipped with a thermometer and an air blowing pipe. Air was blown into the reactor at a rate of 10 ml/min, and the reaction was carried out at 110° C. for 12 hours while stirring. The water produced by the reaction was an azeotrope with toluene, and 12.6 g of water was distilled. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of 15% sodium hydroxide aqueous solution, and it washed with water. Then, toluene was substituted with 118.1 g of diethylene glycol monoethyl ether acetate by an evaporator, and it distilled off, and obtained the novolak-type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing pipe, and air was blown in at a rate of 10 ml/min while stirring. , while slowly adding 62.3 g of tetrahydrophthalic anhydride, and reacting at 95-101° C. for 6 hours to obtain a photosensitive resin paint 1 containing a carboxyl group with an acid value of 88 mgKOH/g as a non-volatile component of 71%.

<Preparation of photosensitive resin composition> The carboxyl group-containing photosensitive resin paint 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as the photosensitive monomer of the acrylate compound, as the thermosetting component Bisphenol A type epoxy resin (EPICLON840-S manufactured by DIC Co., Ltd.) and biphenol novolak type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.) are used as photopolymerization initiators. Omnirad TPO manufactured by IGM Resins or IRGACURE OXE02 manufactured by BASF JAPAN, barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.) and/or spherical silica (Admafine SO-E2 manufactured by Admatechs Co., Ltd.) as filler ), melamine as a thermosetting catalyst, carbon black M-50, C.I.Pigment Violet 23, C.I.Pigment Yellow 147, C.I.Pigment Blue 15:3, and C.I.Pigment Red 177 made by Mitsubishi Chemical Co., Ltd. as colorants The selected components were blended with diethylene glycol monoethyl ether acetate as an organic solvent at the ratio (parts by mass) shown in the following Table 1, preliminarily mixed with a mixer, and then kneaded with a 3-roll mill. Photosensitive resin compositions 1 and 2 were prepared.

<Preparation of Acrylic Melamine Resin 1> AMIDIR G-821-60 (iso-butylated melamine resin, solid content 60%) manufactured by DIC Co., Ltd. and ACRYDIC A-405 (acrylic resin for melamine baking, solid content 50%) manufactured by DIC Co., Ltd. In terms of solid content, the ratio was blended so as to be 25:75, and after preliminary stirring with a mixer, it was kneaded with a three-roll mill to prepare acrylic melamine resin 1 .

<Preparation of the support film 1 with the intermediate layer 1> The acrylic melamine resin 1 obtained as described above was diluted with methyl ethyl ketone to prepare a resin solution having a solid content concentration of 35% by mass. To this resin solution, methyl ethyl ketone was further added to obtain an appropriate solid content concentration according to the thickness of the coating film, and then a polysiloxane-based resin (SYMACUS-270 manufactured by Toagosei Co., Ltd.) and silica were added, Make the mass ratio of acrylic melamine resin 1, polysiloxane resin and silicon dioxide to be 59.7:0.3:40, and fully stir at room temperature to obtain a uniform coating solution. The coating liquid was obtained by a gravure roll method using a polyethylene terephthalate film (Lumirror T60, manufactured by Toray Co., Ltd.) on one side of the support film having fine irregularities on the surface as follows: Coating was carried out according to the conditions, and dried at 130° C. for 20 seconds to prepare a support film 1 having an intermediate layer 1 (the thickness of the intermediate layer was 8 μm, the thickness of the support film was 25 μm, and the total thickness was 33 μm).

<Production of the support film 2 with the intermediate layer 2> A support film 2 with an intermediate layer 2 (the thickness of the intermediate layer 3 μm, the The thickness of the film is 25 μm, and the total thickness is 28 μm).

<Preparation of photosensitive film laminate> Example 1 A support film (CM-25, manufactured by Unitika Co., Ltd.) in which a support film with a thickness of 25 μm and an intermediate layer were integrated, which was coated on one side of a polyethylene terephthalate film, was prepared. After measuring the unevenness average interval Sm' and arithmetic mean surface roughness Ra' of the intermediate layer as follows, the unevenness average interval Sm' was 12.9 μm, and the arithmetic mean surface roughness Ra' was 0.48 μm. In addition, the thickness of the intermediate layer was 3 μm.

The unevenness average interval Sm' and the arithmetic mean surface roughness Ra' were measured using a shape-measuring laser microscope (VK-X100 manufactured by Keyence Co., Ltd.). After starting the shape measurement laser microscope (same as VK-X100) body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Co., Ltd.), place the support film with the intermediate layer to be measured on the x-y stage (The surface with the intermediate layer is the upper part). Rotate the lens rotator of the microscope section (VK-X110 manufactured by Keyence Co., Ltd.), select an objective lens with a magnification of 10 times, and use the image observation mode of the VK observation application (same as VK-H1VX) to roughly adjust the focus and brightness. Operate the x-y stage and adjust so that the part of the sample surface to be measured comes to the center of the screen. Replace the objective lens with a magnification of 10 times to a magnification of 50 times, and use the autofocus function of the image observation mode of the VK observation application (same as VK-H1VX) to focus on the surface of the sample. Select the simple mode of the shape measurement tab (tag) of the VK observation application (same as VK-H1VX), press the measurement start button to measure the surface shape of the sample, and obtain the surface image file. Start the VK analysis application (VK-H1XA manufactured by Keyence Corporation) to display the obtained surface image file, and then perform slope correction.

In addition, the observation measurement range (horizontal) in the measurement of the surface shape of a sample was 270 micrometers. Display the line thickness window, after selecting JIS B0601-1994 in the parameter setting area, select the horizontal line by the measuring line button, display the horizontal line at any place in the surface image, press the OK button, and obtain the average interval Sm of the uneven surface and the arithmetic mean The value of surface roughness Ra'. Further, horizontal lines are displayed at four different positions in the surface image, and the values of the average unevenness interval Sm' and the arithmetic average surface roughness Ra' of each are obtained. The average value of the obtained five numerical values was calculated as the value of the mean interval Sm' of the unevenness on the surface of the sample and the value of the arithmetic mean surface roughness Ra'.

Next, 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above, diluted, and stirred with a mixer for 15 minutes to obtain a coating liquid. The coating liquid was coated on the surface of the support film with the intermediate layer, and dried at a temperature of 80° C. for 15 minutes to form a photosensitive film with a thickness of 20 μm. Next, the 18-micrometer-thick polypropylene film (OPP-FOA by Futamura Chemical Co., Ltd.) was bonded on the photosensitive film, and the photosensitive film laminated body which consisted of three layers was produced.

<Preparation of test board> The surface of the substrate (500mm×600mm×0.8mmt) on which the circuit was formed was chemically polished with CZ8101 manufactured by MEC Co., Ltd., and the chemically polished surface of the substrate was pasted with the photosensitive film laminate obtained as described above. The exposed surface of the photosensitive film exposed by the peeling of the film was then subjected to a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 Mpa, 70° C., 1 minute, and a vacuum degree of 133.3 Pa. Under the conditions of heating and lamination, the substrate and the photosensitive film are brought into close contact.

Next, using a parallel light exposure device equipped with a short-arc high-pressure mercury lamp, the polyethylene terephthalate film adjacent to the photosensitive film was uniformly exposed through an exposure mask, and the polyethylene terephthalate film was peeled off. The ester film exposes the photosensitive film. In addition, the exposure amount is the exposure amount of 7 steps when exposing using Stouffer 41 steps on the polyethylene terephthalate film adjacent to the photosensitive film. After that, the exposed surface of the exposed photosensitive film was developed using a 1 wt % Na ₂ CO ₃ aqueous solution under the conditions of 30° C. and a spray pressure of 2 kg/cm ² for 60 seconds to perform patterning. Next, in a UV conveyor belt furnace equipped with a high-pressure mercury lamp, the patterned photosensitive film was irradiated with an exposure amount of 1 J/cm ² , and then heated at 160° C. for 60 minutes to additionally harden to form a hardened film, which was fabricated on the substrate. The test substrate 1 on which the cured film was formed.

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

Example 3 In Example 1, a support film with a thickness of 125 μm (G-50, manufactured by Kimoto Co., Ltd.), which was coated on one side of a polyethylene terephthalate film, was used instead of polyethylene terephthalate. A support film with a thickness of 25 μm that has been coated on one side of the ethylene glycol film and an integrated support film with an intermediate layer, and the coating solution is applied to the surface of the support film with the intermediate layer, the same as in Example 1. The test substrate 3 was produced in the same manner. After measuring the unevenness average interval Sm' and arithmetic mean surface roughness Ra' of the intermediate layer in the same manner as above, the unevenness average interval Sm' was 17.8 μm, and the arithmetic mean surface roughness Ra' was 0.19 μm. In addition, the thickness of the intermediate layer was 3 μm.

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

Example 5 In Example 1, in addition to using the support film 1 with the intermediate layer 1 to replace the support film with a thickness of 25 μm and the support film integrated with the intermediate layer, the single side of the polyethylene terephthalate film has been coated. , and the test substrate 5 was produced in the same manner as in Example 1, except that the coating liquid was applied to the surface of the support film having the intermediate layer. When the unevenness average interval Sm' and arithmetic mean surface roughness Ra' of the intermediate layer were measured in the same manner as above, the unevenness average interval Sm' was 23.1 μm, and the arithmetic mean surface roughness Ra' was 0.26 μm.

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

Example 7 In Example 1, except using the support film 2 with the intermediate layer 2 to replace the support film with a thickness of 25 μm that has been coated on one side of the polyethylene terephthalate film and the support film integrated with the intermediate layer , and the test substrate 7 was produced in the same manner as in Example 1, except that the coating liquid was applied to the surface of the support film having the intermediate layer. After measuring the unevenness average interval Sm' and arithmetic mean surface roughness Ra' of the intermediate layer in the same manner as above, the unevenness average interval Sm' was 66.8 μm, and the arithmetic mean surface roughness Ra' was 0.42 μm.

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

Comparative Example 1 In Example 1, a polyethylene terephthalate film (E5041, manufactured by Toyobo Co., Ltd.) with a thickness of 25 μm was used as the support film to replace the single side of the polyethylene terephthalate film for overcoating. The processed support film with a thickness of 25 μm and the support film integrated with the intermediate layer, and except for the surface coating liquid with the uneven average interval Sm' and the arithmetic average roughness Ra' described below, is the same as Example 1. The test substrate 9 was produced in the same manner. When the unevenness average interval Sm' and the arithmetic mean surface roughness Ra' of the surface of the support film were measured in the same manner as above, the unevenness mean interval Sm' was 3.7 μm, and the arithmetic mean surface roughness Ra' was 0.02 μm.

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

Comparative Example 3 In Example 1, except for the use of a polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.), a support film with a thickness of 25 μm that had been sandblasted on one side was used instead of polyethylene terephthalate. One side of the film has been coated with a support film with a thickness of 25 μm and an integrated support film with an intermediate layer, and is coated on the surface with the average unevenness interval Sm' and arithmetic average surface roughness Ra' described below. A test substrate 11 was produced in the same manner as in Example 1 except for the liquid coating. After measuring the unevenness average interval Sm' and arithmetic mean surface roughness Ra' of the surface of the support film in the same manner as above, the unevenness average interval Sm' was 140.0 μm, and the arithmetic mean surface roughness Ra' was 4.30 μm.

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

<The edge of the pattern collapses> Using each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above, the edges of 10 openings were observed with a scanning electron microscope (SEM) at a magnification of 1000 times. The evaluation criteria are as follows. ○: The formation of the edges of the 10 openings was all good ×: The resin component contained in the photosensitive film was observed to protrude from the upper part of the edge at one or more openings The evaluation results are shown in Table 2 below.

＜Hammer drop resistance＞ Each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4 prepared as described above was placed on the concrete, and a brass ball with a diameter of 30 mm and a weight of 120 g used as a measuring weight was placed perpendicular to the polyethylene terephthalate. The direction of the surface of the ethylene formate film fell from a height of 30 cm to the surface of the polyethylene terephthalate film of each of the aforementioned test substrates. Next, using a parallel light exposure device equipped with a short arc type high-pressure mercury lamp, the polyethylene terephthalate film and the intermediate layer are peeled off after uniform exposure from the polyethylene terephthalate film through an exposure mask. to expose the photosensitive film. In addition, the exposure amount is the exposure amount of 7 steps when exposing using Stouffer 41 steps on the polyethylene terephthalate film adjacent to the photosensitive film. The cavity formed by dropping the hammer on the surface of the exposed photosensitive film was visually evaluated. The drop of the measuring weight was performed for each of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4, respectively, 10 pieces each. The evaluation criteria are as follows. In addition, this test and evaluation were performed 5 minutes after each test board|substrate was heated and laminated in the said <Preparation of a test board|substrate>. In addition, this test and evaluation were carried out in a test environment of 23°C and 50% relative humidity. ○: No cavities were found on the surface of the exposed photosensitive films of 10 sheets ×: Out of 10 exposed photosensitive film surfaces, more than one cavity was confirmed The evaluation results are shown in Table 2 below.

＜Evaluation of Visual Recognition of Injury＞ On the surface of the hardened film on the exposed area of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4 prepared as described above, a pencil lead with a hardness of 2H was pressed against a state of an angle of 45° and a load of 4.9N. , move 1cm at a speed of 1mm in 1 second, and change the position 3 times in total. The visual recognizability of the damage on the surface of the hardened film was evaluated visually. The evaluation criteria are as follows. In addition, the test and evaluation were performed based on the above-mentioned content within 5 minutes after each test board|substrate was produced. ⊚: No damage was observed on the surface of the cured film in the exposure area in all three times ○: Damage is confirmed on the surface of the cured film in the exposure area 1 to 2 times ×: Damage was observed on the surface of the cured film in the exposure area in all three times The evaluation results are shown in Table 2 below.

<Measurement of the unevenness average interval Sm and the arithmetic mean surface roughness Ra of the surface of the photosensitive film> The surface of the substrate (500mm×600mm×0.8mmt) on which the circuit is formed is chemically polished with CZ8101 manufactured by MEC Co., Ltd., and the chemically polished surface of the substrate is pasted with the chemically polished surfaces of Examples 1-8 and Comparative Examples 1-4. The exposed surface of the photosensitive film exposed by peeling off the polypropylene film from each photosensitive film laminate was then subjected to a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 Mpa, 70 The conditions of ℃, 1 minute, vacuum degree: 133.3Pa were heated and laminated, and the board|substrate and the photosensitive film were made to adhere to each other. After that, the polyethylene terephthalate film was peeled at 90° with respect to the substrate to expose the photosensitive film. After the exposure, within 5 minutes, the unevenness average interval Sm and the arithmetic mean surface roughness Ra of the photosensitive film surface were measured as follows.

The "average interval Sm" of the concavities and convexities on the surface of the photosensitive film is measured using the same device as the average interval Sm' of the concavities and convexities on the surface of the support film. The upper part) was a sample, and the measurement was carried out in the same manner as above except that the support film was replaced. In addition, the "arithmetic mean surface roughness Ra" of the surface of the photosensitive film is also measured using the same device as the arithmetic mean surface roughness Ra' of the surface of the support film. The exposed photosensitive film surface (the upper part) was used as a sample, and the measurement was carried out in the same manner as above, except that the support film was replaced. Table 2 shows the measured "average interval Sm of unevenness" and "arithmetic average surface roughness Ra" on the surface of each photosensitive film.

As a method of simply confirming the yield improvement in the visual inspection of the cured film, a damage visibility test is performed and evaluated. It is apparent from the examples that by using the photosensitive film laminate of the present invention, the edge of the pattern is not easily collapsed, and even if the laminated substrates are overlapped with a strong impact, the photosensitive film will not be damaged. A photosensitive film laminate whose surface affects. Further, it was found that the yield can also be improved in the visual inspection of the cured film. On the other hand, it is clear from the comparative example that the above-mentioned effects cannot be achieved at all even using a photosensitive film laminate that does not satisfy the requirements of the present invention.

1: Photosensitive film laminate 10: Support film 20: middle layer 30: Photosensitive film 40: Protective film

1 is a schematic cross-sectional view showing one embodiment of the photosensitive film laminate of the present invention. 2 is a schematic cross-sectional view showing another embodiment of the photosensitive film laminate of the present invention. FIG. 3 is a conceptual diagram for explaining the roughness curve of the unevenness average interval Sm.

1: Photosensitive film laminate

10: Support film

20: middle layer

30: Photosensitive film

Claims (5)

A photosensitive film laminate comprising a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition in this order, characterized by: The photosensitive film has a surface having a concavo-convex surface, and the concavo-convex average interval Sm of the concavo-convex surface is 5 μm or more and less than 90 μm, The above-mentioned intermediate layer is laminated on the above-mentioned surface side having the concave-convex surface, The said photosensitive resin composition contains a filler at least. The photosensitive film laminate according to claim 1, wherein the photosensitive film has a surface having an uneven surface, and the arithmetic mean surface roughness Ra of the uneven surface is 0.05 μm or more. The photosensitive film laminate according to claim 1 or 2, wherein the photosensitive resin composition contains a crosslinking component. The photosensitive film laminate according to claim 1 or 2, wherein the thickness of the intermediate layer is 0.1 μm or more and 10 μm or less. A cured product characterized by being formed using the photosensitive film laminate according to any one of claims 1 to 4.

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