JP2018116255A - Photosensitive film laminate and cured product formed therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive film laminate that prevents the collapse of edges of a pattern; even when substrates and the like with the photosensitive film laminated thereon are stacked up, prevents the strong shock or pressing force involved in the stacking from affecting the photosensitive film surfaces; and can improve yield in the appearance test of a cured coating.SOLUTION: A photosensitive film laminate has a support film, an intermediate layer, and a photosensitive film formed from a photosensitive resin composition, in this order. The photosensitive film has a face having an uneven surface, and the surface has an average interval of unevenness, Sm, of 5 μm or more and less than 90 μm.SELECTED DRAWING: Figure 1

Description

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

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

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

  In addition, it has also been proposed to form a solder resist layer using a so-called photosensitive film laminate including a photosensitive film without using the liquid photosensitive resin composition as described above. Such a photosensitive film laminate is generally obtained by laminating a photosensitive film formed of a photosensitive resin composition on a support film, and protecting the surface of the photosensitive film as necessary. A film may be attached. In such a photosensitive film laminate, the protective film is peeled off at the time of use and laminated to the wiring board by thermocompression bonding, and the exposure is performed before or after exposure from the support film side, and the support film is peeled off for development. Thus, a patterned solder resist layer can be formed. By using the photosensitive film laminate, a high-definition pattern can be formed. Moreover, the drying process after application | coating can be made unnecessary compared with the case of wet coating. As the surface state of the coating film, there are many smooth surfaces, but in recent years, those having a non-smooth surface have been introduced. For example, Patent Document 1 proposes that a coating film is formed by transferring the surface form of a roughened support film.

  However, when forming a pattern using a photosensitive film, in particular, forming an SRO (solder resist opening), the resin content in the photosensitive film on the top of the opening collapses after exposure and development, and the inside of the opening There is a possibility that the phenomenon of protrusion, that is, the collapse of the pattern may occur, and there is room for improvement.

  Further, in the process of forming the solder resist layer on the wiring board as described above, the laminated wiring boards are sequentially stacked after the photosensitive film laminate is laminated on the wiring board and before proceeding to the next process. May be temporarily stored. In that case, the surface of the photosensitive film laminated body provided on the wiring board may be damaged by the impact at the time of superimposing the wiring board which bonded the photosensitive film laminated body, or the dead weight at the time of superimposing. In particular, due to the impact of the recent thinning of the photosensitive film laminate, not only the support film but also the surface of the photosensitive film laminated on the support film may be damaged due to the impact caused by the overlapping or the pressing due to its own weight. There was a need for improvement.

  On the other hand, the solder resist layer using the above-described photosensitive film laminate is formed as the outermost layer of the substrate and is formed at the final stage of the substrate manufacturing process. In addition, the cured film of the photosensitive film may be damaged when the apparatus is used or by a conveyance tool (for example, Patent Document 2). This scratch may be judged as NG in the appearance inspection before the semiconductor mounting process, and the production yield may deteriorate. In particular, in recent years, even a minute scratch having no problem in quality is one of the important requirements because it causes a decrease in productivity, and a new improvement method is required.

International Patent Publication No. 2015/163455 JP2015-206992A

  Therefore, the object of the present invention is to prevent the pattern from collapsing, and to suppress the influence on the surface of the photosensitive film even by a strong impact or pressing when the substrates laminated with the photosensitive film laminate are laminated. It is also possible to provide a photosensitive film laminate that can improve the yield even in the appearance inspection of a cured film. Another object of the present invention is to provide a cured product formed using the photosensitive film laminate.

  The present inventors are now a layer formed by using a photosensitive film laminate, particularly a solder resist layer, and the ease of visual recognition when the surface is scratched is difficult to see. It has been found that there is a relationship with the uneven average interval. The inventors of the present invention, in a photosensitive film having a surface with irregularities on the surface, use a photosensitive film having a specific irregularity average interval on the surface, thereby providing moderate irregularities on the surface of the solder resist layer. As a result, it is difficult to cause pattern collapse, and even when the surface is scratched, it is difficult to visually recognize the scratch, so that the yield can be improved in appearance inspection. It was. In addition, the damage of the surface of the photosensitive film due to impact or pressing when the substrates laminated with the photosensitive film laminate are overlaid is not only due to the impact resistance of the photosensitive film itself, but the photosensitive film. It has been found that it is largely related to the layer structure of the entire laminate. And when the present inventors made the laminated body which provided the intermediate | middle layer between the support film and the photosensitive film which has an uneven | corrugated surface, when the board | substrate etc. with which the photosensitive film laminated body was laminated | stacked were overlapped It was found that the impact on the surface of the photosensitive film can be suppressed even by a strong impact or pressure. The present invention is based on this finding.

That is, the photosensitive film laminate according to the present invention is a photosensitive film laminate sequentially including a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition,
The photosensitive film has a surface having an uneven surface, and the average unevenness interval Sm of the surface is 5 μm or more and less than 90 μm.

  In the aspect of the present invention, in a photosensitive film that has a surface having an uneven surface and is formed of a photosensitive resin composition, the arithmetic average surface roughness Ra of the surface is preferably 0.05 μm or more.

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

  In the aspect of this invention, it is preferable that the intermediate | middle layer is laminated | stacked on the surface side which has the surface which has an uneven | corrugated surface, and is formed with the photosensitive resin composition on the surface side which has the said uneven surface.

  In the aspect of the present invention, the thickness of the intermediate layer is preferably 0.1 μm or more and 10 μm or less.

  Furthermore, the hardened | cured material by another aspect of this invention is formed using the said photosensitive film laminated body.

  According to the present invention, the photosensitive film is provided with a surface having a specific uneven average interval, so that the pattern is not easily collapsed, and the yield is improved even in the appearance inspection of the cured film. By forming a photosensitive film laminate laminated with an intermediate layer between the photosensitive film having an uneven surface, even when a substrate or the like on which the photosensitive film laminate has been laminated is overlapped with a strong impact or pressure The photosensitive film laminated body which suppresses the influence on the photosensitive film surface is realizable. This is particularly effective when the photosensitive film according to the present invention is used for forming a solder resist layer. Moreover, according to this invention, even if a support film is a thin film, it is effective at the point which has the said effect. Furthermore, according to another aspect of this invention, the hardened | cured material formed using the said photosensitive film laminated body is realizable.

It is the schematic sectional drawing which showed one Embodiment of the photosensitive film laminated body by this invention. It is the schematic sectional drawing which showed other embodiment of the photosensitive film laminated body by this invention. It is a conceptual diagram of the roughness curve for demonstrating uneven | corrugated average space | interval Sm.

The photosensitive film laminated body by this invention is demonstrated referring drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive film laminate according to the present invention. The photosensitive film laminated body 1 by this invention is equipped with the structure which laminated | stacked the support film 10, the intermediate | middle layer 20, and the photosensitive film 30 formed with the photosensitive resin composition in this order. Here, the photosensitive film in the present invention refers to a film obtained by forming a photosensitive resin composition into a film shape, and other layers such as a support film and a protective film are not laminated.
Further, in the present invention, other films or the like may be provided in addition to the above configuration. 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, the photosensitive film laminate 1 has a photosensitive property as shown in FIG. A protective film 40 may be further provided on the surface of the film 30 opposite to the intermediate layer 20. Hereinafter, each component which comprises the film laminated body by this invention is demonstrated.

[Photosensitive film laminate]
The photosensitive film laminate of the present invention refers to a laminate in which an intermediate layer and a support film are laminated on a photosensitive film. Moreover, it is preferable that the photosensitive film laminated body of this invention is further laminated | stacked with a protective film. Details will be described below.

[Support film]
The support film in the photosensitive film laminate of the present invention supports the above-described photosensitive film and imparts a predetermined surface form to the surface of the photosensitive film that is in contact with the support film during exposure and development of the photosensitive film. It has a role to mold.

  As a support film in the photosensitive film laminate of the present invention, any known film can be used without particular limitation. For example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene A film made of a thermoplastic resin such as a film or a polystyrene film can be suitably used. When the thermoplastic resin film is used, a filler is added (kneading treatment) to the resin when the film is formed, mat coating (coating treatment), or the film surface is subjected to sandblast treatment. It may be subjected to a blast treatment, or a treatment such as hairline processing or chemical etching. Among these, a polyester film can be preferably used from the viewpoints of heat resistance, mechanical strength, handleability, and the like. The support film may be a single layer, or two or more layers may be laminated.

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

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

  Moreover, you may use the support film by which the intermediate layer mentioned later by coating was provided in the support film, ie, the support film and the intermediate layer integrated. Examples include CM-25 manufactured by Unitika, G50 manufactured by Kimoto Co., Ltd., and the like.

[Middle layer]
The photosensitive film laminated body of this invention has an intermediate | middle layer between a support film and the photosensitive film which has an uneven | corrugated surface, It is characterized by the above-mentioned. As a result of intensive studies, the present inventors have found that the surface of the photosensitive film is not affected by a strong impact by providing an intermediate layer between the support film and the photosensitive film having an uneven surface. The reason is not necessarily clear, but it is assumed that the intermediate layer protects the uneven surface of the laminated photosensitive film from a strong impact, and as a result, it does not affect the surface state of the photosensitive film. This range is not necessarily limited to this.

  The thickness of the intermediate layer is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 1 μm to 8 μm. By setting the thickness of the intermediate layer to 0.1 μm or more, it is possible to further suppress damage caused by strong impact or pressing when the substrates are overlapped. Further, when the thickness is 10 μm or less, the light transmittance is good and a finer pattern can be easily formed.

  The intermediate layer preferably contains a resin component. For example, an acrylic resin, an epoxy resin, an alkyd resin, a melamine, a mixture of these resins, and the like can be given. Among these, from the viewpoint of impact resistance, acrylic melamine, which is a mixture of acrylic resin and melamine, and epoxy melamine, which is a mixture of epoxy resin and melamine, are preferable. 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. It is a concept including methylol melamine which is a reactant and alkylated methylol melamine which is an alkylated product thereof. The acrylic melamine here refers to a type in which an acrylic resin is cured with melamine. As these resins, known and commonly used resins can be used without any particular limitation.

  The intermediate layer preferably further includes a silicone resin as a resin component. In the photosensitive film laminate according to the present invention, when the photosensitive film is cured to form a cured film, it is necessary to peel the support film and the intermediate layer from the photosensitive film (cured film). By containing the resin, the support film and the intermediate layer can be easily peeled from the photosensitive film, and the adhesion between the support film and the intermediate layer can be maintained. The silicone resin can be used without any particular limitation.

  Further, the intermediate layer may appropriately contain a filler, a curing accelerator, an additive, an antistatic agent and the like as components other than the resin. As a filler, a well-known thing can be used without a restriction | limiting in particular, For example, a silica, a calcium carbonate, etc. are mentioned. Of these, silica is preferred. The average particle diameter 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 2.0 μm or more and 3.0 μm or less. Further preferred. As the antistatic agent, a conventionally known power failure preventing agent can be used, and among them, a cationic surfactant mainly composed of a quaternary ammonium salt represented by the following general formula (I) is preferable. Can be used for By including a cationic surfactant as represented by the following formula in the intermediate layer, the surface of the photosensitive film can be further prevented from being damaged by impact or pressing.

（式中、Ｒは炭素原子数８以上のアルキル基を表し、Ｒ_１は炭素原子数８以下のアルキル基を表し、Ｒ_２は炭素原子数８以下のアルキレン基を表す。）

(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は炭素原子数８以上のアルキル基を表わす。） Among the cationic surfactants of the above formula (I), those represented by the following general formula (II) can be more preferably used.

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

  In the present invention, it is preferable to use an intermediate layer in which the unevenness average interval 11 ′ on the surface side in contact with the photosensitive film is 5 μm or more and less than 90 μm. Moreover, it is more preferable to use an intermediate layer having an arithmetic average surface roughness Ra ′ of 0.05 μm or more on the surface side in contact with the photosensitive film. By using the intermediate layer having such a surface form, it becomes easy to form a photosensitive film having an uneven average interval Sm of 5 μm or more and less than 90 μm, and further has an arithmetic average surface roughness Ra of 0.05 μm or more. It becomes easy to form a photosensitive film. That is, it is effective in that a predetermined surface form of the intermediate layer is formed on the surface of the photosensitive film, so that it is easy to form a photosensitive film that can improve yield in pattern collapse and appearance inspection. is there. The unevenness average interval Sm ′ of the intermediate layer is preferably 6 μm or more and 85 μm or less, and more preferably 7 μm or more and 80 μm or less. Further, the range of the arithmetic average 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 providing an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometers or less. Here, the meanings of the uneven average interval Sm ′ and the arithmetic average surface roughness Ra ′ and the specific measuring method thereof will be described in [Photosensitive film] described later. In addition, although the uneven | corrugated average space | interval Sm 'of an intermediate | middle layer and the uneven | corrugated average space | interval Sm of a photosensitive film, the arithmetic surface roughness Ra' of an intermediate | middle layer and the arithmetic surface roughness Ra of a photosensitive film do not necessarily correspond, respectively, By adjusting, the uneven | corrugated average space | interval Sm and arithmetic surface roughness Ra of a photosensitive film can be made into the specific range as mentioned above.

  Any method may be used for adjusting the intermediate layer having the unevenness average interval Sm ′ and the arithmetic average surface roughness Ra ′ as described above. For example, when a filler is added to the resin, the particle size and the added amount of the filler are changed. Although adjustment is mentioned, it is not restrict | limited to the content mentioned above.

<Photosensitive film>
The photosensitive film constituting the photosensitive film laminate according to the present invention has a surface having an uneven surface and is formed of a photosensitive resin composition, and the average unevenness interval Sm of the surface is 5 μm or more and less than 90 μm. It is characterized by being. First, the average unevenness Sm on the surface will be described with reference to the following formula. As shown in FIG. 3, the average unevenness Sm on the surface is extracted from the roughness curve by a reference length l (el) in the direction of the average line, and corresponds to one peak and one valley adjacent to it. The sum of the line lengths (Sm ₁ , Sm ₂ ,... Sm _i , Sm _n ) is obtained and the average value is expressed. That is, the average unevenness Sm 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 form such that the unevenness average interval Sm is in the above-described range, the surface of the solder resist layer may be damaged. The yield can be improved in the appearance inspection for inspecting the presence or absence. Furthermore, the unexpected excellent effect that the formation of the photosensitive pattern of the solder resist layer, especially the collapse of the pattern can be suppressed 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.

  Further, from the viewpoint of balance of pattern collapse and yield improvement in appearance inspection, the arithmetic average surface roughness Ra of the surface having the uneven surface of the photosensitive film is preferably 0.05 μm or more, and is 0.06 μm or more. More preferably, it is 0.07 μm or more. Moreover, when providing an upper limit, it is preferable that it is 5.0 micrometers or less, It is more preferable that it is 3.0 micrometers or less, It is further more preferable that it is 1.0 micrometers or less.

  In the present invention, the above-mentioned “concave / convex average distance Sm” and “arithmetic average surface roughness Ra” mean values measured by a measuring device based on JIS B0601-1994. Hereinafter, a specific measurement method will be described. The uneven | corrugated average space | interval Sm and arithmetic mean surface roughness Ra can be measured using a shape measurement laser microscope (for example, Keyence Corporation VK-X100). Sample (photosensitive film) to be measured on xy stage after starting shape measurement laser microscope (VK-X100) main body (control unit) and VK observation application (VK-H1VX manufactured by Keyence Corporation) Is placed. Turn the lens revolver of the microscope section (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (same VK-H1VX). To do. The xy stage is operated so that the part to be measured on the sample surface is adjusted to the center of the screen. The objective lens with a magnification of 10 times is changed to a magnification of 50 times, and the surface of the sample is focused with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). By selecting the simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) and pressing the measurement start button, the surface shape of the sample can be measured to obtain a surface image file. After starting the VK analysis application (VK-H1XA manufactured by Keyence Corporation) and displaying the obtained surface image file, tilt correction is performed. The observation measurement range (horizontal) in measuring the surface shape of the sample is 270 μm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. The numerical values of the uneven average interval Sm and the arithmetic average surface roughness Ra are obtained. Further, horizontal lines are displayed at four different positions in the surface image, and the numerical values of the average unevenness interval Sm and the arithmetic average surface roughness Ra are obtained. The average values of the obtained five numerical values are respectively calculated and set as the average unevenness interval Sm and the arithmetic average surface roughness Ra value of the sample surface. In the measurement of the above-described uneven average interval Sm and arithmetic average surface roughness Ra, a photosensitive film in a state before the curing step by exposure or the like is used as a measurement sample. When the intermediate layer and the support film are laminated on the photosensitive film as a laminate as in the present invention, a measurement sample in a state where the intermediate layer and the support film are peeled off before the curing step by exposure or the like is used. . In such a case, after removing the intermediate layer and the support film to expose the photosensitive film, the measurement of the “unevenness average interval Sm” and the “arithmetic average surface roughness Ra” on the sample surface is performed within 5 minutes. .

  In order to make the surface form of the photosensitive film within the range of the above-mentioned specific unevenness average interval Sm and arithmetic mean surface roughness Ra, publicly known and commonly used techniques can be applied. From the viewpoint of ease of formation, it is preferable to form the photosensitive film using the intermediate layer as described above. That is, it is preferable that the surface having the concavo-convex surface in the range of the specific concavo-convex average interval Sm or the arithmetic average surface roughness Ra is a surface in contact with the intermediate layer.

  The photosensitive film provided with the concavo-convex surface having the above-described predetermined concavo-convex average interval Sm and arithmetic average surface roughness Ra is patterned by exposure and development to become a cured coating provided on the circuit board. The cured film is preferably a solder resist layer. Such a photosensitive film can be formed using a photosensitive resin composition, and the photosensitive resin composition can use a conventionally known solder resist ink or the like without limitation. An example of a photosensitive resin composition that can be preferably used will be described.

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

[Crosslinking component]
The cross-linking component is not particularly limited as long as it is a cross-linking component, and known and conventional ones can be used. In particular, a carboxyl group-containing photosensitive resin and a photosensitive monomer are preferable, and when further heated, it is preferable to include a component that is crosslinked by heat (hereinafter referred to as a thermal crosslinking component) by improving characteristics such as heat resistance and insulation reliability. .

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

  Further, as the carboxyl group-containing photosensitive resin, it is preferable to use a carboxyl group-containing resin obtained by synthesizing a carboxyl group-containing photosensitive resin that does not use an epoxy resin as a starting material or a resin other than an epoxy resin. Carboxyl group-containing resins obtained by synthesizing resins other than epoxy resin and carboxyl group-containing photosensitive resins that do not use epoxy resin as a starting material have very low halide ion content and deteriorate insulation reliability. As a result, the electrical characteristics are more excellent. Specific examples of the carboxyl group-containing photosensitive resin include the compounds listed below (which may be either oligomers or polymers).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

（式中、Ｘ_１は、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ_１、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０または１の整数である） In addition, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (III). .

(Wherein, _{X 1} is a hydrogen atom, an alkyl group of 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group of 1 to 17 carbon atoms, 1 to 8 carbon atoms An alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Y ₁ and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, carbon, and an amino group, substituted with an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group) An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms); An alkylamino group having a alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, or an alkyl group having 1 to 8 carbon atoms. Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene , Thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

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

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

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

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

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

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

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

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. As a commercial item, Omnirad (Omnirad) TPO, Omnirad (Omnirad) 819 by IGM Resins, etc. are mentioned.

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

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

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

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

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

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

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

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

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

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

  A block copolymer can be suitably mix | blended with the above-mentioned photosensitive resin composition. The block copolymer is a copolymer having a molecular structure in which two or more kinds of polymers having different properties are connected by a covalent bond to form a long chain. What is solid in the range of 20 degreeC-30 degreeC is preferable. Any solid may be used within this range, and it may be solid even at a temperature outside this range. Since it is solid in the above temperature range, it is excellent in tackiness when it is used as a photosensitive film or when it is applied to a support film and temporarily dried.

  The block copolymer is preferably an XYX or XYX ′ type block copolymer. Of the XYX or XYX ′ type block copolymers, the center Y is a soft block and has a low glass transition point Tg, preferably less than 0 ° C., and both outer sides X to X ′ are hard blocks and have a high Tg. Preferably, those composed of polymer units at 0 ° C. or higher are preferred. The glass transition point Tg is measured by differential scanning calorimetry (DSC).

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

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

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

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

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

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

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

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

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

  Examples of the monoazo red colorant include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like. Examples of the disazo red colorant include Pigment Red 37, 38, and 41. Examples of the monoazo lake red colorant include Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68 and the like. Examples of the benzimidazolone red colorant include Pigment Red 171, 175, 176, 185, 208 and the like. Examples of the perylene red colorant include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, and the like. Examples of the diketopyrrolopyrrole red colorant include Pigment Red 254, 255, 264, 270, and 272. Examples of the condensed azo red colorant include Pigment Red 220, 144, 166, 214, 220, 221, 242 and the like. Examples of the anthraquinone red colorant include Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207, and the like. Examples of the quinacridone red colorant include Pigment Red 122, 202, 206, 207, and 209.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Method for producing cured product and printed wiring board>
A cured product is formed using the photosensitive film or the photosensitive film laminate of the present invention. A method for producing such a cured product and a method for producing a printed wiring board provided with the cured product (cured film) on a substrate on which a circuit pattern is formed will be described. As an example, a method for producing a printed wiring board using a photosensitive film laminate provided with a protective film will be described. First, i) the protective film is peeled off from the above-described photosensitive film laminate to expose the photosensitive film, and ii) the photosensitive film of the photosensitive film laminate is formed on the substrate on which the circuit pattern is formed. Pasted together, iii) exposed from above the support film of the photosensitive film laminate, and iv) peeled off the support film from the photosensitive film laminate and developed, thereby being patterned on the substrate. A printed wiring board is formed by forming a conductive film and v) curing the patterned photosensitive film by light irradiation or heat to form a cured film. In addition, when using the photosensitive film laminated body in which the protective film as shown in FIG. 1 is not provided, it cannot be overemphasized that the peeling process (i process) of a protective film is unnecessary. Hereinafter, each step will be described.

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

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

  Next, exposure (irradiation of active energy rays) is performed on the support film of the photosensitive film laminate. By this step, the exposed photosensitive film is cured. The exposure process is not particularly limited. For example, the exposure process may be selectively performed with active energy rays through a photomask 4 on which a desired pattern is formed by a contact method (or non-contact method). Thus, the desired pattern may be exposed with an active energy ray.

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

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

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

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

  As described above, an appropriate uneven state can be imparted to the surface of the cured product. As a result, the collapse of the pattern is improved and the yield in the appearance inspection is also improved. Therefore, the photosensitive film laminated body by this invention can be used conveniently for printed wiring boards, can be used more suitably by formation of a soldering resist layer, and can be used suitably especially for formation of the soldering resist layer for IC packages.

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

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

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

<Preparation of photosensitive resin composition>
The carboxyl group-containing photosensitive resin varnish 1 obtained as described above, dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), which is a photosensitive monomer, as an acrylate compound, and an epoxy, which is a thermosetting component Bisphenol A type epoxy resin (EPICLON 840-S manufactured by DIC Corporation) and biphenol novolac type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd.) as the resin, and Omnirad (Omnirad) TPO manufactured by IGM Resins as the photopolymerization initiator 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 Admatex Co., Ltd.), and thermosetting Melamine as a catalyst and carbon black M-50, C.I. I. Pigment Violet 23, C.I. I. Pigment Yellow 147, C.I. I. Pigment Blue 15: 3, and C.I. I. Each component selected from Pigment Red 177 and diethylene glycol monoethyl ether acetate as an organic solvent are blended in the proportions (parts by mass) shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. Photosensitive resin compositions 1 and 2 were prepared.

<Preparation of acrylic melamine resin 1>
DIC Corporation Amidia G-821-60 (iso-butylated melamine resin, solid content 60%) and DIC Corporation Acridic A-405 (melamine baking acrylic resin, solid content 50%) in solid mass The mixture was blended so as to be 25:75 in terms of minutes, pre-stirred with a stirrer, and then kneaded with a three-roll mill to prepare acrylic melamine resin 1.

<Preparation of Support Film 1 Having 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. After adding methyl ethyl ketone so that it may become a suitable solid content density | concentration according to the thickness of a coating film further to this resin liquid, a silicone type resin (Symak US-270 by Toa Gosei Co., Ltd.) and a silica, and acrylic melamine resin No. 1 and a silicone resin and silica were added so that each mass ratio was 59.7: 0.3: 40, and the mixture was sufficiently stirred at room temperature to obtain a uniform coating solution. This coating solution was applied so as to satisfy the following conditions by a gravure roll method using a finely uneven surface on one surface of a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) as a support film, and at 130 ° C. The substrate was dried for 20 seconds to produce a support film 1 having an intermediate layer 1 (intermediate layer thickness 8 μm, support film thickness 25 μm, total thickness 33 μm).

<Preparation of Support Film 2 Having Intermediate Layer 2>
In the production of the support film 1 having the intermediate layer 1, the support film 2 having the intermediate layer 2 (thickness of the intermediate layer 3 μm, support is the same as described above, except that the intermediate layer is applied so that the thickness of the intermediate layer is 3 μm. A film thickness of 25 μm and a total thickness of 28 μm) was produced.

<Preparation of photosensitive film laminate>
Example 1
A support film (CM-25 manufactured by Unitika Co., Ltd.) having a thickness of 25 μm and a support film integrated with an intermediate layer was prepared by coating one surface of a polyethylene terephthalate film. When the measurement of the uneven | corrugated average space | interval Sm 'and arithmetic average surface roughness Ra' of an intermediate | middle layer was measured as follows, uneven | corrugated average space | interval Sm 'is 12.9 micrometers, and arithmetic average surface roughness Ra' is 0.00. It was 48 μm. The intermediate layer had a thickness of 3 μm.

  A shape measurement laser microscope (VK-X100 manufactured by Keyence Corporation) was used for measurement of the uneven average interval Sm ′ and the arithmetic average surface roughness Ra ′. Support film having an intermediate layer to be measured on an xy stage after starting a main body (control unit) of a shape measurement laser microscope (VK-X100) and a VK observation application (VK-H1VX manufactured by Keyence Corporation) (The surface having the intermediate layer is the upper part). Turn the lens revolver of the microscope section (VK-X110 manufactured by Keyence Corporation) to select an objective lens with a magnification of 10x, and adjust the focus and brightness roughly in the image observation mode of the VK observation application (same VK-H1VX). did. The xy stage was operated so that the part of the sample surface to be measured was adjusted to the center of the screen. The objective lens with a magnification of 10 times was changed to a magnification of 50 times, and the surface of the sample was focused with the autofocus function in the image observation mode of the VK observation application (VK-H1VX). The simple mode of the shape measurement tab of the VK observation application (same VK-H1VX) was selected, the measurement start button was pressed, the surface shape of the sample was measured, and a surface image file was obtained. The VK analysis application (Keyence Co., Ltd. VK-H1XA) was started and the obtained surface image file was displayed, and then the tilt correction was performed.

  The observation measurement range (horizontal) in measuring the surface shape of the sample was 270 μm. Display the line roughness window, select JIS B0601-1994 in the parameter setting area, select the horizontal line from the measurement line button, display the horizontal line at an arbitrary location in the surface image, and press the OK button. The numerical values of the uneven average interval Sm and the arithmetic average surface roughness Ra ′ of the uneven surface were obtained. Further, horizontal lines were displayed at four different positions in the surface image, and numerical values of the average unevenness interval Sm ′ and arithmetic average surface roughness Ra ′ were obtained. The average value of the obtained five numerical values was calculated and used as the average irregularity spacing Sm ′ value and arithmetic average surface roughness Ra ′ value on the sample surface.

  Subsequently, 300 g of methyl ethyl ketone was added to the photosensitive resin composition 1 obtained as described above for dilution, and the mixture was stirred for 15 minutes with a stirrer to obtain a coating solution. The coating liquid was applied on the surface of the support film having the intermediate layer and dried at a temperature of 80 ° C. for 15 minutes to form a photosensitive film having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (OPP-FOA manufactured by Futamura Chemical Co., Ltd.) was bonded onto the photosensitive film to prepare a photosensitive film laminate composed of three layers.

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

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

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

Example 3
In Example 1, instead of a support film in which a support film and an intermediate layer are integrated with a thickness of 25 μm obtained by coating a single side of a polyethylene terephthalate film, a thickness obtained by performing a coating process on one side of a polyethylene terephthalate film A test substrate 3 was prepared in the same manner as in Example 1 except that a 125 μm support film (K-50 manufactured by Kimoto Co., Ltd.) was used and the coating liquid was applied to the surface of the support film having the intermediate layer. When the measurement of the uneven | corrugated average space | interval Sm 'and arithmetic average surface roughness Ra' of an intermediate | middle layer was measured like the above, uneven | corrugated average space | interval Sm 'is 17.8 micrometers, and arithmetic average surface roughness Ra' is 0.00. It was 19 μm. The intermediate layer had a thickness of 3 μm.

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

Example 5
In Example 1, the support film 1 having the intermediate layer 1 was used instead of the support film in which the support film and the intermediate layer were integrated with a thickness of 25 μm, which was coated on one side of the polyethylene terephthalate film. A test substrate 5 was prepared in the same manner as in Example 1 except that the coating liquid was applied to the surface having the intermediate layer of the film. When the measurement of the uneven | corrugated average space | interval Sm 'of the intermediate | middle layer and arithmetic mean surface roughness Ra' was measured like the above, uneven | corrugated average space | interval Sm 'is 23.1 micrometers, and arithmetic mean surface roughness Ra' is 0.00. It was 26 μm.

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

Example 7
In Example 1, the support film 2 having the intermediate layer 2 was used instead of the support film in which the support film and the intermediate layer were integrated, each having a thickness of 25 μm, which was coated on one surface of the polyethylene terephthalate film. A test substrate 7 was produced in the same manner as in Example 1 except that the coating liquid was applied to the surface having the intermediate layer of the film. The measurement of the average unevenness interval Sm ′ and arithmetic average surface roughness Ra ′ of the intermediate layer was measured in the same manner as described above. The average unevenness interval Sm ′ was 66.8 μm, and the arithmetic average surface roughness Ra ′ was 0.00. It was 42 μm.

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

Comparative Example 1
In Example 1, a polyethylene terephthalate film having a thickness of 25 μm (E5041 manufactured by Toyobo Co., Ltd.) was used instead of the support film having a thickness of 25 μm that was coated on one side of the polyethylene terephthalate film and the support film integrated with the intermediate layer. ) Was used as a support film, and a test substrate 9 was prepared in the same manner as in Example 1 except that the coating liquid was applied to the surface having the uneven average interval Sm ′ and arithmetic average roughness Ra ′ described below. When the measurement of the uneven | corrugated average space | interval Sm 'and arithmetic average surface roughness Ra' of the surface of a support film was measured like the above, uneven | corrugated average space | interval Sm 'was 3.7 micrometers, and arithmetic average surface roughness Ra' was set. It was 0.02 μm.

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

Comparative Example 3
In Example 1, instead of the support film in which the support film and the intermediate layer are integrated with a thickness of 25 μm obtained by coating one side of the polyethylene terephthalate film, on one side of the polyethylene terephthalate film (E5041 manufactured by Toyobo Co., Ltd.) The same procedure as in Example 1 was performed, except that a support film having a thickness of 25 μm that had been sandblasted was used and the coating solution was applied to the surface having the unevenness average interval Sm ′ and arithmetic average surface roughness Ra ′ described below. Thus, a test substrate 11 was produced. When the measurement of the uneven average interval Sm ′ and the arithmetic average surface roughness Ra ′ on the surface of the support film was measured in the same manner as described above, the uneven average interval Sm ′ was 140.0 μm, and the arithmetic average surface roughness Ra ′ was It was 4.30 μm.

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

<Pattern collapse>
Using the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above, the wrinkles of 10 openings were observed with a 1000 × scanning electron microscope (SEM). The evaluation criteria were as follows.
○: The formation of wrinkles is good in all of the 10 openings. ×: The protrusion of the resin contained in the photosensitive film on the upper portion of the wrinkles is observed in one or more openings. As shown in Table 2 below.

<Weight drop resistance>
Each test board of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above was placed on concrete, and the surface of the polyethylene terephthalate film of each test board was 30 mm in diameter and 120 g in weight. A brass sphere was dropped from a height of 30 cm in a direction perpendicular to the surface of the polyethylene terephthalate film. Next, using a parallel light exposure device equipped with a short arc type high-pressure mercury lamp, after the solid exposure from the polyethylene terephthalate film through the exposure mask, the polyethylene terephthalate film and the intermediate layer are peeled off to expose the photosensitive film. It was. In addition, the exposure amount was set to the exposure amount which becomes 7 steps when the exposure is performed using the Stuffer 41 step from the polyethylene terephthalate film in contact with the photosensitive film. The depression of the exposed photosensitive film surface due to the dropped weight was visually evaluated. Ten weights were dropped on each of the test substrates of Examples 1 to 4 and Comparative Examples 1 to 4. The evaluation criteria were as follows. Each test substrate was subjected to the main test and evaluation 5 minutes after the heat lamination in <Preparation of test substrate> above. Moreover, this test and evaluation were performed in the test environment of 23 degreeC and 50% of relative humidity.
○: No depression was confirmed on all the exposed surfaces of the photosensitive film. ×: One or more depressions were confirmed on the surface of the 10 exposed photosensitive films. It was as shown in.

<Scratch visibility evaluation>
A pencil core having a hardness of 2H is applied to the surface of the cured coating in the exposed areas of the test substrates of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above at an angle of 45 ° and a load of 4.9 N. In this state, the film was pressed at a speed of 1 mm per second, and the visibility of scratches on the surface of the cured film was visually evaluated. The evaluation criteria were as follows. In addition, after producing each test board | substrate, based on the said content, the test and evaluation were performed within 5 minutes.
◯: No scratch was confirmed on the surface of the cured film in the exposed region. ×: Scratch was confirmed on the surface of the cured film in the exposed region. The evaluation results were as shown in Table 2 below.

<Measurement of unevenness average interval Sm and arithmetic average surface roughness Ra of photosensitive film surface>
The surface of the substrate on which the circuit was formed (500 mm × 600 mm × 0.8 mmt) was chemically polished with CZ8101 manufactured by Mec Co., Ltd., and used for Examples 1-6 and Comparative Examples 1-4 on the chemically polished surface of the substrate. Then, the exposed surface of the photosensitive film exposed by peeling the polypropylene film from each of the photosensitive film laminates was bonded, and then the degree of pressure was 0 using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.). The laminate was heated and laminated under the conditions of 0.8 MPa, 70 ° C., 1 minute, and a degree of vacuum of 133.3 Pa to adhere the substrate and the photosensitive film. Thereafter, the polyethylene terephthalate film was peeled off at 90 ° from the substrate to expose the photosensitive film. Within 5 minutes after the exposure, the average unevenness interval Sm and the arithmetic average surface roughness Ra on the surface of the photosensitive film were measured as follows.

  The “irregularity average spacing Sm” on the surface of the photosensitive film is the same as the measurement of the average irregularity spacing Sm ′ on the surface of the support film, and the substrate is replaced with the exposed photosensitive film instead of the support film (exposed). The measurement was performed in the same manner as described above except that the photosensitive film surface was the upper portion. In addition, the “arithmetic average surface roughness Ra” of the surface of the photosensitive film is also measured by using the same apparatus as the measurement of the arithmetic average surface roughness Ra ′ of the surface of the support film, replacing the sample with the support film, The measurement was performed in the same manner as described above except that the substrate was bonded (the exposed photosensitive film surface is the upper part). Table 2 shows the “concave / convex average spacing Sm” and “arithmetic average surface roughness Ra” of the measured surface of each photosensitive film.

  As a method for simply confirming the yield improvement in the appearance inspection of the cured coating, a scratch visibility test was conducted and evaluated. As is clear from the examples, by using the photosensitive film laminate of the present invention, it is difficult for the pattern to collapse, and the impact on the surface of the photosensitive film is also caused by a strong impact when the laminated substrates are overlapped. It can be seen that a photosensitive film laminate that does not affect the thickness can be realized. Furthermore, it can be seen that the yield can be improved also in the appearance inspection of the cured coating. On the other hand, as is clear from the comparative example, it can be seen that even if a photosensitive film laminate that does not satisfy the requirements of the present invention is used, all of the above effects cannot be realized.

Claims (6)

A photosensitive film laminate comprising sequentially a support film, an intermediate layer, and a photosensitive film formed of a photosensitive resin composition,
The photosensitive film laminate, wherein the photosensitive film has a surface having a concavo-convex surface, and the average concavo-convex spacing Sm of the surface is 5 μm or more and less than 90 μm.   The photosensitive film laminated body of Claim 1 with which the said photosensitive film is provided with the surface which has an uneven surface, and arithmetic mean surface roughness Ra of the said surface is 0.05 micrometer or more.   The photosensitive film laminated body of Claim 1 or 2 in which the said photosensitive resin composition comprises a filler and a crosslinking component.   In the photosensitive film provided with the surface which has an uneven | corrugated surface, and is formed with the photosensitive resin composition, an intermediate | middle layer is laminated | stacked on the surface side which has the said uneven | corrugated surface. The photosensitive film laminated body of description.   The photosensitive film laminated body as described in any one of Claims 1-4 whose thickness of the said intermediate | middle layer is 0.1 micrometer or more and 10 micrometers or less.   Hardened | cured material formed using the photosensitive film laminated body as described in any one of Claims 1-5.

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