TW201938001A - Printed wiring board manufacturing method including a resin sheet preparation step, a lamination step, an exposure step and a patterned photosensitive resin composition layer formation step - Google Patents

Abstract

Provided is a resin sheet or the like which is capable of forming a cured product having excellent adhesion and covering of wiring, and having a good hole shape. A method of manufacturing a printed wiring board comprises the steps of: (1) a step of preparing a resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition disposed on the support, (2) a step of laminating the resin sheet on the substrate, (3) a step of exposing the photosensitive resin composition layer, and (4) a step of forming a patterned photosensitive resin composition layer by development. The haze of the support is 20% or less. After step (4), the absolute value (|Rv|) of the maximum valley depth of the side surface of the support of the patterned photosensitive resin composition layer is 500 nm or more, and the photosensitive resin composition satisfies the specified condition (I) or (II).

Description

Manufacturing method of printed wiring board

The present invention relates to a resin sheet, a method for manufacturing a printed wiring board using the resin sheet, and a cured product.

A solder resist provided on a printed wiring board serves as a permanent protective film for suppressing the adhesion of solder to a portion where soldering is not required and at the same time suppressing corrosion of a circuit board. For a solder resist, adhesion to a sealing material or an underfill is required. For example, Patent Document 1 discloses a photosensitive element including a support film and a photosensitive resin composition provided on the support film. The formed photosensitive layer has a surface roughness Ra of 200 to 4000 nm on a surface where the supporting film is in contact with the photosensitive layer.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2015/163455

[Problems to be Solved by the Invention]

In recent years, due to the increase in the density of printed wiring boards, the solder resist has also been required to be more commercial in nature or one step higher in performance. When the density of printed wiring boards is increased and the semiconductor wafer is sealed with a sealing material after mounting various semiconductor wafers, the contact surface between the sealing material and the solder resist is reduced. In order to improve the sealing performance, a higher solder resist is required. Adhesion. Furthermore, when increasing the density of a printed wiring board by circuit design, it is also important to shield the wiring with a solder resist and prevent the design from being imitated.

In order to improve the adhesion of the solder resist, as in Patent Document 1, it is considered that the surface unevenness is transferred onto the photosensitive resin composition layer by using a support having surface unevenness. However, as will be described later, this method has a disadvantage that a hole shape is distorted due to light scattering during exposure.

An object of the present invention is to provide a resin sheet capable of forming a cured product having excellent adhesion and wiring shielding properties and a good hole shape; a method for manufacturing a printed wiring board using the resin sheet; and a cured product.

[Means for solving problems]

As a result of intensive research in order to solve the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by the following configuration, and the present invention has been completed.

That is, the present invention includes the following.
[1]. A method for manufacturing a printed wiring board, comprising the following steps:
(1) a step of preparing a resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support,
(2) a step of laminating a resin sheet on a substrate,
(3) a step of exposing the photosensitive resin composition layer and
(4) a step of forming a patterned photosensitive resin composition layer by development,
It is characterized by,
The haze of the support is below 20%,
(4) The absolute value of the maximum valley depth (| Rv |) of the surface of the support side of the patterned photosensitive resin composition layer after the step is 500 nm or more,
The photosensitive resin composition satisfies the following conditions (I) or (II),
(I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of (a) component is 60 Above mass%;
(II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent.
[2]. The method for manufacturing a printed wiring board according to [1], further comprising (5) a step of curing the patterned photosensitive resin composition layer.
[3]. The method for manufacturing a printed wiring board according to [2], wherein the cured product of the patterned photosensitive resin composition layer is a solder resist.
[4]. The method for producing a printed wiring board according to any one of [1] to [3], wherein the photosensitive resin composition is a negative photosensitive resin composition.
[5]. The method for manufacturing a printed wiring board according to any one of [1] to [4], wherein if it is on the support side of the photosensitive resin composition layer after (3) step and (4) step The absolute value of the maximum valley depth of the surface (| Rv |) is set to A1 (nm), and the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after the step (4) is set. When the absolute value (| Rv |) of A is set to A2 (nm), the relationship of 3 <A2 / A1 <100 is satisfied.
[6]. The method for manufacturing a printed wiring board according to any one of [1] to [5], further including (6) a step of peeling the support.
[7]. The method for manufacturing a printed wiring board according to [6], wherein step (6) is performed after step (2) and step (3) is performed.
[8]. A resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support,
It is characterized by,
The haze of the support is below 20%,
The absolute value of the maximum valley depth (| Rv |) on the support-side surface of the patterned photosensitive resin composition layer after development is 500 nm or more,
The photosensitive resin composition satisfies the following conditions (I) or (II),
(I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of (a) component is 60 Above mass%;
(II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent.
[9]. The resin sheet according to [8], wherein the component (b) contains a (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower.
[10]. The resin sheet according to [8] or [9], wherein the photosensitive resin composition layer is used for forming a solder resist.
[11]. The resin sheet according to any one of [8] to [10], wherein if the absolute value of the maximum valley depth of the surface on the support side of the photosensitive resin composition layer before development after exposure (| Rv |) is set to A1 (nm), and the absolute value of the maximum valley depth (| Rv |) of the surface of the support side of the patterned photosensitive resin composition layer after development is set to A2 (nm ), The relationship of 3 <A2 / A1 <100 is satisfied.
[12]. A cured product obtained by curing the photosensitive resin composition layer of the resin sheet according to any one of [8] to [11].

[Effect of the invention]

According to the present invention, it is possible to provide a resin sheet capable of forming a cured product having excellent adhesion and wiring shielding properties and a good hole shape; a method for manufacturing a printed wiring board using the resin sheet; and a cured product.

[Best Mode for Implementing Invention]

As shown in FIG. 4, the conventional resin sheet 11 includes a support body 111 and a photosensitive resin composition layer 112 provided on the support body 111. The surface 111a on the photosensitive resin composition layer 112 side of the support 111 has surface irregularities, and the arithmetic average roughness Ra of the surface is generally 200 to 4000 nm, and the haze of the support 111 is generally 60% or more. The surface 112a on the support 111 side of the photosensitive resin composition layer 112 is transferred with the surface unevenness of the above-mentioned surface 111a. The arithmetic average roughness Ra of the surface 112a has the same arithmetic average roughness Ra as the surface 111a. .

When manufacturing a printed wiring board using the conventional resin sheet 11, as shown in FIG. 5, the conventional resin sheet 11 is first laminated on the substrate 113. After lamination, a specified pattern of the photosensitive resin composition layer 112 is irradiated with active light hν through a mask pattern (not shown), so that the irradiated portion of the photosensitive resin composition layer 112 is light-cured, that is, photosensitive. Exposure of the resin composition layer 112. After the photosensitive resin composition layer 112 is exposed, as shown in FIG. 6, the support 111 is peeled off, and then development is performed. Thereafter, the developed photosensitive resin composition layer 112b is cured, and a conductor layer (not shown) is formed thereon. The surface of the substrate 113 of the developed photosensitive resin composition layer 112b is the surface 112c on the opposite side. The surface 112c is caused by the unevenness of the surface of the support 111. Therefore, the adhesion with a conductor layer (not shown) is improved.

The present inventors have found that when the conventional resin sheet 11 is used for exposure as described above, the active light hν is scattered due to the unevenness of the surface 111a and the surface 112a, and as a result, the hole shape is distorted.

In comparison, in the printed wiring board manufactured in the present invention, the resin sheet used has a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support, and the resin sheet satisfies The following conditions (A) and (B).
(A) The haze of the support is 20% or less.
(B) The absolute value (| Rv |) of the maximum valley depth on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more.

The present inventors have made the insulating layer by using a resin sheet that satisfies the above-mentioned specific conditions (A) and (B) when manufacturing a printed wiring board. Therefore, they have achieved excellent adhesion and shielding properties of the wiring, and A through hole with a good hole shape. The "surface on the support body side" of the photosensitive resin composition layer means the surface facing the support body of the photosensitive resin composition layer after the support body is peeled off, and generally refers to the substrate (It is a layer laminated with a resin sheet.) The surface of the photosensitive resin composition layer on the opposite side.

<Condition (A)>
Condition (A) is that the haze of the support is 20% or less. The inventors have found that when the insulating layer is formed by exposure and development, the haze of the support has a great influence on the adhesion, the shielding property of the wiring, and the hole shape.

As an example shown in FIG. 1, the resin sheet 10 of the present invention includes a support 101 and a photosensitive resin composition layer 102 including a photosensitive resin composition provided on the support 101, and the haze of the support 101 It is less than 20%. In general, the haze is related to the arithmetic average roughness Ra of the surface 101a of the photosensitive resin composition layer 102 side of the support, and if the haze value is reduced, the arithmetic average roughness Ra value becomes low. Since the haze of the support 101 is 20% or less, the surface 101a of the photosensitive resin composition layer 102 side of the support is different from the conventional surface 111a in the conventional resin sheet 11 to have a small unevenness and a smooth surface. The surface 102a on the support 101 side of the photosensitive resin composition layer 102 is transferred with the surface irregularities of the surface 101a. Therefore, the surface shape of the surface 102a is the same as that of the surface 101a, and the surface irregularities are small and smooth.

When a printed wiring board is manufactured using the resin sheet 10, as shown in an example shown in FIG. 2, the resin sheet 10 is laminated on the substrate 103. Exposure was performed after lamination. One embodiment of the exposure is to irradiate a specified portion of the photosensitive resin composition layer 102 with active light hν through a mask pattern (not shown) to harden the irradiated portion of the photosensitive resin composition layer 102. The surface irregularities of the surface 101a and the surface 102a are both small and smooth, so when the active light hν is irradiated during exposure, scattering of the active light hν can be suppressed. As a result, distortion of the hole shape can be suppressed, and further, scattering of the active light hν can be suppressed, so that developability can be improved. In addition, even when the exposure is performed after the support 101 is peeled off, the surface 102a has the same surface unevenness as the surface 101a, and the surface is smooth. Therefore, it can be used in the same way as when the exposure is performed without the support 101 being peeled off. For the same effect.

The haze of the support 101 is 20% or less, preferably 15% or less, and more preferably 10% from the viewpoint of improving the hole shape and developability. The lower limit can be set to, for example, 0.1% or more. The haze of the support 101 can be measured using, for example, a haze meter (HZ-V3) manufactured by Suga Tester.

The absolute value of the maximum valley depth (| Rv |) of the surface 101a of the support body 101 is preferably less than 500 nm and more preferably 400 nm or less from the viewpoint of improving the hole shape and developability, and more preferably Below 300nm. The lower limit can be, for example, 0.1 nm or more. The absolute value of the maximum valley depth of the support can be measured using, for example, a white light interference microscope (Contoure GT-X series) manufactured by Bruker AXS.

The arithmetic average roughness Ra of the surface 101a of the support 101 is preferably less than 150 nm, more preferably 100 nm or less, more preferably 50 nm or less, 40 nm or less from the viewpoint of improving the hole shape and developability. 30 nm or less and 20 nm or less. The lower limit can be, for example, 0.1 nm or more. The arithmetic average roughness Ra can be measured using, for example, a non-contact interference microscope (WYKO Bruker) manufactured by AXS Corporation.

As the supporting system, a resin film is preferable, and examples thereof include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, and triethylpyrene. Acetate films and the like are particularly preferably polyethylene terephthalate (PET) films.

Examples of commercially available supports include polypropylene films manufactured by Oji Paper Co., Ltd. under the product names "Arufun MA-410", "E-200C", and Shin-Etsu Film Co., Ltd .; unitika products under the product name "S-25" ", Polyethylene terephthalate films such as PS series such as" PS-25 "made by Teijin Corporation.

Such a support may be subjected to a matting treatment or a corona discharge treatment to the surface on the side to which the resin composition layer is bonded. Moreover, as a support body, the "support body with a mold release layer" which has a mold release layer on the surface to which the photosensitive resin composition layer is joined can be used. In the support provided with a release layer, the release agent used as the release layer may be selected from the group consisting of alkyd resin, olefin resin, urethane resin, and silicone resin, for example. 1 or more release agents. Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, an alkyd resin-based release agent. The support with a release layer can also be formed by applying a release agent to the support.

The thickness of the support is preferably in a range of 5 μm to 50 μm, and more preferably in a range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, cracking of the support when peeling the support can be suppressed, and by setting the thickness to 50 μm or less, the resolution at the time of exposure from above the support can be improved. Further, a low fisheye support is preferred. Here, the so-called fisheye means that when a material is thermally melted, kneaded and extruded, and a film is manufactured by a biaxial stretching, casting method, etc., foreign materials, undissolved materials, and oxidative degradation materials of the material enter the film. Meaning.

As described above, since the surface 102a of the photosensitive resin composition layer 102 is transferred with the surface irregularities of the surface 101a of the support 101, the surface 102a is the same as the surface of the surface 101a, and the surface irregularities are small and smooth.

The absolute value (| Rv |) of the maximum valley depth of the surface 102a of the photosensitive resin composition layer 102 before the development after the exposure (to be described later after the (3) step and before the (4) step) improves the developability and From the viewpoint of a good hole shape, the thickness is preferably less than 500 nm, more preferably 400 nm or less, and more preferably 300 nm or less. The lower limit can be, for example, 1 nm or more. The maximum valley depth can be measured using, for example, a white light interference microscope (Contoure GT-X series) manufactured by Bruker AXS. In the case where the photosensitive resin composition is a negative photosensitive resin composition, the absolute value of the maximum valley depth is the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer of the active light irradiation portion. When the photosensitive resin composition is a positive photosensitive resin composition, the absolute value of the maximum valley depth is the maximum valley depth of the surface of the photosensitive resin composition layer in the unirradiated portion of the active light. Absolute value.

As the arithmetic average roughness Ra of the surface 102a of the photosensitive resin composition layer 102 before development after exposure (to be described later (after (3) step and before (4) step)), the developability is improved and a good hole shape is obtained. From a viewpoint, 100 nm or less is preferable, 80 nm or less is more preferable, and 50 nm or less is more preferable. The lower limit can be, for example, 1 nm or more. The arithmetic average roughness Ra can be measured using, for example, a non-contact interference microscope (WYKO Bruker) manufactured by AXS Corporation. In the case where the photosensitive resin composition is a negative photosensitive resin composition, the arithmetic average roughness Ra is the arithmetic average roughness of the surface of the photosensitive resin composition layer of the irradiated portion of the active light; When the resin composition is a positive photosensitive resin composition, the arithmetic average roughness Ra is the arithmetic average roughness of the surface of the photosensitive resin composition layer in the unirradiated portion of the active light.

The exposure conditions can also be performed under conventional exposure conditions. For example, as described in the examples described later, specifically, a method of irradiating ultraviolet rays of 10 mJ / cm ² or more and 1000 mJ / cm ² or less.

<Condition (B)>
Condition (B) is that the absolute value (| Rv |) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development is 500 nm or more. The inventors have found that when forming an insulating layer by performing exposure and development, the absolute depth of the maximum valley depth of the surface of the support side of the patterned photosensitive resin composition layer after development (after step (4)) is performed The value (| Rv |) has a great influence on the adhesion and the shielding property of the wiring. Here, the development conditions can also be performed by conventional development conditions. For example, as described in the examples described later, specifically, a spray pressure of 0.2 MPa and a 1% by mass sodium carbonate aqueous solution at 30 ° C. are sprayed. 2 Spray development in minutes.
The patterned photosensitive resin composition layer means a patterned photosensitive resin composition layer formed by exposing and developing the photosensitive resin composition layer.

As an example shown in FIG. 3, the photosensitive resin composition layer 102 is developed after exposure. One embodiment of development uses a developer to remove unexposed portions of the photosensitive resin composition layer 102 to form a patterned photosensitive resin composition layer 102b after development. The surface on the support side before the development of the photosensitive resin composition layer 102 (the surface opposite to the substrate 103 side) 102a has a small surface unevenness and a smooth surface as described above, but the image after development is Since the photosensitive resin composition layer 102b of the type photosensitive resin composition layer is partially removed in the vicinity of the surface of the photosensitive resin composition due to the developer used for development, the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b is removed. The absolute value of the maximum valley depth (| Rv |) becomes 500 nm or more. Since the surface 102c has a designated maximum valley depth, the adhesion with the conductor layer (not shown) is improved due to the anchoring effect.

The absolute value (| Rv |) of the maximum valley depth of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development is from the viewpoint of improving adhesion and shielding of wiring. In other words, it is 500 nm or more, preferably 1000 nm or more, and more preferably 1500 nm or more. The upper limit can be, for example, 10,000 nm or less. In particular, the maximum valley depth Rv is different from the arithmetic average roughness Ra. The maximum valley depth Rv is considered to consider the surface adhesion of the patterned photosensitive resin composition layer and the shielding property of the wiring. In terms of effect, it is a better indicator.

The arithmetic average roughness Ra, which is the surface 102c of the support 101 side of the patterned photosensitive resin composition layer 102b after development, is preferably 10 nm or more, and more preferably 30 nm from the viewpoint of improving adhesion. Above, more preferably at least 50 nm. The upper limit can be, for example, 1000 nm or less.

If the absolute value of the maximum valley depth of the surface 102a of the photosensitive resin composition layer 102 before the development (after (3) and (4)) after the exposure is set to A1, and if After the step (4)) of the patterned photosensitive resin composition layer 102b, when the absolute value of the maximum valley depth of the surface 102c on the support 101 side of the pattern is set to A2, from the viewpoint that the effect of the present invention can be significantly obtained A2 / A1 is preferably more than 3, more preferably 5 or more, more preferably 10 or more, preferably less than 100, still more preferably 70 or less, and even more preferably 40 or less.

The resin sheet 10 requires the absolute value of the maximum valley depth of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development to satisfy the above range. Therefore, the photosensitive resin composition system forming the photosensitive resin composition layer 102 is required to "remove a part of the components contained in the photosensitive resin composition by the developing solution used for development ((4) step)". As such a photosensitive resin composition system, those satisfying the following conditions (I) or (II) can be used.
(I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of the inorganic filler is 60. Above mass%.
(II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent.

-Condition (I)-
Condition (I) is that the photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, and when the non-volatile content of the photosensitive resin composition is 100% by mass, the content of the inorganic filler It is 60% by mass or more. When the average particle diameter of the inorganic filler is 0.5 μm or more, a part of the inorganic filler can be easily removed by a developing solution, so that the absolute value of the maximum valley depth of the surface of the photosensitive resin composition layer can be increased. When the non-volatile content of the photosensitive resin composition is set to 100% by mass, the content of the inorganic filler is set to 60% by mass or more, so that the entire surface 102c after development can be formed uniformly. The surface is uneven. As a result, the absolute value of the maximum valley depth of the entire surface 102c after development can be set to 500 nm or more.

The photosensitive resin composition satisfying the condition (I) may further include an optional component in addition to the component (a). As optional components, for example, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerization initiator, which are essential components of the condition (II), can be contained. In addition, as further optional components, (e) a reactive diluent, (f) a reactive diluent, (g) an organic solvent, and (h) other additives may be contained in the optional component of the condition (II). These components will be described later.

((a) Inorganic filler with an average particle diameter of 0.5 μm or more)
The material of the inorganic filler is not particularly limited, but examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and hydroaluminum Ores, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth acid, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and tungsten zirconium phosphate. Among them, silica is particularly suitable. As the silica series, spherical silica is preferred. The inorganic fillers can be used singly or in combination of two or more.

The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, and more preferably 1 μm or more from the viewpoint of obtaining a hardened product having excellent developability and low average linear thermal expansion coefficient. The upper limit of the average particle diameter is 2.5 μm or less, preferably 2 μm or less, still more preferably 1.5 μm or less, and more preferably 1.3 μm or less in terms of obtaining excellent resolution. Examples of commercially available inorganic fillers having such an average particle diameter include "SC2050", "SC4050", "ADMAFINE" manufactured by Admatechs, "SFP series" manufactured by Denki Chemicals, Nippon Steel & Sumikin Materials "SP (H) series" by the company, "Sciqas series" by the Sakai Chemical Industry Company, "Seahostar series" by the Japan Catalyst Company, "AZ series", "AX series" by Nippon Steel & Sumikin Materials, and Sakai Chemical "B series" and "BF series" made by industrial companies.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device is used to prepare a particle size distribution of an inorganic filler using a volume basis, and the median diameter is set to an average particle size so that To measure. The measurement sample is preferably one in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., "SALD-2200" manufactured by Shimadzu, etc. can be used.

The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 5 m ² / g or more from the viewpoint that the effects of the present invention can be significantly obtained. Although the upper limit is not particularly limited, it is preferably 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. The specific surface area of the inorganic filler can be measured by the BET method.

From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the inorganic filler is surface-treated with a surface-treating agent. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organic silazane compound, and a titanate system. Coupling agent, etc.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM403" (3-Glycidoxypropylpropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Oxysilane), Shin-Etsu Chemical Industry Company "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Industry Company "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Industry "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by the company, "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., Shin-Etsu "SZ-31" (hexamethyldisilazane) manufactured by Chemical Industries, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, and "KBM-4803" (long-chain ring) manufactured by Shin-Etsu Chemical Industries Oxygen-type silane coupling agent). The surface treatment agent can be used alone or in combination of two or more kinds at an arbitrary ratio.

The degree of surface treatment of the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (a). The amount of carbon per unit surface area of the component (a) is preferably 0.02 mg / m ² or more, and more preferably 0.1 mg / m ² or more from the viewpoint of improving the dispersibility of the component (a). 0.2mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the photosensitive resin composition and the melt viscosity in the form of a sheet, the aforementioned carbon content is preferably 1 mg / m ² or less, and more preferably 0.8 mg / m ² or less, particularly preferably 0.5 mg / m ² or less.

(a) The amount of carbon per unit surface area of the component can be washed and treated with the solvent (for example, methyl ethyl ketone (hereinafter referred to as "MEK")) after the surface treatment of the component (a). For measurement. Specifically, a sufficient amount of methyl ethyl ketone was mixed with the component (a) after being surface-treated with a surface-treating agent, and ultrasonically washed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the component (a) can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

From the viewpoint that a cured product having a low average linear thermal expansion ratio can be obtained, when the non-volatile content in the photosensitive resin composition is set to 100% by mass, the content of the component (a) is 60% by mass or more. It is preferably 65% by mass or more, and more preferably 70% by mass or more. From the viewpoint of improving developability, the upper limit is preferably 95% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.
In the present invention, unless otherwise specified, the content of each component in the photosensitive resin composition is a value when the nonvolatile component in the photosensitive resin composition is 100% by mass.

-Condition (II)-
Condition (II) the photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) light Polymerization initiator. By combining and containing the components (a) to (d), a part of each component in the photosensitive resin composition can be easily removed by a developing solution, so that the maximum valley of the surface of the photosensitive resin composition layer can be increased. The absolute value of the depth.

The photosensitive resin composition satisfying the condition (II) may further include an arbitrary component in combination with the components (a) to (d). The optional component system can include, for example, (e) a reactive diluent, (f) an organic solvent, and (g) other additives. Hereinafter, each component contained in a photosensitive resin composition is demonstrated in detail.

((a) Inorganic filler with an average particle diameter of 0.5 μm or more)
The photosensitive resin composition of the condition (II) contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. By containing (a) an inorganic filler having an average particle diameter of 0.5 μm or more, a cured product having a low average linear thermal expansion coefficient can be obtained.

Examples of the (a) inorganic filler having an average particle diameter of 0.5 μm or more used in the condition (II) include the inorganic fillers described in “-condition (I)-”.

The average particle diameter of the inorganic filler is as described in "-condition (I)-".

The (a) inorganic filler having an average particle diameter of 0.5 μm or more used in the condition (II) is preferably treated with a surface treatment agent. The type of surface treatment agent and the degree of surface treatment are as described in "-condition (I)-".

From the viewpoint that a cured product having a low average linear thermal expansion ratio can be obtained, the content of the component (a) used in the condition (II) is 100% by mass of the nonvolatile component in the photosensitive resin composition. It is 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of improving developability, the upper limit is preferably less than 60% by mass, more preferably 55% by mass or less, and still more preferably 50% by mass or less.

((b) Resin containing an ethylenically unsaturated group and a carboxyl group)
The photosensitive resin composition satisfying the condition (II) contains (b) a resin containing an ethylenically unsaturated group and a carboxyl group.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, and a nadimide group. The (meth) acrylfluorenyl group is preferably a (meth) acrylfluorenyl group from the viewpoint of the reactivity of photoradical polymerization. The "(meth) acrylfluorenyl" means the meaning of methacrylfluorenyl and acrylfluorenyl.

(b) The component system has an ethylenically unsaturated group and a carboxyl group, and any compound capable of photoradical polymerization and alkali development can be used. For example, one molecule has a carboxyl group and two or more ethylenically unsaturated groups. Is preferred.

Examples of the same state of the resin containing an ethylenically unsaturated group and a carboxyl group include acid-modified unsaturated epoxy ester resins in which an epoxy compound is reacted with an unsaturated carboxylic acid and then further reacted with an acid anhydride. Specifically, an unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and then an unsaturated epoxy ester resin can be reacted with an acid anhydride to obtain an acid-modified unsaturated epoxy ester resin.

As the epoxy compound, any compound having an epoxy group in the molecule can be used, and examples thereof include copolymers containing epoxy groups, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol F. Type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin and epichlorohydrin are reacted to obtain modified bisphenol F which is more than trifunctional. Type epoxy resins such as bisphenol type epoxy resins; biphenyl type epoxy resins, biphenyl type epoxy resins such as tetramethylbiphenyl type; phenol novolac type epoxy resins, cresol novolac type epoxy resins Novolac epoxy resins such as resins, bisphenol A novolac epoxy resins, alkylphenol novolac epoxy resins, etc .; bisphenol AF epoxy resins, and perfluoroalkyl epoxy resins, etc. Epoxy resin containing fluorine; naphthalene-type epoxy resin, dihydroxynaphthalene-type epoxy resin, polyhydroxy binaphthyl-type epoxy resin, naphthol-type epoxy resin, binaphthol-type epoxy resin, and naphthyl ether type Epoxy naphthol novolac epoxy resin is obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes. Naphthalene-type epoxy resins (epoxy resins containing a naphthalene skeleton) such as naphthalene-type epoxy resins; bixylenol-type epoxy resins; dicyclopentadiene-type epoxy resins; triphenol-type epoxy resins Resin; tert-butyl-catechol-type epoxy resin; epoxy resin containing a condensed ring skeleton such as anthracene-type epoxy resin; glycidylamine-type epoxy resin; glycidyl ester-type epoxy resin; biphenyl type Epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexanedimethanol type Epoxy resin; Trimethylolpropane type epoxy resin; Tetraphenylethane type epoxy resin; Polyglycidyl (meth) acrylate, copolymer of glycidyl methacrylate and acrylate, etc. Based acrylic resins; 茀 -type epoxy resins; halogenated epoxy resins and the like.

From the viewpoint of reducing the average thermal expansion coefficient, the epoxy compound is preferably an epoxy group-containing copolymer or an aromatic skeleton-containing epoxy resin. Here, the so-called aromatic skeleton refers to the concept that also includes polycyclic aromatics and aromatic heterocycles. The epoxy compound is an epoxy resin containing a naphthalene skeleton, an epoxy resin containing a condensed ring skeleton, a biphenyl epoxy resin, a bisphenol F epoxy resin, a bisphenol A epoxy resin, and a cresol novolac type. An epoxy resin and a glycidyl-type epoxy resin are preferable.

The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and an arbitrary monomer as required. Examples of the epoxy-group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 2-methyl-3,4 (meth) acrylate. -An epoxy-group-containing (meth) acrylate monomer such as epoxycyclohexyl ester and allyl glycidyl ether, and glycidyl (meth) acrylate is preferred. A single system containing an epoxy group may be used alone or as a mixture of two or more.

Examples of the arbitrary monomer include styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, N-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl methacrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth) Lauryl acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (formyl) (Cyclo) hexyl acrylate, 4-tert-butyl cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentadiene (meth) acrylate, benzyl (meth) acrylate , Acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, 3- (meth) acrylfluorenylpropyltrimethoxysilane, (meth) acrylic acid N, N-dimethylaminoethyl ester, glycidyl (meth) acrylate, styrene, α -Methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-methyl (meth) acrylate Hydroxy-n-butyl ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4- Cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic acid 2 -Hydroxy-3-phenoxypropyl ester, 2- (meth) acrylfluorenyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate with a hydroxyl group at the terminal, (meth) 1-adamantyl acrylate and the like are preferably n-butyl (meth) acrylate. Any single system can be used alone or in combination of two or more.

As the epoxy resin containing a naphthalene skeleton, a dihydroxynaphthalene type epoxy resin, a polyhydroxybinaphthalene type epoxy resin, and a naphthalene type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and an aldehyde are preferable. Examples of the dihydroxynaphthalene-type epoxy resin include 1,3-diglycidyl ether oxynaphthalene, 1,4-diglycidyl ether oxynaphthalene, 1,5-diglycidyl ether oxynaphthalene, 1, 6-diglycidyl ether naphthalene, 2,3-diglycidyl ether naphthalene, 2,6-diglycidyl ether naphthalene, 2,7-diglycidyl ether naphthalene, and the like. Examples of the polyhydroxy binaphthyl epoxy resin include 1,1'-bi- (2-glycidyl etheroxy) naphthyl and 1- (2,7-diglycidyl etheroxy) -1'- (2'-glycidyl etheroxy) binaphthyl, 1,1'-bi- (2,7-diglycidyl etheroxy) naphthyl, and the like. Examples of the naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis (2,7-diglycidyl ether naphthyl) methane, and 1- (2 , 7-diglycidyl etheroxynaphthyl) -1 '-(2'-glycidyl etheroxynaphthyl) methane, 1,1'-bis (2-glycidyl etheroxynaphthyl) methane.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid. These systems may be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the photocurability of the photosensitive resin composition. In this specification, the epoxy ester resin of the reaction product of the above-mentioned epoxy compound and (meth) acrylic acid may be described as "epoxy (meth) acrylate". The group is substantially eliminated by the reaction with (meth) acrylic acid. The "(meth) acrylate" means the meaning of methacrylate and acrylate. In some cases, acrylic acid and methacrylic acid are collectively referred to as "(meth) acrylic acid".

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, These systems can be used benzophenone tetracarboxylic dianhydride, etc., or two or more of them can be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred in terms of improving the resolution and insulation reliability of the cured product.

When an acid-modified unsaturated epoxy ester resin is obtained, a catalyst, a solvent, a polymerization inhibitor, or the like may be used as required.

The acid-modified unsaturated epoxy ester resin is preferably an acid-modified epoxy (meth) acrylate. In the acid-modified unsaturated epoxy ester resin, the so-called "epoxy" means a structure derived from the aforementioned epoxy compound. For example, the "acid-modified bisphenol epoxy (meth) acrylate" refers to an acid modification obtained by using a bisphenol epoxy resin as an epoxy compound and (meth) acrylic acid as an unsaturated carboxylic acid. Meaning of the unsaturated unsaturated epoxy ester resin.

The acid-modified unsaturated epoxy ester resin is preferably a (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower. The (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower has a particularly low compatibility with the components (a) and (c) to (d) compared to the other (b) components. Therefore, the (meth) acrylic polymer is easily phase-separated in the photosensitive resin composition. Therefore, a domain containing the (meth) acrylic polymer is generally dispersed and formed in the photosensitive resin composition layer. The area system containing the (meth) acrylic polymer can be easily removed by using a developing solution. Therefore, after the development, unevenness is generated in the portion where the (meth) acrylic polymer is removed, so the pattern can be increased after development. The absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer. The (meth) acrylic polymer refers to a structural unit included in the polymer and has a structure formed by polymerizing a (meth) acrylic monomer. Examples of such a (meth) acrylic polymer include a polymer obtained by polymerizing a (meth) acrylic monomer, or a (meth) acrylic monomer and a polymer capable of reacting with the (meth) acrylic monomer. A polymer obtained by copolymerizing monomers copolymerized in bulk.

Examples of the (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower include an acid-modified unsaturated epoxy resin which reacts an epoxy group-containing copolymer with (meth) acrylic acid and then reacts with an acid anhydride. (Meth) acrylic copolymer and the like. In detail, an unsaturated epoxy (meth) acrylic acid copolymer is obtained by reacting a copolymer containing an epoxy group and (meth) acrylic acid, and then an unsaturated epoxy (meth) acrylic acid copolymer is reacted with an acid anhydride, thereby An acid-modified unsaturated epoxy (meth) acrylic acid copolymer can be obtained.

A preferable aspect of the (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower is as follows: A compound containing a ring-containing polymer obtained by polymerizing an epoxy-containing monomer and an arbitrary monomer. A copolymer of an oxy group and a compound reacted with (meth) acrylic acid and an acid anhydride, in which the monomer containing an epoxy group is glycidyl methacrylate, an arbitrary monomer is butyl acrylate, and the anhydride is four Hydrophthalic anhydride.

Commercial products can be used for such acid-modified unsaturated epoxy ester resins. Specific examples include "ZAR-2000" (bisphenol A epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. Reactants), "ZFR-1491H", "ZFR-1533H" (reactants of bisphenol F-type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko Corporation (Cresol novolac epoxy resin, reactant of acrylic acid, and acid anhydride) and the like. These systems can be used alone or in combination of two or more.

Other aspects of the resin containing an ethylenically unsaturated group and a carboxyl group include a (meth) acrylic resin in a structural unit obtained by polymerizing (meth) acrylic acid, and a resin containing an ethylenically unsaturated group. The epoxy compound is reacted to introduce an unsaturated modified (meth) acrylic resin having an ethylenically unsaturated group. Examples of the epoxy compound containing an ethylenically unsaturated group include glycidyl methacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexyl methyl (meth) acrylate. Esters, etc. Furthermore, an acid anhydride may be reacted with a hydroxyl group generated when an unsaturated group is introduced. As the acid anhydride system, those which are the same as those described above can be used, and the preferable ranges are also the same.

Commercially available products of such unsaturated modified (meth) acrylic resins can be used. Specific examples include "SPC-1000", "SPC-3000" manufactured by Showa Denko Corporation, and "SPC-3000" manufactured by Daicel-allnex Corporation. Cyclomer P (ACA) Z-250 "," Cyclomer P (ACA) Z-251 "," Cyclomer P (ACA) Z-254 "," Cyclomer P (ACA) Z-300 "," Cyclomer P (ACA) Z -320 "and so on.

From the viewpoint of film forming properties, the weight average molecular weight as the component (b) is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7500 or less. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

From the viewpoint of improving the alkali developability of the photosensitive resin composition as the acid value of the component (b), an acid value of 0.1 mgKOH / g or more is preferable, and 0.5 mgKOH / g or more is more preferable. More preferably, it is 1 mgKOH / g or more. On the other hand, from the viewpoint of suppressing the elution of the fine pattern of the hardened material due to development and improving the insulation reliability, an acid value of 150 mgKOH / g or less is preferable, and 120 mgKOH / g or less is more preferable. It is more preferably 100 mgKOH / g or less. Here, the acid value refers to the residual acid value of the carboxyl group existing in the component (b), and the acid value can be measured by the following method. First, after measuring approximately 1 g of the resin solution with accurate weighing, 30 g of acetone was added to the resin solution, and the resin solution was uniformly dissolved. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1N KOH aqueous solution. The acid value was calculated based on the following formula.
Formula: A (b) = 10 × Vf × 56.1 / (Wp × I)

In the above formula, A (b) represents the acid value (mgKOH / g), Vf represents the titer of KOH (mL), Wp represents the measurement of the resin solution mass (g), and I represents the measurement of the resin solution. Ratio of volatile matter (% by mass).

In the production of the component (b), the ratio of the molar number of the epoxy group of the epoxy resin to the molar number of the carboxyl group of the unsaturated carboxylic acid and the acid anhydride is based on the improvement of the storage stability. A range of 1: 0.8 to 1.3 is preferable, and a range of 1: 0.9 to 1.2 is still more preferable.

From the viewpoint of improving the flexibility, the glass transition temperature (Tg) of the component (b) is preferably -300 ° C or higher, more preferably -200 ° C or higher, more preferably -80 ° C or higher, and more preferably -20 ° C or lower, preferably -23 ° C or lower, and more preferably -25 ° C or lower. Here, the glass transition temperature of the component (b) refers to the theoretical glass transition temperature of the main chain of the component (b). The theoretical glass transition temperature can be calculated by the FOX formula shown below. . The glass transition temperature obtained by the FOX formula is approximately the same as the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so it can also be measured by differential scanning calorimetry (b) The glass transition temperature of the main chain of the ingredients.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ・ ・ ・ + (Wm / Tgm)
W1 + W2 + ・ ・ ・ + Wm = 1
Wm represents the content (% by mass) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the (b) component.

From the viewpoint of improving the alkali developability, when the solid content of the photosensitive resin composition is 100% by mass as a whole, the component (b) is preferably such that the content is 20% by mass or more. It is more preferable that it is 25 mass% or more, and it is more preferable that it is 30 mass% or more. From the viewpoint of improvement in heat resistance or average linear expansion rate, the upper limit is preferably set to 45% by mass or less, more preferably set to 40% by mass or less, and more preferably set to 35% by mass or less. .

((c) Epoxy)
The photosensitive resin composition satisfying the condition (II) contains (c) an epoxy resin. By containing (c) component, insulation reliability can be improved. However, the component (c) referred to here does not include epoxy resins containing ethylenically unsaturated groups and carboxyl groups.

Examples of the component (c) include fluorine-containing epoxy resins such as bisphenol AF-type epoxy resins and perfluoroalkyl-type epoxy resins; bisphenol A-type epoxy resins; and bisphenol F-type epoxy resins. ; Bisphenol S epoxy resin; Bixylenol epoxy resin; Dicyclopentadiene epoxy resin; Triphenol epoxy resin; Naphthol novolac epoxy resin; Phenol novolac epoxy resin Resin; tert-butyl-catechol epoxy resin; naphthalene epoxy resin; naphthol epoxy resin; anthracene epoxy resin; glycidylamine epoxy resin; glycidyl ester epoxy resin; Cresol novolac epoxy resin; biphenyl epoxy resin; biphenyl aralkyl epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin Alicyclic epoxy resin with ester skeleton; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexanedimethanol epoxy resin; naphthyl ether epoxy resin; trimethylol Propane epoxy resin; tetraphenylethane epoxy resin, halogenated epoxy resin, etc. The epoxy resin can be used alone or in combination of two or more. From the viewpoint of improving insulation reliability and adhesion, the component (c) is preferably a biphenyl epoxy resin or a biphenylaralkyl epoxy resin.

(c) The epoxy resin is preferably one having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50% by mass or more. Epoxy resins include epoxy resins that are liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20 ° C (sometimes called " "Solid epoxy resin"). The photosensitive resin composition may contain only a liquid epoxy resin or a solid epoxy resin as the (c) epoxy resin, but from the viewpoint of improving the insulation reliability of the obtained cured product, A solid epoxy resin is preferred.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, and glycidol. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin , And epoxy resins with a butadiene structure.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) made by DIC; "828US", "jER828EL", and "made by Mitsubishi Chemical" 825 "," Epikote 828EL "(bisphenol A type epoxy resin);" jER807 "and" 1750 "(bisphenol F type epoxy resin) made by Mitsubishi Chemical;" jER152 "(phenol novolac) made by Mitsubishi Chemical Varnish type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) made by Mitsubishi Chemical; "ZX1059" (bisphenol A type epoxy resin and bis Mixture of phenol F-type epoxy resins); "EX-721" (glycidyl ester epoxy resin) made by Nagasechemtex; "CELOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) made by Daicel ; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Type epoxy resin) and so on. These systems can be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Resin is more preferred.

As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, Triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A type Epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are more preferable, and biphenyl type epoxy resin and biphenylaralkyl type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolac-type epoxy resin) manufactured by DIC; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC; "HP- 7200 "," HP-7200HH "," HP-7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "manufactured by DIC Corporation "," EXA-7311-G4S "," HP6000 "(dnaphthyl ether epoxy resin);" EPPN-502H "(triphenol epoxy resin) manufactured by Nippon Kayaku Co .; "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin (biphenylaralkyl ring) Oxygen resin)); "ESN475V" (naphthalene-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; Mitsubishi Chemical "YX4000H", "YX4000", "YL6121" (biphenyl epoxy resin) made by Mitsubishi Chemical; "YX4000HK" (bixylenol epoxy resin) made by Mitsubishi Chemical; "YX8800" (Mitsubishi Chemical) Anthracene-type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" manufactured by Mitsubishi Chemical "(茀 -type epoxy resin);" jER1010 "(solid bisphenol A type epoxy resin) made by Mitsubishi Chemical;" jER1031S "(tetraphenylethane type epoxy resin) made by Mitsubishi Chemical; These systems can be used alone or in combination of two or more.

(c) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1,000. When the content is within this range, the crosslinked density of the cured product of the photosensitive resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. It can also be measured in accordance with JIS K7236. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups.

(c) The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and more preferably 400 to 1500. Here, the weight average molecular weight of an epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC).

From the viewpoint of obtaining a good tensile fracture strength and an insulating layer exhibiting insulation reliability, when the solid content of the photosensitive resin composition is 100% by mass as a whole, the content of the component (c) is relatively small. It is preferably at least 1 mass%, more preferably at least 5 mass%, and even more preferably at least 10 mass%. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, and is preferably 25% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less.

((d) Photopolymerization initiator)
The photosensitive resin composition satisfying the condition (II) contains (d) a photopolymerization initiator. By containing (d) a photopolymerization initiator, the photosensitive resin composition can be effectively photocured.

(d) Any compound can be used as the photopolymerization initiator, and examples thereof include bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide) and 2,4,6-trimethyl. Fluorenylphosphine oxide-based photopolymerization initiators such as benzamyl-diphenyl-phosphine oxide; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl Hydrazine), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime), etc. Oxime ester-based photopolymerization initiators; 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -1-butanone, 2- (dimethylamino) -2 -[(4-methylphenyl) methyl]-[4- (4-morphoyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl Α-Aminobenzoyl ketone-based photopolymerization initiators such as 2-morpholinylpropane-1-one; benzophenone, methylbenzophenone, o-benzophenanthranilic acid, benzene Methyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethylbenzyl) phosphine oxide , Ethyl- (2,4,6-trimethylbenzylidene) phenyl phosphinate, 4,4'-bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl -Phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide; phosphonium salt Photopolymerization initiators. These systems may be used alone or in combination of two or more. Among these, from the viewpoint of more efficiently photo-curing the photosensitive resin composition, a fluorenyl phosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator are preferred, and an oxime ester A photopolymerization initiator is also preferred.

Specific examples of the (d) photopolymerization initiator include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO", "IrgacureOXE-01", manufactured by BASF, and "IrgacureOXE-02", "IrgacureTPO", "Irgacure819", "N-1919" manufactured by ADEKA Corporation, etc.

Furthermore, the photosensitive resin composition may contain N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl- Tertiary amines such as 4-dimethylaminobenzoate, triethylamine, and triethanolamine are used as photopolymerization starting aids, or may include pyrazolines, anthracenes, and coumarins Photosensitizers such as xanthones, thioxanthone and the like are combined with (d) photopolymerization initiators. These systems can be used either alone or in combination of two or more.

From the viewpoint of sufficiently photo-curing the photosensitive resin composition and improving the insulation reliability, when the non-volatile content of the photosensitive resin composition is set to 100% by mass, it is used as (d) a photopolymerization initiator. The content thereof is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 0.3% by mass or more. On the other hand, from the viewpoint of suppressing a reduction in resolution due to excessive sensitivity, the upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1.5 mass% or less. When the photosensitive resin composition contains a photopolymerization initiation aid, the total content of (d) the photopolymerization initiation agent and the photopolymerization initiation aid is preferably within the above range.

((e) Reactive diluent)
The photosensitive resin composition system satisfying the condition (II) can further contain (e) a reactive diluent. By containing (f) component, photoreactivity can be improved. As the (e) component, for example, a photosensitive (meth) acrylate compound having one or more (meth) acrylfluorene groups in one molecule and which is liquid, solid, or semi-solid at room temperature can be used. The so-called room temperature means about 25 ° C.

Typical examples of the photosensitive (meth) acrylate compound include hydroxyalkyl acrylates such as tricyclodecane dimethanol diacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; and the like; Mono- or diacrylates of diols such as diols, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc .; N, N-dimethylacrylamide, N-hydroxymethacrylamide, etc. Allylamines; N, N-dimethylaminoethyl acrylates and other amino alkyl acrylates; trimethylolpropane, pentaerythritol, dipentaerythritol, dipentaerythritol hexa (meth) acrylate, etc. Polyols or polyacrylates of ethylene oxide, propylene oxide, or ε-caprolactone adducts; phenols such as phenoxyacrylate, phenoxyethyl acrylate, or their epoxy Acrylates such as ethane or propylene oxide adducts; epoxy acrylates, melamine acrylates derived from glycidyl ethers, such as trimethylolpropane triglycidyl ether, and / or the like Acrylates correspond to methacrylates and the like. Among these, polyacrylic acid esters or polymethacrylic acid esters are preferred. Examples of trivalent acrylic acid esters or methacrylic acid esters include trimethylolpropane tri (meth) acrylic acid. Ester, pentaerythritol tri (meth) acrylate, trimethylolpropane EO addition tri (meth) acrylate, glycerol PO addition tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol Oligo (meth) acrylate, ethylcarbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate , Trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, Examples of (meth) acrylic acid esters of N ', N'-methyl (β-hydroxyethyl) ethyldiamine, and the like include tri (2- (acrylate) or methacrylic acid esters. (Meth) acrylfluorenyloxyethyl) phosphate, tris (2- (meth) acrylfluorenyloxypropyl) phosphate, tris (3- (meth) acrylfluorenyloxypropyl) phosphate Esters, tris (3- (methyl) propane Fluorenyl-2-hydroxyoxypropyl) phosphate, bis (3- (meth) propenyl-2-hydroxyoxypropyl) (2- (meth) propenyloxyethyl) phosphate Phosphate triesters (meth) acrylates such as esters, (3- (meth) acrylfluorenyl-2-hydroxyoxypropyl) di (2- (meth) acrylfluorenyloxyethyl) phosphate . These photosensitive (meth) acrylate compounds may be used either alone or in combination of two or more.

(e) As a reactive diluent, a commercially available product can be used. Specific examples include "DPHA" (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), "DCA-P" (tricyclodecane dimethanol Acrylate, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

When the photosensitive resin composition contains (e) a reactive diluent, the solid content of the photosensitive resin composition is considered from the viewpoint of promoting light curing and suppressing adhesion when the photosensitive resin composition is used as a cured product. When the entire content is 100% by mass, the content of the (e) reactive diluent is preferably 0.5% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 25% by mass. Hereinafter, it is more preferably 20% by mass or less, and even more preferably 15% by mass or less.

((f) Organic solvents)
The photosensitive resin composition system satisfying the condition (II) can further contain (f) an organic solvent. By containing (f) an organic solvent, the varnish viscosity can be adjusted. Examples of (f) organic solvents include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ethyl acetate Esters, butyl acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol ether acetate and other esters; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha , Petroleum solvents such as hydrogenated petroleum spirit, solvent oil, etc. These systems can be used alone or in combination of two or more. From the viewpoint of the coatability of the resin composition, the content when the organic solvent is used can be appropriately adjusted.

((g) Other additives)
The photosensitive resin composition which satisfies the condition (II) can further contain (g) other additives as long as the object of the present invention is not hindered. (G) Other additives include fine particles such as ion trapping agents, thermoplastic resins, organic fillers, melamine, and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, and titanium oxide. Colorants or pigments such as carbon black, naphthalene black, NV-7-201 (made by Japan Pigment), hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, o Polymerization inhibitors such as pyrogallol, thickeners such as bentonite, microcrystalline kaolinite, polysiloxane-based, fluorine-based, vinyl resin-based defoamers, brominated epoxy compounds, acid-modified brominated Various additives such as epoxy compounds, antimony compounds, aromatic condensation phosphates, halogen-containing condensation phosphates and other flame retardants, phenol-based hardeners, and thermosetting resins such as cyanate-based hardeners.

The photosensitive resin composition system may be either a negative photosensitive resin composition or a positive photosensitive resin composition, but from the viewpoint of improving the physical properties of the photosensitive resin composition layer, in terms of irradiation at the time of exposure A negative-type photosensitive resin composition in which a pattern-type photosensitive resin composition layer is partially formed is preferable.

From the viewpoint of improving the operability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in a range of 5 μm to 500 μm, and is set to A range of 10 μm to 200 μm is still more preferable, a range of 15 μm to 150 μm is more preferable, a range of 20 μm to 100 μm is even more preferable, and a range of 20 μm to 60 μm is particularly preferable.

[Resin sheet]
The resin sheet of the present invention has a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support, and the haze of the support is 20% or less. The photosensitive resin composition after development The absolute value of the maximum valley depth (| Rv |) of the surface on the support side of the object layer is 500 nm or more, and the photosensitive resin composition satisfies the following conditions (I) or (II).
(I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of (a) component is 60 Above mass%.
(II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent.

The support, the haze of the support, the absolute value of the maximum valley depth of the photosensitive resin composition layer, and the conditions (I) and (II) satisfying the photosensitive resin composition are as described above.

In the case of the condition (I), the photosensitive resin composition can be obtained by mixing the above-mentioned (a) component as an essential component and appropriately mixing the above-mentioned (b) to (g) component as an arbitrary component. A resin varnish is produced by kneading or stirring by a kneading means such as a three-roller, a ball mill, a bead mill, a sand mixer, or by a kneading means such as a high-speed rotary mixer, a super-strong mixer, a planetary mixer, or the like.

In the case of the condition (II), the photosensitive resin composition can be obtained by mixing the components (a) to (d) and appropriately mixing the above-mentioned components (e) to (g) as optional components. It is necessary to use a kneading method such as a three-roller, a ball mill, a bead mill, and a sand mixer, or a kneading method such as a high-speed rotating mixer, a super mixer, a planetary mixer, etc. to produce a resin varnish. .

The protective resin film can be used to protect the photosensitive resin composition layer. By protecting the photosensitive resin composition layer side of the resin sheet with a protective film, it is possible to prevent adhesion or scratching of dust or the like on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but a range of 1 μm to 40 μm is preferred, a range of 5 μm to 30 μm is even more preferred, and a range of 10 μm to 30 μm is more preferred. Furthermore, the protective film is preferably: "The adhesive force between the photosensitive resin composition layer and the protective film is smaller than the adhesive force between the photosensitive resin composition layer and the support".

The resin sheet of the present invention can be prepared by, for example, preparing a resin varnish that dissolves a photosensitive resin composition in an organic solvent, coating the resin varnish on a support, and drying the organic solvent by heating or blowing hot air to form a photosensitivity. A resin composition layer is manufactured. Specifically, firstly, after completely removing bubbles in the resin composition by a vacuum defoaming method or the like, the photosensitive resin composition can be coated on a support, and the solvent can be removed by a hot air furnace or a far-infrared furnace. After drying, if necessary, a protective film is laminated on the obtained photosensitive resin composition layer to produce a resin sheet. The specific drying conditions vary depending on the curability of the photosensitive resin composition or the amount of organic solvents in the resin varnish, but for resin varnishes containing 30% to 60% by mass of organic solvents, the temperature can be 80 ° C to 120 ° C. Allow 3 to 13 minutes to dry. The amount of residual organic solvents in the photosensitive resin composition layer is preferably 5 mass% or less, and more preferably 2 mass% or less with respect to the total amount of the photosensitive resin composition layer. Those skilled in the art can set appropriate and suitable drying conditions by simple experiments.

Examples of the coating method of the photosensitive resin composition include a gravure coating method, a micro gravure coating method, a reverse coating method, a kiss reverse method, a die coating method, and a slit method. Coating method, lip coating method, comma coating method, blade coating method, roll coating method, blade coating method, curtain coating method, chamber gravure coating Cloth method, slot coating method, spray coating method, dip coating method, etc.

The photosensitive resin composition system may be applied in several times, may be applied once, or may be applied in combination. Among them, a die coating method which is excellent in uniform coating properties is preferable. Further, in order to avoid mixing of foreign matter, etc., it is preferable to perform the coating step in an environment where foreign matter such as a clean room is little generated.

The use of the photosensitive resin composition layer of the resin sheet is not particularly limited, and it can be used for circuit boards (laminate board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, and semiconductor seals. Materials, resins for hole filling, resins for inserting parts, etc. Among them, it is suitable as a photosensitive resin composition layer for forming a solder resist (a printed wiring board using a cured product of the photosensitive resin composition layer as a solder resist), and a photosensitive resin composition for an insulating layer of a printed wiring board (the (A printed wiring board having a cured product of a photosensitive resin composition layer as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of a photosensitive resin composition layer as an interlayer insulating layer), and plating A photosensitive resin composition for coating formation (a plated printed wiring board is formed on a cured product of a photosensitive resin composition layer).

The photosensitive resin composition system forming the photosensitive resin composition layer is excellent in developability. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent developability can be obtained. For example, the laminated body for evaluation is produced by the method as described in an Example. In this case, a rectangular portion of 1 cm × 2 cm in the exposed portion of the laminate for evaluation was visually observed, and the resin in the exposed portion was not peeled off or a part was not dissolved.

For example, the laminated body for evaluation is produced by the method as described in an Example. In this case, the residue-free minimum opening diameter (minimum pore diameter) of the laminated body for evaluation is preferably 200 μm or less, more preferably 150 μm or less, more preferably 130 μm or less and 100 μm or less. The lower limit is not particularly limited, but can be set to 50 μm or more.

In addition, when the laminated body for evaluation is used to evaluate the appearance according to the method described in the examples, generally, there is no residual resin component in any unexposed portion, and even if holes (opening portions) are observed at any three points Generally speaking, no overhang or undercut is found in the round hole pattern.

Since the photosensitive resin composition layer can form a surface having a high absolute value of the maximum valley depth after development, a cured product having excellent shielding properties for wiring can be obtained. Therefore, an insulating layer and a solder resist layer having excellent shielding properties can be obtained. For example, the laminated body for evaluation is produced by the method as described in an Example. In this case, generally, the pattern cannot be seen in the evaluation laminate by visual inspection.

Since the photosensitive resin composition layer can form a surface having a high absolute value of the maximum valley depth after development, a cured product having excellent adhesion can be obtained. Therefore, an insulating layer and a solder resist layer having excellent adhesion can be obtained. For example, according to the method described in the examples, when a sheet is laminated on the evaluation laminate and the adhesion is evaluated according to the method described in the examples, in general, no peeling is found in all the squares.

[Manufacturing method of printed wiring board]
The method for manufacturing a printed wiring board of the present invention includes the following steps:
(1) a step of preparing a resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support,
(2) a step of laminating a resin sheet on a substrate,
(3) a step of exposing the photosensitive resin composition layer and
(4) A step of forming a patterned photosensitive resin composition layer by development.

The printed wiring board of this invention can be manufactured using the said resin sheet. About the support body, the haze of the support body, the absolute value of the maximum valley depth of the patterned photosensitive resin composition layer after step (4), and the conditions (I) and conditions ( II) is as described above. Hereinafter, a case where the cured product of the photosensitive resin composition layer is a solder resist will be described.

＜ (1) Step ＞
(1) The step is a step of preparing a resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support. The haze of the support system is 20% or less, and the photosensitive resin composition satisfies the condition (I) or (II) described above. In addition, since the photosensitive resin composition satisfies the condition (I) or (II), after the step (4), The absolute value (| Rv |) will be above 500 nm. The resin sheet used in the step (1) is as described above.

＜ (2) Step ＞
(2) The step is a step of laminating a resin sheet on a substrate. If the resin sheet has a protective film in step (2), after removing the protective film, preheat the resin sheet and the substrate as required, and press and heat the photosensitive resin composition layer while pressing the substrate on. For the resin sheet system, a method of laminating on a substrate under reduced pressure by a vacuum lamination method can be suitably used.

The substrate is preferably a circuit substrate in which a patterned conductor layer (circuit) is formed on one or both sides. Examples of the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. A multilayer printed wiring board composed of a conductive layer and an insulating layer alternately laminated, even if one of the outermost layers or both sides of the multilayer printed wiring board is a patterned conductor layer (circuit), it is also included here So-called circuit board. Alternatively, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

(2) The conditions of the step are not particularly limited, but for example, the pressing temperature (lamination temperature) is preferably set to 70 ° C to 140 ° C, and the pressing pressure is preferably set to 1 kgf / cm ² to 11 kgf / cm ² (9.8 × 10 ⁴ N / m ² to 107.9 × 10 ⁴ N / m ² ), the pressing time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to a reduced pressure of 20 mmHg (26.7 hPa) or less It is better to perform lamination. The lamination step may be a batch method or a continuous method using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum laminator made by Nikko Materials, a vacuum pressurized laminator made by Meiji Seisakusho, a roll dry coater made by Hitachi Industries, and a Hitachi AIC made by Hitachi AIC. Vacuum laminator, etc. In this way, a resin sheet is laminated on the substrate.

＜ (3) Step ＞
The step (3) is a step of exposing the photosensitive resin composition layer after the step (2). Specifically, when the photosensitive resin composition is a negative photosensitive resin composition, after a resin sheet is set on the substrate in step (2), the pattern is masked and the photosensitive resin composition layer is masked. A predetermined portion of the substrate is irradiated with active light, thereby photo-curing the photosensitive resin composition layer of the irradiated portion.

Examples of the active light include ultraviolet rays, visible rays, electron beams, and X-rays. Particularly, ultraviolet rays are preferred. The amount of ultraviolet radiation is approximately 10 mJ / cm ² to 1000 mJ / cm ² . The exposure method includes a contact exposure method in which a mask pattern and a printed wiring board are adhered to each other, and a non-contact exposure method in which exposure is performed by using parallel light instead of close contact, and any method may be used.

The solder resist is excellent in developability because the photosensitive resin composition described above is used. Therefore, as the exposure pattern in the mask pattern, for example, a ratio (L / S) of a circuit width (line; L) to a circuit width (gap; S) (L / S) of 100 μm / 100 μm or less (that is, wiring pitch) 200 μm or less), L / S = 90 μm / 90 μm or less (wiring pitch 180 μm or less), L / S = 80 μm / 80 μm or less (wiring pitch 160 μm or less), L / S = 70 μm / 70 μm or less (wiring pitch 140 μm or less), L / S = 60μm / 60μm or less (wiring pitch: 120μm or less), L / S = 50μm / 50μm or less (wiring pitch: 100μm or less). In addition, as the exposure pattern, for example, a pattern having a circular hole having a diameter of 100 μm or less, a circular hole of 90 μm or less, a circular hole of 80 μm or less, a circular hole of 70 μm or less, a circular hole of 60 μm or less and a circular hole of 50 μm or less . However, the pitch need not be the same throughout the entire circuit board.

＜ (4) Step ＞
(4) The step is a step of forming a patterned photosensitive resin composition layer by development. Specifically, if the photosensitive resin composition is a negative photosensitive resin composition, after step (3), the photosensitive resin composition layer is developed on the surface, and the wet development is used to remove The light-cured portion (unexposed portion) can form a patterned photosensitive resin composition layer. In addition, since the patterned photosensitive resin composition layer satisfies the foregoing requirements, the developing solution used in wet development is opposite to the substrate side of the patterned photosensitive resin composition layer after step (4). The absolute value (| Rv |) of the maximum valley depth of the side surface will be 500 nm or more.

The absolute value of the maximum valley depth and the arithmetic average roughness Ra of the surface opposite to the substrate side of the patterned photosensitive resin composition layer after the step (4) are as before, and the preferable ranges are also the same.

As the developing solution, a safe and stable developing solution having an alkali aqueous solution, an aqueous developing solution, an organic solvent, and the like with good operability can be used. Among them, a developing step using an alkaline aqueous solution is preferred. Moreover, as a developing method, well-known methods, such as spraying, shaking dipping, brush coating, and blade coating, can be used suitably.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; sodium phosphate; An aqueous solution of an alkali metal pyrophosphate such as potassium phosphate, sodium pyrophosphate, or potassium pyrophosphate, or an aqueous solution of an organic base that does not contain metal ions, such as tetraalkylammonium hydroxide, does not contain metal ions. Further, in terms of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable.

In order to improve the developing effect, such an alkaline aqueous solution may be added with a surfactant, a defoaming agent, and the like to the developing solution. The pH of the alkaline aqueous solution is, for example, preferably in a range of 8 to 12, and more preferably in a range of 9 to 11.

The alkali concentration of the alkaline aqueous solution is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 50% by mass or less, and still more preferably 40% by mass. Hereinafter, it is more preferably 35% by mass or less.

The temperature of the alkaline aqueous solution is appropriately selected in accordance with the developability of the resin composition layer, and is preferably 10 ° C, more preferably 15 ° C, more preferably 20 ° C, more preferably 50 ° C or less, and still more preferably 45 ° C or lower, more preferably 40 ° C or lower.

The organic solvents used as the developer are, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the entire amount of the developing solution. The temperature of such an organic solvent can be adjusted in accordance with the developability. Furthermore, such an organic solvent system can be used individually or in combination of 2 or more types. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamidine, cyclohexanone, methyl Isobutyl ketone, γ-butyrolactone.

In pattern formation, the above-mentioned two or more types of development methods may be used in combination as needed. Development methods include dipping method, stirring method, spray method, high-pressure spray method, brush coating, and slapping. In order to improve the resolution, a high-pressure spray method is suitable. The spray pressure when the spray method is used is preferably 0.05 MPa or more, more preferably 0.1 MPa or more, more preferably 0.15 MPa or more, more preferably 0.5 MPa or less, still more preferably 0.4 MPa or less, and more preferably 0.3 MPa or less.

＜ (5) Step ＞
The method for manufacturing a printed wiring board of the present invention may further include (5) a step of curing the patterned photosensitive resin composition layer in addition to the steps (1) to (4). By performing step (5), the patterned photosensitive resin composition layer can be thermally cured to form a solder resist. The step (5) is preferably performed after the end of the step (4).

The heating conditions can be appropriately selected according to the type and content of the resin component in the resin composition, and it is preferably in a range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, and more preferably 160 ° C to 200 ° C. Choose between 30 minutes and 120 minutes. Still, before the heating, the ultraviolet irradiation by a high-pressure mercury lamp or the heating step using a clean oven can also be performed. When the ultraviolet rays are irradiated, the irradiation amount can be adjusted as needed, and for example, the irradiation amount can be about 0.05 J / cm ² to 10 J / cm ² .

＜ (6) Step ＞
The method for manufacturing a printed wiring board of the present invention can further include (6) a step of peeling the support in addition to steps (1) to (4). The method of peeling a support body can be implemented by a well-known method.

The timing of performing step (6) is not particularly limited, and may be performed after step (3) and before step (4), for example. From the viewpoint that the absolute value of the maximum valley depth (| Rv |) of the surface opposite to the substrate of the patterned photosensitive resin composition layer (| Rv |) is 500 nm or more and the adhesion is improved, step (6) is based on It is better to carry out after step (2) and step (3). That is, it is preferable to peel off a support body before exposure. Since step (6) is performed after step (2) and step (3), step (3) is performed in a state where oxygen is present on the surface opposite to the substrate of the photosensitive resin composition layer. In particular, in the case of a reaction system using a negative-type photopolymerization initiator, radicals of the photopolymerization initiator having a double radical structure, which are generated by oxygen in the air and irradiated with light, are passivated. In particular, this phenomenon is significant on the outermost layer, and the outermost layer of the photosensitive resin composition is not photo-cured. Therefore, a part of the vicinity of the surface can be easily removed by the developer. As a result, it is considered that a predetermined maximum valley depth can be formed on the surface of the patterned photosensitive resin composition layer, and adhesion and shielding properties can be improved.

＜ Other steps ＞
After the printed wiring board is formed with a solder resist, it may further include a hole-opening step and a slag removing step. These steps can be carried out according to various methods used in the manufacture of printed wiring boards and known to those skilled in the art.

After the solder resist is formed, a hole-opening step is performed on the solder resist formed on the substrate according to the desire, so as to form through holes and through holes. The hole-opening step is performed by a well-known method such as drilling, laser, plasma, and the like, and can be combined according to the needs. However, it is opened by a laser using carbon dioxide gas laser, YAG laser, or the like. The hole step is preferred.

The desmearing step is a step of performing desmear treatment. In the inside of the opening portion formed in the hole-opening step, a resin residue (gel residue) is usually attached. Since the above-mentioned slag is a cause of poor electrical connection, a slag removal process (slag scum removal process) is performed in this step.

The desizing treatment can be carried out by a dry desizing treatment, a wet desizing treatment, or a combination thereof.

Examples of the dry-type desmearing treatment include a desmearing treatment using plasma. The desmearing treatment using plasma can be performed using a commercially available plasma desmearing treatment apparatus. Among the commercially available plasma deslagging treatment apparatuses, as examples suitable for the production of printed wiring boards, there are microwave plasma apparatuses manufactured by Nissin Corporation, and atmospheric pressure plasma etching apparatuses manufactured by Sekisui Chemical Industry Co., Ltd.

Examples of the wet desmearing treatment include a desmearing treatment using an oxidant solution. When using an oxidant solution to perform the desmearing treatment, it is preferable to perform a swelling treatment with a swelling solution, an oxidation treatment with an oxidant solution, and a neutralization treatment with a neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate forming a through hole or the like in a swelling solution heated to 60 ° C to 80 ° C for 5 to 10 minutes. The oxidant solution is preferably an alkaline aqueous solution of permanganic acid, and for example, a solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidant solution is preferably performed by immersing the substrate after the swelling treatment in an oxidant solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. Examples of commercially available products of an alkaline permanganic acid aqueous solution include "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment is preferably performed by immersing the substrate after the oxidation treatment in a neutralization solution at 30 ° C. to 50 ° C. for 3 to 10 minutes. The neutralizing liquid is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan.

If the dry-type deslagging treatment and the wet-type deslagging treatment are combined for implementation, the dry-type deslagging treatment may be performed first, or the wet-type deslagging treatment may be performed first.

When an insulating layer is used as an interlayer insulating layer, it can be performed in the same manner as in the case of a solder resist, or a plating step can be performed as needed.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating, and a plating resist having a pattern opposite to that of the conductor layer can also be formed, and only the electroless plating is used to form the conductor layer. As a method for subsequent pattern formation, for example, a subtractive process, a semi-additive process, and the like known to those skilled in the art can be used.

[Hardened matter]
The cured product of the present invention is obtained by curing the photosensitive resin composition layer of the resin composition sheet of the present invention. As described in the item "[Resin sheet]", this cured product is obtained by curing a photosensitive resin composition that satisfies the conditions (I) or (II). Therefore, the surface has a specific maximum after development Depression depth.

The curing conditions of the photosensitive resin composition layer may be conditions generally used when forming an insulating layer of a printed wiring board, and for example, the conditions of the step (5) may be used. In addition, pre-heating may be performed before the resin composition is thermally cured, and a heating system including pre-heating may be performed a plurality of times.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. However, in the following description, "parts" and "%" of amounts are shown,
Unless otherwise specified, the meanings are "mass parts" and "mass%".

(Measurement of the glass transition temperature of the main chain of the component (b))
(b) The glass transition temperature of the main chain of a component is calculated based on the FOX formula shown below.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ・ ・ ・ + (Wm / Tgm)
W1 + W2 + ・ ・ ・ + Wm = 1
Wm represents the content (% by mass) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the (b) component.

(Measurement of (b) component's weight average molecular weight (Mw))
The weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) was made into the weight average molecular weight of (b) component.

(Synthesis example 1: (b) Synthesis of component)
In a 5-neck reaction container with a content of 2 liters, 350 g of methyl isobutyl ketone, 71 g of glycidyl methacrylate, 136 g of butyl acrylate, and 16 g of azobisisobutyronitrile were charged. Heat at 80 ° C for 6 hours. Next, 36 g of acrylic acid, 4 mg of methoquinone, and 4 mg of triphenylphosphine were added to the obtained reaction solution, and heated at 100 ° C. for 24 hours while blowing air. To the obtained reaction mixture, 48 g of tetrahydrophthalic anhydride was added, heated at 70 ° C. for 10 hours, and a solvent was added to obtain a polymer solution (theoretical Tg value of the polymer)
-28 ° C, solid content: 50% by mass, Mw: 18000, acid value: 52mgKOH / g).

<Manufacturing Examples 1 to 3>
Each component is blended according to the blending ratio shown in the table below, and the resin varnish is adjusted using a high-speed rotary mixer.

The abbreviations and the like in the table are as follows.
・ SC2050: Based on 100 parts by mass of fused silica slurry (manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.9 m ² / g), 0.5 parts by mass of amine silane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") Surface treatment and slurry made by adding MEK. The solid content concentration is 70%.
・ ZAR-2000: Bisphenol A epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99mgKOH / g, solid content concentration about 70%)
・ NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 272)
・ IrgacureOXE-02: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoxime)] (manufactured by BASF)
・ Synthesis Example 1: Component (b) synthesized in Synthesis Example 1 ・ DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent of about 96)
・ NV-7-201: Pigment (carbon black, manufactured by Japan Pigment, solid content concentration 20%)

(Measurement of the absolute value of the maximum valley depth of the support)
The maximum valley depth (Rv) of the support was measured using a white light interference microscope (Contoure GT-X series Bruker AXS). The objective lens was set to 50 times, green light was selected, and the measurement range of the surface shape was set to 125 μm × 100 μm. After that, an inclination angle correction is performed by "Terms Removal (F-Operation)" to obtain the absolute value (| Rv |) of the maximum valley depth on the surface of the support.

(Measurement of the arithmetic mean roughness (Ra) of the support)
The arithmetic mean roughness of the support was measured using a non-contact interference microscope (manufactured by WYKO Bruker AXS).

(Measurement of the haze limb of the support)
The haze of the support was measured using a haze meter HZ-V3 (manufactured by Suga Testing Machine Co., Ltd.).

<Example 1>
(Production of support 1)
Using a die coater, uniformly apply a release agent (manufactured by Lintec Corporation, "AL-5") to a PET film (Unitika, "S-25") so that the thickness of the release agent becomes 1 μm. To produce a support 1. When the haze of the support 1 was measured, it was 6%.

((1) Step: Step of preparing resin sheet)
By using a die coater, the resin varnish of the previous Production Example 1 was uniformly coated on the release agent of the support 1 so that the thickness of the dried photosensitive resin composition layer became 20 μm, and Drying is performed at 80 ° C. to 110 ° C. for 5 minutes to obtain a resin sheet having a photosensitive resin composition layer on a smooth PET film.

((2) step: step of laminating a resin sheet on a substrate)
Next, a glass epoxy substrate (copper-clad laminate) on which a patterned copper layer (roughened by the treatment of CZ8100 manufactured by MEC Corporation) was patterned was formed with the previous resin sheet. The photosensitive resin composition layer is arranged so as to be in contact with the surface of the copper circuit, and laminated using a vacuum laminator (manufactured by Nichigo Materials, VP160) to form the above-mentioned copper-clad laminate, and A photosensitive resin composition layer and a laminate formed with the support. The pressing conditions can be set to a vacuum time of 30 seconds, a pressing temperature of 80 ° C, a pressing pressure of 0.7 MPa, and a pressing time of 30 seconds.

((3) Step: a step of exposing the photosensitive resin composition layer)
This laminate was left to stand at room temperature for 30 minutes or more, and subjected to ultraviolet exposure at 250 mJ / cm ² from above the support of the laminate using a pattern forming device adopting a circular hole pattern. (3) The step is performed without peeling off the support. The exposure pattern is an opening: 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm round holes, 120 μm round holes, 200 μm round holes, 250 μm round holes, 500 μm round holes, L / S (line / gap): 50 μm / 50 μm, 60 μm / 60 μm, 70 μm / 70 μm, 80 μm / 80 μm, 90 μm / 90 μm, 100 μm / 100 μm lines and gaps, and a quartz glass mask depicting exposed and unexposed parts with a shape of 1 cm × 2 cm quadrangle . After standing at room temperature for 10 minutes, the support was peeled from the laminate.

((6) Step: Step of peeling the support)
After step (3), the support is manually peeled.

((Measurement of Rv before development and Ra before development))
For the surface state of the exposed portion of the photosensitive resin composition layer after step (3) and before step (4), a white light interference microscope (Contoure GT-X series Bruker AXS) was used, and the objective lens was set to 50 times. The green light was selected and the measurement range of the surface shape was set to 125 μm × 100 μm. After that, the tilt angle correction was performed through "Terms Removal (F-Operation)" to measure the value of the absolute value (A1) of Rv before the development of the surface of the photosensitive resin composition layer. The arithmetic mean roughness (Ra) before development was measured using a non-contact interference microscope (manufactured by WYKO Bruker AXS).

((4) step: a step of forming a patterned photosensitive resin composition layer by development)
After the step (6), the entire surface of the photosensitive resin composition layer on the laminate was spray-developed for 2 minutes by spraying a 1% by mass sodium carbonate aqueous solution at 30 ° C as a developer at a spray pressure of 0.2 MPa to form a developing solution. Patterned photosensitive resin composition layer.

((Measurement of Rv and Ra after development))
After step (4), the absolute value of Rv (A2 on the surface of the patterned photosensitive resin composition layer after development is measured (A2) is the same as ((Measurement of Rv before development and Ra before development)). ) And arithmetic average roughness (Ra) after development. In addition, the ratio (A2 / A1) of the absolute value (A1) of Rv measured before development to the aforementioned A2 was also calculated.

((5) Step: a step of curing the patterned photosensitive resin composition layer)
After the step (4), the surface of the photosensitive resin composition layer was irradiated with ultraviolet rays at 1 J / cm ² , and further heat-treated at 180 ° C. for 30 minutes to form an insulating layer having an opening portion. This was used as a laminate for evaluation.

<Example 2>
In Example 1, step (6) performed after step (3) and step (4) and before step (2) and step (3) were performed. That is, step (3) is performed after the support is peeled. Except for the above matters, the same manner as in Example 1 was used, and Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced at the same time.

<Example 3>
In Example 2, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 2. Except for the above matters, the same method as in Example 2 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

<Example 4>
In Example 1, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 3. Except for the above matters, the same method as in Example 1 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

〈Comparative example 1〉
In Example 1, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 2. Except for the above matters, the same method as in Example 1 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

〈Comparative example 2〉
Example 1 is changed as follows:
1) The resin varnish of Production Example 1 is changed to the resin varnish of Production Example 2, and
2) The support 1 was changed to the support 2 (a PET film mixed with a filler, "PTH-25", manufactured by Unitika, and a haze value of 25%). Except for the above matters, the same method as in Example 1 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

〈Comparative example 3〉
Example 1 is changed as follows:
1) The resin varnish of Production Example 1 is changed to the resin varnish of Production Example 2, and
2) The support 1 was changed to the support 3 (sandblasted PET film, "T60", manufactured by Toray, haze value 70%). Except for the above matters, the same method as in Example 1 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

〈Comparative example 4〉
Example 1 is changed as follows:
1) The resin varnish of Production Example 1 is changed to the resin varnish of Production Example 2, and
2) The support 1 was changed to a support 4 (a PET film coated with a roughening agent, a haze value of 60%). Except for the above matters, the same method as in Example 1 was used to measure Rv before development, Ra before development, Rv after development, and Ra after development, and a laminate for evaluation was also produced.

＜ Evaluation of developability ＞
A 1 cm × 2 cm square portion of the exposed portion of the laminate for evaluation was visually observed. When the resin in the exposed part is not peeled or a part is not dissolved, it is set to "0"; when the resin in the exposed part is peeled or a part is dissolved, or when resin residue is present in the unexposed part, it is set to "0". "△"; when the exposed and unexposed parts cannot be compared, set it to "×".

＜ Evaluation of hole shape and measurement of minimum opening diameter ＞
SEM (Hitachi High-Technology, S-4800) was used to observe (1000 times magnification) each circular hole pattern formed in the evaluation laminate, and the minimum opening diameter (smallest hole diameter) of the circular hole pattern without residue was measured. path). The hole shape (opening shape) of the circular hole pattern was evaluated based on the following criteria.
○: Observing the pattern of round holes at any three points, no overhang or undercut was found.
×: Observing the pattern of round holes at any three points, it was found that there were overhangs or undercuts.

<Evaluation of the shielding (visibility) of wiring>
For the laminated body for evaluation, those who cannot see the pattern by visual observation are set to "0", and those who can see the base pattern are set to "x".

＜ Evaluation of adhesion ＞
(Production of sealing sheet)
4 parts of bisphenol liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A and bisphenol F), and naphthyl ether 10 parts of epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of about 213), 6 parts of bixylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 6 parts 10 parts of biphenyl epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272) and 4 parts of flame retardant ("PX-200" manufactured by Daiba Chemical Industry Co., Ltd.) in solvent oil 20 Parts and a mixed solvent of 10 parts of cyclohexanone were heated and dissolved while stirring. After cooling to room temperature, a cresol novolac-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, a hydroxyl equivalent of about 151, and a 2-methoxypropanol solution with a solid content of 50% was mixed therein. ) 10 parts, 4 parts of a phenol novolac-based hardener containing a triazine skeleton ("LA-7054" manufactured by DIC Corporation, a hydroxyl equivalent of about 125, and a solids content of 60% MEK solution) 4 parts, a naphthol-based hardener (Nippon Steel) "SN-495V" manufactured by Sumikin Chemical Co., Ltd., hydroxyl equivalent of about 231, MEK solution with 60% solids content, 10 parts, amine hardening accelerator (4-dimethylaminopyridine (DMAP), 5 mass% solids MEK solution) 1 part, 220 parts of SC4500 (manufactured by Admatechs) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), uniformly dispersed with a high-speed rotary mixer, and then coated with a die The cloth machine applies a resin varnish uniformly to the thickness of the cured curable resin composition layer after drying to 25 μm, and releases it with an alkyd resin-based release agent ("AL-5" manufactured by Lintec). PET film ("Lumirror T6AM" manufactured by Toray, thickness of 38 μm, softening point of 130 ° C, T ″), and dried at 80 ° C. to 110 ° C. for 4 minutes to obtain a sealing sheet having a curable resin composition layer on the release PET.

The obtained sealing sheet was laminated on each evaluation laminate. Thereafter, heating was performed in an oven at 180 ° C for 90 minutes. A cut of a total of 100 squares of 10 squares × 10 squares was cut at 1 mm intervals on the surface of the obtained curable resin composition layer, and after attaching Saifan tape thereon, the surface was rapidly turned toward a 180 ° angle. Direction to perform peeling. Evaluation is based on the following judgments.
○: No peeling occurred in all the squares.
×: Peeling of at least one resin was observed.

As can be seen from the above table, in Examples 1 to 4, the surface can be roughened without impairing the shape of the opening of the opening, and the maskability of the pattern can be improved or the density of the surface of the patterned photosensitive resin composition layer can be improved.着 性。 Sex.

In Examples 1 to 3, even if the components (e) to (g) were not contained, the results were different, but it was confirmed that the same results were obtained as in the above examples. In addition, in Example 4, even when the components (b) to (g) are not contained, although the degree is different, it is confirmed that the same results as those of the above-mentioned examples are summarized.

10‧‧‧ resin sheet

101‧‧‧ support

101a‧‧‧Side surface of photosensitive resin composition layer side

102‧‧‧ photosensitive resin composition layer

102a‧‧‧ The face that is in contact with the support

102b‧‧‧Developed patterned photosensitive resin composition layer

102c‧‧‧ The side opposite to the substrate side

103‧‧‧ substrate

11‧‧‧ conventional resin sheet

111‧‧‧ support

111a‧‧‧Side surface of photosensitive resin composition layer side

112‧‧‧ photosensitive resin composition layer

112a‧‧‧ The face that is in contact with the support

112b‧‧‧Developed patterned photosensitive resin composition layer

112c‧‧‧ The side opposite to the substrate side

113‧‧‧ substrate

[FIG. 1] FIG. 1 is a schematic cross-sectional view for explaining an example of a resin sheet of the present invention.

[Fig. 2] Fig. 2 is a schematic cross-sectional view showing an example of a case where a resin sheet of the present invention is laminated on a substrate and exposed.

[Fig. 3] Fig. 3 is a schematic cross-sectional view showing an example of appearance when developed using a resin sheet of the present invention.

4 is a schematic cross-sectional view for explaining a conventional resin sheet.

[FIG. 5] FIG. 5 is a schematic cross-sectional view showing a state when a conventional resin sheet is laminated on a substrate and exposed.

[FIG. 6] FIG. 6 is a schematic cross-sectional view showing the appearance when a conventional resin sheet is used for development.

Claims (12)

A method for manufacturing a printed wiring board includes the following steps: (1) a step of preparing a resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support, (2) a step of laminating a resin sheet on a substrate, (3) a step of exposing the photosensitive resin composition layer and (4) a step of forming a patterned photosensitive resin composition layer by development, It is characterized by, The haze of the support is below 20%, The absolute value of the maximum valley depth (| Rv |) of the surface of the support side of the patterned photosensitive resin composition layer after the step (4) is 500 nm or more, The photosensitive resin composition satisfies the following conditions (I) or (II), (I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of (a) component is 60 Above mass%; (II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent. The method for manufacturing a printed wiring board according to claim 1, further comprising (5) a step of curing the patterned photosensitive resin composition layer. The method for manufacturing a printed wiring board according to claim 2, wherein the cured product of the patterned photosensitive resin composition layer is a solder resist. The method for manufacturing a printed wiring board according to claim 1, wherein the photosensitive resin composition is a negative photosensitive resin composition. For example, the method for manufacturing a printed wiring board according to claim 1, wherein if the absolute value of the maximum valley depth of the surface on the support side of the photosensitive resin composition layer after (3) step and before (4) step (| Rv |) is set to A1 (nm), and the absolute value of the maximum valley depth (| Rv |) of the surface of the support side of the patterned photosensitive resin composition layer after step (4) is set to A2 ( nm), the relationship of 3 <A2 / A1 <100 is satisfied. The method for manufacturing a printed wiring board according to claim 1, further comprising (6) a step of peeling the support. The method for manufacturing a printed wiring board according to claim 6, wherein step (6) is performed after step (2) and step (3). A resin sheet having a support and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support, It is characterized by, The haze of the support is below 20%, The absolute value of the maximum valley depth (| Rv |) on the support-side surface of the patterned photosensitive resin composition layer after development is 500 nm or more, The photosensitive resin composition satisfies the following conditions (I) or (II), (I) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more. When the non-volatile content of the photosensitive resin composition is 100% by mass, the content of (a) component is 60 Above mass%; (II) The photosensitive resin composition contains (a) an inorganic filler having an average particle diameter of 0.5 μm or more, (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) photopolymerization Starting agent. The resin sheet according to claim 8, wherein the component (b) contains a (meth) acrylic polymer having a glass transition temperature of -20 ° C or lower. The resin sheet according to claim 8, wherein the photosensitive resin composition layer is used for forming a solder resist. For example, the resin sheet of claim 8, wherein if the absolute value of the maximum valley depth (| Rv |) of the surface on the support side of the photosensitive resin composition layer before development after exposure is set to A1 (nm), When the absolute value of the maximum valley depth (| Rv |) of the surface of the support side of the patterned photosensitive resin composition layer after development is set to A2 (nm), a value of 3 <A2 / A1 <100 is satisfied. relationship. A cured product obtained by curing the photosensitive resin composition layer of the resin sheet according to any one of claims 8 to 11.