TWI830712B - Printed wiring board manufacturing method, resin sheet and hardened product - Google Patents

Abstract

To provide a resin sheet and the like 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, which includes the following steps: (1) preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support; (2) ) the step of laminating the resin sheet on the substrate, (3) the step of exposing the photosensitive resin composition layer and (4) the step of forming the patterned photosensitive resin composition layer by development, the haze of the support is 20% or less, and the absolute value (|Rv|) of the maximum valley depth on the support side of the patterned photosensitive resin composition layer after step (4) is 500 nm or more, the photosensitive resin composition meets the specified Condition (I) or (II).

Description

Printed wiring board manufacturing method, resin sheet and hardened product

The present invention relates to a resin sheet, a method of 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 to prevent solder from adhering to parts that do not require soldering and to prevent corrosion of the circuit board. The solder resist requires adhesion to a sealing material or an underfill material. For example, Patent Document 1 discloses a photosensitive element including a support film and a photosensitive resin composition provided on the support film. The photosensitive layer is formed, and the surface roughness Ra of the surface connecting the supporting film and the photosensitive layer is 200 to 4000 nm.

[Prior technical literature] [Patent Document]

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

In recent years, in response to the increase in density of printed wiring boards, solder resists are required to have better workability or higher performance. As the density of printed wiring boards increases, when various semiconductor chips are mounted and the semiconductor chips are sealed using a sealing material, the contact surface between the sealing material and the solder resist will be reduced. In order to improve the sealing performance, the solder resist is required to be higher. of tight adhesion. Furthermore, when densifying a printed wiring board through 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 a support having surface unevenness is used to transfer the surface unevenness to the photosensitive resin composition layer. However, as will be described later, this method has disadvantages such as distortion of the hole shape due to light scattering during exposure.

An object of the present invention is to provide a resin sheet that can form a cured product that is excellent in adhesion and wiring shielding properties and has a good hole shape; a method for manufacturing a printed wiring board using the resin sheet; and a cured product.

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

That is, the present invention includes the following contents.

[1]. A method of manufacturing a printed wiring board, which includes the following steps: (1) The step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, (2) Steps of laminating resin sheets on the substrate, (3) The steps of exposing the photosensitive resin composition layer and (4) The step of forming a patterned photosensitive resin composition layer by development, Its characteristics are: The haze of the support is below 20%. (4) The absolute value of the maximum valley depth (|Rv|) of the support-side surface 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 with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter. [2]. The manufacturing method of a printed wiring board according to [1], further comprising (5) the step of hardening the patterned photosensitive resin composition layer. [3]. The manufacturing method of a printed wiring board according to [2], wherein the hardened material of the patterned photosensitive resin composition layer is a solder resist. [4]. The method for manufacturing 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 the photosensitive resin composition layer after the step (3) and before the step (4) is placed on the support side The absolute value (|Rv|) of the maximum valley depth on the surface is set to A1 (nm), and the maximum valley depth on the support side of the patterned photosensitive resin composition layer after step (4) is When the absolute value (|Rv|) 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 comprising (6) the step of peeling off the support. [7]. The manufacturing method of a printed wiring board according to [6], wherein step (6) is performed after step (2) and before step (3). [8]. A resin sheet having a support body and a photosensitive resin composition layer including a photosensitive resin composition provided on the support body, Its characteristics are: The haze of the support is below 20%. The absolute value of the maximum valley depth (|Rv|) on the surface of the support side 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 with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter. [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 solder resist formation. [11]. The resin sheet according to any one of [8] to [10], wherein the absolute value of the maximum valley depth on the support side surface of the photosensitive resin composition layer after exposure and before development (|Rv|) is set to A1 (nm), and the absolute value (|Rv|) of the maximum valley depth on the support side surface 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].

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

[The best way to implement the invention]

As shown in FIG. 4 , the conventional resin sheet 11 has a support 111 and a photosensitive resin composition layer 112 provided on the support 111 . The surface 111a of the support 111 on the side of the photosensitive resin composition layer 112 has surface irregularities, and the arithmetic mean roughness Ra of this surface is generally 200~4000 nm, and the haze of the support 111 is generally more than 60%. The surface 112a of the photosensitive resin composition layer 112 on the support 111 side has the above-mentioned surface irregularities of the surface 111a transferred thereto, and the arithmetic mean roughness Ra of the surface 112a is the same as the arithmetic mean roughness Ra of the surface 111a. .

When the conventional resin sheet 11 is used to manufacture a printed wiring board, as shown in FIG. 5 , the conventional resin sheet 11 is first laminated on the substrate 113 . After lamination, a designated portion 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 photocured, that is, photosensitized 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 developed. Thereafter, the developed photosensitive resin composition layer 112b is hardened, and a conductor layer (not shown) is formed thereon. The surface 112c opposite to the surface of the substrate 113 of the developed photosensitive resin composition layer 112b has surface irregularities caused by the support 111, so the adhesion to the conductor layer (not shown) is improved.

The inventor found that when the conventional resin sheet 11 was used for exposure as described above, the active light hν was scattered due to the surface irregularities of the surfaces 111a and 112a, resulting in distortion of the hole shape.

In contrast, the printed wiring board manufactured in the present invention uses a resin sheet having a support and a photosensitive resin composition layer including 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 of the maximum valley depth (|Rv|) on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more.

The inventors of the present invention formed an insulating layer using a resin sheet that satisfies the above-mentioned specific conditions (A) and (B) when manufacturing a printed wiring board, thereby achieving excellent adhesion and shielding properties for wiring, and Via hole with good hole shape. Furthermore, the so-called "support side surface" of the photosensitive resin composition layer refers to the surface facing the support of the photosensitive resin composition layer after the support is peeled off. Generally speaking, it refers to the surface facing the substrate. It is the surface of the photosensitive resin composition layer on the opposite side (which is laminated with the resin sheet).

＜Condition (A)＞ The condition (A) is that the haze of the support is 20% or less. The inventor 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 shown in FIG. 1 , the resin sheet 10 of the present invention has a support 101 and a photosensitive resin composition layer 102 including a photosensitive resin composition provided on the support 101. The haze of the support 101 is is less than 20%. Generally speaking, haze is correlated with the arithmetic mean roughness Ra of the surface 101a of the support on the photosensitive resin composition layer 102 side. If the haze value is reduced, the arithmetic mean roughness Ra value will become lower. Since the haze of the support 101 is 20% or less, unlike the surface 111a of the conventional resin sheet 11, the surface 101a of the support on the side of the photosensitive resin composition layer 102 has small unevenness and is smooth. The surface 102a of the photosensitive resin composition layer 102 on the support 101 side has the surface irregularities of the surface 101a transferred to it, so the surface shape of the surface 102a is also the same as the surface 101a, with the surface irregularities being small and smooth.

When manufacturing a printed wiring board using the resin sheet 10, as shown in FIG. 2, the resin sheet 10 is laminated|stacked on the board|substrate 103, for example. Exposure is performed after lamination. One embodiment of the exposure is to irradiate a designated portion of the photosensitive resin composition layer 102 with active light hν through a mask pattern (not shown), thereby photocuring 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. Therefore, when the active light hν is irradiated during exposure, the scattering of the active light hν can be suppressed. As a result, the distortion of the hole shape can be suppressed, and the scattering of the active light hν can be suppressed, thereby improving the developability. In addition, even when the support 101 is peeled off and then exposed, the surface unevenness of the surface 102a is small and smooth like the surface 101a. Therefore, it is possible to perform the exposure without peeling off the support 101. For the same effect.

The haze of the support 101 is 20% or less, preferably 15% or less, and still more preferably 10%, from the viewpoint of improving hole shape and developability. The lower limit can be, 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 Testing Machine Co., Ltd.

From the viewpoint of improving the hole shape and developability, the absolute value (|Rv|) of the maximum valley depth of the surface 101a of the support 101 is preferably less than 500 nm, more preferably less than 400 nm, 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 type microscope (Contoure GT-X series) manufactured by Bruker AXS.

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

As a supporting system, a resin film is preferred, and examples thereof include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl film. Acetate film, etc., especially polyethylene terephthalate (PET) film is preferred.

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

The surface of these supports on the side bonded to the resin composition layer may be subjected to matting treatment or corona discharge treatment. Moreover, as a support body, the "support body with a release layer" which has a release layer on the surface of the side which joins a photosensitive resin composition layer can be used. In the support 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 polysiloxane resin. More than 1 type of release agent. Examples of commercially available mold release agents include "SK-1", "AL-5", and "AL-7" made by Lintec Corporation, which are alkyd resin-based mold release agents. The support body with a release layer can also be formed by coating a release agent on the support body.

The thickness of the support body is preferably in the range of 5 μm to 50 μm, and further preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, cracking of the support when peeling off the support can be suppressed. By setting the thickness to 50 μm or less, the resolution when exposing from above the support can be improved. In addition, a support with a low fisheye is preferred. Here, the so-called fisheye means that when the material is thermally melted, kneaded, extruded, and a film is produced by biaxial stretching, casting, etc., foreign matter, undissolved matter, oxidative deterioration, etc. of the material enter the film. its meaning.

As mentioned above, the surface unevenness of the surface 101a of the support 101 is transferred to the surface 102a of the photosensitive resin composition layer 102. Therefore, like the surface of the surface 101a, the surface unevenness is small and smooth.

The absolute value (|Rv|) of the maximum valley depth (|Rv|) on the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (described later after (3) step (4) step) improves developability and From the viewpoint of obtaining a good hole shape, the hole diameter is preferably less than 500 nm, more preferably not more than 400 nm, and more preferably not more than 300 nm. 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 type microscope (Contoure GT-X series) manufactured by Bruker AXS. Furthermore, when 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 in the irradiation part of the active light ray. value; if the photosensitive resin composition is a positive photosensitive resin composition, the absolute value of the maximum valley depth is the maximum valley depth on the surface of the photosensitive resin composition layer that is not irradiated with active light rays Absolute value.

As the arithmetic mean roughness Ra of the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (to be described later after (3) step (4) step), it improves developability and achieves a good hole shape. From a viewpoint, the thickness is preferably 100 nm or less, more preferably 80 nm or less, and more preferably 50 nm or less. The lower limit can be, for example, 1 nm or more. The arithmetic mean roughness Ra can be measured using, for example, a non-contact interference microscope (WYKO Bruker) manufactured by AXS Corporation. However, if the photosensitive resin composition is a negative photosensitive resin composition, the arithmetic mean roughness Ra is the arithmetic mean roughness of the surface of the photosensitive resin composition layer in the irradiation part of the active light; if the photosensitive When the resin composition is a positive photosensitive resin composition, the arithmetic mean roughness Ra is the arithmetic mean roughness of the surface of the photosensitive resin composition layer in the portion not irradiated with active light.

Exposure conditions can also be carried out according to conventional exposure conditions, such as those described in the examples described below. Specifically, the method is to irradiate 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 on the surface of the support side of the patterned photosensitive resin composition layer after development is 500 nm or more. The present inventors found that when an insulating layer is formed by exposure and development, the absolute maximum valley depth of the support-side surface of the patterned photosensitive resin composition layer after development (after step (4) is performed) value (|Rv|), which has a great impact on the adhesion and shielding of wiring. Here, the development conditions can also be carried out according to the conventional development conditions, for example, as described in the examples described below, specifically, a 1 mass % sodium carbonate aqueous solution at 30° C. is sprayed with a spray pressure of 0.2 MPa 2 Minute spray development. The so-called patterned photosensitive resin composition layer refers to a patterned photosensitive resin composition layer formed by exposing and developing the photosensitive resin composition layer.

As an example shown in FIG. 3 , the post-exposure photosensitive resin composition layer 102 is developed. One embodiment of development uses a developer to remove the unexposed portions of the photosensitive resin composition layer 102 to form the developed patterned photosensitive resin composition layer 102b. The surface on the support side (the surface opposite to the surface on the substrate 103 side) 102a before development of the photosensitive resin composition layer 102 has small surface irregularities and a smooth surface as described above. However, the image after development In the patterned photosensitive resin composition layer 102b, a part of the surface of the patterned photosensitive resin composition is removed due to the developer used in development, so that the surface 102c of the patterned photosensitive resin composition layer 102b on the support 101 side is removed. The absolute value of the maximum valley depth (|Rv|) becomes 500nm or more. Surface 102c has a specified maximum valley depth, so the adhesion to the conductor layer (not shown) will be improved due to the anchoring effect.

As the absolute value (|Rv|) of the maximum valley depth on the support 101 side surface 102c of the patterned photosensitive resin composition layer 102b after development, from the viewpoint of improving the adhesion and wiring shielding properties It is said to be 500nm or more, preferably 1000nm or more, further preferably 1500nm or more, and the upper limit can be, for example, 10000nm or less. In particular, the maximum valley depth Rv is different from the arithmetic mean roughness Ra. The maximum valley depth Rv is considered to be used to consider the surface adhesion of the patterned photosensitive resin composition layer and the shielding property of the wiring. In terms of performance, it is a better indicator.

The arithmetic mean roughness Ra of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development is preferably 10 nm or more, and further preferably 30 nm, from the viewpoint of improving adhesion. or above, more preferably 50nm or above. 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 after exposure and before development (after (3) step (4) step) is set to A1, and if after development ( When the absolute value of the maximum valley depth of the surface 102c of the patterned photosensitive resin composition layer 102b on the support 101 side is A2, the effect of the present invention can be significantly obtained. , the A2/A1 series is preferably more than 3, more preferably 5 or more, more preferably 10 or more, preferably less than 100, more preferably 70 or less, and more preferably 40 or less.

The resin sheet 10 requires that the absolute value of the maximum valley depth of the surface 102c of the support 101 side of the patterned photosensitive resin composition layer 102b after development satisfies the above range. Therefore, the photosensitive resin composition forming the photosensitive resin composition layer 102 requires that "a part of the components contained in the photosensitive resin composition be removed by the developer used in development ((4) step)". As such a photosensitive resin composition, one that satisfies the following condition (I) or (II) can be used. (I) The photosensitive resin composition contains (a) an inorganic filler with 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 Quality% or more. (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter.

-Condition(I)- Condition (I) is that the photosensitive resin composition contains (a) an inorganic filler with 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 It is more than 60 mass%. When the average particle diameter of the inorganic filler is 0.5 μm or more, part of the inorganic filler can be easily removed by the developer, so the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer can be increased. Furthermore, when the non-volatile component of the photosensitive resin composition is set to 100% by mass, by setting the content of the inorganic filler to 60% by mass or more, a uniform layer can be formed on the entire surface 102c after development. 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 condition (I) may further contain optional components in addition to 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 condition (II), can be contained. Moreover, as further optional components, (e) reactive diluent, (f) reactive diluent, (g) organic solvent, and (h) other additives can be contained as any optional component of condition (II). Each of 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. Mineral, 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, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate, etc. Among these, silica is particularly suitable. As for the silica system, spherical silica is preferred. The inorganic filler system can be used individually by 1 type, or can be used in combination of 2 or more types.

The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, and further preferably 1 μm or more, from the viewpoint of obtaining a cured product that is excellent in developability and has a 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, more preferably 1.5 μm or less, and more preferably 1.3 μm or less from the viewpoint 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 Chemical Industry Co., Ltd., and Nippon Steel & Sumikin Materials "SP(H) series" made by the company, "Sciqas series" made by Sakai Chemical Industry Co., Ltd., "Seahostar series" made by Nippon Shokubai Co., Ltd., "AZ series" and "AX series" made by Nippon Steel & Sumikin Materials Co., Ltd., Sakai Chemical Industrial company-made "B series", "BF series", etc.

The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler using a volume basis, and the median diameter is set as the average particle diameter. to measure. It is better to use the test sample that can disperse the inorganic filler into water through ultrasonic waves. As a laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation, 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 of significantly obtaining the effects of the present invention. 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, the inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate ester compounds. Coupling agent, etc.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM403" (3-glycidoxypropyltrimethylsilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., Shin-Etsu Chemical Industries "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) made by Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) made by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long chain ring) made by Shin-Etsu Chemical Industry Co., Ltd. Oxygen silane coupling agent), etc. The surface treatment agent can be used alone or in combination of two or more types at an arbitrary ratio.

The degree of surface treatment by the surface treatment agent can be evaluated based on the amount of carbon per unit surface area of component (a). From the viewpoint of improving the dispersibility of component (a), the amount of carbon per unit surface area of component (a) is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and particularly preferably 0.2mg/ ^m2 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 sheet form, the carbon amount is preferably 1 mg/m ² or less, and more preferably 0.8 mg/m 2 m ² or less, preferably 0.5 mg/m ² or less.

The amount of carbon per unit surface area of component (a) can be determined by washing the surface-treated component (a) with a solvent (such as methyl ethyl ketone (hereinafter referred to as "MEK")). , for measurement. Specifically, a sufficient amount of methyl ethyl ketone and component (a) surface-treated with a surface treatment agent are mixed, and ultrasonic cleaning is performed at 25° C. for 5 minutes. Thereafter, the supernatant liquid is removed and the solid content is dried, and then the amount of carbon per unit surface area of the component (a) can be measured using a carbon analyzer. As a carbon analyzer system, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

From the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient, when the non-volatile components in the photosensitive resin composition are set to 100 mass %, the content of component (a) is 60 mass % or more, which is less than 60 mass %. Preferably, it is 65 mass % or more, and more preferably, it is 70 mass % or more. From the viewpoint of improving developability, the upper limit is preferably 95 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less. Incidentally, unless otherwise specified in the present invention, the content of each component in the photosensitive resin composition is the value when the non-volatile component in the photosensitive resin composition is 100% by mass.

-Condition(II)- Condition (II) is that the photosensitive resin composition contains (a) an inorganic filler with 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), part of each component in the photosensitive resin composition can be easily removed by the developer, so the maximum valley on the surface of the photosensitive resin composition layer can be increased. The absolute value of depth.

The photosensitive resin composition that satisfies condition (II) may further contain optional components in combination with the components (a) to (d). The optional component system can include, for example, (e) reactive diluent, (f) organic solvent, and (g) other additives. Each component contained in the photosensitive resin composition will be described in detail below.

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

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

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

The inorganic filler (a) with an average particle diameter of 0.5 μm or more used in 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 of obtaining a cured product with a low average linear thermal expansion coefficient, if the non-volatile component in the photosensitive resin composition is 100% by mass, the content of component (a) used in condition (II) It is 10 mass % or more, preferably 20 mass % or more, more preferably 30 mass % or more. From the viewpoint of improving developability, the upper limit is preferably less than 60 mass %, more preferably 55 mass % or less, and still more preferably 50 mass % or less.

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

Examples of the ethylenically unsaturated group include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide group, and nadimide group. , (meth)acrylyl group, from the viewpoint of reactivity in photoradical polymerization, (meth)acrylyl group is preferred. The so-called "(meth)acrylyl group" refers to the meaning of methacrylyl group and acrylyl group.

The component (b) has an ethylenically unsaturated group and a carboxyl group, and can be any compound that can be photoradically polymerized and alkali developable at the same time. For example, a compound having a carboxyl group and two or more ethylenically unsaturated groups can be combined in one molecule. The resin is better.

Examples of resins containing an ethylenically unsaturated group and a carboxyl group include an acid-modified unsaturated epoxy ester resin in which an epoxy compound is reacted with an unsaturated carboxylic acid and 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 the 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. Examples thereof include epoxy group-containing copolymers, bisphenol A-type epoxy resins, hydrogenated bisphenol A-type epoxy resins, and bisphenol F. type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, modified bisphenol F modified to have more than three functions by reacting bisphenol F type epoxy resin with epichlorohydrin Bisphenol-type epoxy resins such as bisphenol-type epoxy resin; biphenyl-type epoxy resins, tetramethylbiphenyl-type and other biphenyl-type epoxy resins; phenol novolak-type epoxy resin, cresol novolak-type epoxy Resins, novolak-type epoxy resins such as bisphenol A-type novolak-type epoxy resins, alkylphenol novolac-type epoxy resins, etc.; bisphenol AF-type epoxy resins, and perfluoroalkyl-type epoxy resins, etc. Fluorine-containing epoxy resin; naphthalene-type epoxy resin, dihydroxynaphthalene-type epoxy resin, polyhydroxybinaphthyl-type epoxy resin, naphthol-type epoxy resin, binaphthol-type epoxy resin, naphthyl ether type Epoxy resins include naphthol novolak-type epoxy resins, naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, and other epoxy resins with a naphthalene skeleton (epoxy resins containing a naphthalene skeleton); Dixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; condensed ring skeleton containing anthracene type epoxy resin, etc. Epoxy resin; glycidyl amine type ring Oxygen 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 resins containing spiro rings; cyclohexanedimethanol-type epoxy resins; trimethylolpropane-type epoxy resins; tetraphenylethane-type epoxy resins; polyglycidyl(meth)acrylate, methacrylic acid Acrylic resins containing glycidyl groups such as copolymers of glycidyl esters and acrylates; fluorine-type epoxy resins; halogenated epoxy resins, etc.

From the viewpoint of reducing the average linear thermal expansion coefficient, the epoxy compound is preferably an epoxy group-containing copolymer or an epoxy resin containing an aromatic skeleton. Here, the so-called aromatic skeleton refers to a concept that also includes polycyclic aromatic and aromatic heterocyclic rings. Epoxy compounds include epoxy resins containing naphthalene skeletons, epoxy resins containing condensed ring skeletons, biphenyl-type epoxy resins, bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, and cresol novolac-type epoxy resins. Epoxy resin and glycidyl ester type epoxy resin are preferred.

The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and any desired monomer. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 2-methyl-3,4 (meth)acrylate. - Epoxy group-containing (meth)acrylate monomers such as epoxycyclohexyl and allyl glycidyl ether, with glycidyl (meth)acrylate being preferred. The epoxy group-containing monosystem can be used alone, or two or more types can be mixed and used.

Examples of the optional monomer include styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and iso(meth)acrylate. Propyl ester, n-butyl (meth)acrylate Ester, 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 (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, Tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, benzyl (meth)acrylate, acrylamide, N, N-dimethyl(meth)acrylamide, (meth)acrylonitrile, 3-(meth)acrylylpropyltrimethoxysilane, (meth)acrylic acid N,N-dimethylamino Ethyl ester, glycidyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth)acrylate, (meth)acrylate 3-hydroxypropyl acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth)acrylate, (meth)acrylate base) 3-hydroxy-n-butyl acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, Polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acrylyl-2-hydroxyethyl phthalate, terminal hydroxyl group Lactone-modified (meth)acrylate, 1-adamantyl (meth)acrylate, etc., with n-butyl (meth)acrylate being preferred. Any single system can be used alone, or two or more types can be mixed and used.

As the epoxy resin containing naphthalene skeleton, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthyl type epoxy resin, polyhydroxynaphthalene and aldehydes are used. The naphthalene type epoxy resin obtained by the condensation reaction is preferred. Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyl etheroxynaphthalene, 1,4-diglycidyl etheroxynaphthalene, 1,5-diglycidyl etheroxynaphthalene, 1, 6-diglycidyl etheroxynaphthalene, 2,3-diglycidyl etheroxynaphthalene, 2,6-diglycidyl etheroxynaphthalene, 2,7-diglycidyl etheroxynaphthalene, etc. Examples of the polyhydroxybinaphthyl epoxy resin include 1,1'-bis-(2-glycidyl etheroxy)naphthyl and 1-(2,7-diglycidyl etheroxy)-1'- (2'-glycidyl etheroxy)binaphthyl, 1,1'-bi-(2,7-diglycidyl etheroxy)naphthyl, etc. Examples of the naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2 ,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, 1,1'-bis(2-glycidyloxynaphthyl)methane.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and the like, and these may be used alone or in combination of two or more types. Among them, acrylic acid and methacrylic acid are preferred from the viewpoint of improving the photocurability of the photosensitive resin composition. Furthermore, in this specification, the epoxy ester resin that is the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid is sometimes described as "epoxy (meth)acrylate". In this specification, the epoxy resin of the epoxy compound is group, resulting in substantial destruction due to reaction with (meth)acrylic acid. The so-called "(meth)acrylate" refers to both methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes 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, and pyromellitic anhydride. Benzophenone tetracarboxylic dianhydride, etc., any one type may be used, or two or more types may be used in combination. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred in terms of improving the resolution and insulation reliability of the hardened product.

When obtaining acid-modified unsaturated epoxy ester resin, catalysts, solvents, polymerization inhibitors, etc. can also be used as needed.

As the acid-modified unsaturated epoxy ester resin, acid-modified epoxy (meth)acrylate is preferred. In the acid-modified unsaturated epoxy ester resin, "epoxy" means a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to an acid-modified product obtained by using bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid. The meaning of sexually unsaturated epoxy ester resin.

The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic acid polymer with a glass transition temperature of -20°C or lower. The (meth)acrylic polymer with a glass transition temperature of -20°C or lower has particularly low compatibility with the component (a) and components (c) to (d) compared to the other components (b). Therefore, the (meth)acrylic polymer is easily phase-separated in the photosensitive resin composition. Therefore, domains containing the (meth)acrylic polymer are generally dispersed and formed in the photosensitive resin composition layer. The area containing the (meth)acrylic acid polymer can be easily removed using a developer. Therefore, after development, unevenness will be generated in the area where the (meth)acrylic acid polymer is removed, so it can be added to the pattern after development. The absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer. A (meth)acrylic acid polymer refers to a structural unit contained in a polymer and has a structure formed by polymerizing a (meth)acrylic acid monomer. Examples of such a (meth)acrylic acid polymer include a polymer obtained by polymerizing a (meth)acrylic acid monomer, or a (meth)acrylic acid monomer and a polymer capable of being combined with the (meth)acrylic acid monomer. A polymer formed by the copolymerization of monomers.

Examples of (meth)acrylic polymers having a glass transition temperature of -20° C. or lower include acid-modified unsaturated epoxy in which an epoxy group-containing copolymer is reacted with (meth)acrylic acid and further reacted with an acid anhydride. (meth)acrylic acid copolymer, etc. In detail, an unsaturated epoxy (meth)acrylic acid copolymer is obtained by reacting a copolymer containing an epoxy group with (meth)acrylic acid, and then the unsaturated epoxy (meth)acrylic acid copolymer is reacted with an acid anhydride, thereby Acid-modified unsaturated epoxy (meth)acrylic acid copolymers can be obtained.

A preferred aspect of the (meth)acrylic polymer having a glass transition temperature of -20°C or less is as follows: a compound containing a ring-containing compound obtained by polymerizing an epoxy group-containing monomer and an optional monomer. A copolymer of oxygen groups, a compound obtained by reacting with (meth)acrylic acid and an acid anhydride, in which the monomer containing an epoxy group is glycidyl methacrylate, an optional monomer is butyl acrylate, and the acid anhydride is tetramethacrylate. Hydrophthalic anhydride.

Commercially available products can be used as such acid-modified unsaturated epoxy ester resins. Specific examples include "ZAR-2000" (bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. Reactant), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" manufactured by Showa Denko Co., Ltd. (Reactant of cresol novolak type epoxy resin, acrylic acid, and acid anhydride), etc. These systems may be used individually by 1 type, or may be used in combination of 2 or more types.

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

Commercially available products can be used as such unsaturated modified (meth)acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko Co., Ltd., and "SPC-3000" manufactured by Daicel-allnex Co., Ltd. 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" etc.

From the viewpoint of film-forming properties, the weight average molecular weight of component (b) is preferably 1,000 or more, more preferably 1,500 or more, and 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 more preferably 7,500 or less. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As for the acid value of component (b), from the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value is preferably 0.1 mgKOH/g or more, and further preferably 0.5 mgKOH/g or more. More than 1 mgKOH/g is more preferable. 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, the acid value is preferably 150 mgKOH/g or less, and is further preferably 120 mgKOH/g or less. , 100mgKOH/g or less is better. Here, the acid value refers to the residual acid value of the carboxyl group present in component (b), and the acid value can be measured by the following method. First, approximately 1 g of the resin solution is accurately weighed and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. 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. Moreover, the acid value was calculated based on the following formula. Formula: A(b)=10×Vf×56.1/(Wp×I)

However, in the above formula, A(b) represents the acid value (mgKOH/g), Vf represents the titer of KOH (mL), Wp represents the measured mass of the resin solution (g), and I represents the measured mass of the resin solution. Proportion of volatile matter (mass %).

In the production of component (b), from the viewpoint of improvement of storage stability, the ratio of the molar number of the epoxy group of the epoxy resin and the molar number of the carboxyl group of the unsaturated carboxylic acid and the acid anhydride is The range of 1:0.8~1.3 is preferred, and the range of 1:0.9~1.2 is further preferred.

From the viewpoint of improving flexibility, the glass transition temperature (Tg) of 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, more preferably -25°C or lower. Here, the glass transition temperature of component (b) refers to the theoretical glass transition temperature of the main chain of component (b). This theoretical glass transition temperature can be calculated by the FOX formula expressed below . The glass transition temperature obtained by the FOX formula is approximately consistent with the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so (b) can also be measured by differential scanning calorimetry. The glass transition temperature of the component's backbone. 1/Tg=(W1/Tg1)+(W2/Tg2)+・・・+(Wm/Tgm) W1+W2+・・・+Wm=1 Wm represents the content (mass %) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (b).

From the viewpoint of improving alkali developability, when the total solid content of the photosensitive resin composition is 100% by mass, the content of component (b) is preferably 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 improving heat resistance or average linear expansion rate, the upper limit is preferably 45 mass% or less, more preferably 40 mass% or less, and more preferably 35 mass% or less. .

((c) Epoxy resin) The photosensitive resin composition satisfying condition (II) contains (c) epoxy resin. By containing component (c), insulation reliability can be improved. However, the component (c) 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 resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; and bisphenol F type epoxy resin. ; Bisphenol S type epoxy resin; Dixylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naphthol novolak type epoxy resin; Phenol novolac type epoxy Resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type epoxy resin; glycidyl amine type epoxy resin; glycidyl ester type epoxy resin; Cresol novolak type epoxy resin; biphenyl type epoxy resin; biphenyl aralkyl type 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 type epoxy resin; naphthyl ether type epoxy resin; trimethylol Propane type epoxy resin; tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. The epoxy resin system can be used individually by 1 type, or can be used in combination of 2 or more types. From the viewpoint of improving insulation reliability and adhesion, biphenyl-type epoxy resin and biphenyl aralkyl-type epoxy resin are preferred as component (c).

(c) The epoxy resin preferably has two or more epoxy groups per molecule. When the non-volatile content of the epoxy resin is 100% by mass, the content of the epoxy resin having two or more epoxy groups per molecule is preferably at least 50% by mass. 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 (hereinafter referred to as "liquid epoxy resins") solid epoxy resin"). The photosensitive resin composition may contain only liquid epoxy resin or may contain only solid epoxy resin as (c) epoxy resin. However, from the viewpoint of improving the insulation reliability of the obtained cured product, Solid epoxy resin is preferred.

As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl ester type epoxy resin. 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 resin with butadiene structure, etc.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL" and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "jER152" (phenol novolac Varnish type epoxy resin); "630" and "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "ZX1059" (bisphenol A type epoxy resin and bisphenol A type epoxy resin) manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. Mixed product of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) made by Nagasechemtex Co., Ltd.; "CELOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) made by Daicel Co., Ltd. ; "PB-3600" manufactured by Daicel Corporation (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These systems may be used individually or in combination of two or more types.

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 is preferred. Resin is better.

Solid epoxy resins include dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type Epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin are further preferred.

Specific examples of solid epoxy resins 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 novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" made by DIC Corporation ", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; manufactured by Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin (biphenyl aralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Oxygen resin)); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Company; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Company; manufactured by Mitsubishi Chemical Company "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin); "YX4000HK" (bixylenol-type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene) made by Mitsubishi Chemical Co., Ltd. Type epoxy resin); "PG-100" and "CG-500" made by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "YL7800" made by Mitsubishi Chemical Co., Ltd. (Fluid type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) made by Mitsubishi Chemical Co., Ltd.; "jER1031S" (tetraphenyl ethane type epoxy resin) made by Mitsubishi Chemical Co., Ltd., etc. These systems may be used individually or in combination of two or more types.

(c) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and even more preferably 110 to 1000. Since it is within this range, the crosslinking density of the cured product of the photosensitive resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. However, it can be measured according to JIS K7236, and 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 100~5000, more preferably 250~3000, and more preferably 400~1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

From the viewpoint of obtaining an insulating layer that has good tensile strength at break strength and exhibits insulation reliability, when the total solid content of the photosensitive resin composition is 100% by mass, the content of component (c) is relatively small. Preferably, it is 1 mass % or more, More preferably, it is 5 mass % or more, More preferably, it is 10 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be exerted, but it is preferably 25 mass% or less, more preferably 20 mass% or less, and more preferably 15 mass% or less.

((d) Photopolymerization initiator) The photosensitive resin composition satisfying condition (II) contains (d) photopolymerization initiator. By containing (d) the 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), 2,4,6-trimethyl Benzyl phosphine oxide photopolymerization initiators such as benzyl-diphenyl-phosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzyl Acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), etc. Oxime ester photopolymerization initiator; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-(dimethylamino)-2 -[(4-methylphenyl)methyl]-[4-(4-morpholyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl ]-2-morpholinopropan-1-one and other α-aminophenylalkyl ketone photopolymerization initiators; benzophenone, methylbenzophenone, o-benzoyl benzoic acid, benzene Formyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide , Ethyl-(2,4,6-trimethylbenzoyl)phenylphosphonite, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl -Phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -Methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; sharp salt photopolymerization initiator, etc. These systems may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of photohardening the photosensitive resin composition more efficiently, phosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred, and oxime ester-based photopolymerization initiators are preferred. It is also preferred to use a photopolymerization initiator.

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

Furthermore, the photosensitive resin composition may also contain N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, and amyl- Tertiary amines such as 4-dimethylaminobenzoate, triethylamine, and triethanolamine are used as photopolymerization starting auxiliaries, or may also include pyrazolines, anthracenes, and coumarins. , xanthone, thioxanthone, etc., to be combined with (d) photopolymerization initiator. Any one of these systems may be used, or two or more types may be used in combination.

From the viewpoint of fully photocuring the photosensitive resin composition and improving insulation reliability, when the non-volatile content of the photosensitive resin composition is 100% by mass, as (d) photopolymerization initiator The content of is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and more preferably 0.3 mass% or more. On the other hand, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity, the upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and more preferably 1.5 mass% or less. Furthermore, when the photosensitive resin composition contains a photopolymerization initiating auxiliary agent, the total content of (d) the photopolymerization initiator and the photopolymerization initiating auxiliary agent is preferably within the above range.

((e) Reactive diluent)

The photosensitive resin composition satisfying condition (II) can further contain (e) a reactive diluent. By containing component (e), photoreactivity can be improved. As the component (e), for example, a photosensitive (meth)acrylate compound that is liquid, solid or semi-solid at room temperature and has one or more (meth)acrylyl groups per molecule can be used. The so-called room temperature refers to about 25°C.

Representative photosensitive (meth)acrylate compounds include hydroxyalkyl acrylates such as tricyclodecane dimethanol diacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; ethanol; Mono- or diacrylate esters of glycols such as glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N,N-dimethylacrylamide, N-hydroxymethylacrylamide, etc. Acrylamides; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; trimethylolpropane, pentaerythritol, dipentaerythritol, dipentaerythritol hexa(meth)acrylate, etc. Polyacrylates of polyols or polyethylene oxide, propylene oxide or ε-caprolactone adducts; phenols such as phenoxy acrylate, phenoxyethyl acrylate, or their epoxy Acrylates such as ethane or propylene oxide adducts; epoxy acrylates derived from glycidyl ether such as trimethylolpropane triglycidyl ether, melamine acrylates, and/or combinations with the above Methacrylates corresponding to acrylates, etc. Among these, polyacrylates or polymethacrylates are preferred. Examples of trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylic acid. Ester, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition to tri(meth)acrylate, glycerol PO addition to 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 trivalent or higher acrylic acid esters or methacrylic acid esters such as (meth)acrylic acid esters of N',N'-4(β-hydroxyethyl)ethyldiamine include tri(2-( Meth)acryloxyethyl)phosphate, tris(2-(meth)acryloxypropyl)phosphate, tris(3-(meth)acryloxypropyl)phosphate Ester, tris(3-(meth)acrylyl-2-hydroxyoxypropyl)phosphate, bis(3-(meth)acrylyl-2-hydroxyoxypropyl)(2-(methyl) (3-(meth)acryloxyethyl)phosphate, (3-(meth)acryloxyethyl)bis(2-(meth)acryloxyethyl)phosphate Phosphate triester (meth)acrylate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more types.

(e) The reactive diluent system can use commercially available products. Specific examples include "DPHA" (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), "DCA-P" (tricyclodecane dimethanol dimethacrylate). Acrylate, Kyeisha Chemical Co., Ltd.), etc.

When the photosensitive resin composition contains (e) a reactive diluent, from the viewpoint of promoting photocuring and suppressing adhesion when the photosensitive resin composition is used as a cured product, if the solid content of the photosensitive resin composition is When the total is 100% by mass, the content of (e) the 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 more preferably 25% by mass. or less, preferably 20% by mass or less, more preferably 15% by mass or less.

((f) organic solvent) The photosensitive resin composition satisfying condition (II) can further contain (f) organic solvent. By containing (f) organic solvent, the viscosity of the varnish can be adjusted. Examples of the (f) organic solvent 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, triethylene glycol monoethyl ether; ethyl acetate Esters such as esters, butyl acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol ether acetate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha , hydrogenated naphtha, solvent oil and other petroleum-based solvents. These systems can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of the coating properties of the resin composition, the content when using an organic solvent can be appropriately adjusted.

((g)Other additives) The photosensitive resin composition satisfying condition (II) can further contain (g) other additives to the extent that the object of the present invention is not hindered. Examples of (g) other additives include ion trapping agents, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, and titanium oxide. , NV-7-201 (manufactured by Japan Pigment Co., Ltd.) and other carbon blacks, naphthalene black and other colorants or pigments, hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, ortho Polymerization inhibitors such as phloroglucinol, thickeners such as bentonite, microcrystalline kaolinite, etc., defoaming agents for polysiloxane, fluorine, and vinyl resins, brominated epoxy compounds, acid-modified brominated Various additives such as flame retardants such as epoxy compounds, antimony compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates, and thermosetting resins such as phenol-based hardeners and cyanate ester-based hardeners.

The photosensitive resin composition may be either a negative photosensitive resin composition or a positive photosensitive resin composition. However, from the viewpoint of improving the physical properties of the photosensitive resin composition layer, in terms of the irradiation during exposure A negative photosensitive resin composition in which a portion becomes a patterned photosensitive resin composition layer is preferred.

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

[Resin sheet] The resin sheet of the present invention has a support body and a photosensitive resin composition layer including a photosensitive resin composition provided on the support body. The haze of the support body is 20% or less. The photosensitive resin composition after development The absolute value of the maximum valley depth (|Rv|) of the support-side surface 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 with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Quality% or more. (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter.

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 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) components as optional components, and according to the needs The resin varnish is produced by kneading or stirring using a kneading means such as a three-roller machine, a ball mill, a bead mill, a sand mixer, or the like, or a stirring means such as a high-speed rotating mixer, a super mixer, or a planetary mixer.

In addition, in the case of condition (II), the photosensitive resin composition can be obtained by mixing the components (a) to (d) and appropriately mixing the above-mentioned (e) to (g) components as optional components. Resin varnish needs to be produced by kneading or stirring using a three-roller machine, ball mill, bead mill, sand mixer, etc., or a high-speed rotating mixer, super mixer, planetary mixer, etc. .

A protective 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 dust or the like from adhering to or scratching the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the above-mentioned support body can be used. The thickness of the protective film is not particularly limited, but it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and more preferably in the range of 10 μm to 30 μm. Furthermore, the protective film is preferably: "The one in which 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 made photosensitive 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. Resin composition layer to produce. Specifically, the bubbles in the resin composition can be completely removed by vacuum degassing, etc., and then the photosensitive resin composition can be coated on the support, and the solvent can be removed using a hot air furnace or a far-infrared furnace. After drying, a protective film is laminated on the obtained photosensitive resin composition layer as necessary to produce a resin sheet. Specific drying conditions vary depending on the hardening properties of the photosensitive resin composition or the amount of organic solvent in the resin varnish. However, for resin varnishes containing 30% to 60% by mass of organic solvents, 80°C to 120°C can be used. Allow 3 to 13 minutes to dry. The amount of residual organic solvent in the photosensitive resin composition layer is preferably 5 mass% or less, and more preferably 2 mass% or less relative to the total amount of the photosensitive resin composition layer. Those with ordinary knowledge in the art can set appropriate and suitable drying conditions through simple experiments.

Examples of coating methods for the photosensitive resin composition include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, and slit coating. Coating method, lip coating method, comma coating method, blade coating method, roller 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 can be applied in divided portions, can be applied once, or can be applied in combination of multiple types. Among them, a die coating method with excellent uniform coating properties is preferred. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to perform the coating step in an environment such as a clean room where foreign matter is rarely generated.

The use of the photosensitive resin composition layer of the resin sheet is not particularly limited. It can be used in circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, and semiconductor sealing. A wide range of materials, hole-filling resins, and part-embedding resins. Among them, it is suitable as a photosensitive resin composition layer for solder resist formation (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 (using a cured product of the photosensitive resin composition layer as a solder resist). A printed wiring board in which a cured product of a photosensitive resin composition layer serves as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board in which a cured product of a photosensitive resin composition layer serves as an interlayer insulating layer), and plating Photosensitive resin composition for coating formation (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition layer).

The photosensitive resin composition forming the photosensitive resin composition layer has excellent developability. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent developability can be obtained. For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, a 1 cm×2 cm quadrangular portion of the exposed portion of the evaluation laminate was visually observed, and it was found that the resin in the exposed portion was not peeled off or partially dissolved.

For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, the residue-free minimum opening diameter (minimum pore diameter) of the laminate 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 it can be set to 50 μm or more.

In addition, when the appearance of the laminate for evaluation was evaluated according to the method described in the examples, generally speaking, no resin component remained in any unexposed portion, and even if holes (openings) were observed at any three points Generally speaking, no overhang or undercut is found in the round hole pattern.

The photosensitive resin composition layer can form a surface with a high absolute value of the maximum valley depth after development, so a cured product with excellent wiring shielding properties can be obtained. Therefore, an insulating layer and a solder resist layer having excellent shielding properties can be obtained. For example, a laminate for evaluation is produced according to the method described in the Examples. In this case, generally speaking, the pattern cannot be seen visually in the laminate for evaluation.

The photosensitive resin composition layer can form a surface with a high absolute value of the maximum valley depth after development, so a cured product with excellent adhesion can be obtained. Therefore, an insulating layer and a solder resist layer having excellent adhesion can be obtained. For example, when a sheet is laminated on a laminate for evaluation according to the method described in the Examples and the adhesion is evaluated according to the method described in the Examples, peeling is generally not found in all squares.

[Manufacturing method of printed wiring board] The manufacturing method of the printed wiring board of the present invention includes the following steps: (1) The step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, (2) Steps of laminating resin sheets on the substrate, (3) The steps 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 the present invention can be manufactured using the aforementioned resin sheet. Regarding the support, the haze of the support, the absolute value of the maximum valley depth of the patterned photosensitive resin composition layer after step (4), and the conditions (I) and conditions (I) satisfied by the photosensitive resin composition II) is as mentioned above. Hereinafter, a case where the cured product of the photosensitive resin composition layer is a solder resist will be described.

＜(1) Step＞ The step (1) is a step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support. The haze of the support system is less than 20%, and the photosensitive resin composition meets the above conditions (I) or (II). Furthermore, the photosensitive resin composition satisfies condition (I) or (II). Therefore, the maximum valley depth of the surface opposite to the substrate side of the patterned photosensitive resin composition layer after step (4) is The absolute value (|Rv|) will be above 500nm. The resin sheet used in the step (1) is as described above.

＜(2) Step＞ (2) The step is to laminate the resin sheet on the substrate. If the resin sheet has a protective film in step (2), remove the protective film and preheat the resin sheet and the substrate as needed, and press the photosensitive resin composition layer on the substrate while pressing and heating it. superior. The resin sheet can be suitably laminated on a substrate under reduced pressure by a vacuum lamination method.

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

(2) The conditions of the step are not particularly limited, but for example, the pressing temperature (laminating temperature) is preferably 70°C to 140°C, and the pressing pressure is preferably 1kgf/cm ² to 11kgf/cm ² (9.8×10 ⁴ N/m ² ~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 below 20mmHg (26.7hPa) It is better to lay it down. Moreover, the lamination step may be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum laminator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. Vacuum laminator, etc. In this way, the 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 the resin sheet is placed on the substrate in step (2), the photosensitive resin composition layer is masked with a mask pattern. A designated portion is irradiated with active light, thereby photo-hardening the photosensitive resin composition layer in the irradiated portion.

Examples of active rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The amount of ultraviolet irradiation is approximately 10mJ/cm ² ~1000mJ/cm ² . The exposure method can be either a contact exposure method in which the mask pattern and the printed wiring board are closely adhered to each other, or a non-contact exposure method in which parallel light is used for exposure without close adhesion.

Since the solder resist uses the aforementioned photosensitive resin composition, it has excellent developability. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width between circuits (space; S) can be 100 μm/100 μm or less (that is, the wiring pitch L /S=60μm/60μm or less (wiring pitch 120μm or less), L/S=50μm/50μm or less (wiring pitch 100μm or less) patterns. In addition, as the exposure pattern, for example, a pattern having openings of circular holes of 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less can be used. . However, the pitch does not need to be the same throughout the circuit substrate.

＜(4) Step＞ (4) The step is a step of forming a patterned photosensitive resin composition layer through development. Specifically, when the photosensitive resin composition is a negative photosensitive resin composition, after the step (3), the surface of the photosensitive resin composition layer is developed to remove unidentified layers by wet development. The photohardened portion (unexposed portion) can form a patterned photosensitive resin composition layer. In addition, the patterned photosensitive resin composition layer satisfies the aforementioned requirements. Therefore, by using the developer used in wet development, the substrate side of the patterned photosensitive resin composition layer after step (4) is opposite to that of the patterned photosensitive resin composition layer. The absolute value (|Rv|) of the maximum valley depth on the side surface will be 500 nm or more.

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

As the developer, a safe, stable and operable developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. can be used. Among them, the development step using an alkali aqueous solution is preferred. In addition, as the development method, well-known methods such as spraying, shaking dipping, brushing, and blade coating can be appropriately adopted.

Alkaline aqueous solutions used as the developer include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; sodium phosphate; Aqueous solutions of alkali metal phosphates such as potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, or aqueous solutions of organic bases such as tetraalkyl ammonium hydroxide that do not contain metal ions do not contain metal ions. In terms of not affecting the semiconductor wafer, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

In order to improve the development effect of these alkaline aqueous solutions, surfactants, defoaming agents, etc. can be added to the developer. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8 to 12, and further preferably in the range of 9 to 11.

Moreover, the alkali concentration of the above-mentioned alkaline aqueous solution is preferably 0.1 mass% or more, more preferably 1 mass% or more, more preferably 5 mass% or more, preferably 50 mass% or less, and more preferably 40 mass%. or less, more preferably 35% by mass or less.

The temperature of the above-mentioned alkaline aqueous solution is appropriately selected according to the developability of the resin composition layer. It is preferably 10°C or higher, more preferably 15°C or higher, more preferably 20°C or higher, and preferably 50°C or lower. The temperature is preferably 45°C or lower, and more preferably 40°C or lower.

Organic solvents used as developers include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethanol, isopropyl alcohol, butanol, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of such an organic solvent is preferably 2 mass % to 90 mass % relative to the total amount of the developer. In addition, the temperature of such an organic solvent can be adjusted according to 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-dimethylformamide, cyclohexanone, methyl Isobutyl ketone, γ-butyrolactone.

In pattern formation, two or more of the above-mentioned developing methods may be used in combination as needed. The methods of development include dipping, stirring, spraying, high-pressure spraying, brushing, tapping, etc. In order to improve the resolution, high-pressure spray method is suitable. The spray pressure when using the spray method is preferably 0.05MPa or more, more preferably 0.1MPa or more, more preferably 0.15MPa or more, preferably 0.5MPa or less, further preferably 0.4MPa or less, and more preferably 0.3 Below MPa.

<(5)Step>

The manufacturing method of the printed wiring board of the present invention can further include (5) the step of hardening 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 step (4) is completed.

The heating conditions can be appropriately selected according to the type and content of the resin component in the resin composition. The preferred range is 150°C to 220°C for 20 minutes to 180 minutes, and the preferred range is 160°C to 200°C. Choose from the range of 30 minutes to 120 minutes. However, before heating, ultraviolet irradiation by a high-pressure mercury lamp or heating steps using a clean oven can also be performed. When irradiating ultraviolet rays, the irradiation dose can be adjusted according to needs. For example, the irradiation dose can be about 0.05J/cm ² ~10J/cm ² .

<(6) Step>

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

The timing of performing step (6) is not particularly limited. For example, it can be performed after step (3) and step (4). From the viewpoint of making the absolute value of the maximum valley depth (|Rv|) on the surface opposite to the substrate of the patterned photosensitive resin composition layer 500 nm or more and improving the adhesion, step (6) is based on It is better to perform step (3) after step (2). That is, it is preferable to peel off the support before exposure. By performing step (6) after step (2) and before step (3), step (3) will be performed under the condition that oxygen exists on the surface opposite to the substrate of the photosensitive resin composition layer. Especially when a reaction system using a negative photopolymerization initiator is used, the free radicals of the photopolymerization initiator with a diradical structure generated by oxygen in the air and irradiation with light will be passivated. This phenomenon is particularly noticeable on the outermost layer, and since the outermost layer of the photosensitive resin composition is in an unphotocured state, a portion near the surface can be easily removed with a developer. As a result, it is considered that a specified maximum valley depth can be formed on the surface of the patterned photosensitive resin composition layer, and the adhesion and shielding properties can be improved.

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

After the solder resist is formed, a hole opening step is performed on the solder resist formed on the substrate as desired, thereby forming through-holes and through-holes. The hole opening step is performed by well-known methods such as drilling, laser, plasma, etc., and these methods can be combined according to the needs. The hole step is better.

The desmearing step is a step of desmearing. Resin residue (smear) usually adheres to the inside of the opening formed in the hole drilling step. Since the above-mentioned smear is the cause of poor electrical connection, a process of removing smear (smear removal process) is performed in this step.

The desmearing treatment can be implemented by dry desmearing treatment, wet desmearing treatment or a combination thereof.

Examples of the dry desmearing process include desmearing using plasma. The desmearing treatment using plasma can be carried out using a commercially available plasma desmearing treatment device. Among commercially available plasma desmear treatment devices, examples suitable for use in manufacturing printed wiring boards include a microwave plasma device manufactured by Nissin Co., Ltd. and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Industry Co., Ltd.

Examples of the wet desmearing treatment include desmearing treatment using an oxidizing agent solution. When using an oxidant solution for desmearing, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidant solution, and 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 the substrate on which via holes or the like is formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, and an example thereof is a solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment by the oxidizing agent solution is preferably performed by immersing the swelling-treated substrate in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline permanganic acid aqueous solutions include "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment by the neutralization liquid is preferably performed by immersing the oxidized substrate in a neutralization liquid at 30°C to 50°C for 3 minutes to 10 minutes. An acidic aqueous solution is preferred as the neutralizing liquid, and an example of a commercially available product is "Reduction solution Securiganth P" manufactured by Atotech Japan.

If a combination of dry desmearing and wet desmearing is performed, the dry desmearing may be performed first or the wet desmearing may be performed first.

When the insulating layer is used as an interlayer insulating layer, it can be performed in the same manner as in the case of solder resist, and the plating step can also 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. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed by electroless plating alone. As a subsequent pattern forming method, for example, a subtractive process, a semiadditive process, etc., which are well known to those skilled in the art, can be used.

[hardened material] 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 explained in the item "[resin sheet]", the hardened material is obtained by hardening the photosensitive resin composition that satisfies the condition (I) or (II). Therefore, the surface has a specific maximum density after development. Valley depth.

The curing conditions of the photosensitive resin composition layer may be those generally used when forming an insulating layer of a printed wiring board. For example, the conditions of the above-mentioned step (5) may be used. In addition, before thermally curing the resin composition, preheating may be performed, and the heating system including preheating may be performed multiple times. [Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. However, in the following description, "parts" and "%" of the amount are expressed. Unless otherwise specified, the meanings are "mass parts" and "mass %" respectively.

((b) Measurement of the glass transition temperature of the main chain of the component) (b) The glass transition temperature of the main chain of the 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 (mass %) of each monomer constituting the component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (b).

((b) Measurement of the weight average molecular weight (Mw) of the component)

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) was defined as the weight average molecular weight of the component (b).

(Synthesis Example 1: (b) Synthesis of Components)

In a 5-neck reaction vessel with an internal capacity of 2 liters, add 350g of methyl isobutyl ketone, 71g of glycidyl methacrylate, 136g of butyl acrylate, and 16g of azobisisobutyronitrile, while blowing in nitrogen. Heating 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 the mixture was 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 is -28°C, solid content: 50 Mass %, Mw: 18000, acid value: 52mgKOH/g).

<Manufacturing Examples 1~3>

Prepare each component according to the proportion shown in the table below, and use a high-speed rotating mixer to adjust the resin varnish.

The abbreviations in the table are as follows.

‧SC2050: 0.5 part by mass of aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") based on 100 parts by mass of molten silica slurry (manufactured by Admatechs, average particle diameter 0.5 μm, specific surface area 5.9 m ² /g) To carry out surface treatment and add MEK slurry. The solid content concentration is 70%.

‧ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration approximately 70%)

‧NC3000H: biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 272)

‧IrgacureOXE-02: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime)( BASF system)

‧Synthesis Example 1: Component (b) synthesized in Synthesis Example 1

・DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic acid equivalent: approximately 96) ・NV-7-201: Pigment (carbon black, manufactured by Japan Pigment Co., Ltd., 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 type microscope (Contoure GT-X series Bruker AXS). The objective lens was set to 50x, green light was selected, and the surface shape measurement range was set to 125 μm × 100 μm. After that, by performing a tilt angle correction through "Terms Removal (F-Operation)", the absolute value of the maximum valley depth (|Rv|) of the surface of the support body is obtained.

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

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

((1) Step: Preparing the resin sheet) By using a die coater, the resin varnish of the previous production example 1 was evenly coated on the release agent of the support 1 so that the thickness of the dried photosensitive resin composition layer became 20 μm, and then Drying was 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 resin sheets on the substrate) Next, a glass epoxy substrate (copper-clad laminate) on which a circuit was formed by patterning a copper layer with a thickness of 18 μm (roughened by treatment with CZ8100 manufactured by MEC Corporation) was used. The photosensitive resin composition layer is arranged so as to be in contact with the surface of the copper circuit, and is laminated using a vacuum laminator (VP160 manufactured by Nichigo Materials Co., Ltd.) to form the aforementioned copper-clad laminate, the aforementioned A laminate composed of a photosensitive resin composition layer and the aforementioned support. The pressing conditions can be set as vacuuming time of 30 seconds, pressing temperature of 80°C, pressing pressure of 0.7MPa, and pressurizing time of 30 seconds.

((3) Step: Exposing the photosensitive resin composition layer) The laminate is left to stand at room temperature for more than 30 minutes, and a pattern forming device that adopts a circular hole pattern is used to remove the laminate from the support of the laminate. UV exposure of 250mJ/ ^cm2 was performed above the body. (3) The step is performed without peeling off the support. The exposure pattern is opening: 50μm, 60μm, 70μm, 80μm, 90μm, 100μm round hole, 120μm round hole, 200μm round hole, 250μm round hole, 500μm round hole, L/S (line/space): Lines and gaps of 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/90μm, 100μm/100μm, and a quartz glass mask depicting exposed and unexposed parts having a 1cm×2cm square shape . After leaving it to stand at room temperature for 10 minutes, the support was peeled off from the laminate.

((6) Step: Step of peeling off the support) After step (3), peel off the support manually.

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

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

((Measurement of Rv after development and Ra after development)) After the step (4), use the same method as ((Measurement of Rv before development and Ra before development)) to measure the absolute value of Rv (A2) on the surface of the patterned photosensitive resin composition layer after development ) and the arithmetic mean roughness (Ra) after development. Furthermore, the ratio of the absolute value of Rv before development (A1) measured in advance to the aforementioned A2 (A2/A1) was also calculated.

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

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

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

＜Comparative example 1＞ In Example 1, the resin varnish of Production Example 1 was changed into the resin varnish of Production Example 2. Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.

＜Comparative example 2＞ Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 2 (PET film mixed with filler, "PTH-25", manufactured by Unitika Co., Ltd., haze value 25%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.

＜Comparative Example 3＞ Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 3 (sandblasted PET film, "T60", manufactured by Toray Co., Ltd., haze value 70%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.

＜Comparative Example 4＞ Modify Example 1 as follows: 1) Change the resin varnish of Production Example 1 to the resin varnish of Production Example 2, and 2) Change the support body 1 to the support body 4 (PET film coated with roughening agent, haze value 60%). Except for the above matters, in the same manner as in Example 1, Rv before development, Ra before development, Rv after development, and Ra after development were measured, and a laminate for evaluation was also produced.

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

＜Evaluation of hole shape and determination of minimum opening diameter＞ Each circular hole pattern formed on the evaluation laminate was observed using SEM (S-4800, manufactured by Hitachi High-Technology Co., Ltd.) (magnification: 1000 times), and the minimum opening diameter of the circular hole pattern without residue (the smallest hole) was measured. diameter). In addition, the hole shape (opening shape) of the circular hole pattern is evaluated based on the following criteria. ○: Observe the round hole pattern at any three points, and no overhang or undercut is found. ×: Observe the circular hole pattern at any three points and find that there are overhangs or undercuts.

<Evaluation of shielding (visibility) of wiring> Regarding the laminate for evaluation, those in which the pattern could not be seen visually were marked as "O", and those in which the pattern of the base was visible were marked as "×".

＜Evaluation of Adhesion＞ (Preparation of sealing sheets) Mix 4 parts of bisphenol type liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), alkylene ether 10 parts of type epoxy resin ("EXA-7311-G4" made by DIC Corporation, epoxy equivalent of about 213), 6 parts of dixylenol type epoxy resin ("YX4000HK" made by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185) , 10 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Industry Co., Ltd., epoxy equivalent approximately 272), and 4 parts of flame retardant ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.), in 20 parts of solvent oil part and 10 parts of cyclohexanone in a mixed solvent while stirring and heating to dissolve. After cooling to room temperature, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50% was mixed with a cresol novolak-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation). ) 10 parts of a phenol novolak-based hardener containing a triazine skeleton ("LA-7054" manufactured by DIC Corporation, a MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%), 4 parts of a naphthol-based hardener (Nippon Steel "SN-495V" manufactured by Sumitomo Chemical Co., Ltd., MEK solution with a hydroxyl equivalent of about 231 and a solid content of 60%) 10 parts, an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid content of 5 mass%) 1 part of MEK solution) and 220 parts of SC4500 (manufactured by Admatechs) that has been surface-treated with an aminosilane coupling agent ("KBM573" produced by Shin-Etsu Chemical Industry Co., Ltd.), dispersed uniformly using a high-speed rotating mixer, and then used die coating Using a cloth machine, the resin varnish is evenly applied to the mold-released surface using an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation) so that the thickness of the curable resin composition layer after drying becomes 25 μm. on a PET film ("Lumirror T6AM" manufactured by Toray Corporation, thickness 38 μm, softening point 130°C, "release PET") and dried at 80°C to 110°C for 4 minutes to obtain hardened release PET Sheet for sealing the flexible resin composition layer.

The obtained sealing sheet was laminated on each evaluation laminate. Thereafter, heating was performed in an oven at 180° C. for 90 minutes. On the surface of the obtained curable resin composition layer, a total of 100 squares of 10 squares × 10 squares were cut at intervals of 1 mm, and after affixing cellulose tape on top, the incisions were quickly made toward the 180° direction for peeling. The evaluation is based on the following judgments. ○: No peeling occurs in all squares. ×: At least one peeling of the resin is observed.

It can be seen from the above table that in Examples 1 to 4, the surface can be roughened without damaging the opening shape of the opening, and the shielding property of the pattern can be improved or the density of the surface of the photosensitive resin composition layer of the pattern can be improved. Attachment.

In Examples 1 to 3, even when components (e) to (g), etc. are not contained, although there are differences in degree, it is confirmed that the results are the same as those in the above-mentioned Examples. In addition, in Example 4, even when components (b) to (g), etc. are not contained, although there is a difference in degree, it was confirmed that the same result as that of the above-mentioned Example can be summarized.

10‧‧‧Resin sheet 101‧‧‧Support 101a‧‧‧Photosensitive resin composition layer side 102‧‧‧Photosensitive resin composition layer 102a‧‧‧The surface connecting with the support body 102b‧‧‧Patterned photosensitive resin composition layer after development 102c‧‧‧The side opposite to the substrate side 103‧‧‧Substrate 11‧‧‧Conventional resin sheets 111‧‧‧Support 111a‧‧‧Photosensitive resin composition layer side 112‧‧‧Photosensitive resin composition layer 112a‧‧‧The surface connecting with the support body 112b‧‧‧Patterned photosensitive resin composition layer after development 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 the resin sheet of the present invention. [Fig. 2] Fig. 2 is a schematic cross-sectional view showing an example of a state in which the 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 a development using the resin sheet of the present invention. [Fig. 4] Fig. 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 in which a conventional resin sheet is laminated on a substrate and exposed. [Fig. 6] Fig. 6 is a schematic cross-sectional view showing how a conventional resin sheet is used and developed.

10:Resin sheet

101:Support

101a: Photosensitive resin composition layer side

102: Photosensitive resin composition layer

102a: Surface connecting with the support body

Claims (12)

A method of manufacturing a printed wiring board, which includes the following steps: (1) The step of preparing a resin sheet having a support and a photosensitive resin composition layer including a photosensitive resin composition provided on the support, (2) Steps of laminating resin sheets on the substrate, (3) The steps of exposing the photosensitive resin composition layer and (4) The step of forming a patterned photosensitive resin composition layer by development, Its characteristics are: The haze of the support is below 20%, The absolute value of the maximum valley depth (|Rv|) on the surface of the support side of the patterned photosensitive resin composition layer after 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 with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter. The method for manufacturing a printed wiring board according to claim 1 further includes (5) the step of hardening the patterned photosensitive resin composition layer. The method of manufacturing a printed wiring board according to claim 2, wherein the hardened material 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. The manufacturing method of a printed wiring board according to claim 1, wherein if the absolute value of the maximum valley depth of the surface of the support side of the photosensitive resin composition layer after the step (3) and before the step (4) is (| Rv|) is set to A1 (nm), and the absolute value of the maximum valley depth (|Rv|) on the support side surface 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 includes (6) the step of peeling off the support. As claimed in claim 6, the method for manufacturing a printed wiring board is wherein step (6) is performed before step (3) after step (2). A resin sheet having a support body and a photosensitive resin composition layer including a photosensitive resin composition provided on the support body, Its characteristics are: The haze of the support is below 20%. The absolute value of the maximum valley depth (|Rv|) on the surface of the support side 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 with an average particle diameter of 0.5 μm or more. When the non-volatile component of the photosensitive resin composition is 100% by mass, the content of component (a) is 60 Mass% or more; (II) The photosensitive resin composition contains (a) an inorganic filler with 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) a photopolymerizable resin. starter. 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. The resin sheet of claim 8, wherein the absolute value (|Rv|) of the maximum valley depth on the support side surface of the photosensitive resin composition layer after exposure and before development is set to A1 (nm), And when the absolute value (|Rv|) of the maximum valley depth on the support side of the patterned photosensitive resin composition layer after development is set to A2 (nm), 3<A2/A1<100 is satisfied relation. A cured product obtained by curing the photosensitive resin composition layer of the resin sheet according to any one of claims 8 to 11.