KR102626371B1 - Method for manufacturing printed wiring board - Google Patents

Abstract

[Problem] Provision of a resin sheet, etc. capable of forming a cured product that has excellent adhesion and wiring shielding properties and has a good via shape.
[Solutions] (1) a step of preparing a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition, (2) a step of laminating the resin sheet on a substrate, (3) photosensitive A process of exposing the resin composition layer to light, and (4) forming a patterned photosensitive resin composition layer through development, wherein the haze of the support is 20% or less, and (4) the support side of the patterned photosensitive resin composition layer after the process. The absolute value (│Rv│) of the maximum valley depth of the surface is 500 nm or more, and the photosensitive resin composition satisfies the predetermined condition (I) or (II).

Description

Manufacturing method of printed wiring board {METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

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

In printed wiring boards, solder resist is provided as a permanent protective film to prevent solder from adhering to unnecessary solder parts and to prevent corrosion of the circuit board. The solder resist is required to have adhesion to the encapsulant or underfill. For example, Patent Document 1 describes a photosensitive element provided with a support film and a photosensitive layer formed on the support film and formed of a photosensitive resin composition, and is provided with electrical support. The film is disclosed as a photosensitive element whose surface in contact with the photosensitive layer has a surface roughness (Ra) of 200 to 4000 nm.

International Publication No. 2015/163455

In recent years, in response to the increase in density of printed wiring boards, improvements in workability and higher performance have also been required for solder resists. As the density of printed wiring boards increases, when sealing semiconductor chips with an encapsulant after mounting various semiconductor chips, the contact surface between the encapsulant and the solder resist is reduced, so the solder resist is required to have higher adhesion to improve encapsulation performance. Additionally, when increasing the density of a printed wiring board through circuit design, it has become important to prevent imitation of the design by shielding the wiring with solder resist.

In order to increase the adhesion of the solder resist, it is conceivable to use a support having surface irregularities, as in Patent Document 1, and to transfer the surface irregularities to the photosensitive resin composition layer. However, as will be described later, this method sometimes causes problems such as distortion of the via shape due to light scattering during exposure.

The object of the present invention is to provide a resin sheet capable of forming a cured product that has excellent adhesion and shielding properties for wiring and has a good via shape; A method for manufacturing a printed wiring board using the resin sheet; and providing a cured product.

As a result of intensive studies to solve the above problem, the present inventors have found that the above problem can be solved by the following structure, and have completed the present invention.

That is, the present invention includes the following contents.

[1] (1) A process of preparing a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition,

(2) a process of laminating a resin sheet on a substrate,

(3) a process of exposing the photosensitive resin composition layer, and

(4) A method for manufacturing a printed wiring board including the step of forming a patterned photosensitive resin composition layer by development,

The haze of the support is less than 20%,

(4) The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after the process is 500 nm or more,

A method for producing a printed wiring board, wherein 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, and the content of component (a) is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass. .

(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 photopolymerization initiator.

[2] The method for producing a printed wiring board according to [1], further comprising the step of (5) curing the patterned photosensitive resin composition layer.

[3] The method for producing a printed wiring board according to [2], wherein the cured product of the pattern photosensitive resin composition layer is a solder resist.

[4] The method for producing a printed wiring board according to any one of [1] to [3], wherein the photosensitive resin composition is a negative photosensitive resin composition.

[5] (3) After the process (4) Before the process The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the photosensitive resin composition layer is set to A1 (nm), and (4) The pattern photosensitive resin after the process When the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the composition layer is set to A2 (nm), any of [1] to [4] satisfies the relationship of 3<A2/A1<100. A method of manufacturing a printed wiring board described in one.

[6] The method for manufacturing a printed wiring board according to any one of [1] to [5], further comprising the step of (6) peeling off the support.

[7] The method for manufacturing 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 and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition,

The haze of the support is less than 20%,

The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development is 500 nm or more,

A resin sheet in which 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, and the content of component (a) is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass. .

(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 photopolymerization initiator.

[9] The resin sheet according to [8], wherein the component (b) contains a (meth)acrylic polymer with 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 for forming a solder resist.

[11] The absolute value (│Rv│) of the maximum valley depth of the support side surface of the photosensitive resin composition layer after exposure and before development is set to A1 (㎚), and the maximum valley depth of the support side surface of the patterned photosensitive resin composition layer after development is set to The resin sheet according to any one of [8] to [10], which satisfies the relationship of 3<A2/A1<100 when the absolute value (│Rv│) of the valley depth is set to A2 (nm).

[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, a resin sheet capable of forming a cured product that has excellent adhesion and shielding properties for wiring and has a good via shape; A method for manufacturing a printed wiring board using the resin sheet; And a cured product can be provided.

1 is a schematic cross-sectional view for explaining an example of the resin sheet of the present invention.
Figure 2 is a schematic cross-sectional view showing an example of the resin sheet of the present invention when laminated on a substrate and exposed to light.
Figure 3 is a schematic cross-sectional view showing an example of the resin sheet of the present invention when developed.
Figure 4 is a schematic cross-sectional view for explaining a conventional resin sheet.
Fig. 5 is a schematic cross-sectional view showing a state when a conventional resin sheet is laminated on a substrate and exposed to light.
Figure 6 is a schematic cross-sectional view showing a state when developed using a conventional resin sheet.

As shown in FIG. 4, the conventional resin sheet 11 has a support body 111 and a photosensitive resin composition layer 112 provided on the support body 111. The surface 111a of the support 111 on the photosensitive resin composition layer 112 side has surface irregularities, and the arithmetic mean roughness (Ra) of the surface is usually 200 to 4000 nm, and the haze of the support 111 is is usually more than 60%. The surface 112a of the photosensitive resin composition layer 112 on the support 111 side has the surface irregularities of the surface 111a transferred, and the arithmetic average roughness Ra of the surface 112a is the surface 111a. ) has the same arithmetic average roughness (Ra).

When manufacturing a printed wiring board using the conventional resin sheet 11, first, the conventional resin sheet 11 is laminated on the substrate 113, as shown in FIG. 5. After lamination, actinic light (hν) is irradiated to a predetermined portion of the photosensitive resin composition layer 112 through a mask pattern (not shown), and the irradiated portion of the photosensitive resin composition layer 112 is photocured, that is, the photosensitive resin composition. The layer 112 is exposed. After exposure of the photosensitive resin composition layer 112, as shown in FIG. 6, the support 111 is peeled off and development is performed. Thereafter, the developed photosensitive resin composition layer 112b is cured, and a conductor layer (not shown) is formed thereon. Since the surface 112c of the developed photosensitive resin composition layer 112b opposite to the surface of the substrate 113 has surface irregularities due to the support 111, adhesion to the conductor layer (not shown) is improved. .

The present inventors have found that when performing exposure using the conventional resin sheet 11 as described above, the actinic light hν is scattered by the surface irregularities of the surface 111a and the surface 112a, and as a result, It was found that the via shape was distorted.

In contrast, in the present invention, a resin sheet that satisfies the following conditions (A) and (B) is used as a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition. This produces a printed wiring board.

(A) The haze of the support is 20% or less.

(B) The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development is 500 nm or more.

The present inventor, when manufacturing a printed wiring board, forms an insulating layer using a resin sheet that satisfies the above-mentioned specific conditions (A) and (B), thereby achieving excellent adhesion and shielding of wiring, and also providing a good via shape. It is possible to form a via hole with . In addition, the "surface on the support side" of the photosensitive resin composition layer refers to the surface of the photosensitive resin composition layer that faces the support after peeling of the support, and usually, the photosensitive surface on the opposite side from the substrate laminated with the resin sheet is used. The surface of the resin composition layer is shown.

<Condition (A)>

Condition (A) relates to the haze of the support being 20% or less. The present inventor found that when forming an insulating layer by exposure phenomenon, the haze of the support greatly affects the adhesion, the shielding properties of the wiring, and the via shape.

As an example is shown in Figure 1, the resin sheet 10 of the present invention has a support body 101 and a photosensitive resin composition layer 102 containing a photosensitive resin composition provided on the support body 101, The haze of the support 101 is 20% or less. The haze is usually correlated with the arithmetic mean roughness (Ra) of the surface 101a on the photosensitive resin composition layer 102 side of the support. When the haze value is lowered, the arithmetic mean roughness (Ra) value is lowered. Since the haze of the support 101 is 20% or less, it is different from the surface 111a of the conventional resin sheet 11, and the surface irregularities of the surface 101a on the photosensitive resin composition layer 102 side of the support are different. is small and has a smooth surface. Since the surface 102a of the photosensitive resin composition layer 102 on the support 101 side has the surface irregularities of the surface 101a transferred, the surface shape of the surface 102a is also irregular like that of the surface 101a. This is a small, smooth surface.

When manufacturing a printed wiring board using the resin sheet 10, the resin sheet 10 is laminated on the substrate 103, as an example is shown in FIG. 2. After lamination, exposure is performed. In one embodiment of exposure, actinic light (hν) is irradiated to a predetermined portion of the photosensitive resin composition layer 102 through a mask pattern (not shown), and the irradiated portion of the photosensitive resin composition layer 102 is photocured. The surface irregularities of the surface 101a and the surface 102a are both small, and since they are smooth surfaces, scattering of the actinic light hν can be suppressed when the actinic light hν is irradiated during exposure. As a result, distortion of the via shape is suppressed, and scattering of actinic light (hν) can be suppressed, thereby improving developability. Furthermore, even in the case where exposure is performed after peeling off the support 101, the surface irregularities of the surface 102a are small and smooth like the surface 101a, so it is the same as when exposure is performed without peeling off the support 101. It can show an effect.

The haze of the support 101 is 20% or less, preferably 15% or less, and more preferably 10% from the viewpoint of improving via 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 Shikenki Co., Ltd.

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 400 nm or less, from the viewpoint of improving the via shape and developability. Preferably it is 300 nm or less. The lower limit can be, for example, 0.1 nm or more. The absolute value of the maximum valley depth of the support can be measured using, for example, a white light interference microscope (Contoure GT-X series) manufactured by Bruker AXS.

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

As the support, a resin film is preferable, and examples include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film, etc., especially polyethylene terephthalate film. This is desirable.

Commercially available supports include, for example, polypropylene films such as product names "AlpanMA-410" and "E-200C" manufactured by Oshi Seishi Corporation and manufactured by Shin-Etsu Film Corporation; Polyethylene terephthalate films such as the PS series, such as product name "S-25" manufactured by Unitika Corporation and "PS-25" manufactured by Teijin Corporation; etc. can be mentioned.

These supports may be subjected to mat treatment or corona treatment on the surface on the side bonded to the resin composition layer. Additionally, as the support, you may use a support with a release layer that has a release layer on the surface of the photosensitive resin composition layer and the side bonded to it. Examples of the release agent used in the release layer of the support with a release layer include one or more types of release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec, which are alkyd resin-based release agents. The support with a release layer may be formed by applying a release agent onto the support.

The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, cracking of the support can be suppressed when peeling off the support, and by setting the thickness to 50 μm or less, resolution when exposing from above the support can be improved. Additionally, a low fisheye support is preferred. Here, the fish eye refers to foreign substances, undissolved substances, oxidation-deteriorated substances, etc. of the material that enter the film when the material is heat-melted and the film is manufactured by kneading, extrusion, biaxial stretching, casting, etc.

As described above, since the surface irregularities of the surface 101a of the support 101 are transferred to the surface 102a of the photosensitive resin composition layer 102, the surface irregularities are small like the surface of the surface 101a, It is a smooth surface.

The absolute value (│Rv│) of the maximum valley depth of the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (after the (3) process and before the (4) process described later) improves the developability and , from the viewpoint of forming a good via shape, it is preferably less than 500 nm, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit can be, for example, 1 nm or more. The maximum valley depth can be measured using, for example, a white light interference microscope (Contoure GT-X series) manufactured by Bruker AXS. In addition, the absolute value of this maximum valley depth is the absolute value of the maximum valley depth of the surface of the photosensitive resin composition layer in the irradiated portion of actinic light when the photosensitive resin composition is a negative photosensitive resin composition, and when the photosensitive resin composition is a positive type photosensitive resin composition In the case of a resin composition, it is the absolute value of the maximum valley depth of the surface of the photosensitive resin composition layer in the unirradiated area of actinic light.

The arithmetic average roughness (Ra) of the surface 102a of the photosensitive resin composition layer 102 after exposure and before development (after the (3) process and before the (4) process described later) shows that the developability is improved and a good via shape is obtained. From this point of view, it is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less. The lower limit can be, for example, 1 nm or more. Arithmetic average roughness (Ra) can be measured, for example, using a non-contact interference microscope (WYKO Bruker) manufactured by AXS. In addition, this arithmetic average roughness (Ra) is the arithmetic average roughness of the surface of the photosensitive resin composition layer in the irradiated portion of actinic light when the photosensitive resin composition is a negative photosensitive resin composition, and when the photosensitive resin composition is a positive type photosensitive resin composition. In this case, it is the arithmetic average roughness of the surface of the photosensitive resin composition layer in the unirradiated area of actinic light.

Exposure conditions may be performed according to conventional exposure conditions, and, for example, as described in the Examples described later, specifically, a method of irradiating ultraviolet rays of 10 mJ/cm 2 or more and 1000 mJ/cm 2 or less is used.

<Condition (B)>

Condition (B) relates to the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development being 500 nm or more. The present inventor found that when forming an insulating layer by performing exposure and development, the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development (after performing step (4)) ) was found to have a significant impact on the adhesion and shielding properties of the wiring. Here, the conditions of development may be performed according to the conditions of conventional development, for example, as described in the examples described later, and specifically, a 1% by mass aqueous sodium carbonate solution at 30° C. is sprayed at a spray pressure of 0.2 MPa. It is a spray phenomenon that sprays for 2 minutes.

The patterned photosensitive resin composition layer refers to a photosensitive resin composition layer in which a pattern is formed by exposing and developing the photosensitive resin composition layer.

As an example is shown in FIG. 3, the photosensitive resin composition layer 102 is developed after exposure. In one embodiment of development, a developing solution is used to remove unexposed portions of the photosensitive resin composition layer 102 and form a patterned photosensitive resin composition layer 102b after development. The surface 102a on the support side (the surface on the opposite side to the surface on the substrate 103 side) before development of the photosensitive resin composition layer 102 is a smooth surface with small surface irregularities as described above, but after development, A part of the patterned photosensitive resin composition layer 102b near the surface of the photosensitive resin composition is removed by the developer used in development, so that the maximum surface 102c of the patterned photosensitive resin composition layer 102b on the support 101 side is removed. The absolute value (│Rv│) of the valley depth is 500㎚ or more. Since the surface 102c has a predetermined maximum valley depth, adhesion to a conductor layer (not shown) is improved by the anchor effect.

The absolute value (│Rv│) of the maximum valley depth of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development is 500 nm or more from the viewpoint of improving adhesion and shielding of wiring. , Preferably it is 1000 nm or more, more preferably 1500 nm or more, and the upper limit can be, for example, 10000 nm or less. In particular, the maximum valley depth (Rv), unlike the arithmetic mean roughness (Ra), is considered a more desirable index for considering the effects of surface adhesion of the patterned photosensitive resin composition layer and shielding of wiring.

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

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) process and (4) before process) is set to A1, and after development (after (4) process) When the absolute value of the maximum valley depth of the surface 102c of the pattern photosensitive resin composition layer 102b on the support 101 side is A2, from the viewpoint of significantly obtaining the effect of the present invention, A2/A1 is preferable. Preferably it exceeds 3, more preferably 5 or more, still more preferably 10 or more, preferably less than 100, more preferably 70 or less, even more preferably 40 or less.

The resin sheet 10 is required to have an absolute value of the maximum valley depth of the surface 102c on the support 101 side of the patterned photosensitive resin composition layer 102b after development that satisfies the above range. For this reason, the photosensitive resin composition forming the photosensitive resin composition layer 102 is required to have some of the components contained in the photosensitive resin composition removed by the developer used in development (step (4)). As such a photosensitive resin composition, one that satisfies the following conditions (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, and the content of the inorganic filler is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass.

(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 photopolymerization initiator.

-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, and the content of the inorganic filler is 60% by mass when the nonvolatile component of the photosensitive resin composition is 100% by mass. It is more than %. If the average particle diameter of the inorganic filler is 0.5 μm or more, a part of the inorganic filler is easily removed by the developer, and the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer can be increased. Additionally, by setting the content of this inorganic filler to 60% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass, it becomes possible to form surface irregularities uniformly on the entire surface 102c after development. As a result, it becomes possible to set the absolute value of the maximum valley depth of the entire surface 102c after development to 500 nm or more.

The photosensitive resin composition that satisfies condition (I) may further contain an arbitrary component in addition to component (a). Optional components may include, for example, the essential components of condition (II), (b) a resin containing an ethylenically unsaturated group and a carboxyl group, (c) an epoxy resin, and (d) a photopolymerization initiator. Additionally, the optional components include the optional components of condition (II). It may contain (e) a reactive diluent, (f) a reactive diluent, (g) an organic solvent, and (h) other additives. Each of these components will be described later.

((a) Inorganic filler with an average particle diameter of 0.5㎛ or more)

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, bismuth titanate, titanium oxide, zirconium oxide, barium titanate. , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Additionally, spherical silica is preferred as the silica. One type of inorganic filler may be used alone, or two or more types may be used in combination.

The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, and more preferably 1 μm or more from the viewpoint of obtaining a cured product that is excellent in developability and has a low average linear thermal swelling ratio. 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 further preferably 1.3 μm or less from the viewpoint of obtaining excellent resolution. Commercially available inorganic fillers having such an average particle diameter include, for example, "SC2050", "SC4050", and "Adoma Fine" manufactured by Adomatex Corporation, "SFP Series" manufactured by Denki Chemical, and Shin-Niptetsu Sumikin. “SP(H) Series” manufactured by Materials, “Sciqas Series” manufactured by Sakai Chemical Co., Ltd., “Sea Poster Series” manufactured by Nippon Shokubai, “AZ Series” and “AX” manufactured by Nippon Shokubai Co., Ltd. series”, “B series” and “BF series” manufactured by Sakai Chemical Industries, etc.

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

The specific surface area of the inorganic filler is preferably 1 m2/g or more, more preferably 2 m2/g or more, and particularly preferably 5 m2/g or more from the viewpoint of significantly obtaining the effects of the present invention. There is no particular limitation on the upper limit, but it is preferably 60 m2/g or less, 50 m2/g or less, or 40 m2/g or less. The specific surface area of the inorganic filler can be measured by the BET method.

The inorganic filler is preferably surface treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. .

Commercially available surface treatment agents include, for example, “KBM22” (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical. “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, “KBM903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical, “KBM573” (N) manufactured by Shin-Etsu Chemical -phenyl-3-aminopropyltrimethoxysilane), “KBM5783” (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical, “SZ-31” (HEXA) manufactured by Shin-Etsu Chemical methyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical, and “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical. Surface treatment agents may be used individually, or two or more types may be used in combination at any ratio.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of component (a). The amount of carbon per unit surface area of component (a) is preferably 0.02 mg/m2 or more, more preferably 0.1 mg/m2 or more, and particularly preferably 0.2 mg/m2, from the viewpoint of improving the dispersibility of component (a). It is more than ㎡. 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 sheet form, the carbon amount is preferably 1 mg/m2 or less, more preferably 0.8 mg/m2 or less, and particularly preferably Typically, it is less than 0.5 mg/㎡.

The amount of carbon per unit surface area of component (a) is determined by washing the surface-treated component (a) with a solvent (e.g., methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). It can be measured. 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 is removed, the solid content is dried, and the amount of carbon per unit surface area of component (a) can be measured using a carbon analyzer. As a carbon analyzer, “EMIA-320V” manufactured by Horiba Seksho Co., Ltd. can be used.

The content of component (a) is 60% by mass or more, preferably 65% by mass or more, when the non-volatile component in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. Preferably it is 70% by 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 even more preferably 75 mass% or less.

In addition, in this invention, unless otherwise specified, content of each component in the photosensitive resin composition is a value when the non-volatile component in the photosensitive resin composition is 100 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) a photopolymerization initiator. Contains. By containing the components (a) to (d) in combination, a part of each component in the photosensitive resin composition becomes easy to be removed by the developer, and the absolute value of the maximum valley depth on the surface of the photosensitive resin composition layer can be increased.

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

((a) Inorganic filler with an average particle diameter of 0.5㎛ or more)

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

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

The average particle diameter of the inorganic filler is as described in “-Condition (I)-”.

The inorganic filler (a) used under condition (II) with an average particle diameter of 0.5 μm or more 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)-”.

The content of component (a) used in condition (II) is 10% by mass or more, preferably 10% by mass or more, when the nonvolatile component in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a low average linear thermal expansion coefficient. is 20% by mass or more, more preferably 30% by 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 even more preferably 50 mass% or less.

((b) Resin containing ethylenically unsaturated group and carboxyl group)

The photosensitive resin composition that satisfies condition (II) contains (b) a resin containing an ethylenically unsaturated group and a carboxyl group.

Examples of ethylenically unsaturated groups include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, and (meth)acryloyl group, From the viewpoint of reactivity of radical photopolymerization, (meth)acryloyl group is preferable. “(meth)acryloyl group” refers to methacryloyl group and acryloyl group.

The component (b) can be any compound that has an ethylenically unsaturated group and a carboxyl group and enables radical photopolymerization and alkaline development. For example, a carboxyl group and two or more ethylene molecules per molecule. A resin that also has a sexually unsaturated group is preferred.

One form of the resin containing an ethylenically unsaturated group and a carboxyl group includes an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting with an acid anhydride. In detail, an unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, an epoxy group-containing copolymer, bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, Bisphenol-type epoxy resins such as bisphenol S-type epoxy resins and modified bisphenol F-type epoxy resins obtained by reacting epichlorohydrin with bisphenol F-type epoxy resins and modifying them to trifunctional or higher levels; Biphenol-type epoxy resins such as biphenol-type epoxy resins and tetramethylbiphenol-type; Novolak-type epoxy resins such as phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol A-type novolak-type epoxy resin, and alkylphenol novolak-type epoxy resin; Fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; Naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, binaphthol type epoxy resin, naphthylene ether type epoxy resin, naphthol novolac type epoxy resin, polyhydroxy Epoxy resins having a naphthalene skeleton, such as a naphthalene-type epoxy resin obtained by a condensation reaction of naphthalene and an aldehyde (epoxy resin containing a naphthalene skeleton); Non-xylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; Epoxy resins containing a condensed ring skeleton such as anthracene type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having a butadiene structure; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spirocyclic-containing epoxy resin; Cyclohexanedimethanol type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin; Acrylic resins containing glycidyl groups, such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylic acid ester; Fluorene type epoxy resin; Halogenated epoxy resin, etc. can be mentioned.

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

An epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and, if necessary, an optional monomer. Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 2-methyl-3,4-epoxycyclohexyl (meth)acrylate, and allyl glycylate. Examples include epoxy group-containing (meth)acrylate monomers such as dil ether, and glycidyl (meth)acrylate is preferred. The epoxy group-containing monomer may be used individually, or two or more types may be mixed.

Optional monomers include, for example, styrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl. (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (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 Latex, dicyclofentanyl (meth)acrylate, benzyl (meth)acrylate, acrylamide, N, N-dimethyl (meth)acrylate, (meth)acrylonitrile, 3-(meth)acryloylpropyltrime Toxysilane, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth) ) Acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth) ) Acrylate, 3-hydroxy-n-butyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, Polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone with a hydroxyl group at the terminal. Modified (meth)acrylate, 1-adamantyl (meth)acrylate, etc. are included, and n-butyl (meth)acrylate is preferable. Arbitrary monomers may be used individually, or two or more types may be mixed.

As the naphthalene skeleton-containing epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxynaphthalene type epoxy resin, and naphthalene type epoxy resin obtained by condensation reaction of polyhydroxynaphthalene and aldehydes are preferable. Examples of dihydroxynaphthalene-type epoxy resins include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, and 1,6-diglycidyloxynaphthalene. Glycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc. are mentioned. Examples of the polyhydroxybinaphthalene type epoxy resin include 1,1'-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-( 2'-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl, etc. can be mentioned. Examples of naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7- diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane and 1,1'-bis(2-glycidyloxynaphthyl)methane.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid, and these may be used individually or in combination of two or more types. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in this specification, the epoxy ester resin, which is a reaction product of the above-mentioned epoxy compound and (meth)acrylic acid, may be described as “epoxy (meth)acrylate”, where the epoxy group of the epoxy compound is (meth)acrylic acid and is practically destroyed by the reaction. “(Meth)acrylate” refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as “(meth)acrylic acid.”

Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid 2. Anhydrides and the like can be mentioned, and any one of these may be used individually or two or more types may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferable in terms of improving resolution and insulation reliability of the cured product.

In obtaining the acid-modified unsaturated epoxy ester resin, catalysts, solvents, polymerization inhibitors, etc. may be used as needed.

As the acid-modified unsaturated epoxy ester resin, acid-modified epoxy (meth)acrylate is preferable. “Epoxy” in acid-modified unsaturated epoxy ester resin refers to a structure derived from the above-described epoxy compound. For example, “acid-modified bisphenol-type epoxy (meth)acrylate” refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth)acrylic acid as an unsaturated carboxylic acid. .

The acid-modified unsaturated epoxy ester resin is preferably a (meth)acrylic polymer with a glass transition temperature of -20°C or lower. In the case of (meth)acrylic polymers with a glass transition temperature of -20°C or lower, the compatibility of component (a) and components (c) to (d) is particularly low compared to the other component (b). Therefore, this (meth)acrylic polymer is prone to phase separation in the photosensitive resin composition. For this reason, domains containing this (meth)acrylic polymer are usually dispersed and formed in the photosensitive resin composition layer. Since the domain containing this (meth)acrylic polymer is easy to remove with a developer, after development, irregularities occur at the locations where the (meth)acrylic polymer was removed, and the maximum valley depth on the surface of the patterned photosensitive resin composition layer after development is The absolute value of can be increased. A (meth)acrylic polymer is a polymer containing a structural unit having a structure formed by polymerizing (meth)acrylic monomers. Examples of such (meth)acrylic polymers include polymers obtained by polymerizing a (meth)acrylic monomer, or polymers obtained by copolymerizing a (meth)acrylic monomer and a monomer copolymerizable with the (meth)acrylic monomer.

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

Preferred forms of the (meth)acrylic polymer with a glass transition temperature of -20°C or lower include an epoxy group-containing copolymer obtained by polymerizing an epoxy group-containing monomer and an arbitrary monomer, and a compound obtained by reacting (meth)acrylic acid and an acid anhydride, wherein the epoxy group-containing monomer is is glycidyl methacrylate, the optional monomer is butylacrylate, and the acid anhydride is tetrahydrophthalic anhydride.

These acid-modified unsaturated epoxy ester resins can be commercially available, and specific examples include "ZAR-2000" (a reaction product of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nihon Kayaku Co., Ltd., "ZFR-1491H", “ZFR-1533H” (reactant of bisphenol F-type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), “PR-300CP” manufactured by Showa Denko (reactant of cresol novolak-type epoxy resin, acrylic acid, and acid anhydride) etc. can be mentioned. These may be used individually or in combination of two or more types.

As another form of the resin containing an ethylenically unsaturated group and a carboxyl group, an ethylenically unsaturated group is introduced by reacting an epoxy compound containing an ethylenically unsaturated group with a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid. and unsaturated modified (meth)acrylic resin. Epoxy compounds containing ethylenically unsaturated groups include, for example, glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate. I can hear it. It is also possible to react an acid anhydride with the hydroxyl group generated upon introduction of an unsaturated group. As the acid anhydride, the same acid anhydride as the above-mentioned acid anhydride can be used, and the preferable range is also the same.

These unsaturated modified (meth)acrylic resins can be commercially available, and specific examples include “SPC-1000” and “SPC-3000” manufactured by Showa Denko, and “Cychroma P (ACA)” manufactured by Daicel Ornex. Z-250”, “Cychroma P(ACA)Z-251”, “Cychroma P(ACA)Z-254”, “Cychroma P(ACA)Z-300”, “Cychroma P(ACA)Z- 320”, etc.

The weight average molecular weight of the component (b) is preferably 1000 or more, more preferably 1500 or more, and still more preferably 2000 or more from the viewpoint of film forming properties. The upper limit is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7500 or less from the viewpoint of developability. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the acid value of the 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, more preferably 0.5 mgKOH/g or more, and 1 mgKOH/g or more. It is more desirable. On the other hand, from the viewpoint of suppressing elution of the fine pattern of the cured product by development and improving insulation reliability, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and 100 mgKOH It is more preferable that it is /g or less. 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, after measuring approximately 1 g of the resin solution, 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein, an indicator, is added to the solution, and titration is performed using a 0.1N KOH aqueous solution. Then, the acid value is calculated by the following formula.

Formula: A(b)=10×Vf×56.1/(Wp×I)

In addition, in the above formula, A(b) represents the acid value (mgKOH/g), Vf represents the appropriate amount of KOH (mL), Wp represents the mass of the measured resin solution (g), and I represents the measured resin solution. It represents the ratio (mass %) of non-volatile matter.

In the production of component (b), from the viewpoint of improving storage stability, the ratio of the number of moles of the epoxy group of the epoxy resin to the number of moles of the carboxyl group of the sum of the unsaturated carboxylic acid and the acid anhydride is preferably in the range of 1:0.8 to 1.3, It is more preferable that it is in the range of 1:0.9 to 1.2.

The glass transition temperature (Tg) of the component (b) is preferably -300°C or higher, more preferably -200°C or higher, further preferably -80°C or higher from the viewpoint of improving flexibility, and preferably -20°C or lower, more preferably -23°C or lower, and even more preferably -25°C or lower. Here, the glass transition temperature of component (b) is the theoretical glass transition temperature of the main chain of component (b), and this theoretical glass transition temperature can be calculated using the FOX equation shown below. Since the glass transition temperature determined by FOX's equation is almost identical to the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), the main chain of component (b) is released by differential scanning calorimetry. You may measure the transition temperature.

1/Tg=(W1/Tg1)+(W2/Tg2)+… +(Wm/Tgm)

W1+W2+… +Wm=1

Wm represents the content (mass %) of each monomer constituting component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting component (b).

From the viewpoint of improving alkali developability, the content of component (b) is preferably 20% by mass or more, and more preferably 25% by mass or more when the total solid content of the photosensitive resin composition is 100% by mass. And, it is more preferable to set it to 30% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less from the viewpoint of improving heat resistance and average linear thermal expansion coefficient.

((c) epoxy resin)

The photosensitive resin composition that satisfies condition (II) contains (c) epoxy resin. By containing the component (c), insulation reliability can be improved. However, component (c) herein does not contain an epoxy resin containing an ethylenically unsaturated group and a carboxyl group.

(c) Examples of the component include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and pafluoroalkyl type epoxy resin; Bisphenol A type epoxy resin; Bisphenol F-type epoxy resin; Bisphenol S-type epoxy resin; Non-xylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naphthol novolac 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; Glycidylamine 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 having a butadiene structure; Alicyclic epoxy resin; Alicyclic epoxy resin having an ester skeleton; Heterocyclic epoxy resin; Spirocyclic-containing epoxy resin; Cyclohexanedimethanol type epoxy resin; Naphthylene ether type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. are mentioned. Epoxy resins may be used individually, or two or more types may be used in combination. The component (c) is preferably a biphenyl type epoxy resin or biphenyl aralkyl type epoxy resin from the viewpoint of improving insulation reliability and adhesion.

(c) The epoxy resin preferably has two or more epoxy groups per molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (sometimes referred to as “solid epoxy resins”). there is. The photosensitive resin composition may contain only a liquid epoxy resin or a solid epoxy resin as the (c) epoxy resin; however, from the viewpoint of increasing the insulation reliability of the resulting cured product, a solid epoxy resin is preferable.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins 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, glycidylamine-type epoxy resin, and phenol novolak-type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER807” and “1750” (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER152” (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630” and “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Tetsu Sumiking Chemical Co., Ltd. (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Ceroxide 2021P” manufactured by Daicel (alicyclic epoxy resin with an ester skeleton); “PB-3600” manufactured by Daicel Corporation (epoxy resin with a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Tetsu Sumiking Chemicals, etc. are included. These may be used individually or in combination of two or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable.

Examples of the solid epoxy resin include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, Phenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin Epoxy resin and biphenyl aralkyl type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation; “N-695” (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; “EXA-7311,” “EXA-7311-G3,” “EXA-7311-G4,” “EXA-7311-G4S,” and “HP6000” manufactured by DIC (naphthylene ether type epoxy resin); “EPPN-502H” manufactured by Nihon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy resin (biphenyl aralkyl type epoxy resin)) manufactured by Nihon Kayaku Co., Ltd.; "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Tetsu Sumiking Chemical Co., Ltd.; “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Tetsu Sumiking Chemicals; “YX4000H”, “YX4000”, and “YL6121” (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals; “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These 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, further preferably 80 to 2000, and even more preferably 110 to 1000. By falling within this range, the crosslinking density of the cured product of the photosensitive resin composition becomes sufficient and an insulating layer with small surface roughness can be produced. In addition, the epoxy equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of an epoxy group.

(c) The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 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).

The content of component (c) is preferably 1 mass% or more, more preferably 1 mass% or more, when the total solid content of the photosensitive resin composition is 100 mass%, from the viewpoint of obtaining an insulating layer showing good tensile fracture strength and insulation reliability. It is 5 mass% or more, more preferably 10 mass% or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, but is preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.

((d) Photopolymerization initiator)

The photosensitive resin composition that satisfies condition (II) contains (d) a photopolymerization initiator. (d) By containing a photopolymerization initiator, the photosensitive resin composition can be efficiently photocured.

(d) Any compound can be used as the photopolymerization initiator, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), 2,4,6-trimethylbenzoyl-diphenyl-phos Acylphosphine oxide-based photopolymerization initiators such as pin oxide; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime), ethane, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -1]-, 1-(O-acetyloxime), and other oxime ester photopolymerization initiators; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morph α-aminoalkylphenone-based photopolymerization initiators such as polynyl)phenyl]-1-butanone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; Benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetphenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine Oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy -1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2 ,4,6-trimethylbenzoyl)-phenylphosphine oxide; and sulfonium salt-based photopolymerization initiators. These may be used individually, or two or more types may be used together. Among these, from the viewpoint of photocuring the photosensitive resin composition more efficiently, an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator are preferable, and an oxime ester-based photopolymerization initiator is more preferable.

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

In addition, the photosensitive resin composition is combined with (d) a photopolymerization initiator and, as a photopolymerization initiation aid, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-dimethylaminobenzoate. It may contain tertiary amines such as ate, triethylamine, and triethanolamine, and may contain photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones. Any one of these may be used individually or two or more types may be used together.

(d) The content of the photopolymerization initiator is preferably 0.01% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability. Preferably it is 0.1 mass% or more, 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 even more preferably 1.5 mass% or less. In addition, when the photosensitive resin composition contains a photopolymerization initiation aid, it is preferable that the total content of (d) the photopolymerization initiator and the photopolymerization initiation aid is within the above range.

((e) Reactive diluent)

The photosensitive resin composition satisfying condition (II) may further contain (e) a reactive diluent. By containing the 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)acryloyl groups per molecule can be used. Room temperature refers to approximately 25°C.

Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as tricyclodecane dimethanol diacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; Mono or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, and dipentaerythritol hexa(meth)acrylate, or polyacrylates of these adducts with ethylene oxide, propylene oxide, or ε-caprolactone; phenols such as phenoxyacrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof; Examples include epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and/or methacrylates corresponding to the above acrylates. Among these, polyhydric acrylates or polyhydric methacrylates are preferable. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Rate, trimethylolpropane EO addition tri(meth)acrylate, glycerin PO addition tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethylcarbitol oligo(meth)acrylate ) Acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropan oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethyl Olmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (meth)acrylic acid ester of N,N,N',N'-tetrakis(β-hydroxyethyl)ethyldiamine, etc. Examples of trivalent or higher acrylates or methacrylates include tri(2-(meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl)phosphate, and tri(3-( Meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl)phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2 -(meth)acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth)acryloyloxyethyl)phosphate, etc. Phosphate triesters (meth) ) Acrylates can be mentioned. These photosensitive (meth)acrylate compounds may be used individually or in combination of two or more types.

(e) The reactive diluent can be a commercially available product, and specific examples include “DPHA” (dipentaerythritol hexaacrylate, manufactured by Nihon Kayaku Co., Ltd.) and “DCA-P” (tricyclodecane dimethanol diacrylate, manufactured by Kyoesha). (manufactured by Kagaku Corporation), etc. are mentioned.

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

((f) organic solvent)

The photosensitive resin composition that satisfies condition (II) may further contain (f) an organic solvent. (f) The varnish viscosity can be adjusted by containing an organic solvent. (f) Examples of the organic solvent include ketones such as ethylmethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate; Aliphatic hydrocarbons such as octane and decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. These are used individually or in combination of two or more types. When using an organic solvent, the content can be adjusted appropriately from the viewpoint of the applicability of the resin composition.

((g) Other additives)

The photosensitive resin composition that satisfies condition (II) may further contain (g) other additives to an extent that does not impair the purpose of the present invention. (g) Other additives include, for example, ion trapping agents, thermoplastic resins, organic fillers, melamine, fine particles such as organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, Colorants and pigments such as carbon black such as NV-7-201 (manufactured by Nihon Pigment Co., Ltd.) and naphthalene black, hydroquinone, phenothiazine, methylhydroquinone, hydroquinonomonomethyl ether, catechol, pyrogallol, etc. polymerization inhibitors, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, vinyl resin-based defoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, and other flame retardants, phenol-based Various additives such as curing agents, thermosetting resins such as cyanate ester-based curing agents, etc. can be mentioned.

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, the irradiated portion during exposure becomes the patterned photosensitive resin composition layer. It is preferable that it is a composition.

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 10 μm to 200 μm from the viewpoint of improving handleability and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer. It is more preferable to set it in the range of ㎛, more preferably in the range of 15㎛ to 150㎛, even more preferably in the range of 20㎛ to 100㎛, especially in the range of 20㎛ to 60㎛. It is more desirable.

[Resin sheet]

The resin sheet of the present invention is a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition, the haze of the support is 20% or less, and the support side of the photosensitive resin composition layer after development is The absolute value (│Rv│) of the maximum valley depth of the surface 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, and the content of component (a) is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass. .

(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 photopolymerization initiator.

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 conditions (II) that the photosensitive resin composition satisfies are as described above.

In the case of condition (I), the photosensitive resin composition is prepared 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, if necessary, three rolls, It can be manufactured as a resin varnish by kneading or stirring using a kneading means such as a ball mill, bead mill, or sand mill, or a stirring means such as a high-speed rotating mixer, super mixer, or planetary mixer.

In addition, in the case of condition (II), the photosensitive resin composition is prepared by mixing components (a) to (d), and appropriately mixing the components (e) to (g) as optional components, and, if necessary, three components. It can be manufactured as a resin varnish by kneading or stirring using a kneading means such as a roll, ball mill, bead mill, or sand mill, or a stirring means such as a high-speed rotating mixer, super mixer, or planetary mixer.

The photosensitive resin composition layer may be protected with a protective film. By protecting the photosensitive resin composition layer side of the resin sheet with a protective film, adhesion of dust or the like to the surface of the photosensitive resin composition layer and scratches can be prevented. As a protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. In addition, it is preferable that the protective film has a smaller adhesive force between the photosensitive resin composition layer and the support than the adhesive force between the photosensitive resin composition layer and the support.

The resin sheet of the present invention is prepared by, for example, preparing a resin varnish in which a photosensitive resin composition is dissolved in an organic solvent, applying this resin varnish on a support, drying the organic solvent by heating or spraying hot air, etc. to form a photosensitive resin composition layer. It can be manufactured by forming. Specifically, first, after completely removing the bubbles in the resin composition by a vacuum degassing method or the like, the photosensitive resin composition is applied onto the support, the solvent is removed using a hot stove or a far-infrared ray furnace, and the resulting photosensitive resin composition is dried, if necessary. A resin sheet can be manufactured by laminating a protective film on the resin composition layer. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish, but for resin varnishes containing 30% by mass to 60% by mass of organic solvent, 3 minutes at 80°C to 120°C. It can be dried for 13 minutes. The amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total amount of the photosensitive resin composition layer. A person skilled in the art can appropriately set suitable drying conditions through simple experimentation.

Application methods of the photosensitive resin composition include, for example, gravure coat method, microgravure coat method, reverse coat method, kiss reverse coat method, die coat method, slow die method, lip coat method, comma coat method, blade coat method, Examples include roll coat method, knife coat method, curtain coat method, chamber gravure coat method, slot orifice method, spray coat method, and dip coat method.

The photosensitive resin composition may be applied several times, may be applied once, or may be applied by combining multiple different methods. Among these, the die coat method, which is excellent in uniform applicability, is preferable. Additionally, in order to avoid contamination of foreign substances, it is desirable to carry out the application process in an environment with low occurrence of foreign substances, such as a clean room.

The use of the photosensitive resin composition layer of the resin sheet is not particularly limited, but can be used for circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resist, underfill material, die bonding material, semiconductor encapsulant, hole filling resin, and component filling resin. etc. can be used widely. Among these, the photosensitive resin composition layer for forming solder resist (printed wiring board using the cured product of the photosensitive resin composition layer as the solder resist), the photosensitive resin composition for the insulating layer of the printed wiring board (printer using the cured product of the photosensitive resin composition layer as the insulating layer) wiring board), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board using the cured product of the photosensitive resin composition layer as an interlayer insulating layer), and a photosensitive resin composition for forming plating (a printed wiring board with plating formed on the cured product of the photosensitive resin composition layer). It can be used appropriately.

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 excellent in developability can be obtained. For example, a laminate for evaluation is produced by the method described in the Examples. In this case, a 1 cm x 2 cm square portion of the exposed portion of the laminate for evaluation was observed with the naked eye, and the resin in this exposed portion was not peeled off or partially dissolved.

For example, a laminate for evaluation is produced by the method described in the Examples. In this case, the minimum opening diameter (minimum via diameter) without residue in the evaluation laminate is preferably 200 μm or less, more preferably 150 μm or less, further preferably 130 μm or less, and 100 μm or less. The lower limit is not particularly limited, but may be 50 μm or more.

In addition, when the appearance of the evaluation laminate is evaluated by the method described in the Examples, generally, no resin component remains in any unexposed portion, and even if the round hole pattern of any three points of the via (opening portion) is observed, Normally, no overhang or undercut appears.

Since the photosensitive resin composition layer can form a surface with a high absolute value of maximum valley depth after development, a cured product excellent in shielding properties for wiring can be obtained. Therefore, an insulating layer and a solder resist layer with excellent shielding properties can be obtained. For example, a laminate for evaluation is produced by the method described in the Examples. In this case, usually, in the laminate for evaluation, the pattern is not visible to the naked eye.

Since the photosensitive resin composition layer can form a surface with a high absolute value of maximum valley depth after development, a cured product with excellent adhesion can be obtained. Therefore, an insulating layer and a solder resist layer with excellent adhesion can be obtained. For example, when a sheet is laminated on a laminate for evaluation by the method described in the Example and the adhesion is evaluated by the method described in the Example, peeling is usually not confirmed in any of the masses.

[Manufacturing method of printed wiring board]

The method for manufacturing a printed wiring board of the present invention is:

(1) A process of preparing a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition,

(2) a process of laminating a resin sheet on a substrate,

(3) a process of exposing the photosensitive resin composition layer, and

(4) A method for producing a printed wiring board including the step of forming a patterned photosensitive resin composition layer by development.

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

<(1) Process>

The step (1) is a step of preparing a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition. The support has a haze of 20% or less, and the photosensitive resin composition satisfies the above-mentioned conditions (I) or (II). In addition, since the photosensitive resin composition satisfies condition (I) or (II), (4) the absolute value (│Rv│) of the maximum valley depth on the surface of the patterned photosensitive resin composition layer opposite to the substrate side after the process is 500 It becomes more than ㎚. (1) The resin sheet used in the process is as described above.

<(2) Process>

(2) The process is a process of laminating a resin sheet on a substrate. In step (2), if the resin sheet has a protective film, the protective film is removed, and then the resin sheet and substrate are preheated as needed, and the photosensitive resin composition layer is pressed to the substrate while being pressed and heated. For the resin sheet, a method of laminating it to a substrate under reduced pressure by a vacuum lamination method is suitably used.

The substrate is preferably a circuit board having a conductor layer (circuit) patterned on one or both sides. Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a board in which one or both sides of the outermost layer of the multilayer printed wiring board is patterned with a conductor layer (circuit) is also included in the circuit board herein. . Additionally, the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, etc.

(2) The conditions of the process are not particularly limited, but for example, the pressing temperature (lamination temperature) is preferably 70°C to 140°C, and the pressing pressure is preferably 1 kgf/cm2 to 11 kgf/cm2 ( 9.8×10 ⁴ N/m2 to 107.9×10 ⁴ N/m2), the pressing time is preferably 5 to 300 seconds, and it is preferable to laminate under reduced pressure with air pressure of 20 mmHg (26.7 hPa) or less. . Additionally, the lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Sesakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. In this way, the resin sheet is laminated on the substrate.

<(3) Process>

The (3) process is a process of exposing the photosensitive resin composition layer after the (2) process. Specifically, when the photosensitive resin composition is a negative photosensitive resin composition, in step (2), after the resin sheet is installed on the substrate, actinic light is irradiated to a predetermined portion of the photosensitive resin composition layer through a mask pattern, The photosensitive resin composition layer of the irradiated area Light cure.

Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is approximately 10mJ/cm2 to 1000mJ/cm2. The exposure method includes a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without bringing the mask pattern into close contact with the printed wiring board. Either method may be used.

Since the solder resist uses the photosensitive resin composition described above, it has excellent developability. For this reason, as an exposure pattern in a mask pattern, for example, the ratio (L/S) of the circuit width (line; L) to the width (space; S) between circuits is 100 μm/100 μm or less (i.e., wiring Pitch 200㎛ or less), L/S=90㎛/90㎛ or less (wiring pitch 180㎛ or less), L/S=80㎛/80㎛ or less (wiring pitch 160㎛ or less), L/S=70㎛/70 Patterns of ㎛ or less (wiring pitch 140㎛ or less), L/S=60㎛/60㎛ or less (wiring pitch 120㎛ or less), L/S=50㎛/50㎛ or less (wiring pitch 100㎛ or less) can be used. do. In addition, the exposure pattern includes, for example, a pattern of a round hole with an opening of 100 μm or less, a round hole of 90 μm or less, a round hole of 80 μm or less, a round hole of 70 μm or less, a round hole of 60 μm or less, and a round hole of 50 μm or less. Available. Additionally, the pitch need not be the same throughout the circuit board.

<(4) Process>

The (4) 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, (3) after the process, the portion that has not been photocured (unexposed portion) is removed by wet development on the surface of the photosensitive resin composition layer and developed, A patterned photosensitive resin composition layer can be formed. In addition, since the patterned photosensitive resin composition layer satisfies the above-mentioned requirements, the developer used for wet development determines (4) the absolute value of the maximum valley depth of the surface of the patterned photosensitive resin composition layer after the process opposite to the substrate side. (│Rv│) becomes 500 nm or more.

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

As a developer, a developer that is safe, stable, and has good operability, such as an aqueous alkaline solution, an aqueous developer, or an organic solvent, is used, and among these, a development process using an aqueous alkaline solution is preferable. Additionally, as a developing method, known methods such as spraying, shaking immersion, brushing, and scraping are appropriately employed.

Examples of the alkaline aqueous solution used as a developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, and sodium pyrrolinate. , an aqueous solution of an alkali metal pyrrolate such as potassium pyrrolate, or an aqueous solution of an organic base containing no metal ions such as tetraalkylammonium hydroxide, which does not contain metal ions and does not affect the semiconductor chip. In this regard, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable.

To these alkaline aqueous solutions, surfactants, antifoaming agents, etc. can be added to the developing solution to improve the developing effect. The pH of the alkaline aqueous solution is preferably, for example, in the range of 8 to 12, and more preferably in the range of 9 to 11.

In addition, the base concentration of the alkaline aqueous solution is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 5 mass% or more, preferably 50 mass% or less, more preferably 40 mass% or more. It is % by mass or less, more preferably 35 mass% or less.

The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the resin composition layer, but is preferably 10°C or higher, more preferably 15°C or higher, further preferably 20°C or higher, and preferably 50°C or lower. More preferably, it is 45°C or lower, and even more preferably, it is 40°C or lower.

Organic solvents used as a developer include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and diethylene glycol mono. Ethyl ether, diethylene glycol monobutyl ether.

The concentration of this organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Additionally, the temperature of this organic solvent can be adjusted according to developability. Additionally, these organic solvents can be used individually or in combination of two or more types. Examples of organic solvent-based developers used individually include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ- Examples include butyrolactone.

In pattern formation, if necessary, two or more of the above-described developing methods may be used in combination. Development methods include dip method, battle method, spray method, high pressure spray method, brushing, and scraping, and the high pressure spray method is suitable for improving resolution. The spray pressure when adopting the spray method is preferably 0.05 MPa or more, more preferably 0.1 MPa or more, further preferably 0.15 MPa or more, preferably 0.5 MPa or less, more preferably 0.4 MPa or less, More preferably, it is 0.3 MPa or less.

<(5) Process>

The method for manufacturing a printed wiring board of the present invention may further include (5) a step of curing the patterned photosensitive resin composition layer in addition to the steps (1) to (4). (5) By performing the process, it becomes possible to heat-cure the patterned photosensitive resin composition layer and form a solder resist. It is desirable to carry out step (5) after completing step (4).

Heating conditions can be appropriately selected depending on the type and content of the resin component in the resin composition, but are preferably in the range of 20 minutes to 180 minutes at 150°C to 220°C, more preferably 30 minutes at 160°C to 200°C. It is selected from the range of to 120 minutes. Additionally, before heating, ultraviolet ray irradiation using a high-pressure mercury lamp or a heating process using a clean oven may be performed. When irradiating ultraviolet rays, the irradiation amount can be adjusted as needed. For example, irradiation can be performed at an irradiation amount of about 0.05 J/cm2 to 10 J/cm2.

<(6) Process>

The method for manufacturing a printed wiring board of the present invention may include, in addition to steps (1) to (4), an additional step (6) of peeling off the support. The method of peeling off the support may be performed by a known method.

The timing of performing the (6) process is not particularly limited, and may be performed, for example, after the (3) process and before the (4) process. (6) In the process, the absolute value (│Rv│) of the maximum valley depth on the surface opposite to the substrate of the patterned photosensitive resin composition layer is set to 500 nm or more, and from the viewpoint of improving adhesion, (2) after process (3) ) It is desirable to do this before the process. That is, it is preferable to peel the support before exposure. By performing step (6) after (2) after step (3) and before step (3), step (3) is performed in a situation where oxygen exists on the surface of the photosensitive resin composition layer opposite to the substrate. In particular, in a reaction system using a negative photopolymerization initiator, the radicals of the photopolymerization initiator generated by light irradiation are deactivated by oxygen in the air, which has a non-radical structure. This phenomenon is especially noticeable in the outermost layer, and the outermost layer of the photosensitive resin composition is in a non-photocured state, making it easy for a part near the surface to be removed by the developer. As a result, it is believed that a predetermined maximum valley depth is formed on the surface of the patterned photosensitive resin composition layer, making it possible to improve adhesion and shielding properties.

<Other processes>

The printed wiring board may further include a drilling process and a desmear process after forming the solder resist. These processes may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards.

After forming the solder resist, a perforation process is performed on the solder resist formed on the substrate to form via holes and through holes, as desired. The drilling process can be performed, for example, by known methods such as drill, laser, plasma, etc., or by combining these methods as needed, but the drilling process by laser such as carbon dioxide laser or YAG laser is preferable. .

The desmear process is a desmear process. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause defective electrical connections, treatment to remove smears (desmear treatment) is performed in this process.

The desmear treatment may be performed by dry desmear treatment, wet desmear treatment, or a combination thereof.

Examples of dry desmear treatment include desmear treatment using plasma. Desmear processing using plasma can be performed using a commercially available plasma desmear processing device. Among commercially available plasma desmear processing devices, examples suitable for use in manufacturing printed wiring boards include a microwave plasma device manufactured by Nisshin Corporation and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd.

Examples of wet desmear treatment include desmear treatment using an oxidizing agent solution. When performing desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling liquid, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing liquid in this order. Examples of the swelling liquid include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate on which via holes or the like are formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. As the oxidizing agent solution, an alkaline permanganate aqueous solution is preferable, for example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline aqueous permanganic acid solutions include “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan. Neutralization treatment with a neutralizing liquid is preferably performed by immersing the oxidized substrate in a neutralizing liquid at 30°C to 50°C for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, “Reduction Solution Securigant P” manufactured by Atotech Japan.

When performing a combination of dry desmear treatment and wet desmear treatment, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

Even when the insulating layer is used as an interlayer insulating layer, it can be performed in the same way as in the case of solder resist, and a plating process may be performed if necessary.

The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist with a reverse pattern to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method, a semiadditive method, etc. known to those skilled in the art can be used.

[Hardened product]

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. Since this cured product is obtained by curing a photosensitive resin composition that satisfies condition (I) or (II), as explained in the section “[Resin Sheet]”, after development, its surface has a specific maximum valley depth. .

The curing conditions for the photosensitive resin composition layer may be those normally employed when forming the insulating layer of a printed wiring board. For example, the conditions of the above-mentioned process (5) may be used. Additionally, preheating may be performed before thermosetting the resin composition, and heating may be performed multiple times including preheating.

[ Example ]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

((b) Measurement of the glass transition temperature of the main chain of the component)

(b) The glass transition temperature of the main chain of component was calculated using 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 component (b), and Tgm represents the glass transition temperature (K) of each monomer constituting component (b).

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

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

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

In a 5-neck reaction vessel with an internal volume of 2 liters, 350 g of methyl isobutyl ketone, 71 g of glycidyl methacrylate, 136 g of butylacrylate, and 16 g of azobisisobutyronitrile were added, and the mixture was heated at 80°C for 6 hours while blowing nitrogen gas. Heated. 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 (the theoretical Tg value of the polymer was -28°C, solid content: 50% by mass, Mw: 18000, Acid value: 52 mgKOH/g).

<Production Examples 1 to 3>

Each component was mixed in the mixing ratio shown in the table below, and the resin varnish was adjusted using a high-speed rotating mixer.

Abbreviations in the table are as follows.

SC2050: Surface treatment with 0.5 parts by mass of aminosilane (manufactured by Shin-Etsu Chemical, “KBM573”) for 100 parts by mass of fused silica slurry (manufactured by Adomatex, average particle diameter 0.5 ㎛, specific surface area 5.9 m2/g) and slurry to which MEK was added. Solids concentration 70%.

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

・NC3000H: Biphenyl type epoxy resin (manufactured by Nihon Kayaku Co., Ltd., epoxy equivalent weight approximately 272)

Irgacure OXE-02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)] (manufactured by BASF)

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

DPHA: Dipentaerythritol hexaacrylate (manufactured by Nihon Kayaku Co., Ltd., acrylic equivalent weight approximately 96)

・NV-7-201: Pigment (carbon black, manufactured by Nihon Pigment Co., Ltd., solid concentration 20%)

(Measurement of the absolute value of the maximum valley depth of the support)

In measuring the maximum valley depth (Rv) of the support, a white light interference microscope (Contoure GT-X series, manufactured by Bruker AXS) was used. The objective lens was set at 50x, green light was selected, and the measurement range of the surface shape was 125 ㎛ x 100 ㎛. After that, the absolute value (│Rv│) of the maximum valley depth of the support surface was obtained by performing primary tilt correction using 『Terms Removal (F-Operation)』.

(Measurement of arithmetic mean roughness (Ra) of support)

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

(Haze measurement of support)

The haze of the support was measured using a haze meter HZ-V3 (manufactured by Sugashi Kenki Co., Ltd.).

<Example 1>

(Production of Support 1)

A release agent (“AL-5”, manufactured by Lintec) was uniformly applied onto the PET film (“S-25”, manufactured by Unichika) with a die coater so that the thickness of the release agent was 1 μm, and the support 1 was applied. Produced. The haze of support 1 was measured and found to be 6%.

((1) Process: Process of preparing the resin sheet)

The resin varnish of Production Example 1 above was uniformly applied with a die coater on the release agent of Support 1 so that the thickness of the photosensitive resin composition layer after drying was 20 ㎛, and dried from 80°C to 110°C for 5 minutes to smoothen. A resin sheet having a photosensitive resin composition layer on a PET film was obtained.

((2) Process: Process of laminating a resin sheet on a substrate)

Next, for a glass epoxy substrate (copper-clad laminate) on which a circuit patterned with an 18㎛ thick copper layer (processed using CZ8100 manufactured by Meksa) is formed, the photosensitive resin composition layer of the preceding resin sheet is aligned with the copper circuit surface. They were placed in contact with each other and laminated using a vacuum laminator (VP160, manufactured by Nichigo Materials Co., Ltd.) to form a laminate in which the electrical copper-clad laminate, the electrical photosensitive resin composition layer, and the electrical support were laminated in this order. The compression conditions were vacuum exhaust time of 30 seconds, compression temperature of 80°C, compression pressure of 0.7 MPa, and pressurization time of 30 seconds.

((3) Process: Process of exposing the photosensitive resin composition layer)

The laminate was left to stand at room temperature for 30 minutes or more, and exposure to ultraviolet rays at 250 mJ/cm 2 was performed from above the support of the laminate using a pattern forming device using a round hole pattern. (3) The process was performed without peeling off the support. The exposure pattern has apertures: 50㎛, 60㎛, 70㎛, 80㎛, 90㎛, 100㎛ round hole, 120㎛ round hole, 200㎛ round hole, 250㎛ round hole, 500㎛ round hole, L/S (Line/Space): Line and space of 50㎛/50㎛, 60㎛/60㎛, 70㎛/70㎛, 80㎛/80㎛, 90㎛/90㎛, 100㎛/100㎛, 1 A quartz glass mask was used to draw exposed and unexposed areas having a square shape of cm x 2 cm. After standing at room temperature for 10 minutes, the support was removed from the electrical laminate.

((6) Process: Process of peeling off the support)

(3) After the process, the support was peeled off manually.

((Measurement of Rv before development and Ra before development))

(3) After the process (4) Before the process, the surface condition of the exposed portion of the photosensitive resin composition layer was examined using a white light interference microscope (Contoure GT-X series, manufactured by Bruker AXS), with the objective lens set at 50x. Then, green light was selected, and the surface shape measurement range was set to 125㎛×100㎛. After that, the absolute value (A1) of Rv before development on the surface of the photosensitive resin composition layer was measured by performing primary tilt correction by “Terms Removal (F-Operation)”. In addition, the arithmetic mean roughness (Ra) before development was measured using a non-contact interference microscope (manufactured by WYKO Bruker AXS).

((4) Process: Process of forming a patterned photosensitive resin composition layer by development)

(6) After the process, the entire surface of the photosensitive resin composition layer on the laminate was subjected to spray development 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 a patterned photosensitive resin composition layer.

((Measurement of Rv after development and Ra after development))

(4) After the process, measure the absolute value of Rv (A2) and the arithmetic mean roughness (Ra) of the surface of the patterned photosensitive resin composition layer after development in the same manner as ((Measurement of Rv before development and Ra before development)). did. In addition, the ratio (A2/A1) of the absolute value of Rv before development (A1) and the electrical A2 measured in advance was also calculated.

((5) Process: Process of curing the patterned photosensitive resin composition layer)

(4) After the process, the surface of the photosensitive resin composition layer was irradiated with ultraviolet rays at 1 J/cm2 and heat treated at 180°C for 30 minutes to form an insulating layer with openings. This was used as a laminate for evaluation.

<Example 2>

In Example 1, step (6), which was performed after step (3) and before step (4), was performed after step (2) and before step (3). That is, step (3) was performed after peeling off the support. Except for the above, 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 produced.

<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, 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 produced.

<Example 4>

In Example 1, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 3. Except for the above, 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 produced.

<Comparative Example 1>

In Example 1, the resin varnish of Production Example 1 was changed to the resin varnish of Production Example 2. Except for the above, 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 produced.

<Comparative Example 2>

In Example 1,

1) Change the resin varnish of Preparation Example 1 to the resin varnish of Preparation Example 2,

2) Support 1 was changed to Support 2 (PET film with filled filler, “PTH-25”, manufactured by Unitika Co., Ltd., haze value 25%). Except for the following, 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 produced.

<Comparative Example 3>

In Example 1,

1) Change the resin varnish of Preparation Example 1 to the resin varnish of Preparation Example 2,

2) Support 1 was changed to Support 3 (Sand blasted PET film, “T60”, manufactured by Torres, haze value 70%). Except for the following, 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 produced.

<Comparative Example 4>

In Example 1,

1) Change the resin varnish of Preparation Example 1 to the resin varnish of Preparation Example 2,

2) Support 1 was changed to Support 4 (PET film coated with a roughening agent, haze value 60%). Except for the following, 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 produced.

<Evaluation of developability>

A 1 cm x 2 cm square portion of the exposed portion of the laminate for evaluation was observed with the naked eye. If the resin in the exposed area is not peeling or partially dissolved, it is marked as “○.” If the resin in the exposed area is peeling or partially dissolved, or if there is resin residue in the unexposed area, it is marked as “△.” And, in cases where there was no contrast in the exposed and unexposed areas, it was marked as “×”.

<Evaluation of via shape and measurement of minimum opening diameter>

Each round hole pattern formed on the evaluation laminate was observed with an SEM (S-4800, manufactured by Hitachi High-Technology Co., Ltd.) (1000x magnification), and the minimum opening diameter (minimum via diameter) of the round hole pattern without residue was measured. did. Additionally, the via shape (opening shape) of the round hole pattern was evaluated based on the following standards.

○: A random three-point round hole pattern is observed, and no overhang or undercut appears.

×: Observe a random three-point round hole pattern, and overhang or undercut appears.

<Evaluation of shielding (visibility) of wiring>

In the laminate for evaluation, those in which the pattern was not visible to the naked eye were designated as “○”, and those in which the pattern shape of the underlying layer was visible were designated as “×”.

<Evaluation of adhesion>

(Production of bag sheets)

4 parts of bisphenol-type liquid epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumiking Chemicals, epoxy equivalent of about 169, 1:1 mixture of bisphenol A and bisphenol F), naphthylene ether-type epoxy resin (manufactured by DIC) EXA-7311-G4”, epoxy equivalent weight approximately 213) 10 parts, bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 185) 6 parts, biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Corporation) ”, 10 parts of epoxy equivalent (approximately 272), and 4 parts of flame retardant (“PX-200” manufactured by Ohachi Chemical Co., Ltd.) were heated and dissolved with stirring in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone. After cooling to room temperature, 10 parts of a cresol novolak-based curing agent containing a triazine skeleton (“LA3018-50P” manufactured by DIC, hydroxyl equivalent weight of approximately 151, 2-methoxypropanol solution with a solid content of 50%) was added thereto, and triazine. 4 parts of a skeleton-containing phenol novolak-based curing agent (“LA-7054” manufactured by DIC, hydroxyl equivalent of about 125, MEK solution with a solid content of 60%), 4 parts of a naphthol-based curing agent (“SN-495V” manufactured by Nippon-Steel Sumitkin Chemical, hydroxyl group) 10 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of solids) 1 part, aminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd.) 220 parts of SC4500 (manufactured by Adomatex) surface-treated with (manufactured by "KBM573") were mixed, uniformly dispersed with a high-speed rotating mixer, and then mold-release treated with an alkyd resin-based release agent ("AL-5" by Lintech) A resin varnish was uniformly applied onto the film (“Lumira T6AM” manufactured by Torres, thickness 38 μm, softening point 130°C, “release PET”) using a die coater so that the thickness of the curable resin composition layer after drying was 25 μm. By drying from 80°C to 110°C for 4 minutes, a sealing sheet having a curable resin composition layer on release PET was obtained.

The obtained sealing sheet was laminated on each laminate for evaluation. Afterwards, it was heated in an oven at 180°C for 90 minutes. On the surface of the obtained curable resin composition layer, 100 notches (10 units x 10 units) were inserted at 1 mm intervals, and a cellophane tape was attached thereto, followed by rapid peeling in a 180° direction. The evaluation was based on the following judgment.

○: Peeling is not confirmed in all masses.

×: Peeling of the resin is observed even in one piece.

From the above table, it was seen that in Examples 1 to 4, it was possible to roughen the surface without damaging the opening shape of the opening, improve the shielding properties of the pattern, and improve the adhesion of the surface of the pattern photosensitive resin composition layer.

In Examples 1 to 3, it has been confirmed that even in the case where components (e) to (g), etc. are not contained, the same results as in the above Examples are obtained, although there is a difference in degree. In addition, in Example 4, it was confirmed that even in the case where components (b) to (g), etc. were not contained, the same results as in the above examples were obtained, although there was a difference in degree.

10 resin sheets
101 support
101a Surface of photosensitive resin composition layer side
102 Photosensitive resin composition layer
102a Surface in contact with support
102b Patterned photosensitive resin composition layer after development
102c The side opposite to the substrate side
103 substrate
11 Conventional resin sheet
111 support
111a Surface of photosensitive resin composition layer side
112 Photosensitive resin composition layer
112a Surface in contact with support
112b Patterned photosensitive resin composition layer after development
112c The side opposite to the board side
113 substrate

Claims (12)

(1) A process of preparing a resin sheet having a support and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition,
(2) a process of laminating a resin sheet on a substrate,
(3) a process of exposing the photosensitive resin composition layer, and
(4) A method for manufacturing a printed wiring board including the step of forming a patterned photosensitive resin composition layer by development,
The haze of the support is less than 20%,
(4) The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after the process is 500 nm or more,
A method for producing a printed wiring board, wherein 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, and the content of component (a) is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass. .
(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 photopolymerization initiator. The method for manufacturing a printed wiring board according to claim 1, further comprising the step of (5) curing the patterned photosensitive resin composition layer. The method for manufacturing a printed wiring board according to claim 2, wherein the cured product of the patterned photosensitive resin composition layer is solder resist. The method for producing a printed wiring board according to claim 1, wherein the photosensitive resin composition is a negative photosensitive resin composition. The method according to claim 1, wherein the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the photosensitive resin composition layer (3) after the process (4) before the process is set to A1 (㎚), and (4) after the process A method of manufacturing a printed wiring board that satisfies the relationship of 3<A2/A1<100 when the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer is set to A2 (nm). The method of manufacturing a printed wiring board according to claim 1, further comprising the step of (6) peeling off the support. The method of manufacturing a printed wiring board according to claim 6, wherein step (6) is performed after step (2) and before step (3). A resin sheet having a support and a photosensitive resin composition layer provided on the support and containing a photosensitive resin composition,
The haze of the support is less than 20%,
The absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the patterned photosensitive resin composition layer after development is 500 nm or more,
A resin sheet in which 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, and the content of component (a) is 60% by mass or more when the nonvolatile component of the photosensitive resin composition is 100% by mass. .
(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 photopolymerization initiator. The resin sheet according to claim 8, wherein component (b) contains a (meth)acrylic polymer with a glass transition temperature of -20°C or lower. The resin sheet according to claim 8, wherein the photosensitive resin composition layer is for forming solder resist. The method according to claim 8, wherein the absolute value (│Rv│) of the maximum valley depth of the surface on the support side of the photosensitive resin composition layer after exposure and before development is set to A1 (nm), and 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 A1 (㎚). A resin sheet that satisfies the relationship 3<A2/A1<100 when the absolute value (│Rv│) of the maximum valley depth of the surface is set to A2 (㎚). A cured product obtained by curing the photosensitive resin composition layer of the resin sheet according to any one of claims 8 to 11.

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