Multilayer Substrate and Method for Manufacturing Multilayer Substrate

Abstract

To provide a production method of a double-layered substrate including an insulation layer where a recess part having a wall surface capable of forming a conductor layer with high adhesion is formed.SOLUTION: A production method of a double-layered substrate comprising a base substrate and an insulation layer having a recess part formed, includes a step for forming a layer of a photosensitive resin composition containing a filler on the base substrate, a step for subjecting the photosensitive resin composition to first exposure treatment, a step for subjecting the layer of a photosensitive resin composition to development, a step for subjecting the layer of a photosensitive resin composition to second exposure treatment, and a step for subjecting the layer of a the photosensitive resin composition to heat treatment in this order. The heat treatment includes heating the photosensitive resin composition from an initiation temperature of 80°C or lower to a maximum temperature of 150°C or higher and 250°C or lower. In the heat treatment, a time of 30 minutes or more is spent heating the layer of a photosensitive resin composition from 80°C to the maximum temperature.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a multilayer substrate and a method for manufacturing the multilayer substrate.

Background Art

[0002] Semiconductor devices are usually provided with members such as printed wiring boards and wafer-level packages. These are usually plate-like members having an insulating layer, and include a base substrate (hereinafter sometimes referred to as a "base substrate") and an insulating layer provided on the base substrate. Conventionally, a technique for manufacturing the insulating layer with a photosensitive resin composition has been known (Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the above-mentioned insulating layer, recesses such as holes and trenches may be formed. Further, a conductor layer may be formed as wiring in the recess. For example, a via hole may be formed as a recess penetrating the insulating layer, and a conductor layer may be formed on the wall surface of the via hole. In this case, since the conductor layer formed on the wall surface can electrically connect the wiring formed on one side of the insulating layer and the wiring formed on the other side, interlayer connection can be achieved.

[0005] However, in the insulating layer manufactured from a conventional photosensitive resin composition, the adhesion between the conductor layer formed on the wall surface of the recess and the insulating layer was low. Therefore, it was sometimes impossible to stably form the conductor layer on the wall surface of the recess, or the formed conductor layer was easily peeled off. As a result, the connection reliability of the above-mentioned interlayer connection was low.

[0006] The present invention was devised in view of the above problems, and aims to provide a method for manufacturing a multilayer substrate including an insulating layer in which a recess having a wall surface capable of forming a conductor layer with high adhesion is formed, and a multilayer substrate including an insulating layer in which a recess having a wall surface capable of forming a conductor layer with high adhesion is formed.

Means for Solving the Problems

[0007] The present inventor earnestly studied to solve the above problems. As a result, the present inventor found that a manufacturing method including forming a layer of a photosensitive resin composition containing a filler on a base substrate, forming a latent image by a first exposure treatment, a development treatment, a second exposure treatment, and a heat treatment under specific conditions in this order can manufacture a multilayer substrate capable of solving the above problems, and completed the present invention. That is, the present invention includes the following.

[0008] 〔1〕 A method for manufacturing a multilayer substrate including a base substrate and an insulating layer in which a recess is formed, comprising: forming a layer of a photosensitive resin composition containing a filler on the base substrate; performing a first exposure treatment on the layer of the photosensitive resin composition; performing a development treatment on the layer of the photosensitive resin composition; performing a second exposure treatment on the layer of the photosensitive resin composition; performing a heat treatment on the layer of the photosensitive resin composition in this order, wherein the heat treatment includes raising the temperature of the layer of the photosensitive resin composition from a starting temperature of 80°C or lower to a maximum temperature of 150°C or higher and 250°C or lower; In the heat treatment, the layer of the photosensitive resin composition is heated from 80°C to the maximum temperature over a period of 30 minutes or more, a method for manufacturing a multilayer substrate. 〔2〕 The method for manufacturing a multilayer substrate according to 〔1〕, wherein holes are formed in the wall surface of the recess of the insulating layer. 〔3〕 The method for manufacturing a multilayer substrate according to 〔1〕 or 〔2〕, wherein the opening diameter of the recess is 0.1 μm or more and 5 μm or less. 〔4〕 The photosensitive resin composition is (A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule, (B) a crosslinking agent, (C) a photoacid generator, and (D) the filler The method for manufacturing a multilayer substrate according to any one of 〔1〕 to 〔3〕, comprising. 〔5〕 The method for manufacturing a multilayer substrate according to any one of 〔1〕 to 〔4〕, further comprising a step of forming a conductor layer on the insulating layer. 〔6〕 The method for manufacturing a multilayer substrate according to any one of 〔1〕 to 〔5〕, wherein the heating rate from 80°C to the maximum temperature in the heat treatment is 5.7°C / min or less. 〔7〕 The method for manufacturing a multilayer substrate according to any one of 〔1〕 to 〔6〕, wherein the base substrate is a wafer. 〔8〕 A method for manufacturing a multilayer substrate, comprising a base substrate and an insulating layer having a recess formed therein; A step of forming a layer of a photosensitive resin composition containing a filler on the base substrate; A step of subjecting the layer of the photosensitive resin composition to a first exposure treatment; A step of subjecting the layer of the photosensitive resin composition to a development treatment to form a recess; A step of subjecting the layer of the photosensitive resin composition to a second exposure treatment; A step of subjecting the layer of the photosensitive resin composition to a heat treatment, in this order; The heat treatment includes heating the layer of the photosensitive resin composition at a heating rate such that holes are formed in the wall surface of the recess, a method for manufacturing a multilayer substrate. 〔9〕 Comprising a base substrate and an insulating layer having a recess with an opening diameter of 0.1 μm or more and 100 μm or less, The insulating layer is formed of a cured product of a photosensitive resin composition containing a filler. The recess has a wall surface formed with a plurality of holes. 1 μm of the wall surface 2 A multilayer substrate in which the number of holes per wall surface is 10 or more.

[10] The photosensitive resin composition is (A) An alkali-soluble resin having a phenolic hydroxyl group in the molecule, (B) A crosslinking agent, (C) A photoacid generator, and (D) The filler The multilayer substrate according to [9], which contains the above. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a method for manufacturing a multilayer substrate including an insulating layer in which a recess having a wall surface capable of forming a conductor layer with high adhesion is formed, and a multilayer substrate including an insulating layer in which a recess having a wall surface capable of forming a conductor layer with high adhesion is formed. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail by showing embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications listed below, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0012] [1. Outline of the manufacturing method of the multilayer substrate according to the first embodiment] The manufacturing method according to the first embodiment of the present invention is a manufacturing method of a multilayer substrate including a base substrate and an insulating layer formed with a recess. In the multilayer substrate manufactured by the manufacturing method according to the first embodiment, the insulating layer is formed on the base substrate. This manufacturing method includes, in this order, a step (I) of forming a layer of a photosensitive resin composition containing a filler on the base substrate, a step (II) of performing a first exposure treatment on the layer of the photosensitive resin composition, a step (III) of performing a development treatment on the layer of the photosensitive resin composition, a step (IV) of performing a second exposure treatment on the layer of the photosensitive resin composition, a step (V) of performing a heat treatment on the layer of the photosensitive resin composition.

[0013] The heat treatment in step (V) includes heating the layer of the photosensitive resin composition from a certain starting temperature to a maximum temperature. In this heat treatment, the layer of the photosensitive resin composition is heated over a specific time within a specific temperature range set from the starting temperature to the maximum temperature.

[0014] According to the above manufacturing method, after the heat treatment in step (V), an insulating layer formed of the cured photosensitive resin composition is obtained. Hereinafter, the cured photosensitive resin composition may be referred to as the "cured product" of the photosensitive resin composition. In this insulating layer, a recess having a wall surface not parallel to the layer plane of the insulating layer is formed. In a multilayer substrate, a conductor layer can be formed on this wall surface with high adhesion. The "layer plane" of a certain layer refers to a plane parallel to the surface of the layer when the layer is viewed macroscopically.

[0015] The inventor of the present invention considers the mechanism for forming a conductor layer with high adhesion on the wall surface of the recess as follows. Usually, holes that open to the wall surface are formed on the wall surface. Hereinafter, this hole may be referred to as a "fine hole". Therefore, when a conductor layer is formed on the wall surface, a part of the conductor layer is formed in the fine holes, so that an anchor effect acts between the wall surface and the conductor layer, improving the adhesion. Usually, a plurality of fine holes are formed on the wall surface, so that the adhesion can be improved by the anchor effect over a wide range of the wall surface. Therefore, peeling of the conductor layer from the wall surface is suppressed, and thus high adhesion as described above can be realized. However, the technical scope of the present invention is not limited to the above mechanism.

[0016] The manufacturing method according to the first embodiment of the present invention may further include an arbitrary step in combination with the above-described steps (I) to (V). For example, the manufacturing method according to the first embodiment may include a step (VI) of heating the layer of the photosensitive resin composition between step (II) and step (III). Further, for example, the manufacturing method according to the first embodiment may include a step (VII) of forming a conductor layer on the insulating layer after step (V).

[0017] The multilayer substrate manufactured by the manufacturing method according to the first embodiment of the present invention can be used as a wide-ranging member including a base substrate and an insulating layer, and its specific use is not limited. Among them, from the viewpoint of effectively utilizing the point that a conductor layer can be formed with high adhesion on the wall surface of the concave portion of the insulating layer, the multilayer substrate is suitable as a circuit board or an intermediate substrate manufactured in the process of manufacturing the circuit board. Examples of the circuit board include semiconductor chip packages such as multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages; package substrates including the semiconductor chip packages; printed wiring boards such as rigid boards, flexible boards, single-sided multilayer boards, thin boards, and component-embedded boards; However, it is not limited to these examples.

[0018] [2. Photosensitive resin composition] In the manufacturing method according to the first embodiment of the present invention, an insulating layer is formed on a base substrate using a photosensitive resin composition containing a filler. Specifically, a layer of the photosensitive resin composition is formed on the base substrate, and the layer of the photosensitive resin composition is cured to form an insulating layer containing a cured product of the photosensitive resin composition. As this photosensitive resin composition, a composition capable of obtaining an insulating layer having recesses formed by exposure, development, and heat treatment can be used.

[0019] The filler contained in the photosensitive resin composition is usually incompatible with components other than the filler contained in the photosensitive resin composition and is contained as particles in the photosensitive resin composition. The filler may be only an organic filler, only an inorganic filler, or a combination of an organic filler and an inorganic filler. Among them, since the scattering of light during exposure by the filler is small, and thus the resolution dimension of the recesses formed in the insulating layer can be reduced, the filler preferably contains an organic filler, and more preferably contains only an organic filler. Here, the resolution dimension represents the minimum dimension of the recesses that can be formed in the intended shape and can be measured by the method described in the examples.

[0020] Since the organic filler is formed of an organic material, it generally has flexibility. Therefore, when using an organic filler, it becomes possible to disperse stress in the insulating layer, and the crack resistance and insulation of the insulating layer can be improved. The organic filler may have a core-shell structure. Examples of the organic filler include urethane particles, rubber particles, polyamide particles, and silicone particles.

[0021] As the urethane particles, commercially available products may be used. For example, “MM-101SW”, “MM-101SWA”, “MM-101SM”, “MM-101SMA”, “MM-110SMA” manufactured by Negami Kogyo Co., Ltd.; RKB series manufactured by Resinas Kasei Co., Ltd., etc. may be mentioned.

[0022] As the rubber particles, resin particles that have been chemically cross-linked and are insoluble and infusible in an organic solvent can be used, which exhibit rubber elasticity. Examples of the rubber particles include acrylonitrile-butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, methyl methacrylate-butadiene-styrene copolymer particles, etc. As the rubber particles, commercially available products may be used. For example, “EXL-2655” manufactured by Dow Chemical Japan Co., Ltd.; “AC3816N”, “AC3355”, “AC3816”, “AC3832”, “AC4030”, “AC3364”, “IM101” manufactured by Gants Kasei Co., Ltd.; “Paraloid EXL2655”, “EXL2602” manufactured by Kureha Chemical Co., Ltd.; “B-11A”, “B513”, “B22”, “B-521”, “B-561”, “B-564”, “FM-21”, “FM-40”, “FM-50”, “M-701”, “M-711”, “M-732”, “M-300”, “FM-40”, “M-570”, “M-210” manufactured by Kaneka Corporation; RKB series manufactured by Resinas Kasei Co., Ltd., etc. may be mentioned.

[0023] As the polyamide particles, particles of a resin having an amide bond can be used. Examples of the polyamide particles include particles of aliphatic polyamides such as nylon, particles of aromatic polyamides such as Kevlar, and polyamideimide particles. As the polyamide particles, commercially available products may be used. For example, "VESTOSINT 2070" manufactured by Daicel-Huels; "SP500" manufactured by Toray Industries, Inc., etc. may be mentioned.

[0024] The organic filler may be used alone or in combination of two or more.

[0025] The average particle size of the organic filler is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.02 μm or more, still more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.6 μm or less. The average particle size of the organic filler can be measured using the dynamic light scattering method. Specifically, the average particle size of the organic filler can be measured by uniformly dispersing the organic filler in a suitable organic solvent by ultrasonic waves, creating a particle size distribution of the organic filler based on mass using a concentrated system particle size analyzer (for example, "FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.), and taking the median diameter thereof as the average particle size.

[0026] As the inorganic filler, particles of an inorganic compound can be used. When using an inorganic filler, the insulating property of the insulating layer can be improved. Examples of the material of the inorganic filler 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, etc. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, as silica, spherical silica is preferable.

[0027] Examples of commercially available products of the inorganic filler include "UFP-30" manufactured by Denka Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" manufactured by Admatechs Co., Ltd., etc.

[0028] The inorganic filler may be used alone or in combination of two or more kinds.

[0029] The average particle diameter of the inorganic filler can be in the same range as that of the organic filler. The average particle diameter of the inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler using a laser diffraction / scattering type particle size distribution measuring device and taking the median diameter as the average particle diameter. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the light source wavelengths of blue and red and the flow cell method, and the average particle diameter can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0030] The specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, particularly preferably 3 m 2 / g or more. There is no particular limitation on the upper limit, but it is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area can be measured by adsorbing nitrogen gas on the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multi-point method.

[0031] From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxy silane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, etc. Also, the surface treatment agent may be used alone or in any combination of two or more.

[0032] Examples of commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-503" (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0033] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably surface-treated with 0.2 to 3 parts by mass of the surface treatment agent, and still more preferably surface-treated with 0.3 to 2 parts by mass of the surface treatment agent.

[0034] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the photosensitive resin composition, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg / m 2 or less.

[0035] The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used, etc.

[0036] When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of the filler in the photosensitive resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less.

[0037] The photosensitive resin composition may contain a resin in combination with the above-described filler. The type and amount of this resin can be appropriately selected according to the type of the photosensitive resin composition. From the viewpoint of smoothly obtaining an insulating layer having a recess with an excellent adhesion wall surface, as the photosensitive resin composition, a negative photosensitive resin composition containing a filler is preferable. As the negative photosensitive resin composition, for example, a composition containing a combination of a radically polymerizable resin, a photo radical generator, and a filler may be used. Further, as the negative photosensitive resin composition, for example, a composition containing a combination of a resin soluble in a developer, a photoacid generator, a crosslinking agent that can be promoted to crosslink in the presence of an acid, and a filler may be used.

[0038] As described above, the insulating layer obtained by the manufacturing method according to the first embodiment of the present invention can improve the adhesion between the wall surface of the recess of the insulating layer and the conductor layer by the physical action of the anchor effect. Therefore, even when using a photosensitive resin composition having a composition with low chemical affinity with the conductor layer and having high difficulty in obtaining high adhesion due to such low affinity in the past, according to the manufacturing method according to the first embodiment of the present invention, it is possible to improve the adhesion. Therefore, when using a photosensitive resin composition having a composition that conventionally tends to have low adhesion with the conductor layer on the wall surface of the recess of the insulating layer, the advantage of improving the adhesion can be particularly effectively utilized, which is preferable.

[0039] From the viewpoint of effectively utilizing the effect of improving the adhesion as described above, as the photosensitive resin composition, it is preferable to include a combination of (A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule, (B) a crosslinking agent, (C) a photoacid generator, and (D) a filler. Hereinafter, taking this photosensitive resin composition as an example, the manufacturing method of the multilayer substrate will be described in detail.

[0040] [2.1. (A) Alkali-soluble resin having a phenolic hydroxyl group in the molecule] The “(A) alkali-soluble resin having a phenolic hydroxyl group in the molecule” as the component (A) can be dissolved in an appropriate type of developer, and in particular, can be well dissolved in an alkaline developer. Further, when an appropriate type of (B) crosslinking agent is used, the phenolic hydroxyl group of the component (A) can react with the (B) crosslinking agent, so that the crosslinking reaction can proceed smoothly.

[0041] The phenolic hydroxyl group represents a hydroxyl group bonded to an aromatic ring such as a benzene ring or a naphthalene ring. The number of phenolic hydroxyl groups contained in the component (A) may be 1 or more than 2 per molecule. Among them, from the viewpoint of promoting the processing reaction by the (B) crosslinking agent and increasing the degree of crosslinking to enhance the mechanical strength of the insulating layer, the component (A) preferably has 2 or more phenolic hydroxyl groups per molecule.

[0042] (A) component may be used alone or in combination of two or more. Preferred examples of (A) component include compounds containing a structure represented by the following formula (A-1), compounds containing a structure represented by formula (A-2), and compounds having a structure represented by formula (A-3). In the following description, the compound containing the structure represented by formula (A-1), the compound containing the structure represented by formula (A-2), and the compound having the structure represented by formula (A-3) may be referred to as (A-1) component, (A-2) component, and (A-3) component, respectively. From the viewpoint of reducing the resolution dimension of the recess formed in the insulating layer, (A) component preferably contains a combination of (A-1) component, (A-2) component, and (A-3) component.

[0043] [Chemical formula]

[0044] (In formula (A-1), R 1 each independently represents a divalent group represented by the following formula (a), and X 1 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n1 represents an integer from 0 to 4, and m1 represents an integer from 1 to 200. * represents a bond. In formula (A-2), R 2 each independently represents a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), a divalent group composed of a combination of the divalent group represented by the following formula (b) and the divalent group represented by the following formula (c), a divalent group composed of a combination of the divalent group represented by the following formula (a) and the divalent group represented by the following formula (b), or a divalent group composed of a combination of the divalent group represented by the following formula (a) and the divalent group represented by the following formula (c), and X 2 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n2 represents an integer from 0 to 4, and m2 represents an integer from 1 to 200. * represents a bond. In formula (A-3), R3 represents a divalent group consisting of a divalent group represented by the following formula (a), a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), or a combination thereof, and X 3 and X 4 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n3 and n4 each independently represent an integer from 0 to 4.)

[0045]

Chemical formula

[0046] (In formula (a), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. * represents a bond.) In formula (b), X 11 each independently represents an alkyl group which may have a substituent. p1 represents an integer from 0 to 4. * represents a bond.) In formula (c), X 12 and X 13 each independently represent an alkyl group which may have a substituent. p2 and p3 each independently represent an integer from 0 to 4. * represents a bond.)

[0047] -(Component (A-1): A compound containing the structure represented by formula (A-1)- (Component (A-1) represents a compound containing the structure represented by the following formula (A-1). Component (A-1) may be used alone or in combination of two or more.)

[0048]

Chemical formula

[0049] (In formula (A-1), R 1 each independently represents a divalent group represented by the following formula (a), and X 1 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n1 represents an integer from 0 to 4, and m1 represents an integer from 1 to 200. * represents a bond.)

[0050] [Chemical formula]

[0051] (In formula (a), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a group composed of a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. * represents a bond.)

[0052] In formula (A-1), X 1 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. Among them, X 1 is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a halogen atom, more preferably an alkyl group which may have a substituent and an aryl group which may have a substituent, and even more preferably an alkyl group which may have a substituent.)

[0053] The alkyl group may be a linear, branched, or cyclic alkyl group. The cyclic alkyl group may be either monocyclic or polycyclic. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is even more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an s-butyl group, a t-butyl group, a 2-methylpropyl group, a 3-heptyl group, and the like. Among them, a methyl group is particularly preferable.

[0054] As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is even more preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and the like.

[0055] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable.

[0056] As the monovalent heterocyclic group, a monovalent heterocyclic group having 3 to 21 carbon atoms is preferable, a monovalent heterocyclic group having 3 to 15 carbon atoms is more preferable, and a monovalent heterocyclic group having 3 to 9 carbon atoms is even more preferable. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. Among them, a pyrrolidyl group is preferable. The monovalent heterocyclic group means a group obtained by removing one hydrogen atom from the heterocyclic ring of a heterocyclic compound.

[0057] X 1 The alkyl group, aryl group, and monovalent heterocyclic group represented by may have a substituent. Examples of the substituent include a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-6 alkyl group)2, C1-6 an alkyl group, C 6-10 an aryl group, -NH2, -NH(C 1-6 alkyl group), -CN, -C(O)O-C 1-6 alkyl group, -C(O)H, -NO2, etc. are exemplified.

[0058] In this specification, the expression "may have a substituent" means, unless otherwise specified, unsubstituted or having usually 1 to 5 (preferably 1, 2 or 3) substituents. When having a plurality of substituents, these substituents may be the same or different from each other. Further, in this specification, the term "C p-q "(p and q are positive integers and satisfy p < q.) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-6 alkyl group" indicates an alkyl group having 1 to 6 carbon atoms.

[0059] In formula (A-1), R 1 each independently represents a divalent group represented by formula (a). The bond in formula (a) is preferably bonded to the OH group at the phenolic site in formula (A-1) at any of the ortho, meta, and para positions, more preferably bonded to either the meta or para position, and even more preferably a mixture of those bonded to the meta and para positions. When the bonds in formula (a) are a mixture of those bonded to the meta and para positions of the OH group at the phenolic site in formula (A-1), let the mass of the bond in formula (a) bonded to the meta position be m, and the mass of the bond in formula (a) bonded to the para position be p. At this time, the mixing ratio (m:p) is preferably 1:0.1 to 1:10, more preferably 1:0.1 to 1:5, even more preferably 1:0.1 to 1:2, and particularly preferably 1:0.5 to 1:1.

[0060] In formula (a), R 11 and R 12represents a group independently composed of a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. Among them, a hydrogen atom and an alkyl group are preferred.

[0061] R 11 and R 12 The alkyl group which may have a substituent, the aryl group which may have a substituent, and the monovalent heterocyclic group which may have a substituent represented by may be the same as the alkyl group which may have a substituent, the aryl group which may have a substituent, and the monovalent heterocyclic group which may have a substituent represented by X in formula (A-1). 1 It may be the same.

[0062] Examples of the group composed of these combinations include a group composed of a combination of an alkyl group and a carbonyl group, a group composed of a combination of an aryl group and a carbonyl group, a group composed of a combination of an alkyl group, an amino group, and a carbonyl group, a group composed of a combination of an aryl group, an amino group, and a carbonyl group, and the like.

[0063] R 11 and R 12 may be bonded to each other to form a ring. R 11 and R 12 The ring structure that may be formed includes spiro rings and fused rings. In this case, R 11 and R 12 are preferably a group forming a cyclopentane ring, a group forming a cyclohexane ring, a group forming a 2,2-dimethyl-4-methylcyclohexane ring, a group forming a fluorene ring, a group forming a pyrrolidine ring, or a group forming a γ-lactam ring.

[0064] Specific examples of the divalent group represented by formula (a) include the following groups. In the formula, "*" represents a bond.

[0065] [Chemical formula]

[0066] [Chemical formula]

[0067] In formula (A-1), n1 represents an integer from 0 to 4, preferably represents an integer from 0 to 3, more preferably represents 0 or 1, and particularly preferably represents 1.

[0068] In formula (A-1), m1 represents an integer from 1 to 200, preferably represents an integer from 1 to 150, more preferably represents an integer from 1 to 100, and even more preferably represents an integer from 1 to 50.

[0069] Specific examples of the component (A-1) can include the resin represented by the following formula (1). In the specific examples, the OH groups at the phenol sites are mixed at a ratio of 60% at the meta position and 40% at the para position. In the following formula (1), n represents an integer from 1 to 200.

[0070] [Chemical formula]

[0071] (Component (A-1) may be a commercially available product. Specific examples of commercially available component (A-1) include "TR4020G" (resin represented by formula (1)) manufactured by Asahi Organic Materials Co., Ltd.; AV Light series such as "TR4050G", "TR4080G", "TR5020G", "TR5050G", "TR6020G", "TR6050G", "TR6080G", etc. manufactured by Asahi Organic Materials Co., Ltd.; resin series for photoresist manufactured by Sumitomo Bakelite Co., Ltd.; Reditop series manufactured by Gunei Chemical Industry Co., Ltd.; Phenolite series such as "PR-30-40P", "PR-100L", "PR-100H", "PR-50", "PR-55", "PR-56-1", "PR-56-2", "WR-101", "WR-102", "WR-103", "WR-104", etc. manufactured by DIC Corporation; "LF-100", "LF-110", "LF-120", "LF-200", "LF-400", "LF-500" manufactured by Lignite Co., Ltd.; base resin series for photoresist manufactured by Meiwafosis Co., Ltd., etc.

[0072] (A-1) component can usually be obtained by polycondensation of phenol or its derivative with aldehyde and / or ketone. The polycondensation can be carried out in the presence of a catalyst such as an acid or a base. Therefore, the terminal of (A-1) component is usually a hydroxyphenyl group or an aldehyde group which may have a substituent, and it is preferable that both terminals are hydroxyphenyl groups which may have a substituent.

[0073] The weight average molecular weight of (A-1) component is preferably 500 or more, more preferably 700 or more, still more preferably 1000 or more, and preferably 150000 or less, more preferably 100000 or less, still more preferably 50000 or less. The weight average molecular weight can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

[0074] When the total of component (A) is 100% by mass, the amount of component (A-1) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 85% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

[0075] When the amount of the component (A-1) is based on 100% by mass of the non-volatile components of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.

[0076] When the amount of the component (A-1) is based on 100% by mass of the resin components of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less. The resin components of the photosensitive resin composition refer to the components excluding the (D) filler among the non-volatile components of the photosensitive resin composition.

[0077] -(Component (A-2): A compound containing the structure represented by formula (A-2)- The component (A-2) represents a compound containing the structure represented by the following formula (A-2). The component (A-2) may be used alone or in combination of two or more.

[0078] [Chemical formula]

[0079] (In formula (A-2), R 2 each independently represents a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), a divalent group composed of a combination of the divalent group represented by the following formula (b) and the divalent group represented by the following formula (c), a divalent group composed of a combination of the divalent group represented by the following formula (a) and the divalent group represented by the following formula (b), or a divalent group composed of a combination of the divalent group represented by the following formula (a) and the divalent group represented by the following formula (c), and X 2represents an alkyl group which may independently have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n2 represents an integer from 0 to 4, and m2 represents an integer from 1 to 200. * represents a bond.)

[0080] [Chemical formula]

[0081] (In formula (a), R 11 and R 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a group composed of a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. * represents a bond.) In formula (b), X 11 each independently represents an alkyl group which may have a substituent. p1 represents an integer from 0 to 4. * represents a bond.) In formula (c), X 12 and X 13 each independently represent an alkyl group which may have a substituent. p2 and p3 each independently represent an integer from 0 to 4. * represents a bond.)

[0082] In formula (A-2), R 2represents, independently of each other, a divalent group consisting of a divalent group represented by formula (b), a divalent group represented by formula (c), a divalent group consisting of a combination of a divalent group represented by formula (b) and a divalent group represented by formula (c), a divalent group consisting of a combination of a divalent group represented by formula (a) and a divalent group represented by formula (b), or a divalent group consisting of a combination of a divalent group represented by formula (a) and a divalent group represented by formula (c). The divalent group represented by formula (a) is as described above. The bonds in formulas (a) to (c) are preferably bonded to the OH group at the phenolic site in formula (A-2) at any of the ortho, meta, and para positions, more preferably bonded to either the meta or para position, and even more preferably a mixture of those bonded to the meta and para positions. The mixing ratio in the case where the bonds in formulas (a) to (c) are a mixture of those bonded to the meta and para positions of the OH group at the phenolic site in formula (A-2) can be the same as the above-described mixing ratio explained by the group represented by formula (A-1).

[0083] X in formulas (b) to (c) 11 , X 12 , and X 13 each independently represents an alkyl group which may have a substituent. X 11 ~X 13 can be the same as the alkyl group which may have a substituent represented by X 1 in formula (A-1).

[0084] p1, p2, and p3 in formulas (b) to (c) each independently represent an integer of 0 to 4, preferably represent an integer of 0 to 3, and more preferably represent 0 or 1.

[0085] Specific examples of the divalent group represented by formula (b) can include the following groups. In the formula, "*" represents a bond.

[0086]

Chemical formula

[0087] Specific examples of the divalent group represented by formula (c) include the following groups. In the formula, "*" represents a bond.

[0088]

Chemical formula

[0089] Specific examples of the divalent group composed of a combination of the divalent group represented by formula (b) and the divalent group represented by formula (c), the divalent group composed of a combination of the divalent group represented by formula (a) and the divalent group represented by formula (b), and the divalent group composed of a combination of the divalent group represented by formula (a) and the divalent group represented by formula (c) include the following groups. In the formula, "*" represents a bond.

[0090]

Chemical formula

[0091] In formula (A-2), X 2 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. X 2 may be the same as X 1 in formula (A-1).

[0092] In formula (A-2), n2 represents an integer from 0 to 4 and may be the same as n1 in formula (A-1).

[0093] In formula (A-2), m2 represents an integer from 1 to 200 and may be the same as m1 in formula (A-1).

[0094] Specific examples of the component (A-2) include the resin represented by the following formula (2) and the resin represented by the following formula (3). In the specific examples, the OH groups at the phenol sites are mixed at a ratio of 60% at the meta position and 40% at the para position. In the following formulas (2) and (3), n represents an integer from 1 to 200.

[0095] [Chemical formula]

[0096] (Component (A-2) may be a commercially available product. Specific examples of commercially available component (A-2) include "MEHC-7851SS" (resin represented by formula (2)), "MEHC-78004S" (resin represented by formula (3)) manufactured by Meiwa Kasei Co., Ltd., "MEHC-7851-SS", "MEHC-7851-S", "MEHC-7851-M", "MEHC-7851-H", "MEHC-7800-4S", "MEHC-7800-SS", "MEHC-7800-S", "MEHC-7800-M", "MEHC-7800-H" manufactured by Meiwa Kasei Co., Ltd., "GPH-65", "GPH-103", "MEHC-7841-4S" manufactured by Nippon Kayaku Co., Ltd., and the like.

[0097] (Component (A-2) can usually be obtained by polycondensation of phenol or its derivative and a compound other than phenol. The polycondensation is usually carried out in the presence of a catalyst such as an acid or a base. Therefore, the terminal of component (A-2) is preferably a hydroxyphenyl group which may have a substituent, and more preferably a hydroxyphenyl group in which both terminals may have a substituent.

[0098] (The weight average molecular weight of component (A-2) is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and preferably 50000 or less, more preferably 10000 or less, still more preferably 5000 or less.

[0099] (When the total amount of component (A) is 100% by mass, the amount of component (A-2) is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.

[0100] When the amount of the non-volatile components of the photosensitive resin composition is 100% by mass, the amount of the component (A-2) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

[0101] When the resin component of the photosensitive resin composition is 100% by mass, the amount of the component (A-2) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.

[0102] -(Component (A-3): A compound having a structure represented by formula (A-3)- The component (A-3) represents a compound having a structure represented by the following formula (A-3). The component (A-3) may be used alone or in combination of two or more.

[0103]

Chemical formula

[0104] (In formula (A-3), R 3 represents a divalent group represented by the following formula (a), a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), or a divalent group composed of a combination thereof, and X 3 and X 4 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. n3 and n4 each independently represent an integer of 0 to 4.)

[0105]

Chemical formula

[0106] (In formula (a), R 11 and R 12represents a group independently composed of a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, an amino group, a carbonyl group, a carboxyl group, or a combination thereof, and R 11 and R 12 may be bonded to each other to form a ring. * represents a bond. In formula (b), X 11 each independently represents an alkyl group which may have a substituent. p1 represents an integer from 0 to 4. * represents a bond. In formula (c), X 12 and X 13 each independently represents an alkyl group which may have a substituent. p2 and p3 each independently represent an integer from 0 to 4. * represents a bond.)

[0107] R 3 represents a divalent group composed of a divalent group represented by formula (a), a divalent group represented by formula (b), a divalent group represented by formula (c), or a combination thereof. The divalent groups represented by formulas (a) to (c) are as described above.

[0108] The bond in formulas (a) to (c) is preferably bonded to the OH group at the phenolic site in formula (A-3) at any of the ortho, meta, and para positions, more preferably bonded to either the meta or para position, and even more preferably bonded to the para position.

[0109] In formula (A-3), X 3 and X 4 each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a halogen atom, or a monovalent heterocyclic group which may have a substituent. X 3 and X 4 each independently may be the same as X 1 in formula (A-1).

[0110] In formula (A-3), n3 and n4 each independently represent an integer from 0 to 4, and may be the same as n1 in formula (A-1).

[0111] Specific examples of the component (A-3) can include the following groups.

[0112]

Chemical formula

[0113]

Chemical formula

[0114]

Chemical formula

[0115]

Chemical formula

[0116]

Chemical formula

[0117]

Chemical formula

[0118]

Chemical formula

[0119]

Chemical formula

[0120]

Chemical formula

[0121]

Chem.

[0122] (Component (A-3) may be a commercially available product. Specific examples of commercially available component (A-3) include "BisE", "BisP-TMC" manufactured by Honshu Chemical Co., Ltd.; "BisA", "BisF", "BisP-M" manufactured by Mitsui Chemicals Fine Co., Ltd.; "BisP-AP", "BisP-MIBK", "BisP-B", "Bis-Z", "BisP-CP", "o,o'-BPF", "BisP-IOTD", "BisP-IBTD", "BisP-DED", "BisP-BA" manufactured by Honshu Chemical Co., Ltd.; "Bis-C", "Bis26X-A", "BisOPP-A", "BisOTBP-A", "BisOCHP―A", "BisOFP-A", "BisOC-Z", "BisOC-FL", "BisOC-CP", "BisOCHP-Z", "methylene bis P-CR", "TM-BPF", "BisOC-F", "Bis3M6B-IBTD", "BisOC-IST", "BisP-IST", "BisP-PRM", "BisP-LV", etc. manufactured by Honshu Chemical Co., Ltd.)

[0123] (The molecular weight of component (A-3) is preferably 150 or more, more preferably 160 or more, still more preferably 170 or more, and preferably 1000 or less, more preferably 800 or less, still more preferably 500 or less.)

[0124] (When the total amount of component (A) is 100% by mass, the amount of component (A-3) is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.)

[0125] (When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of component (A-3) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.)

[0126] When the resin component of the photosensitive resin composition is 100% by mass, the amount of the component (A-3) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less.

[0127] When the mass of the component (A-1) with respect to 100% by mass of the whole component (A) is Wa1, and the mass of the component (A-2) with respect to 100% by mass of the whole component (A) is Wa2, the mass ratio Wa2 / Wa1 is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less.

[0128] When the mass of the component (A-3) with respect to 100% by mass of the whole component (A) is Wa3, the mass ratio Wa3 / Wa1 is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less.

[0129] The mass ratio Wa2 / Wa3 is preferably 0.2 or more, more preferably 0.25 or more, still more preferably 0.3 or more, and is preferably 5 or less, more preferably 3 or less, still more preferably 1.5 or less.

[0130] When the non-volatile component of the photosensitive resin composition is 100% by mass, the amount of the component (A) is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

[0131] The amount of the component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less when the resin component of the photosensitive resin composition is 100% by mass.

[0132] [2.2. (B) Crosslinking agent] The (B) crosslinking agent as the component (B) can cause a crosslinking reaction. By this crosslinking reaction of the (B) crosslinking agent, the photosensitive resin composition can be insolubilized in a developer or cured to form an insulating layer. However, the (B) crosslinking agent does not include those corresponding to the component (A). As the (B) crosslinking agent, those capable of causing a crosslinking reaction with the component (A) are preferable. Examples of the (B) crosslinking agent capable of causing a crosslinking reaction with the component (A) include compounds containing two or more alkoxymethyl groups in the molecule.

[0133] The alkoxymethyl group represents a group represented by the following formula (B-1). In the formula (B-1), "*" represents a bond.

[0134] [Chemical formula]

[0135] In the formula (B-1), R 21 represents an alkyl group which may have a substituent. The alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. The cyclic alkyl group may be a monocyclic or polycyclic group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is still more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an s-butyl group, a t-butyl group, etc. Among them, a methyl group and a butyl group are preferable, and a methyl group is more preferable.

[0136] R21 The alkyl group represented by may have a substituent.

[0137] The alkoxymethyl group is preferably contained in an alkoxymethylamino group represented by the following formula (B-1'). Therefore, the (B) crosslinking agent preferably contains an alkoxymethylamino group represented by formula (B-1'), and more preferably contains two or more alkoxymethylamino groups represented by formula (B-1') in the molecule. In the formula, "*" represents a bond.

[0138] [ka]

[0139] In formula (B-1'), R 22 is R in formula (B-1) 21 R represents a hydrogen atom or an alkoxymethyl group.

[0140] Preferable examples of the (B) crosslinking agent include amino resins containing two or more alkoxymethyl groups in the molecule, phenol resins containing two or more alkoxymethyl groups in the molecule, etc. Among them, from the viewpoint of obtaining a photosensitive resin composition having superior photosensitivity, amino resins containing two or more alkoxymethyl groups in the molecule are preferred.

[0141] Examples of amino resins containing two or more alkoxymethyl groups in the molecule include melamine resins and urea resins, with melamine resins being preferred.

[0142] As the melamine resin, for example, a melamine resin having a structure represented by the following formula (B-2) is preferable.

[0143] [ka]

[0144] In formula (B-2), X 21 , X 22 , X 23and X 24 each independently represents a hydrogen atom or an alkoxymethyl group. R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxymethylamino group represented by the formula (B-1’). However, when R 50 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, X 21 X 22 X 23 and X 24 at least two of them are alkoxymethyl groups.

[0145] X 21 ~X 24 The alkoxymethyl group represented by may be the same as the group represented by the formula (B-1). When R 50 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, at least two of X 21 ~X 24 are alkoxymethyl groups. Preferably, when R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, at least two or more of X 21 ~X 24 are alkoxymethyl groups. Preferably, at least three of X 21 ~X 24 are alkoxymethyl groups, and more preferably at least four of X 21 ~X 24 are alkoxymethyl groups.

[0146] R 50 represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxymethylamino group represented by the formula (B-1’). An aryl group which may have a substituent and an alkoxymethylamino group represented by the formula (B-1’) are preferred, and an alkoxymethylamino group represented by the formula (B-1’) is more preferred. The alkyl group which may have a substituent is R 11The aryl group which may be the same as the alkyl group represented by and may have a substituent is R in formula (a). 11 may be the same as the aryl group represented by.

[0147] The melamine resin having the structure represented by formula (B-2) is preferably a melamine resin having the structure represented by formula (B-2’).

[0148]

Chemical formula

[0149] In formula (B-2’), X 25 , X 26 , X 27 , X 28 , X 29 and X 30 each independently represents a hydrogen atom or an alkoxymethyl group. However, at least two of X 25 , X 26 , X 27 , X 28 , X 29 and X 30 are alkoxymethyl groups.

[0150] The alkoxymethyl group represented by X 25 ~X 30 may be the same as the group represented by formula (B-1). At least two of X 25 ~X 30 are alkoxymethyl groups, and it is preferable that at least three of X 25 ~X 30 are alkoxymethyl groups, more preferably at least four of X 25 ~X 30 are alkoxymethyl groups, and even more preferably all of X 25 ~X 30 are alkoxymethyl groups.

[0151] Specific examples of the melamine resin include the following melamine resins.

[0152] [Chemical formula]

[0153] Melamine resin may be a commercially available product. Examples of commercially available products include "MW-390", "MW-100LM", "MX-750LM" manufactured by Sanwa Chemical Co., Ltd.; Cymel series manufactured by Ornex Japan Co., Ltd., etc.

[0154] Melamine resin can be prepared, for example, by polycondensation of melamine and formaldehyde.

[0155] As the urea resin, for example, a urea resin having either the structure represented by the following formula (B-3) or the structure represented by the following formula (B-4) is preferred.

[0156] [Chemical formula]

[0157] In formula (B-3), X 31 , X 32 , X 33 and X 34 each independently represent a hydrogen atom or an alkoxymethyl group. However, at least two of X 31 , X 32 , X 33 and X 34 are alkoxymethyl groups. In formula (B-4), X 35 and X 36 represent an alkoxymethyl group.

[0158] The alkoxymethyl group represented by X 31 ~X 36 can be the same as the group represented by formula (B-1). At least two of X 31 ~X 34 are alkoxymethyl groups, and it is preferable that at least three of X 31 ~X 34 are alkoxymethyl groups, and at least three of X 31 ~X 34It is more preferable that at least four of them are alkoxymethyl groups.

[0159] As the urea resin, commercially available products may be used. Examples of the commercially available products include "MX-270", "MX-279", "MX-280" manufactured by Sanwa Chemical Co., Ltd.; Cymel series manufactured by Ornex Japan Co., Ltd., and the like.

[0160] The urea resin can be prepared, for example, by polycondensation of urea and formaldehyde.

[0161] As the phenol resin containing two or more alkoxymethyl groups in the molecule, for example, a phenol resin having a structure represented by the following formula (B-5) is preferable.

[0162]

Chemical formula

[0163] In formula (B-5), X 39 each independently represents an alkoxymethyl group, R 23 and R 24 each independently represents an alkyl group which may have a substituent, and R 25 represents a single bond or a divalent organic group. s and t each independently represent an integer of 1 to 3, and u and v each independently represent an integer of 0 to 4.

[0164] The alkoxymethyl group represented by X 39 may be the same as the group represented by formula (B-1). The alkyl group which may have a substituent represented by R 23 and R 24 may be the same as the alkyl group which may have a substituent represented by X 1 in formula (A-1).

[0165] R 25represents a single bond or a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group, a group in which some or all of the hydrogen atoms of the divalent hydrocarbon group are substituted with halogen atoms such as fluorine atoms, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, an amide bond, and the like. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group; an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group; an arylene group having 6 to 30 carbon atoms such as a phenylene group.

[0166] (B) The crosslinking agent may be used alone or in combination of two or more.

[0167] When the non-volatile components of the photosensitive resin composition are 100% by mass, the amount of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.

[0168] When the resin components of the photosensitive resin composition are 100% by mass, the amount of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.

[0169] [2.3. (C) Photoacid generator] The (C) photoacid generator as component (C) generates an acid upon irradiation with actinic rays such as ultraviolet rays, and the generated acid can promote the crosslinking reaction of the (B) crosslinking agent. Therefore, the solubility of the photosensitive resin composition in the developer can be effectively reduced by exposure, and thus the formation of a negative-type pattern by exposure can be effectively advanced. The (C) photoacid generator may be used alone or in combination of two or more.

[0170] As the photoacid generator, a compound that generates an acid upon irradiation with actinic rays can be used. Examples of the photoacid generator include halogen-containing compounds, onium salt compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, oxime ester compounds, and the like. Among them, halogen-containing compounds are preferred.

[0171] Examples of the halogen-containing compounds that can be suitably used as the photoacid generator include halogenoalkyl group-containing hydrocarbon compounds, halogenoalkyl group-containing heterocyclic compounds, and the like. Specific preferred examples of the halogen-containing compounds include 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, and other s-triazine derivatives. Commercially available products can be used as the halogen-containing compounds. Examples of the commercially available products include "TFE-triazine", "TME-triazine", "MP-triazine", "MOP-triazine", "dimethoxytriazine" (halogen-containing compound-based photoacid generator having a triazine skeleton) manufactured by Sanko Chemical Co., Ltd.

[0172] Examples of onium salt compounds that can be suitably used as photoacid generators include, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Suitable specific examples of onium salt compounds include tris(4-methylphenyl)sulfonium trifluoromethanesulfonate, tris(4-methylphenyl)sulfonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl·diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl·diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, and the like. Commercially available products can be used as the onium salt compounds. Examples of commercially available products include "TS-01" and "TS-91" manufactured by Sanwa Chemical Co., Ltd.; "CPI-110A", "CPI-210S", "HS-1", "LW-S1", "IK-1", "CPI-310B" manufactured by San-Apro Ltd.; "SI-110L", "SI-180L", "SI-100L" manufactured by Sanshin Chemical Industry Co., Ltd., and the like.

[0173] Examples of diazoketone compounds that can be suitably used as photoacid generators include, for example, 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Suitable specific examples of diazoketone compounds include 1,2-naphthoquinone diazide-4-sulfonic acid ester compounds of phenols, and the like.

[0174] Examples of sulfone compounds that can be suitably used as photoacid generators include, for example, β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Preferable specific examples of the sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis(phenacylsulfonyl)methane, and the like.

[0175] Examples of sulfonic acid compounds that can be suitably used as photoacid generators include, for example, alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, iminosulfonates, and the like. Preferable specific examples of the sulfonic acid compounds include benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

[0176] Specific examples of sulfonimide compounds that can be suitably used as photoacid generators include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, and the like.

[0177] Specific examples of diazomethane compounds that can be suitably used as photoacid generators include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, and the like. Commercially available products can be used as the diazomethane compounds.

[0178] Specific examples of the oxime ester compounds that can be suitably used as photoacid generators include benzenacetonitrile, 2-methyl-α-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene], benzenacetonitrile, 2-methyl-α-[2-[[[(4-methylphenyl)sulfonyl]oxy]imino]-3(2H)-thienylidene], and the like. Commercially available products include, for example, "PAG103", "PAG121", "PAG169", "PAG203", etc. manufactured by BASF.

[0179] (C) When the non-volatile components in the photosensitive resin composition are 100% by mass, the amount of the photoacid generator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 1.5% by mass or less.

[0180] [2.4. (D) Filler] (D) The (D) filler as the component (D) is as described above. In the photosensitive resin composition containing the components (A) to (D) in combination, the amount ratio of the component (A) to the (D) filler is preferably in a specific range. Specifically, when the non-volatile components in the photosensitive resin composition are 100% by mass, let the amount of the component (A) be α and the amount of the (D) filler be β. In this case, the mass ratio β / α is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, or 1 or less.

[0181] [2.5. (E) Optional Additives] (A) The photosensitive resin composition containing the components (A) to (D) in combination may further contain (E) optional additives. This (E) optional additive does not include those corresponding to the above-mentioned components (A) to (D). The (E) optional additive may be used alone or in combination of two or more.

[0182] (E) Examples of any additives include nitrogen atom- and / or sulfur atom-containing compounds. When the photosensitive resin composition contains a nitrogen atom- and / or sulfur atom-containing compound, further improvement in adhesion is possible. Examples of the nitrogen atom- and / or sulfur atom-containing compounds include triazinethiols (e.g., 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, N’-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine), piperidines, pyrazoles (e.g., 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone), triazoles (e.g., 1,2,4-triazole, 3-mercapto-1,2,4-triazole), benzotriazoles (e.g., 1,2,3-benzotriazole, 1-hydroxybenzotriazole), and the like.

[0183] Examples of commercially available nitrogen atom- and / or sulfur atom-containing compounds include "Disnet F (TTCA)", "Disnet DB", "SanAlga 1907" manufactured by Sankyo Kasei Co., Ltd.; "BSH", "IBSH", "ASH", "IPSH", "ESH" of the Actor (registered trademark) series manufactured by Kawaguchi Chemical Co., Ltd., and "VBATDT" (6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol) manufactured by Kawaguchi Chemical Co., Ltd.; "Noxeller TCA", "Noxeller H", "Noxeller 8", "Noxeller 8-N", "Noxeller TMU", "Noxeller EUR", "Noxeller D", "Noxeller DT", "Noxeller PR", "Noxeller M-P", "Noxeller DM-P", "Noxeller MZ", "Noxeller M-60-OT", "Noxeller MDB-P", "Noxeller CZ-G", "Noxeller MSA-G", "Noxeller TT-P", "Noxeller TET-G", "Noxeller TBT.TBT-N", "Noxeller TOT-N", "Noxeller TS", "Noxeller TRA", "Noxeller PZ", "Noxeller EZ", "Noxeller BZ-P", "Noxeller PX", "Noxeller ZP", "Noxeller ZTC", "Noxeller TP", "Noxeller TTCU", "Noxeller TTTE", "Noxeller ZIX-O", "Noxeller F", "Noxeller MIX No.2", "Noxeller MIX No.3", "Noxeller EP-55", "Noxeller EP-60", "Noxeller EP-90", "Nocrack 224", "Nocrack AW", "Nocrack AW-N", "Nocrack B", "Nocrack B-N", "Nocrack PA", "Nocrack ODA", "Nocrack ODA-N", "Nocrack AD-F", "Nocrack CD", "Nocrack TD", "Nocrack White", "Nocrack 810-NA", "Nocrack 6C", "Nocrack G-1", "Nocrack 300", "Nocrack MB", "Nocrack MMB", "Nocrack MBZ", "Nocrack NBC", "Nocrack TNP", "Nocrack 400", "Sconock", "Retarder CTP", "Barnock GM-P", "Barnock DGM", "Barnock R", "Barnock DNB", "Barnock AB-S", "Barnock PM", "Noctizer SS" manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.;"BT-120", "BT-120SG", "BT-LX", "CBT-1", "CBT-SG", "TT-LX", "TT-LYK", "JCL-400", "TT-130F", "JF-77", "JF-79", "JF-80", "JF-83", "JF-832", "JAST-500", "JF-90G", "JF-95" manufactured by Johoku Chemical Co., Ltd.; 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1-hydroxybenzotriazole manufactured by Otsuka Chemical Co., Ltd.; "VERZONE" series of "Crystal#120" (1,2,3-benzotriazole), "TTA" (tolyltriazole), "VT-120M" (5-methyl-1H-benzotriazole), "C-BTA" (carboxybenzotriazole), "N-BTA" (nitro-1H-benzotriazole), "TT-250A" (benzotriazole derivative), "OA-386" (benzotriazole derivative), "OA-372" (N,N-bis(2-ethylhexyl)(1H-benzotriazol-1-yl)methylamine), "NEW DAIN SILVER OIL RD" manufactured by Daiwa Kasei Co., Ltd. Preferred examples of these commercial products include "BSH", "IBSH", "ASH", "IPSH", "ESH" of the Actor (registered trademark) series manufactured by Kawaguchi Chemical Co., Ltd., "VBATDT" (6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol) manufactured by Kawaguchi Chemical Co., Ltd., "Disnet F (TTCA)" (triazinethiol) manufactured by Sankyo Kasei Co., Ltd., "Disnet DB" (2-butylamino-4,6-dimercapto-s-triazine) manufactured by Ouchi Shinsei Chemical Co., Ltd., "Noxeller TCA" (triazinethiol) manufactured by Ouchi Shinsei Chemical Co., Ltd., "BT-120" (1,2,3-benzotriazole) and "BT-120SG" (1,2,3-benzotriazole) manufactured by Johoku Chemical Co., Ltd., and "VERZONE Crystal#120" (1,2,3-benzotriazole) manufactured by Daiwa Kasei Co., Ltd.;

[0184] When the amount of the nitrogen atom and / or sulfur atom-containing compound is based on 100% by mass of the non-volatile components in the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less.

[0185] (E) As another example of an optional additive, a silane coupling agent can be mentioned. When the photosensitive resin composition contains a silane coupling agent, further improvement in adhesion is possible. Examples of the silane coupling agent include vinylsilane-based coupling agents, epoxy-silane-based coupling agents, styrylsilane-based coupling agents, methacryl-silane-based coupling agents, acrylic-silane-based coupling agents, aminosilane-based coupling agents, isocyanurate-silane-based coupling agents, ureidosilane-based coupling agents, mercaptosilane-based coupling agents, isocyanate-silane-based coupling agents, and acid anhydride-silane-based coupling agents.

[0186] Examples of commercially available silane coupling agents include "KBM-1003", "KBE-1003", "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403", "KBM-1403", "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575", "KBM-9659", "KBE-585A", "KBM-802", "KBM-803", "KBE-9007N", "X-12-967C" manufactured by Shin-Etsu Chemical Co., Ltd. Preferable examples among these commercially available products include "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403", and among these, it is more preferable to use "KBM-403". The silane coupling agent as an optional additive (E) is preferably used separately from the surface treatment agent for the inorganic filler.

[0187] (E) As yet another example of any additive, there may be mentioned thermoplastic resins; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.; polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.; thickeners such as benton, montmorillonite, etc.; antifoaming agents of silicone type, fluorine type, vinyl resin type; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, etc.; thermosetting resins, and the like.

[0188] [2.6. (F) Solvent] The photosensitive resin composition may contain, as a volatile component, an (F) solvent in combination with the non-volatile components such as the components (A) to (E) described above. According to the (F) solvent as this (F) component, the viscosity of the photosensitive resin composition can be adjusted. Examples of the (F) solvent include organic solvents.

[0189] Examples of the (F) solvent include ketone solvents such as ethyl methyl ketone, cyclohexanone, etc.; aromatic hydrocarbon solvents such as toluene, xylene, tetramethylbenzene, etc.; glycol ether solvents such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ester solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diglycol acetate, etc.; aliphatic hydrocarbon solvents such as octane, decane, etc.; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. The solvent may be used alone or in combination of two or more.

[0190] The amount of the solvent is preferably appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

[0191] [2.7. Method for manufacturing photosensitive resin composition] The photosensitive resin composition can be manufactured by mixing each component to be included in the photosensitive resin composition. Thus, for example, a photosensitive resin composition containing components (A) to (D) can be manufactured by mixing components (A) to (D) and, if necessary, components (E) to (F). When mixing, if necessary, kneading may be performed using a kneading device such as a three-roll mill, ball mill, bead mill, sand mill, etc., or stirring may be performed using a stirring device such as a super mixer, planetary mixer, etc. There is no restriction on the order of mixing each component. Also, cooling or heating may be performed during the process of mixing each component.

[0192] [2.8. Photosensitive film] The photosensitive resin composition may be prepared as a photosensitive film. The photosensitive film includes a support and a layer of the photosensitive resin composition formed on the support. The thickness of the layer of the photosensitive resin composition is preferably the same as the thickness of the layer of the photosensitive resin composition formed on the base substrate in step (I). When using a photosensitive film, the formation of the layer of the photosensitive resin composition on the base substrate can be performed by a lamination method.

[0193] Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film, etc., and polyethylene terephthalate film is particularly preferred. Examples of commercially available supports include polyethylene terephthalate films such as the product names "Alphan MA-410", "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films such as those manufactured by Shin-Etsu Film Co., Ltd., and the PS series such as the product name "PS-25" manufactured by Teijin Limited. In order to facilitate the peeling of the support after lamination, a release agent such as an alkyd-based release agent or a silicone coating agent may be applied to the surface of the support. The thickness of the support is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm.

[0194] The photosensitive film may include a protective film that protects the layer of the photosensitive resin composition. Usually, the protective film is provided on the side opposite to the support of the layer of the photosensitive resin composition. As the protective film, for example, a film formed of the same material as the support can be used. It is preferable that the adhesive force between the protective film and the layer of the photosensitive resin composition is smaller than the adhesive force between the support and the layer of the photosensitive resin composition. Usually, the photosensitive film is used after peeling off the protective film.

[0195] The photosensitive film can be manufactured, for example, by applying a photosensitive resin composition on a support. From the viewpoint of performing the coating smoothly, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied. When the photosensitive resin composition containing a solvent is applied, drying may be performed after the coating, if necessary.

[0196] The layer of the photosensitive resin composition included in the photosensitive film may contain a solvent, but the amount of the solvent is preferably small. In one example, the amount of the solvent contained in the layer of the photosensitive resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less with respect to 100% by mass of the total amount of the layer of the photosensitive resin composition.

[0197] [3. Step (I): Formation of the layer of the photosensitive resin composition] FIG. 1 is a schematic cross-sectional view for explaining step (I) in the manufacturing method according to the first embodiment of the present invention. The manufacturing method of the multilayer substrate according to the first embodiment of the present invention includes, as shown in FIG. 1, step (I) of forming a layer 200 of a photosensitive resin composition containing a filler on a base substrate 100.

[0198] As the base substrate 100, an appropriate member to be provided on the multilayer substrate can be used. For example, when manufacturing a printed wiring board as a multi-layer substrate, as the base substrate 100, an inner layer substrate that can be provided on the printed wiring board can be used. The inner layer substrate is a member that serves as the base material of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the inner layer substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. Further, the inner layer substrate also includes an intermediate product in which an insulating layer and / or a conductor layer should be further formed when manufacturing the printed wiring board. Further, an inner layer substrate incorporating components may also be used.

[0199] For example, a wafer may be used as the base substrate 100. When a wafer is used as the base substrate 100, a wafer-level package can be manufactured as the multi-layer substrate. As the wafer, a semiconductor wafer or a dummy wafer may be used. Examples of the semiconductor wafer include a silicon wafer, a gallium arsenide (GaAs) wafer, an indium phosphide (InP) wafer, a gallium phosphide (GaP) wafer, a gallium nitride (GaN) wafer, a gallium telluride (GaTe) wafer, a zinc selenide (ZnSe) wafer, a silicon carbide (SiC) wafer, and the like. Further, as the dummy wafer, for example, a plate-like member including a mold resin and electronic components embedded in the mold resin can be used. The dummy wafer can be manufactured, for example, by a method including arranging electronic components in a circular mold, filling the mold with the mold resin, and curing the mold resin. Usually, a wafer is prepared as a disk including a semiconductor, but the shape of the wafer is not limited to a disk shape. Further, the wafer may have a conductor layer on its surface or inside, and this conductor layer may be pattern-processed.

[0200] The photosensitive resin composition is as described above. In step (I), the layer 200 of this photosensitive resin composition is formed on the base substrate 100. There is no particular limitation on the method for forming the layer 200 of the photosensitive resin composition. For example, the layer 200 of the photosensitive resin composition may be formed by applying the photosensitive resin composition on the base substrate 100. From the viewpoint of performing the application smoothly, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied.

[0201] Examples of the coating method include, for example, gravure coating method, microgravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, screen printing method, etc.

[0202] The photosensitive resin composition may be applied once or may be applied in multiple portions. Further, different coating methods may be combined and implemented. In order to avoid foreign matter mixing, it is preferable that the application is carried out in an environment with little generation of foreign matter such as a clean room.

[0203] After applying the photosensitive resin composition, if necessary, the layer 200 of the photosensitive resin composition may be dried. The drying can be performed using a drying device such as a hot air furnace or a far-infrared furnace. The drying conditions are preferably set appropriately according to the composition of the photosensitive resin composition. For specific examples, the drying temperature is preferably 50 °C or higher, more preferably 70 °C or higher, particularly preferably 80 °C or higher, and preferably 150 °C or lower, more preferably 130 °C or lower, particularly preferably 120 °C or lower. Also, the drying time is preferably 30 seconds or longer, more preferably 60 seconds or longer, particularly preferably 120 seconds or longer, and preferably 60 minutes or shorter, more preferably 20 minutes or shorter, particularly preferably 5 minutes or shorter.

[0204] The formation of the layer 200 of the photosensitive resin composition may be performed, for example, using a photosensitive film. For specific examples, by laminating the layer of the photosensitive resin composition of the photosensitive film onto the base substrate, the layer 200 of the photosensitive resin composition can be formed on the base substrate 100. Lamination is usually performed by pressing the layer of the photosensitive resin composition of the photosensitive film onto the base substrate 100 while heating. This lamination is preferably performed under reduced pressure by the vacuum lamination method. Also, before lamination, if necessary, a preheating treatment for heating the photosensitive film and the base substrate may be performed.

[0205] The lamination conditions can be, for example, performed under the conditions of a crimping temperature (lamination temperature) of 70 °C to 140 °C, a crimping pressure of 1 kgf / cm 2 ~11 kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ) and a crimping time of 5 seconds to 300 seconds. Also, lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or lower. Lamination may be performed batchwise or continuously using a roll.

[0206] The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include, for example, the Vacuum Applicator manufactured by Nikkō Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll Dry Coater manufactured by Hitachi Industries Co., Ltd., the Vacuum Laminator manufactured by Hitachi AIC Inc., and the like.

[0207] In step (I), the layer 200 of the photosensitive resin composition formed on the base substrate 100 usually contains the photosensitive resin composition, and preferably contains only the photosensitive resin composition. The thickness of the layer 200 of the photosensitive resin composition is preferably the same as the thickness of the insulating layer of the multilayer substrate to be manufactured.

[0208] [4. Step (II): First exposure treatment] FIG. 2 is a schematic cross-sectional view for explaining step (II) in the manufacturing method according to the first embodiment of the present invention. The manufacturing method of the multilayer substrate according to the first embodiment of the present invention includes, as shown in FIG. 2, step (II) of performing a first exposure treatment on the layer 200 of the photosensitive resin composition after step (I).

[0209] In step (II), a latent image is formed in the layer 200 of the photosensitive resin composition by the first exposure treatment. Specifically, in the first exposure treatment, light L is selectively irradiated to a specific portion of the layer 200 of the photosensitive resin composition. Therefore, by the first exposure treatment, the layer 200 of the photosensitive resin composition is provided with an exposed portion 210 irradiated with light and an unexposed portion 220 not irradiated with light. In the example shown in this embodiment, since a negative-type photosensitive resin composition containing components (A) to (D) is used, a latent image corresponding to the concave portion is formed by the unexposed portion 220.

[0210] From the perspective of performing selective exposure, the first exposure process is usually carried out using a mask 300. Specifically, in the first exposure process, light L is irradiated onto the layer 200 of the photosensitive resin composition through the mask 300 including a light-transmitting portion 310 and a light-shielding portion 320. The light L passes through the light-transmitting portion 310 and enters the exposed portion 210, but cannot pass through the light-shielding portion 320, so it cannot enter the unexposed portion 220. Therefore, the exposed portion 210 and the unexposed portion 220 corresponding to the light-transmitting portion 310 and the light-shielding portion 320 can be provided in the layer 200 of the photosensitive resin composition. The mask 300 may be brought into close contact with the layer 200 of the photosensitive resin composition as shown in FIG. 2 (contact exposure method), or exposure may be performed using parallel light rays without bringing them into close contact (non-contact exposure method).

[0211] Generally, one of the light-transmitting portion 310 and the light-shielding portion 320 of the mask 300 is formed to have a planar shape corresponding to a recess (not shown) to be formed in the insulating layer of the multilayer substrate. The "planar shape" represents the shape as viewed from the thickness direction unless otherwise specified. When using a negative-type photosensitive resin composition as in the example shown in this embodiment, recesses of the insulating layer can be formed in the unexposed portion 220 of the layer 200 of the photosensitive resin composition. Therefore, usually, the light-shielding portion 320 of the mask 300 is formed to have the same planar shape as the recess of the insulating layer. The light-transmitting portion 310 or the light-shielding portion 320 formed in a planar shape corresponding to the recess of the insulating layer may be hereinafter referred to as a "mask pattern".

[0212] As the light L used in the first exposure process, it is preferable to use appropriate actinic rays according to the composition of the photosensitive resin composition. The wavelength of the actinic rays is usually 190 nm to 1000 nm, preferably 240 nm to 550 nm, but light rays with other wavelengths may also be used. Specific examples of the actinic light source include ultraviolet rays, visible light rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferable.

[0213] The exposure amount of the light L is preferably set so that a desired recess (not shown) can be formed after development in step (III). In one example, the specific range of the exposure amount is preferably 10 mJ / cm 2 above, more preferably 50 mJ / cm 2Above, particularly preferably 200 mJ / cm 2 or more, preferably 10,000 mJ / cm 2 or less, more preferably 8,000 mJ / cm 2 or less, particularly preferably 1,000 mJ / cm 2 or less.

[0214] When a support (not shown) exists on the layer 200 of the photosensitive resin composition, exposure may be performed through the support, or exposure may be performed after peeling off the support.

[0215] In the example shown in this embodiment, since a negative photosensitive resin composition containing components (A) to (D) is used, in the exposed portion 210, the (C) photoacid generator generates an acid. And since the acid acts as a catalyst, the crosslinking reaction of the (B) crosslinking agent proceeds, and the solubility in the developer decreases. On the other hand, in the unexposed portion 220, since the (C) photoacid generator does not generate an acid, the crosslinking reaction of the (B) crosslinking agent does not proceed or the progress is small, and thus the solubility in the developer is high. Utilizing the difference in solubility between this exposed portion 210 and the unexposed portion 220, the development process in the subsequent step (III) is performed.

[0216] [5. Step (VI): Heat treatment] The method for manufacturing a multilayer substrate according to the first embodiment of the present invention may include a step (VI) of heating the layer 200 of the photosensitive resin composition after step (II) and before step (III). According to the heating in step (VI), the crosslinking reaction of the (B) crosslinking agent can be promoted. Therefore, the solubility of the exposed portion in the developer can be rapidly decreased.

[0217] The heating in step (VI) may be performed on a hot plate or in an oven. The heating temperature may be, for example, 40°C or higher and 110°C or lower. Also, the heating time may be, for example, 30 seconds or longer and 60 minutes or shorter. In particular, when heating is performed using a hot plate, the heating temperature is preferably 50°C or higher, more preferably 60°C or higher, particularly preferably 70°C or higher, and preferably 110°C or lower, more preferably 100°C or lower, particularly preferably 90°C or lower. Also, the heating time is preferably 30 seconds or longer, more preferably 60 seconds or longer, particularly preferably 120 seconds or longer, and preferably 60 minutes or shorter, more preferably 20 minutes or shorter, particularly preferably 5 minutes or shorter. When heating is performed using an oven, the heating temperature is preferably 40°C or higher, more preferably 50°C or higher, and preferably 100°C or lower, more preferably 90°C or lower. Also, the heating time is preferably 3 minutes or longer, more preferably 10 minutes or longer, particularly preferably 15 minutes or longer, and preferably 60 minutes or shorter, more preferably 50 minutes or shorter, particularly preferably 40 minutes or shorter.

[0218] [6. Step (III): Development process] FIG. 3 is a schematic cross-sectional view for explaining step (III) in the manufacturing method according to the first embodiment of the present invention. The manufacturing method of the multilayer substrate according to the first embodiment of the present invention includes step (III) of subjecting the layer of the photosensitive resin composition to a development process after step (II). According to the development process, the latent image formed in step (II) can be developed. When a negative-type photosensitive resin composition is used as in the example shown in this embodiment, the exposed portion 210 (see FIG. 2) is not removed by the development process, but the unexposed portion 220 (see FIG. 2) is removed. Therefore, as shown in FIG. 3, a recess 230 can be formed in the layer 200 of the photosensitive resin composition.

[0219] Since the recessed portion 230 is formed in the non-exposed portion 220, it may have the same planar shape as the mask pattern of the light-shielding portion 320 (see FIG. 2) of the mask 300 used in the step (II). In the present embodiment, an example in which the recessed portion 230 is formed as a hole penetrating the layer 200 of the photosensitive resin composition will be described. Therefore, in the example shown in FIG. 3, the surface 100U of the base substrate 100 is exposed at the bottom 231 of the recessed portion 230. Further, the recessed portion 230 has a wall surface 232 that is non-parallel to the layer plane of the layer 200 of the photosensitive resin composition, and this wall surface 232 is formed from the main surface 200D on the base substrate 100 side of the layer 200 of the photosensitive resin composition to the main surface 200U on the opposite side.

[0220] As the development method, usually, a wet development method of bringing the layer 200 of the photosensitive resin composition into contact with a developer is performed. Examples of the developer include an alkaline aqueous solution, an aqueous developer, and an organic solvent.

[0221] Examples of the alkaline aqueous solution as the developer include an aqueous solution of an alkali metal compound. Examples of the alkali metal compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and the like. Further, examples of the alkaline aqueous solution include an aqueous solution of an organic base containing no metal ions, such as tetraalkylammonium hydroxide. The alkaline aqueous solution may be used alone or in combination of two or more. Among them, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable in that it does not contain metal ions and has little influence on the semiconductor chip. The pH of the alkaline aqueous solution is preferably in the range of 8 to 14, for example. Further, the base concentration of the above alkaline aqueous solution is preferably 0.1 mass% to 10 mass%.

[0222] Examples of the organic solvent as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. The organic solvent may be used alone or in combination of two or more. The concentration of the organic solvent is usually 2% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more based on the total amount of the developer. The developer may be 100% by mass of the organic solvent. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0223] The developer may contain additives such as a surfactant and an antifoaming agent as necessary to improve the developing action.

[0224] The developing time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly defined, but is preferably 20°C or higher, preferably 50°C or lower, and more preferably 40°C or lower.

[0225] Examples of the developing method include a paddle method, a spray method, a dipping method, a brushing method, a slapping method, and an ultrasonic method.

[0226] After development using the developer, the layer 200 of the photosensitive resin composition may be rinsed. The rinsing is preferably performed with a solvent different from the developer. For example, rinsing may be performed using the same type of solvent or water contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

[0227] [7. Step (IV): Second Exposure Treatment] FIG. 4 is a schematic cross-sectional view for explaining step (IV) in the manufacturing method according to the first embodiment of the present invention. The manufacturing method of the multilayer substrate according to the first embodiment of the present invention includes step (IV) of subjecting the layer 200 of the photosensitive resin composition to a second exposure treatment as shown in FIG. 4 after step (III).

[0228] In the second exposure treatment in step (IV), light L is irradiated onto at least the portion of the layer 200 of the photosensitive resin composition where the recess 230 is formed. From the viewpoint of easy operation, it is preferable to irradiate the entire layer 200 of the photosensitive resin composition including the recess 230 with light L.

[0229] When the development treatment is performed in step (III), the components generated by the first exposure treatment can be removed from the wall surface 232 of the recess 230 of the layer 200 of the photosensitive resin composition. For example, when a photosensitive resin composition containing components (A) to (D) is used, the acid generated by the (C) photoacid generator can be removed from the wall surface 232 of the recess 230. According to the second exposure treatment, the components removed in this way can be generated again on the wall surface 232 of the recess 230.

[0230] As the light L used in the second exposure treatment, the same actinic ray as that used in the first exposure treatment can be used.

[0231] The exposure amount of the light L is preferably set to such an extent that fine pores can be formed on the wall surface 232 of the recess 230 by the heat treatment in step (V). In one example, the specific range of the exposure amount is preferably 10 mJ / cm 2 or more, more preferably 50 mJ / cm 2 or more, particularly preferably 200 mJ / cm 2 or more, and preferably 10,000 mJ / cm 2 or less, more preferably 8,000 mJ / cm 2 or less, and particularly preferably 4,000 mJ / cm 2 or less.

[0232] In the second exposure process, in addition to the device for generating light rays such as an exposure apparatus, a device for generating light rays such as a plasma processing apparatus can be used. As the plasma processing apparatus, for example, an atmospheric pressure plasma processing apparatus or a low pressure plasma processing apparatus can be used. As the power source, for example, a high frequency power source or a microwave power source can be used. Examples of the gas species include, but are not limited to, oxygen, nitrogen, argon, hydrogen, water, hydrocarbons, fluorine, fluorides, chlorine, chlorides, etc. The same effect as the light rays generated by the exposure apparatus can be obtained by the light rays such as ultraviolet rays generated during the plasma processing.

[0233] [8. Step (V): Heat Treatment] The method for manufacturing a multilayer substrate according to the first embodiment of the present invention includes a step (V) of subjecting the layer of the photosensitive resin composition to a heat treatment after the step (IV). By the heat treatment, the photosensitive resin composition is cured, so that an insulating layer can be formed by the cured product of the photosensitive resin composition. Therefore, a multilayer substrate including a base substrate and an insulating layer can be obtained. In the present embodiment, the above heat treatment is performed under certain specific temperature rising conditions.

[0234] FIG. 5 is a graph showing an example of the temperature conditions of the heat treatment in the step (V) of the method for manufacturing a multilayer substrate according to the first embodiment of the present invention. In FIG. 5, the horizontal axis represents time, and the vertical axis represents the processing temperature. As shown in FIG. 5, the heat treatment in the step (V) includes raising the temperature of the layer of the photosensitive resin composition from a certain starting temperature T S to the maximum temperature T H . The starting temperature T S is set to 80° C. or lower. Specifically, the starting temperature T S is preferably 20° C. or higher, usually 80° C. or lower, more preferably 70° C. or lower, and particularly preferably 50° C. or lower.

[0235] The maximum temperature T H is the maximum temperature reached in the heat treatment in the step (V) and is set within a specific temperature range. Specifically, the maximum temperature T His usually 150 °C or higher, preferably 160 °C or higher, more preferably 170 °C or higher, and is usually 250 °C or lower, more preferably 220 °C or lower, still more preferably 200 °C or lower, and particularly preferably 190 °C or lower.

[0236] In the heat treatment in step (V), the temperature of the layer of the photosensitive resin composition is raised over a specific range of time t1 from 80 °C to the maximum temperature T H up to. That is, the temperature increase process P0 of the layer of the photosensitive resin composition from the starting temperature T S to the maximum temperature T H includes the process P1 from when the layer of the photosensitive resin composition starts to be heated from 80 °C until it reaches the maximum temperature T H The time t1 of this process P1 is sometimes referred to as the "controlled temperature increase time" below. In the present embodiment, this controlled temperature increase time t1 is kept within a specific range. Specifically, the above-mentioned controlled temperature increase time t1 is usually 30 minutes or more, preferably 40 minutes or more, more preferably 50 minutes or more. The upper limit of the controlled temperature increase time t1 is not particularly limited, but from the viewpoint of shortening the time required for manufacturing the multilayer substrate, it is preferably 24 hours or less, more preferably 18 hours or less, and particularly preferably 12 hours or less.

[0237] In the above process P1, the heating rate from 80 °C to the maximum temperature T H is preferably 5.7 °C / min or less, more preferably 4 °C / min or less, still more preferably 3 °C / min or less, and particularly preferably 2.3 °C / min or less from the viewpoint of obtaining a concave wall surface having particularly high adhesion to the conductor layer. In process P1, it is preferable that the heating rate is always within the above range. In the processes other than process P1 in process P0, the heating rate may not be within the above range, and it may not be heated temporarily. Therefore, for example, in the process of heating the layer of the photosensitive resin composition from a starting temperature T S below 80 °C to 80 °C, the temperature of the layer of the photosensitive resin composition may be temporarily maintained at one or more temperatures above the starting temperature T S and below 80 °C.

[0238] The heat treatment in step (V) starts at the starting temperature TS to maximum temperature T H Before the process P0, the temperature of the layer of the photosensitive resin composition is increased to the starting temperature T S It is preferable to include a step P2 of maintaining the temperature at the starting temperature T 0 immediately after the step P2 is performed. S When the heat treatment including the process P2 is performed, the curing of the layer of the photosensitive resin composition can be prevented from proceeding non-uniformly, and therefore unintended deformation of the recesses can be prevented. S The time t2 for which the temperature is maintained is preferably 5 minutes or more, more preferably 10 minutes or more, particularly preferably 20 minutes or more, and is preferably 120 minutes or less, more preferably 90 minutes or less, particularly preferably 60 minutes or less.

[0239] The heat treatment in step (V) is performed at a starting temperature T S to maximum temperature T H After the process P0 of heating the layer of the photosensitive resin composition to the maximum temperature T H It is preferable to include a process P3 of maintaining the temperature of the layer of the photosensitive resin composition at the maximum temperature T 0 . Preferably, the process P0 and the process P3 are performed continuously, and therefore, the temperature of the layer of the photosensitive resin composition is maintained at the maximum temperature T 0 . H When the heat treatment including the process P3 is performed, the curing of the layer of the photosensitive resin composition can be sufficiently advanced, so that an insulating layer having excellent mechanical strength can be obtained. H The time t3 for maintaining the temperature at this temperature is preferably 10 minutes or more, more preferably 20 minutes or more, particularly preferably 40 minutes or more, and is preferably 12 hours or less, more preferably 6 hours or less, particularly preferably 2 hours or less.

[0240] The above heat treatment can be carried out using a heating device such as a hot plate, an oven, a heating furnace, etc. Usually, since the layer of the photosensitive resin composition is thin, the temperature of the layer of the photosensitive resin composition can be quickly adjusted to the set temperature of the heating device. Therefore, the set temperature of the heating device can be adopted as the temperature of the layer of the photosensitive resin composition during the above-described heat treatment.

[0241] FIG. 6 is a schematic cross-sectional view for explaining step (V) in the manufacturing method according to the first embodiment of the present invention. By performing the above-described heat treatment, the layer of the photosensitive resin composition is cured. Therefore, as shown in FIG. 6, an insulating layer 400 formed of a cured product of the photosensitive resin composition is obtained on the base substrate 100. Accordingly, a multilayer substrate 10 including the base substrate 100 and the insulating layer 400 is obtained.

[0242] Since the insulating layer 400 is obtained by curing the layer 200 of the photosensitive resin composition in which the recess 230 is formed (see FIG. 4), it can have a recess 430. In the example shown in the present embodiment, the recess 430 of the insulating layer 400 is formed as a hole penetrating the insulating layer 400, similar to the recess 230 of the layer 200 of the photosensitive resin composition. Therefore, the surface 100U of the base substrate 100 is exposed at the bottom 431 of the recess 430. Further, the recess 430 has a wall surface 432 that is non-parallel to the layer plane of the insulating layer 400, and this wall surface 432 is formed from the main surface 400D on the base substrate 100 side of the insulating layer 400 to the opposite main surface 400U.

[0243] Fine holes 433 can be formed in the wall surface 432 of the recess 430 of the insulating layer 400. These fine holes 433 are depressions formed in the wall surface 432, and usually a plurality of them are formed per one recess 430. By these fine holes 433, the adhesion between the wall surface 432 and a conductor layer (not shown) formed on the wall surface 432 can be enhanced. The opening diameter of such fine holes is not particularly limited, but can be, for example, about 1 nm to 400 nm. Such fine holes 433 can be confirmed by observation with an electron microscope.

[0244] According to the study by the present inventor, the mechanism in which the micropores 433 are formed in the wall surface 432 of the recess 430 is considered as follows.

[0245] In the heat treatment in step (V), some or all of the resin components contained in the photosensitive resin composition undergo reactions such as crosslinking reactions, so the density of the bonds contained in the composition is improved. Therefore, as the curing progresses, the heat resistance temperatures such as the glass transition temperature and the softening point temperature are improved. Also, usually, when curing progresses, shrinkage stress can occur in the resin component.

[0246] If the temperature of the photosensitive resin composition becomes higher than the heat resistance temperature, the resin component of the photosensitive resin composition becomes fluidized, and the shrinkage stress can be eliminated by the fluidization. Also, if the fluidization is excessive, the recess may be filled with the photosensitive resin composition. However, in the above step (V), the temperature rising process P1 from 80°C to the maximum temperature T H is slowly carried out over the controlled temperature rising time t1. Then, the photosensitive resin composition can increase the temperature of the photosensitive resin composition while improving the heat resistance temperature to such an extent that the fluidization of the resin component can be suppressed. That is, while increasing the heat resistance temperature so as to suppress the fluidization of the resin component, the temperature of the photosensitive resin composition can be increased so as not to exceed the heat resistance temperature. Therefore, in the temperature rising process P1 from 80°C to the maximum temperature T H excessive fluidization of the resin component is suppressed, so that filling of the recess can be suppressed, and the resin component can undergo shrinkage due to shrinkage stress.

[0247] If the photosensitive resin composition does not contain a filler, the resin component can shrink uniformly. However, the photosensitive resin composition used in the present embodiment contains a filler. Since the filler is not compatible with the resin component, it may have a different degree of shrinkage from the resin component. And generally, the degree of shrinkage of the filler is smaller than that of the resin component. Therefore, from 80°C to the maximum temperature T HIn the temperature-rising process P1 up to [a certain temperature], the filler can either not shrink or have a small shrinkage. Therefore, since a difference in the degree of shrinkage occurs between the filler and the resin component, a portion where neither the resin component nor the filler can be filled may be formed on the wall surface 332 of the recess 330. And, fine pores can be formed by this portion.

[0248] As described above, the fine pores are formed by the resin component curing and shrinking in the surface layer portion of the wall surface 232 of the recess 230 of the photosensitive resin composition layer 200. Therefore, if the resin component does not cure in the surface layer portion of the wall surface 232, significant fluidization of the resin component can proceed. For example, if components such as acids or radicals that can occur in the photosensitive resin composition due to the exposure treatment are washed away by the developer, the curing of the resin component does not proceed in the surface layer portion of the wall surface, and fine pores may not be formed. However, in this embodiment, since the second exposure treatment is performed in step (IV) after development, components washed away by the developer can be generated again in the surface layer portion of the wall surface 232. Therefore, since the curing of the resin component can proceed in the surface layer portion of the wall surface 232, the formation of fine pores is possible. However, the technical scope of the present invention is not limited to the above mechanism.

[0249] [Step (VII) of forming the conductor layer] FIG. 7 is a schematic cross-sectional view for explaining step (VII) in the manufacturing method according to the first embodiment of the present invention. The manufacturing method of the multilayer substrate according to the first embodiment of the present invention may include, after step (V), a step (VII) of forming a conductor layer 500 on an insulating layer 400 as shown in FIG. 7.

[0250] In step (VII), the conductor layer 500 may be formed on a part of the insulating layer 400, or may be formed on the entire insulating layer 400. From the viewpoint of utilizing the high adhesion of the wall surface 432 of the recess 430, it is preferable that the conductor layer 500 is formed at least on the wall surface 432 of the recess 430. In the present embodiment, an example in which the conductor layer 500 is formed on the main surface 400U of the insulating layer 400, the wall surface 432 of the recess 430 of the insulating layer 400, and the surface 100U of the base substrate 100 exposed at the bottom 431 of the recess 430 will be described.

[0251] The conductor material used for the conductor layer 500 is not particularly limited. For example, the conductor layer 500 contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer 500 may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

[0252] The conductor layer 500 may have a single-layer structure, or may have a multilayer structure including two or more single metal layers or alloy layers made of different types of metals or alloys. When the conductor layer 500 has a multilayer structure, the layer in contact with the insulating layer 400 is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0253] The thickness of the conductor layer 500 depends on the design of the multilayer substrate 10, but is usually 1 μm to 35 μm, preferably 2 μm to 30 μm.

[0254] There is no limitation on the method for forming the conductor layer 500. For example, the conductor layer 500 may be formed by sputtering. Also, for example, the conductor layer 500 may be formed by combining electroless plating and electroplating. Further, the conductor layer 500 may be formed only by electroless plating after forming a plating resist having a pattern opposite to that of the conductor layer 500.

[0255] Among them, the conductor layer 500 is preferably formed by sputtering. When forming the conductor layer 500 by sputtering, usually, a conductor seed layer is formed on the insulating layer 400 by sputtering, and then a conductor sputter layer is further formed on the conductor seed layer by sputtering. Also, before forming the conductor seed layer by sputtering, the surface of the insulating layer 400 may be cleaned by reverse sputtering. As the gas used for reverse sputtering, Ar gas, O2 gas, and N2 gas are preferable. In particular, when the conductor seed layer is Cu or a Cu alloy, Ar gas, O2 gas, or a mixed gas of Ar and O2 is preferable. Also, when the conductor seed layer is Ti, Ar gas, N2 gas, or a mixed gas of Ar and N2 is preferable. Further, when the conductor seed layer is Cr or a Cr alloy (such as nichrome), Ar gas, O2 gas, or a mixed gas of Ar and O2 is preferable. Sputtering can be performed using various sputtering apparatuses such as magnetron sputtering and mirrortron sputtering. Examples of the metal for forming the conductor seed layer include Cr, Ni, Ti, nichrome, etc. In particular, Cr and Ti are preferable. The thickness of the conductor seed layer is preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. Examples of the metal for forming the conductor sputter layer include Cu, Pt, Au, Pd, etc. In particular, Cu is preferable. The thickness of the conductor sputter layer is preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, and more preferably 1000 nm or less.

[0256] A copper plating layer may be further formed by electrolytic copper plating on the layer formed by sputtering. The thickness of the copper plating layer is preferably 1 μm or more, more preferably 2 μm or more, and is preferably formed to be 75 μm or less, more preferably 35 μm or less.

[0257] Pattern formation may be performed on the conductor layer 500. As a method of pattern formation, for example, methods such as a subtractive method and a semi-additive method can be used.

[0258] [10. Optional process] The method for manufacturing a multilayer substrate according to the first embodiment of the present invention may further include an arbitrary process in combination with the above-described processes (I) to (VII).

[0259] For example, the method for manufacturing a multilayer substrate may include a process of drilling holes in the insulating layer. The formed holes may be trenches that do not penetrate the insulating layer, via holes that penetrate only the insulating layer, or through holes that penetrate the entire multilayer substrate. Drilling can be performed by, for example, methods such as drilling, laser, and plasma.

[0260] Further, the method for manufacturing a multilayer substrate may include a process of performing desmear treatment on the insulating layer. When the insulating layer is drilled, resin residues (smear) may adhere to the formed holes. In the desmear treatment, this smear is removed. The desmear treatment may be performed by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0261] Furthermore, the method for manufacturing a multilayer substrate may include a process of dicing the manufactured multilayer substrate.

[0262] The method for manufacturing a multilayer substrate may repeat the above-described processes. For example, processes (I) to (VII) may be repeated to manufacture a multilayer substrate having a multilayer structure in which insulating layers and conductor layers are alternately provided on a base substrate.

[0263] [11. Manufacturing Method of Multilayer Substrate According to Second Embodiment] In the manufacturing method according to the above-described first embodiment, in step (V), heat treatment was performed under certain specific temperature-raising conditions to obtain an insulating layer having a concave portion with a wall surface capable of forming a conductor layer with high adhesion. However, even when performing heat treatment that deviates from the temperature-raising conditions described in the first embodiment, if heat treatment under conditions where fine pores can be formed on the wall surface is performed in step (V), an insulating layer having a concave portion with a wall surface capable of forming a conductor layer with high adhesion can be obtained. Therefore, in order to manufacture a multilayer substrate including such an insulating layer, the manufacturing method according to the following second embodiment may be implemented.

[0264] The manufacturing method according to the second embodiment of the present invention is a manufacturing method of a multilayer substrate including a base substrate and an insulating layer having a concave portion. The manufacturing method according to the second embodiment is the same as the manufacturing method according to the first embodiment, except that the specific conditions of the heat treatment are not limited to the specific temperature-raising conditions described in step (V) of the first embodiment as long as the heat treatment performed after step (IV) of subjecting the layer of the photosensitive resin composition to a second exposure treatment includes raising the temperature of the layer of the photosensitive resin composition at a rate of temperature rise such that fine pores are formed on the wall surface of the concave portion.

[0265] Therefore, the manufacturing method according to the second embodiment includes, in this order: step (I) of forming a layer of a photosensitive resin composition containing a filler on a base substrate; step (II) of subjecting the layer of the photosensitive resin composition to a first exposure treatment; step (III) of subjecting the layer of the photosensitive resin composition to a development treatment; step (IV) of subjecting the layer of the photosensitive resin composition to a second exposure treatment; step (V’) of subjecting the layer of the photosensitive resin composition to a heat treatment. And the heat treatment in step (V’) includes raising the temperature of the layer of the photosensitive resin composition at a rate of temperature rise such that fine pores are formed on the wall surface of the concave portion.

[0266] According to the manufacturing method according to the second embodiment, recesses can be formed in the layer of the photosensitive resin composition by development in step (III). Then, after the heat treatment in the subsequent step (V'), an insulating layer formed of a cured product of the photosensitive resin composition is obtained. Since micropores are formed in the wall surface of the recesses of this insulating layer by the heat treatment in step (V'), it is possible to form the conductor layer with high adhesion.

[0267] In addition, the manufacturing method according to the second embodiment may further include optional steps such as step (VI) and step (VII) in combination with the above-described steps (I) to (IV) and (V'). Steps (I) to (IV) and the optional steps may be the same as those in the first embodiment. Also, in the manufacturing method according to the second embodiment, the same photosensitive resin composition as that in the first embodiment can be used.

[0268] Hereinafter, step (V') of the manufacturing method according to the second embodiment will be described in detail. In step (V') of the manufacturing method according to the second embodiment, the layer of the photosensitive resin composition is subjected to heat treatment. By the heat treatment, the photosensitive resin composition is cured, so that an insulating layer can be formed of the cured product of the photosensitive resin composition. This heat treatment includes raising the temperature of the layer of the photosensitive resin composition at a rate of temperature increase such that micropores are formed in the wall surface of the recesses.

[0269] The timing of raising the temperature at a rate of temperature increase such that micropores are formed is not limited as long as micropores can be formed in the wall surface of the recesses. Preferably, step (V') of the manufacturing method according to the second embodiment, like step (V) of the manufacturing method according to the first embodiment, includes raising the temperature of the layer of the photosensitive resin composition from the starting temperature T S to the maximum temperature T H The starting temperature T S and the maximum temperature T H in the second embodiment may be the same as those in the first embodiment. And in step (V') of the manufacturing method according to the second embodiment, among the process P0 of raising the temperature of the layer of the photosensitive resin composition from the starting temperature T S to the maximum temperature T H after the layer of the photosensitive resin composition starts to be heated from 80°C to the maximum temperature T HIn the process P1 until reaching [a certain state], it is preferable to increase the temperature at a rate such that fine pores are formed on the wall surface of the concave portion.

[0270] The rate of temperature increase in the above-mentioned process P1 can be controlled, for example, by the controlled temperature increase time t1 during which the process P1 is performed. Preferably, the range of the controlled temperature increase time t1 according to the second embodiment is the same as that of the controlled temperature increase time t1 according to the first embodiment.

[0271] Also, in the process P1 according to the second embodiment, from 80°C to the maximum temperature T H The specific rate of temperature increase up to can be the same as the specific rate of temperature increase in the process P1 according to the first embodiment. Therefore, the rate of temperature increase in the process P1 is preferably 5.7°C / min or less, more preferably 4°C / min or less, still more preferably 3°C / min or less, and particularly preferably 2.3°C / min or less. Also, in the process P1, it is preferable that the rate of temperature increase is always within the above range. Further, in the processes other than the process P1 in the process P0, the rate of temperature increase may not be within the above range, and it may not be temporarily heated.

[0272] Furthermore, the heat treatment in the step (V') of the manufacturing method according to the second embodiment, similar to the step (V) of the manufacturing method according to the first embodiment, may include a process P2 of maintaining the temperature of the photosensitive resin composition layer at the starting temperature T S before the process P0 of raising the temperature of the photosensitive resin composition layer from the starting temperature T H to the maximum temperature T. S to the starting temperature T.

[0273] Also, the heat treatment in the step (V') of the manufacturing method according to the second embodiment, similar to the step (V) of the manufacturing method according to the first embodiment, may include a process P3 of maintaining the temperature of the photosensitive resin composition layer at the maximum temperature T S after the process P0 of raising the temperature of the photosensitive resin composition layer from the starting temperature T H to the maximum temperature T. H to the maximum temperature T.

[0274] According to the manufacturing method according to the second embodiment, by performing heat treatment in step (V'), the layer of the photosensitive resin composition is cured, so that an insulating layer formed of the cured product of the photosensitive resin composition is obtained on the base substrate. Therefore, a multilayer substrate including the base substrate and the insulating layer is obtained. The multilayer substrate obtained by the manufacturing method according to the second embodiment is the same as the multilayer substrate obtained by the manufacturing method according to the first embodiment, except that fine holes are always formed on the wall surface of the recess. The fine holes formed in the second embodiment can be the same as those described in the first embodiment. Due to these fine holes, it is possible to form an insulating layer with high adhesion on the wall surface of the recess. Further, according to the manufacturing method according to the second embodiment, usually, the same advantages as those of the manufacturing method according to the first embodiment can be obtained.

[0275] [12. Multilayer Substrate] According to the manufacturing method according to the above-described embodiment, a multilayer substrate including a base substrate and an insulating layer formed of a cured product of a photosensitive resin composition can be manufactured. A recess is formed in the insulating layer of this multilayer substrate. Usually, the recess opens at least on the surface of the insulating layer opposite to the base substrate and has a wall surface that is not parallel to the layer plane of the insulating layer. And usually, fine holes are formed on the wall surface of the recess. Due to the anchor effect of the fine holes, a conductor layer can be formed on the wall surface with high adhesion. Therefore, a conductor layer can be stably formed on the wall surface, and peeling of the formed conductor layer can be suppressed.

[0276] Usually, a plurality of fine holes are formed on the wall surface of one recess. The number of fine holes formed on the wall surface of one recess is usually 10 or more, preferably 20 or more, particularly preferably 30 or more per 1 μm of the wall surface, but is not limited thereto. The upper limit can be, for example, 1000 or less. 2 per, usually 10 or more, preferably 20 or more, particularly preferably 30 or more, but not limited to this. The upper limit can be, for example, 1000 or less.

[0277] There is no particular limitation on the opening shape of the recess. Examples of the opening shape of the recess include a circular shape; a polygonal shape such as a quadrangular shape; a linear shape such as a straight line or a curve; and the like. Further, the recess may be formed so as to penetrate the insulating layer in the thickness direction, or may be formed only in a part of the thickness direction so as not to penetrate the insulating layer. Examples of such a recess include a via hole that penetrates the insulating layer, a trench that does not penetrate the insulating layer, and the like.

[0278] There is no particular limitation on the opening diameter of the recess, and for example, it may be in the range of 0.1 μm or more and 100 μm or less. Here, the opening diameter of the recess refers to the diameter of the opening of the recess on the surface of the insulating layer on the side opposite to the base substrate. When the opening shape of the recess is circular, the opening diameter represents the diameter of the circle. When the opening shape of the recess is square, the opening diameter represents the length of one side of the square. When the opening shape of the recess is linear, the opening diameter represents the width of the line.

[0279] According to the manufacturing method according to the above-described embodiment, the temperature increase during the heat treatment is carried out slowly, and since the filler hinders the flow of the resin component, the flow of the photosensitive resin composition can be suppressed during the heat treatment. Therefore, it is possible to suppress the photosensitive resin composition from flowing and deforming or filling the recess during the heat treatment. Therefore, the resolution dimension of the recess formed in the insulating layer can be reduced. For example, even in the case of a recess with a small opening diameter, it is possible to form the recess so as to penetrate the insulating layer in the thickness direction. Therefore, from the viewpoint of utilizing the fact that the resolution dimension can be reduced in this way, it is preferable to reduce the opening diameter of the recess formed in the insulating layer. The specific range of the opening diameter of the recess is preferably 0.1 μm or more, more preferably 1.0 μm or more, preferably 5 μm or less, and more preferably 4 μm or less. Further, in the multilayer substrate manufactured by the above-described manufacturing method, since the conductor layer can be formed with high adhesion on the wall surface of the recess, even when the opening diameter of the recess is small, a highly reliable interlayer connection can be achieved through the conductor layer formed in the recess. Here, the interlayer connection means electrically connecting the wiring formed on one surface of the insulating layer and the wiring formed on the other surface.

[0280] The number of recesses formed in the insulating layer may be 1 or 2 or more. Further, the shapes and dimensions of the formed recesses may be the same or different.

[0281] There is no particular limitation on the thickness of the insulating layer. Specifically, the thickness of the insulating layer is preferably 1 μm or more, more preferably 2 μm or more, preferably 100 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less.

[0282] As described above, a conductor layer may be formed on the insulating layer. The multilayer substrate may include two or more layers of the insulating layer and the conductor layer, respectively.

[0283] The multilayer substrate can be used, for example, in a semiconductor chip package, a package substrate, a printed wiring board, etc., and is particularly suitable for a wafer-level package. Examples of the wafer-level package include a fan-in type wafer-level package and a fan-out type wafer-level package, and it can be applied to any of them.

[0284] [13. Semiconductor device] The above-mentioned multilayer substrate can be used in the manufacture of semiconductor measures. The semiconductor device includes a multilayer substrate, and examples thereof include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

Example

[0285] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified. Further, the operations described below were performed in the air at normal temperature and normal pressure (23 °C and 1 atm) unless otherwise specified.

[0286] [Example 1] <Manufacture of Photosensitive Resin Composition> 10 parts by mass of "TR4020G" (manufactured by Asahi Organic Materials Co., Ltd.) as component (A-1), 5 parts by mass of "MEHC-7851SS" (manufactured by Meiwa Kasei Co., Ltd.) as component (A-2), 5 parts by mass of "BisE" (manufactured by Honshu Chemical Co., Ltd.) as component (A-3), 5 parts by mass of melamine resin (manufactured by Sanwa Chemical Co., Ltd. "MW-390") as crosslinking agent (B), 0.1 part by mass of oxime ester compound (manufactured by BASF Japan Ltd. "PAG-169") as photoacid generator (C), 4 parts by mass of rubber particles (manufactured by DOW "EXL-2655", average particle size 0.2 μm) as organic filler (D), 0.05 part by mass of 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol (manufactured by Kawaguchi Chemical Industry Co., Ltd. "VBATDT") as component (E), and 20 parts by mass of propylene glycol monomethyl ether acetate (PGMEA: manufactured by Junsei Chemical Co., Ltd.) as solvent (F) were mixed to obtain a photosensitive resin composition.

[0287] <Manufacture of Multilayer Substrate> A multilayer substrate having an insulating layer with a thickness of 2 μm and a multilayer substrate having an insulating layer with a thickness of 6 μm were each manufactured by the following method.

[0288] Ti / Cu was sputtered on an 8-inch silicon wafer, and an electrolytically plated copper-plated wafer was prepared as a base substrate.

[0289] The photosensitive resin composition was spin-coated on the base substrate. Next, a drying treatment was performed on a hot plate at 80°C for 3 minutes to form a photosensitive resin composition layer on the base substrate.

[0290] Next, a first exposure treatment was performed on the photosensitive resin composition layer through a rectangle as a mask using a projection exposure apparatus with a numerical aperture NA = 0.18 (wavelength 365 nm). As the rectangle, a mask pattern for forming square via holes with side dimensions of 2 μm, 3 μm, 4 μm, and 5 μm, and a mask pattern for forming lines with line / space dimensions of 2 μm / 2 μm, 3 μm / 3 μm, 4 μm / 4 μm, and 5 μm / 5 μm were used. The exposure dose was 50 mJ / cm2 from 1000 mJ / cm 2 in the range, it was set to the optimum value. Here, the "optimum value" represents the value that can obtain the smallest resolution dimension.

[0291] Next, on a hot plate, the photosensitive resin composition layer was heated at 80 °C for 3 minutes to promote crosslinking.

[0292] Next, a developing treatment was performed by bringing a developer at 23 °C (an aqueous solution of tetraammonium hydroxide with 2.38% by mass) into contact with the photosensitive resin composition layer for 60 seconds. This developing treatment was performed by the paddle development method.

[0293] After development, a second exposure treatment was performed by irradiating the photosensitive resin composition layer with ultraviolet light of 1 J / cm 2 .

[0294] Furthermore, a heat treatment was performed on the photosensitive resin composition layer in nitrogen to obtain an insulating layer. The heat treatment was performed using a furnace capable of adjusting the temperature along a set program. Also, the program was set to hold at 50 °C for 30 minutes, increase the temperature from 50 °C to 190 °C at a rate of 2 °C / min, and further hold at 190 °C for 60 minutes. In this heat treatment, the temperature increase time from 80 °C to 190 °C was 55 minutes. Through the above operations, a multilayer substrate having an insulating layer with a thickness of 2 μm and a multilayer substrate having an insulating layer with a thickness of 6 μm were obtained.

[0295] <Evaluation of the Resolution Dimension of the Pattern> The obtained insulating layer was observed with a scanning electron microscope (SEM), and the resolution dimensions of the via holes and lines were measured.

[0296] The resolution dimension of the via hole formed in the insulating layer represents the design value of the minimum via hole formed in the insulating layer. Further, the minimum via hole means that the via hole penetrates the insulating layer by opening to the surface of the base substrate, and the dimension of the diameter of the bottom of the via hole is in the range of 60% or more and 120% or less of the design value of the via hole. Furthermore, the design value of the via hole represents the dimension of one side of the rectangular mask pattern corresponding to the via hole.

[0297] The resolution dimension of the line formed in the insulating layer represents the design value of the minimum line formed in the insulating layer. Further, the minimum line means that the line penetrates the insulating layer by opening to the surface of the base substrate, and the dimension of the line in the line / space is in the range of 60% or more and 120% or less of the design value of the line. Furthermore, the design value of the line represents the dimension of the width of the rectangular mask pattern corresponding to the line.

[0298] <Measurement of the number of micropores formed on the wall surface> An insulating layer with a thickness of 2 μm was observed with a scanning electron microscope (SEM), and the number of micropores formed on the wall surface of the minimum via hole formed in the insulating layer was counted. Specifically, from the SEM image, a range of 1 μm in height × 1 μm in width was set on the wall surface, and the number of micropores in that range was counted.

[0299] <Evaluation of the adhesion of the conductor layer> On an insulating layer including a via hole and a portion where a line is formed, reverse sputtering treatment was performed using a sputtering apparatus. This reverse sputtering treatment was carried out using Ar gas under the conditions of a pressure of 0.3 Pa, an output of 200 W, and a treatment time of 10 minutes. Then, by sputtering, a Ti layer with a thickness of 50 nm was formed as a conductor seed layer, and further a Cu layer with a thickness of 300 nm was formed as a conductor sputtering layer. Furthermore, a copper plating layer with a thickness of 10 μm was formed on the conductor sputtering layer by electrolytic plating. Thereafter, the multilayer substrate was cut, and the cross sections in the via hole and the line were observed. When no peeling was observed at the interface between the insulating layer and the Ti layer, the adhesion was determined to be "good". Also, when peeling was observed at the interface between the insulating layer and the Ti layer, the adhesion was determined to be "poor".

[0300] [Example 2] The program of the furnace used during the heat treatment was set to hold at 50 °C for 30 minutes, increase the temperature from 50 °C to 190 °C at a rate of 0.2 °C / min, and further hold at 190 °C for 60 minutes. In this heat treatment, the temperature increase time from 80 °C to 190 °C was 9 hours and 10 minutes. Except for the above matters, the multilayer substrate was manufactured and evaluated in the same manner as in Example 1.

[0301] [Example 3] As the (A-3) component, instead of 5 parts by mass of "BisE" (manufactured by Honshu Chemical Co., Ltd.), 5 parts by mass of "BisP-M" (manufactured by Honshu Chemical Co., Ltd.) was used. Also, as the (C) photoacid generator, instead of 0.1 part by mass of an oxime ester compound ("PAG-169" manufactured by BASF Japan Ltd.), 0.1 part by mass of another oxime ester compound ("PAG-103" manufactured by BASF Japan Ltd.) was used. Except for the above matters, the multilayer substrate was manufactured and evaluated in the same manner as in Example 1.

[0302] [Example 4] Except for not using 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol ("VBATDT" manufactured by Kawaguchi Chemical Industry Co., Ltd.) as the (E) component, the multilayer substrate was manufactured and evaluated in the same manner as in Example 1.

[0303] [Example 5] Instead of 5 parts by mass of "BisE" (manufactured by Honshu Chemical Industry Co., Ltd.), 5 parts of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol ("TrisP-PA" manufactured by Honshu Chemical Industry Co., Ltd.) as component (A) was used. Also, 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol ("VBATDT" manufactured by Kawaguchi Chemical Industry Co., Ltd.) as component (E) was not used. Except for the above matters, the multilayer substrate was manufactured and evaluated in the same manner as in Example 1.

[0304] [Comparative Example 1] The multilayer substrate was manufactured and evaluated in the same manner as in Example 1, except that the second exposure treatment was not performed after development.

[0305] [Comparative Example 2] The program of the furnace used during the heat treatment was set to hold at 50°C for 30 minutes, increase the temperature from 50°C to 190°C at a rate of 5°C / min, and further hold at 190°C for 60 minutes. In this heat treatment, the temperature increase time from 80°C to 190°C was 22 minutes. Except for the above matters, the multilayer substrate was manufactured and evaluated in the same manner as in Example 1.

[0306] [Comparative Example 3] The multilayer substrate was manufactured and evaluated in the same manner as in Example 1, except that rubber particles ("EXL-2655" manufactured by DOW) as the organic filler (D) were not used.

[0307] [Results] The results of the above-described Examples and Comparative Examples are shown in the following table. Also, an SEM photograph of a via hole with a side length of 2 μm formed in the insulating layer with a thickness of 2 μm obtained in Example 1 is shown in FIG. 8, and an SEM photograph of a via hole with a side length of 3 μm formed in the insulating layer with a thickness of 6 μm is shown in FIG. 9. Further, an SEM photograph of a via hole with a side length of 5 μm formed in the insulating layer with a thickness of 6 μm obtained in Comparative Example 3 is shown in FIG. 10. In the columns of "Number of micropores" and "Adhesion" in the following table, "-" means that the via holes did not open and the number of micropores and adhesion could not be evaluated.

[0308] [Table 1]

[0309] [Consideration] In Comparative Example 1, recesses were formed in the layer of the photosensitive resin composition by development, but the second exposure treatment was not performed. Therefore, the photosensitive resin composition around the recesses flowed by heat treatment, and the recesses were filled. Therefore, via holes were not formed in the insulating layer.

[0310] In Comparative Example 2, recesses were formed in the layer of the photosensitive resin composition by development, but the controlled heating-up time t1 was short during the heat treatment. That is, during the heat treatment, the temperature rise of the layer of the photosensitive resin composition advanced rapidly. Therefore, the temperature rise speed of the photosensitive resin composition itself became faster than the rise speed of the heat-resistant temperature (glass transition temperature in Comparative Example 2) of the photosensitive resin composition, the temperature of the layer of the photosensitive resin composition became higher than the heat-resistant temperature, and the photosensitive resin composition around the recesses was fluidized. Therefore, the recesses were filled with the fluidized photosensitive resin composition, and via holes were not formed in the insulating layer.

[0311] Furthermore, in Comparative Example 3, since the photosensitive resin composition did not contain a filler, the shrinkage of the photosensitive resin composition proceeded uniformly, and micropores could not be formed (see FIG. 10).

[0312] On the other hand, in Examples 1 to 5, micropores were formed on the wall surfaces of the recesses (see FIGS. 8 and 9). And the conductor layer formed on the wall surface where such micropores were formed did not undergo peeling. Therefore, from the results of the above-described examples, it was confirmed that according to the present invention, a multilayer substrate including an insulating layer in which recesses having a wall surface capable of forming a conductor layer with high adhesion was formed can be manufactured. [Explanation of symbols]

[0313] 10 Multilayer substrate 100 Base substrate Surface of the 100U base substrate 200 Layer of photosensitive resin composition Principal surface of the layer of 200D photosensitive resin composition Principal surface of the layer of 200U photosensitive resin composition 210 Exposed portion 220 Unexposed portion 230 Recess 231 Bottom 232 Wall surface 300 Mask 310 Light-transmitting portion 320 Light-shielding portion 400 Insulating layer Principal surface of the 400D insulating layer Principal surface of the 400U insulating layer 430 Recess 431 Bottom 432 Wall surface 433 Micro-pore 500 Conductor layer L Light

Claims

1. A method for manufacturing a multi-layer substrate, comprising a base substrate and an insulating layer having recesses formed therein; forming a layer of a photosensitive resin composition containing a filler on the base substrate; performing a first exposure treatment on the layer of the photosensitive resin composition; performing a development treatment on the layer of the photosensitive resin composition; performing a second exposure treatment on the layer of the photosensitive resin composition; including, in this order, performing a heat treatment on the layer of the photosensitive resin composition; the heat treatment includes heating the layer of the photosensitive resin composition from a starting temperature of 80°C or lower to a maximum temperature of 150°C or higher and 250°C or lower; in the heat treatment, the layer of the photosensitive resin composition is heated over a period of 30 minutes or more from 80°C to the maximum temperature; the heat treatment includes a process P1 from when the layer of the photosensitive resin composition starts to be heated from 80°C until it reaches the maximum temperature, and the heating rate in the process P1 is always in the range of 4°C / min or less, a method for manufacturing a multi-layer substrate.

2. The method for manufacturing a multi-layer substrate according to claim 1, wherein holes are formed in the wall surface of the recesses of the insulating layer.

3. The method for manufacturing a multi-layer substrate according to claim 1 or 2, wherein the opening diameter of the recess is 0.1 μm or more and 5 μm or less.

4. The photosensitive resin composition is (A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule, (B) a crosslinking agent, (C) a photoacid generator, and (D) the filler The method for manufacturing a multi-layer substrate according to any one of claims 1 to 3.

5. The method for manufacturing a multi-layer substrate according to any one of claims 1 to 4, further including forming a conductor layer on the insulating layer.

6. The manufacturing method of the multilayer substrate according to any one of claims 1 to 5, wherein the base substrate is a wafer.

7. A manufacturing method of a multilayer substrate, comprising: a base substrate and an insulating layer formed with recesses; forming a layer of a photosensitive resin composition containing a filler on the base substrate; performing a first exposure treatment on the layer of the photosensitive resin composition; performing a development treatment on the layer of the photosensitive resin composition to form recesses; performing a second exposure treatment on the layer of the photosensitive resin composition; including, in this order, a step of performing a heat treatment on the layer of the photosensitive resin composition; The manufacturing method of the multilayer substrate, wherein the heat treatment includes heating the layer of the photosensitive resin composition at a temperature rising rate at which the temperature of the layer of the photosensitive resin composition does not exceed the glass transition temperature and the softening point temperature of the photosensitive resin composition, and forming holes in the wall surface of the recess.

8. The number of holes per wall surface of 1 μm ２ The manufacturing method of the multilayer substrate according to claim 2 or 7, wherein the number of holes is 10 or more.

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