Method for manufacturing wiring board

Abstract

To provide a method for manufacturing a wiring board that can more easily and accurately manufacture a wiring board.SOLUTION: A method for manufacturing a wiring board according to the present invention includes a step 1 of filling a liquid curable composition L into recesses 12 of a mold member 10 having recesses 12 arranged on its surface and first protrusions 14 arranged on the bottom of the recesses 12, and placing a laminate 20 including a substrate 22 and wiring 24 on the mold member 10 such that the first protrusions 14 face the wiring 24, a step 2 of curing the liquid curable composition L filled in the recesses 12 to obtain a cured product 30, a step 3 of peeling the mold member 10 from the cured product 30, and a step 4 of filling a metal into first holes that are continuous from the surface of the cured product 30 to the surface of the wiring 24, thereby forming a connection that connects to the wiring 24.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a wiring board. [Background technology]

[0002] Various methods have been studied for manufacturing semiconductor packages, and one known method is a manufacturing method using an imprinting method. Patent Document 1 discloses a method for manufacturing a semiconductor package using an imprinting method in which a non-photosensitive insulating resin layer is formed on a conductor pattern provided on the surface of an insulating substrate, and then a mold having convex portions is pressed against the non-photosensitive insulating resin layer to form concave portions such as vias in the non-photosensitive insulating resin layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-220547 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, there has been a demand for a method for manufacturing wiring boards, such as semiconductor packages, that is simpler and more accurate. Here, the method of manufacturing a wiring board by forming a pattern (e.g., grooves and vias for forming wiring) in an insulating layer using an imprint method as described in Patent Document 1 does not require various processes (e.g., development process, cleaning process, etc.) compared to a method of manufacturing a wiring board by forming a pattern in an insulating layer using photolithography. Also, compared to a method of forming a pattern in an insulating layer using a laser or the like, the method allows for simpler manufacturing of a wiring board. However, in a wiring board formed using the imprint method as described in Patent Document 1, the precision of the pattern formed on the insulating layer may be insufficient, resulting in poor conductivity of the wiring board.

[0005] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for manufacturing a wiring board that can more easily and accurately manufacture a wiring board. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0007] [1] A method for manufacturing a wiring substrate, a step 1 of filling a liquid curable composition into a recess of a mold member having a surface on which a recess is arranged and a first protrusion on the bottom surface of the recess, and placing a laminate including a substrate and wiring on the mold member so that the first protrusion and the wiring face each other; Step 2: curing the liquid curable composition filled in the recesses obtained in Step 1 to obtain a cured product; Step 3 of peeling the mold member from the cured product; and step 4 of filling a first hole portion, which is provided on the surface of the cured material at a position corresponding to the first convex portion and which continues from the surface of the cured material to the surface of the wiring, with a metal to form a connection portion that connects to the wiring. [2] The method for producing a wiring board according to [1], wherein the liquid curable composition contains a resin. [3] The method for manufacturing a wiring board according to [2], wherein the resin comprises at least one selected from the group consisting of a polyimide precursor, a silicone resin, an epoxy resin, a polyimide resin, a polyamide resin, a maleimide resin, and a polyphenylene ether resin. [4] a second protrusion having a height lower than that of the first protrusion on the bottom surface of the recess, The method for manufacturing a wiring board according to any one of [1] to [3], wherein in step 4, a wiring portion is formed by filling a metal into a second hole portion that is provided on the surface of the cured material at a position corresponding to the second convex portion and does not penetrate the cured material. [5] The method for producing a wiring board according to any one of [1] to [4], wherein in step 4, the metal is filled by plating. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for manufacturing a wiring board that can more easily and accurately manufacture a wiring board. [Brief explanation of the drawings]

[0009] [Figure 1A] 1 is a schematic cross-sectional view illustrating an example of step 1 in the method for manufacturing a wiring board of the present invention. [Figure 1B] 1 is a schematic cross-sectional view illustrating an example of step 1 in the method for manufacturing a wiring board of the present invention. [Figure 2] 4 is a schematic cross-sectional view illustrating an example of step 2 in the method for manufacturing a wiring board of the present invention. FIG. [Figure 3] 4 is a schematic cross-sectional view illustrating an example of step 3 in the method for manufacturing a wiring board according to the present invention. FIG. [Figure 4A] 4 is a schematic cross-sectional view illustrating an example of step 4 in the method for manufacturing a wiring board of the present invention. FIG. [Figure 4B] 4 is a schematic cross-sectional view illustrating an example of step 4 in the method for manufacturing a wiring board of the present invention. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In the present specification, in the numerical ranges described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] The term "step" in this specification includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0013] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified.

[0014] In this specification, the term "transparent" means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0015] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light, extreme ultraviolet light, X-rays, EUV light, etc., as typified by mercury lamps and excimer lasers, but also exposure using particle beams such as electron beams and ion beams.

[0016] In this specification, the "solid content" of a composition refers to the components that form a film formed using the composition. Typically, when the composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, liquid components that form a film are also considered to be solid content.

[0017] In this specification, unless otherwise specified, the content ratio of each repeating unit in a resin is a molar ratio. In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0018] In this specification, "(meth)acrylic acid" is a concept that encompasses both acrylic acid and methacrylic acid, "(meth)acryloyl group" is a concept that encompasses both acryloyl group and methacryloyl group, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate, and "(meth)acrylamide group" is a concept that encompasses both acrylamide group and methacrylamide group.

[0019] In this specification, the bonding direction of a divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "XYZ," the compound may be "XO-CO-Z" or "X-CO-OZ." Unless otherwise specified, the compounds described herein may include isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, only one type of isomer or isotope may be included, or multiple types may be included.

[0020] Unless otherwise specified, the layer thickness (film thickness) in this specification is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0021] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg). In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0022] A method for manufacturing a wiring board according to an embodiment of the present invention will be described below.

[0023] [Method of manufacturing wiring board] The method for producing a wiring board of the present invention includes the following steps 1 to 4 in this order. Step 1: A step of filling a liquid curable composition into a recess of a mold member having a surface on which a recess is arranged and a first protrusion on the bottom surface of the recess, and placing a laminate including a substrate and wiring on the mold member so that the first protrusion and the wiring face each other. Step 2: A step of curing the liquid curable composition filled in the recesses obtained in Step 1 to obtain a cured product. Step 3: Peeling the mold member from the cured product Step 4: A step of filling a first hole portion, which is provided on the surface of the cured product at a position corresponding to the first protrusion and which continues from the surface of the cured product to the surface of the wiring, with metal to form a connection portion that connects to the wiring.

[0024] According to the method for manufacturing a wiring board of the present invention, a wiring board can be manufactured more easily and accurately. Although the details of the reason for this are not clear, it is generally assumed as follows. In conventional imprinting methods for forming a pattern on an insulating layer, a mold member is pressed into the insulating layer, which can lead to misalignment of the mold member when the mold member is pressed in. Furthermore, since the insulating layer is already in a non-fluid state, it can be difficult to fully transfer the pattern of the mold member. In contrast, in the method for producing a wiring board of the present invention, a liquid curable composition is filled into the recess of a mold member, and a laminate including a substrate and wiring is placed so that the liquid curable composition in the recess comes into contact with the laminate, and then the liquid curable composition is cured. In this way, because a flowable liquid curable composition is filled into the mold member, the liquid curable composition is evenly placed along the pattern of the mold member. Furthermore, because the liquid curable composition is in a flowable state when the laminate is placed, it is easy to align the laminate with the mold member. As a result, compared to when using conventional imprinting methods, it is presumed that the pattern of the cured product of the liquid curable composition is formed with greater precision, resulting in improved conductivity of the resulting wiring board. Furthermore, the method for manufacturing a wiring board of the present invention does not require various processes (e.g., development process, cleaning process, etc.) compared to a method for forming a pattern on an insulating layer using photolithography. Furthermore, compared to a method for forming a pattern on an insulating layer using a laser or the like, detailed condition settings and large-scale manufacturing equipment are not required. Therefore, the method for manufacturing a wiring board of the present invention allows for easy manufacturing of a wiring board.

[0025] The procedure of each step will be described in detail below with reference to the drawings.

[0026] [Process 1] 1A and 1B are schematic cross-sectional views for explaining step 1, showing cross sections of a mold member 10 and a laminate 20 along the thickness direction.

[0027] 1A is a diagram showing a state in which a liquid curable composition L has been filled into a recess 12 arranged on the surface of a mold member 10. A first protrusion 14 and a second protrusion 16 that is shorter in height than the first protrusion 14 are arranged on a bottom surface 12b of the recess 12 in the mold member 10. The heights of the first protrusion 14 and the second protrusion 16 are both smaller than the depth of the recess 12. In step 1, a process is carried out in which the liquid curable composition L is filled into the recesses 12. The filling method is not particularly limited, and filling can be carried out using a known coating method such as inkjet coating, spray coating, curtain coating, and slit coating. The liquid curable composition L is preferably filled so that the entire side surfaces of the first convex portions 14 and the second convex portions 16 are covered with the liquid curable composition L. The liquid curable composition L may also be filled so that the tips of the first convex portions 14 are covered with the liquid curable composition L.

[0028] 1B is a diagram showing a state in which the laminate 20 is placed on the mold member 10. As shown in FIG. 1B, the laminate 20 is placed on the mold member 10, and the laminate 20 and the mold member 10 surround the liquid curable composition L filled in the recess 12. The laminate 20 includes a substrate 22 , a first wiring 24 disposed on one surface of the substrate 22 , and a second wiring 26 disposed on one surface of the substrate 22 . Specifically, the laminate 20 is disposed on the mold member 10 so that the first wiring 24 and the first protrusion 14 face each other, and the second wiring 26 and the second protrusion 16 face each other. The method for placing the laminate 20 on the mold member 10 is not particularly limited, but for example, alignment marks can be attached to the laminate 20 or the mold member 10 and the laminate 20 can be placed in a position where the first wiring 24 and the first convex portion 14 face each other, and the second wiring 26 and the second convex portion 16 face each other, and the laminate 20 can be placed in a position where the first wiring 24 and the first convex portion 14 face each other, using an apparatus equipped with a known alignment mechanism. After the laminate 20 is placed on the mold member 10, pressure may be applied so that the laminate 20 and the mold member 10 come into close contact with each other. 1B, the first wiring 24 and the first protrusion 14 may be in contact with each other, but this is not limiting, and the first wiring 24 and the first protrusion 14 may not be in contact with each other and may be spaced apart when the laminate 20 is placed on the mold member 10. If the first wiring 24 and the first protrusion 14 are spaced apart when the laminate 20 is placed on the mold member 10, a liquid curable composition L is placed between the first wiring 24 and the first protrusion 14. Furthermore, when the laminate 20 is placed on the mold member 10, the second wiring 26 and the second convex portion 16 are not in contact with each other but are spaced apart, and the liquid curable composition L is placed between the second wiring 26 and the second convex portion 16.

[0029] <Molding material> Materials constituting the mold member 10 include metal (for example, stainless steel) and glass, with metal being preferred from the standpoint of durability and heat resistance.

[0030] A recess 12 is provided on one surface of the mold member 10 so as to hold the liquid curable composition L. The depth of the recess 10 is not particularly limited, but is preferably 0.1 to 500 μm, and more preferably 1 to 100 μm.

[0031] On the bottom surface 12b of the recess 12, a first protrusion 14 and a second protrusion 16 that is lower in height than the first protrusion 14 are arranged. The first protrusions 14 are preferably used to form a pattern having vias (specifically, through holes or via holes) in a cured product (described below) obtained by curing the liquid curable composition L. In this case, examples of the cross-sectional shape of the first protrusions 14 (the shape of a cross section along the height direction of the first protrusions 14) include a rectangle (including a trapezoid) and a shape combining two or more rectangles of different sizes (specifically, corresponding to the shape of the first protrusions 14 in FIG. 1A). Examples of the front shape of the first protrusions 14 (the shape when the first protrusions 14 are observed from a direction in which the bottom surface 12b of the mold member 10 is visible) include a circle and a rectangle. When the primary protrusions 14 are used to form a pattern having vias in a cured product, the diameter of the primary protrusions 14 is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and the height of the primary protrusions 14 is preferably 0.1 to 500 μm, more preferably 1 to 100 μm. In the example of Figures 1A and 1B, the number of first protrusions 14 is one, but this is not limited to this, and two or more first protrusions 14 may be arranged.

[0032] The second protrusions 16 are preferably used to form linear grooves in a cured product (described later). In this case, the cross-sectional shape of the second protrusions 16 (a cross section intersecting the extension direction of the second protrusions 16 and along the height direction of the second protrusions 16) may be a rectangle (including a trapezoid). When the second protrusions 16 are used to form linear grooves in the cured product, the diameter (width) of the second protrusions 16 is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm. The height of the second protrusions 16 is preferably 0.01 to 50 μm, more preferably 1 to 30 μm. 1A and 1B show the case where the number of second protrusions 16 is three, but the present invention is not limited to this and the number of second protrusions 16 may be two or less, or four or more. When the number of second protrusions 16 is two or more, the distance between adjacent second protrusions 16 is preferably 0.01 to 100 μm, and more preferably 0.1 to 50 μm.

[0033] A release layer (not shown) may be provided on the surface of the mold member 10 that comes into contact with the liquid curable composition L. This improves the releasability of the mold member 10 in step 3 described below. The release layer is not particularly limited, and examples thereof include a layer formed using a fluororesin, a hard chrome layer, and the like.

[0034] <Laminate> The substrate 22 in the laminate 20 may be a glass substrate, a glass epoxy substrate, a silicon substrate, or a resin substrate, with a resin substrate being preferred because it can be manufactured by a roll-to-roll process. The refractive index of the substrate 22 is preferably 1.50 to 1.52. The substrate 22 may be made of a light-transmitting substrate such as a glass substrate, and may be made of tempered glass such as Corning Gorilla Glass. Materials contained in the substrate 22 include, for example, materials used in Japanese Patent Application Laid-Open Nos. 2010-086684, 2010-152809, and 2010-257492. When the substrate 22 is a resin substrate, a resin film with small optical distortion and / or high transparency is more preferable as the resin substrate. Specific examples of the resin substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0035] The first wiring 24 and the second wiring 26 in the laminate 20 may be any wiring used in general circuit wiring or touch panel wiring. The material constituting the first wiring 24 and the second wiring 26 is preferably one or more materials selected from the group consisting of simple metals, conductive metal oxides, graphene, carbon nanotubes, and conductive polymers, and simple metals are more preferred. Examples of the metal element include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au, and among these, Cu and Ag are preferred. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO2. The conductivity is determined by the volume resistivity of 1×10 6 This means that the volume resistivity is less than 1×10 4 It is preferably less than Ωcm.

[0036] The first wiring 24 and the second wiring 26 are preferably formed in a pattern on the substrate 22. Examples of methods for manufacturing the patterned wiring (first wiring 24 and second wiring 26) include etching methods (e.g., subtractive methods and additive methods). Examples of etching methods include wet etching methods described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching. The etching method may also be a method using an etching resist.

[0037] <Liquid curable composition> The liquid curable composition is a composition that is liquid at 23° C. Specifically, the viscosity of the liquid curable composition at 23° C. is preferably 100 Pa s or less, more preferably 20 Pa s or less. There is no particular lower limit, but the viscosity is preferably 0.001 Pa s or more, more preferably 0.01 Pa s or more. The viscosity of the curable liquid composition can be measured at 23° C. using, for example, a B-type viscometer (manufactured by Eiko Seiki Co., Ltd., product name "LVDVE"), and the arithmetic mean value of three measurements can be used.

[0038] The liquid curable composition is preferably a composition that is cured by the action of heat or light (such as ultraviolet light).

[0039] Various components that may be contained in the curable liquid composition will be described in detail below.

[0040] (resin) The liquid curable composition preferably contains a resin. The resin preferably contains at least one selected from the group consisting of a polyimide precursor, a silicone resin, an epoxy resin, a polyimide resin, a polyamide resin, a maleimide resin, and a polyphenylene ether resin, in order to further improve the curability of the liquid curable composition. Among these, the resin preferably contains at least one selected from the group consisting of an epoxy resin, a polyimide precursor, and a silicone resin, more preferably contains at least one selected from the group consisting of a polyimide precursor and a silicone resin, from the viewpoint of further improving the curability of the liquid curable composition, further preferably contains a polyimide precursor or a polysilsesquioxane, and particularly preferably is a polyimide precursor or a polysilsesquioxane. The precursors of various resins are resins that can be converted into various resins by heat treatment, light treatment, or chemical treatment.

[0041] The resin may have a reactive group. Examples of the reactive group include a polymerizable group and a functional group other than a polymerizable group. Examples of the polymerizable group include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, and the radical polymerizable group is preferred. The radical polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, with a (meth)acryloyl group being preferred. Examples of functional groups other than polymerizable groups include amino groups, hydroxyl groups, and thiol groups, with amino groups being preferred, and secondary amino groups (e.g., phenylamino groups, methylamino groups, and ethylamino groups) or primary amino groups (-NH2) being more preferred.Functional groups other than silanol groups (Si-OH) are also preferred.

[0042] The resin may have an acid-decomposable group. Examples of the acid-decomposable group include the acid-decomposable groups described in paragraphs 0024 to 0031 of WO 2019 / 187881.

[0043] Polyimide resins and polyimide precursors The polyimide resin is a resin having an imide structure. The polyimide resin is preferably a resin having a cyclic imide structure. The polyimide may have a substituent. The polyimide resin is preferably a resin synthesized from a polyimide precursor having a repeating unit represented by formula (1) (e.g., a resin obtained by a ring-closing reaction). The polyimide precursor preferably has a repeating unit represented by formula (1).

[0044] [ka]

[0045] In formula (1), A 1 and A 2 R each independently represents an oxygen atom or -NH-. 111 represents a divalent organic group. 113 and R 114 R each independently represents a hydrogen atom or a monovalent organic group. 115 represents a tetravalent organic group.

[0046] In formula (1), A 1 and A 2 each independently represents an oxygen atom or —NH—. A 1 and A 2 is preferably an oxygen atom.

[0047] In formula (1), R 111 represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a combination thereof. The divalent organic group is preferably a divalent aliphatic group having 2 to 20 carbon atoms, a divalent aromatic ring group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a divalent aromatic ring group having 6 to 20 carbon atoms. The aliphatic group may be linear, branched, or cyclic. The aromatic ring group may be monocyclic or polycyclic. The aliphatic group and the aromatic ring group may contain a heteroatom. The heteroatom may be contained in the divalent organic group as, for example, -O-, -CO-, -S-, -SO2-, or -NHCO-. R 111 As the diamine, a divalent organic group derived from a diamine is also preferred. As the diamine, a diamine used in the production of a polyimide precursor is preferred, and an aliphatic diamine or an aromatic diamine is more preferred. The diamine is preferably a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a group that combines these, and more preferably a diamine having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamine). Examples of the aromatic ring group include groups having the following structure:

[0048] [ka]

[0049] In AR-8 to AR-10, A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO- or a combination thereof, or a single bond. A is preferably an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S- or -SO2-, more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-, and still more preferably -O-.

[0050] R 111 As for *-Ar 0 -L 0 -Ar 0 -* is also preferred. Ar 0 L each independently represents a divalent aromatic hydrocarbon group. 0 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO- or a group formed by combining these, or a single bond. * represents the bonding position. Ar 0 They may be the same or different from each other.

[0051] Ar 0 The number of carbon atoms in the divalent aromatic hydrocarbon group represented by the following formula is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. As the aromatic hydrocarbon group, a phenylene group is preferred. L 0 has the same meaning as A described above, and the preferred embodiments are also the same.

[0052] Examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; meta- or para- Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethyl Biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4 -amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraafluorobenzoate 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5- Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl. , Further, examples of diamines include compounds represented by any one of formulas (DA-1) to (DA-18).

[0053] [ka]

[0054] [ka]

[0055] The diamine may also be one having two or more alkylene glycol units in the main chain, and the diamine having two or more alkylene glycol units in the main chain is preferably one having two or more ethylene glycol chains and / or propylene glycol chains in one molecule. Also preferred is a diamine that does not contain an aromatic ring. Examples of the diamine include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0056] In formula (1), R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group. R 113 and R 114 Preferably, at least one of R represents a group having a reactive group, 113 and R 114 It is more preferable that both of the following represent a group having a reactive group. Examples of the reactive group include the groups exemplified above as the reactive group that the resin may have. The monovalent organic group may be a monovalent organic group X, which will be described later. R 113 and R 114 Examples of the reactive group include the reactive groups described above, and a group having an ethylenically unsaturated double bond is preferred, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferred.

[0057] [ka]

[0058] In formula (III), R 200 represents a hydrogen atom or a methyl group. 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. * represents the bonding position.

[0059] In formula (III), R 200 represents a hydrogen atom or a methyl group. R 200 As the alkyl group, a methyl group is preferred.

[0060] In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. The number of carbon atoms in the alkylene group constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of repetitions of oxyalkylene in the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The (poly)oxyalkylene group is a concept that encompasses both an oxyalkylene group and a polyoxyalkylene group. R 201 Examples of the alkyl group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and -CHCH(OH)CH-. An ethylene group, a propylene group, a trimethylene group, or -CHCH(OH)CH- is preferred, and an ethylene group is more preferred.

[0061] R 113 or R 114 Examples of the monovalent organic group represented by the formula (I) include an aliphatic group, an aromatic ring group, and an arylalkyl group having 1 to 3 acid groups. Examples include an aromatic ring group having 6 to 20 carbon atoms and having an acid group, and an arylalkyl group having 7 to 25 carbon atoms and having an acid group. More specifically, examples include a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably a hydroxyl group or a carboxy group. R 113 and R 114 Also preferred as is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group. R 113 or R 114The monovalent organic group represented by the formula (I) also includes a leaving group that is eliminated by the action of an acid.

[0062] In formula (1), R 115 represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group having an aromatic ring, and more preferably a group represented by formula (5) or (6).

[0063] [ka]

[0064] In formula (5), R 112 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO- or a group formed by combining these, or a single bond. * represents the bonding position. In formula (6), * represents a bonding position.

[0065] In formula (5), R 112 has the same meaning as A described above, and the preferred embodiments are also the same.

[0066] The tetravalent organic group may be, for example, a tetracarboxylic acid residue remaining after removing the acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic acid dianhydride is preferably a compound represented by formula (7).

[0067] [ka]

[0068] In formula (7), R 115 represents a tetravalent organic group. R in equation (7) 115 is R in Eq. (1) 115 The same definition and preferred embodiments are also the same.

[0069] Examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride. Water, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Examples thereof include tetracarboxylic dianhydrides, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0070] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0071] [ka]

[0072] The monovalent organic group X is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic, and the cyclic group may be monocyclic or polycyclic. The linear or branched alkyl group preferably has 1 to 30 carbon atoms. The cyclic alkyl group (cycloalkyl group) preferably has 3 to 30 carbon atoms. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl groups; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl groups. The substituent that the alkyl group may have is preferably an aromatic ring group, which will be described later.

[0073] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may be either a monocyclic or polycyclic group. Examples of the ring constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, and a pyrrole ring; aromatic heterocyclic groups such as an imidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring; The substituent that the aromatic ring group may have is preferably the alkyl group described above.

[0074] The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or a repeating unit represented by formula (1-B).

[0075] [ka]

[0076] In formula (1-A) and formula (1-B), A 11 and A 12 represents an oxygen atom or -NH-. 111 and R 112 R each independently represents a divalent organic group. 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0077] In formula (1-A) and formula (1-B), A 11 , A 12 , R 111 , R 113 , and R 114are respectively expressed as A in equation (1). 1 , A 2 , R 111 , R 113 , and R 114 The same definition and preferred embodiments are also the same. In formula (1-A), R 112 is R in equation (5). 112 The same definition and preferred embodiments are also the same.

[0078] In formula (1-A), the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A). In formula (1-B), the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).

[0079] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0080] The content of the repeating unit represented by formula (1) is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more, based on all repeating units of the polyimide precursor, and the upper limit is preferably 100 mol % or less.

[0081] The polyimide precursor also preferably contains a fluorine atom. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor, and the upper limit is preferably 50% by mass or less.

[0082] The polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, which can improve adhesion to the substrate. Examples of the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

[0083] The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polydispersity (Mw / Mn) of the polyimide precursor is preferably from 1.5 to 3.5, more preferably from 2.0 to 3.0.

[0084] Silicone resin Silicone resin is a polymer with a siloxane bond as the main skeleton, specifically, M units (RSiO 1 / 2 ), D units (RSiO 2 / 2 ), T units (RSiO 3 / 2 ), and Q units (SiO 4 / 2 ) wherein R represents a monovalent organic group. Examples of silicone resins include curable silicone resins, silicone graft resins, and modified silicone resins such as alkyl-modified silicone resins, with curable silicone resins being preferred. Examples of the curable silicone resin include an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet or electron beam curable silicone resin.

[0085] Examples of addition reaction type silicone resins include resins obtained by reacting and curing polydimethylsiloxane, which has vinyl groups introduced at the terminals or side chains, with hydrogen siloxane using a platinum catalyst. An example of a condensation reaction type silicone resin is a resin having a three-dimensional crosslinked structure formed by condensing polydimethylsiloxane having a hydroxyl group at its terminal with polydimethylsiloxane having a hydrogen atom at its terminal using an organotin catalyst. Examples of UV-curable silicone resins include those that utilize the same radical reaction as silicone rubber crosslinking, those that are photocured by introducing unsaturated groups, those that use UV or electron beams to decompose onium salts to generate strong acids, which then cleave epoxy groups to crosslink, and those that crosslink via an addition reaction of thiol to vinyl siloxane.Specific examples include acrylate-modified polydimethylsiloxane and glycidoxy-modified polydimethylsiloxane. Examples of silicone resins include a dimethylsiloxane-methylvinylsiloxane copolymer terminated at both molecular chain ends with trimethylsiloxy groups, a dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer terminated at both molecular chain ends with trimethylsiloxy groups, and a dimethylsiloxane-diphenylsiloxane copolymer terminated at both molecular chain ends with dimethylvinylsiloxy groups.

[0086] The silicone resin preferably has an aromatic ring. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and even more preferably a benzene ring.

[0087] As the silicone resin, a modified silicone resin obtained by reacting an organosilicon compound with a hydrosilylation agent is also preferred. The organosilicon compound preferably further has a polymerizable group, such as a polymerizable group contained in a resin. The organosilicon compound may be, for example, a compound having a silyl group, and 1,4-bis(dimethylsilyl)benzene or trivinylphenylsilane is preferred. Examples of hydrosilylation agents include platinum-based catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate; and platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. The reaction temperature is preferably 100 to 200° C., and the reaction time is preferably 1 to 10 hours.

[0088] Examples of silicone resins include resins obtained from organosiloxanes and curable compositions described in JP 2020-026502 A.

[0089] One preferred embodiment of the silicone resin is polysilsesquioxane. Polysilsesquioxane is a general term for polymers whose constituent units are the above-mentioned T units. The skeleton structure of the polysilsesquioxane is not particularly limited, and may be any of a cage polysilsesquioxane, a ladder polysilsesquioxane, a double-decker polysilsesquioxane, and a random polysilsesquioxane, with a ladder polysilsesquioxane or a cage polysilsesquioxane being preferred. The cage polysilsesquioxane may be either a complete cage polysilsesquioxane or an incomplete cage polysilsesquioxane, but a complete cage polysilsesquioxane is preferred. The cage polysilsesquioxanes include T8 polysilsesquioxanes consisting of eight T3 structural units, which will be described later, and T 10 Polysilsesquioxane and 12 T3 structural units described below 12 The polysilsesquioxane may be any of the polysilsesquioxanes.

[0090] The polysilsesquioxane preferably has a polymerizable group, since this leads to a smaller coefficient of linear expansion in the in-plane direction of a cured product formed from the liquid curable composition and superior thermocycling resistance. Examples of the polymerizable group include known polymerizable groups such as radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. The radical polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a vinyl group, a styryl group, a (meth)acryloyl group, a (meth)acrylamide group, an allyl group, and a vinyl ether group, and the vinyl group, the styryl group, or the (meth)acryloyl group is preferred, and the styryl group is more preferred.

[0091] The polysilsesquioxane preferably has a chain hydrocarbon group, since this provides a cured product formed from the liquid curable composition with better conformability to unevenness. Examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group being preferred. The chain hydrocarbon group may be either a straight chain or a branched chain, and is preferably a straight chain. The chain hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 4 to 12 carbon atoms.

[0092] The polysilsesquioxane preferably contains a structural unit selected from the structural unit T1 represented by formula (T1), the structural unit T2 represented by formula (T2), and the structural unit T3 represented by formula (T3), more preferably contains a structural unit selected from the structural unit T2 and the structural unit T3, and even more preferably contains the structural unit T3. The structural units T1 to T3 belong to so-called T units. Formula (T1):R 1 -Si(OX 1 )2O 1 / 2 Formula (T2):R 1 -Si(OX 1 )O 2 / 2 Formula (T3):R 1 -SiO 3 / 2 In formulas (T1) to (T3), R 1 Each of X independently represents a monovalent organic group. 1 each independently represents a hydrogen atom or an alkyl group. In polysilsesquioxane, multiple R 1may be the same or different. In other words, the polysilsesquioxane may contain different R 1 The copolymer may be a copolymer containing a plurality of structural units having the following structure:

[0093] In formulas (T1) to (T3), R 1 each independently represents a monovalent organic group. Examples of the monovalent organic group include a hydrocarbon group and a heteroatom-containing group. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be either chain or cyclic, preferably chain. The chain aliphatic hydrocarbon group may be either linear or branched, preferably linear. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms. The aromatic hydrocarbon group preferably has 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably 5 or 6 carbon atoms. Examples of the heteroatom-containing group include groups in which one or more carbon atoms of the hydrocarbon group are substituted with heteroatoms. The heteroatom is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The hydrocarbon group and heteroatom-containing group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, or the polymerizable group described above.

[0094] In terms of achieving better effects of the present invention, the liquid curable composition preferably contains at least one selected from a ladder-type polysilsesquioxane and a cage-type polysilsesquioxane, more preferably contains a cage-type polysilsesquioxane, and even more preferably contains a ladder-type polysilsesquioxane and a cage-type polysilsesquioxane. The skeletal structure of the polysilsesquioxane is determined by the molecular weight obtained by GPC (Gel Permeation Chromatography) and 29It can be identified from the structural units, etc., obtained from the peak positions in Si-NMR (Nuclear Magnetic Resonance) spectrum measurements. Specifically, for example, the cage polysilsesquioxane has a peak top molecular weight of T8 polysilsesquioxane, T 10 Polysilsesquioxane, or T 12 It is detected as a peak corresponding to the molecular weight of polysilsesquioxane. The molecular weight of each of the above cage polysilsesquioxanes is calculated appropriately depending on the substituents possessed by the cage polysilsesquioxane, and is often detected as a peak at a weight average molecular weight (Mw) of 300 to 4,000.

[0095] Epoxy resin The epoxy resin is a resin having an epoxy group. Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, and trimethylol type epoxy resins.

[0096] The epoxy resin preferably contains an epoxy resin that is liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resin"), in terms of excellent flexibility and improved breaking strength of the resulting cured product.

[0097] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin or naphthalene type epoxy resin is preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin or naphthalene type epoxy resin is more preferred. Examples of liquid epoxy resins include HP4032, HP4032D, EXA4032SS, and HP4032SS (naphthalene-type epoxy resins) manufactured by DIC Corporation; jER828EL (bisphenol A-type epoxy resin), jER807 (bisphenol F-type epoxy resin), and jER152 (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and ZX1059 (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. As the liquid epoxy resin, HP4032SS or ZX1059 is preferred.

[0098] As the solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is preferred, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferred, and a biphenyl type epoxy resin is even more preferred. Examples of solid epoxy resins include HP-4700, HP-4710 (tetrafunctional naphthalene type epoxy resins), N-690 (cresol novolac type epoxy resin), N-695 (cresol novolac type epoxy resin), HP7200, HP7200H, HP7200K-65I (dicyclopentadiene type epoxy resins), EXA7311, EXA7311-G3, and HP6000 (naphthylene ether type epoxy resins), and EPPN-502H (trisphenol A type epoxy resins) manufactured by DIC Corporation. Examples of epoxy resins include NC7000L (naphthol novolac epoxy resin), NC3000H, NC3000, NC3000L, and NC3100 (biphenyl-type epoxy resins), manufactured by Nippon Kayaku Co., Ltd.; ESN475 (naphthol novolac-type epoxy resin) and ESN485 (naphthol novolac-type epoxy resin), manufactured by Nippon Steel Chemical Co., Ltd.; and YX4000H, YL6121 (biphenyl-type epoxy resin), and YX4000HK (bixylenol-type epoxy resin), manufactured by Mitsubishi Chemical Corporation. As the solid epoxy resin, YX4000HK, NC3000L or HP7200H is preferred.

[0099] Polyamide resin The polyamide resin is a resin having an amide bond. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins.

[0100] Maleimide resin The maleimide resin is a resin having a maleimide group. The maleimide resin is preferably a bismaleimide resin, and more preferably at least one selected from the group consisting of a bismaleimide resin represented by the following formula (III) and a novolac-type maleimide resin represented by the following formula (IV).

[0101] [ka] In formula (III), R represents a divalent organic group containing an aromatic ring or a linear, branched, or cyclic aliphatic hydrocarbon group. R is preferably a divalent group consisting of a benzene group, a toluene group, a xylene group, a naphthalene group, a linear, branched, or cyclic saturated hydrocarbon group, or a combination thereof. R is preferably a divalent group represented by the following formula (v), (vi), or (vii):

[0102] [ka]

[0103] [ka]

[0104] In formula (IV), s represents an integer of 0 to 20.

[0105] The maleimide resin may be a compound described in paragraphs 0020 to 0023 of JP-A No. 2003-321608. Commercially available maleimide resins include BMI-1000, 2000, 3000, 4000, 5000, 5100, and 7000 (bismaleimide resins manufactured by Daiwa Chemical Industry Co., Ltd.), BANI-X (bismaleimide resins manufactured by Shin-Nakamura Chemical Co., Ltd.), and BANI-M (bismaleimide resins manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0106] Polyphenylene ether resin The polyphenylene ether resin is a resin having a phenylene ether group. The polyphenylene ether resin may have either a linear structure or a branched structure, and preferably has a branched structure. In the polyphenylene ether resin having a branched structure, it is preferable that ether bonds are directly bonded to at least three positions, i.e., the ipso position, the ortho position, and the para position, of at least one benzene ring constituting the polyphenylene ether resin.

[0107] The polyphenylene ether resin having a branched structure can be obtained, for example, by polymerizing two or more kinds of phenol compounds. The phenol compound is preferably a phenol compound having hydrogen atoms at the ortho and para positions and having a reactive group, or a mixture of a phenol compound having hydrogen atoms at the ortho and para positions and no reactive group and a phenol compound having no hydrogen atom at the ortho position, a hydrogen atom at the para position and having a reactive group.

[0108] Examples of phenol compounds used in the synthesis of polyphenylene ether resins include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinyl-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6-ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 2-dodecylphenol. , 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2,6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethylphenol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, and 2,6-ditolylphenol. Of these, the phenol compound is preferably 2,6-dimethylphenol or 2-allylphenol.

[0109] The polyphenylene ether resin also preferably has a reactive group, preferably a group having an ethylenically unsaturated double bond, more preferably a vinylphenyl group or a (meth)acryloyl group. When the polyphenylene ether resin has a reactive group, the liquid curable composition preferably contains a maleimide compound, which reacts with the polyphenylene ether resin to give a modified polyphenylene ether. Examples of modified polyphenylene ethers include resins obtained by curing the resin compositions described in WO 2022 / 102756.

[0110] Examples of polyphenylene ether resins include poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. Examples of polyphenylene ether resins include those described in JP-A-2022-157695.

[0111] Other resins The resin may contain other resins in addition to the various resins described above. Examples of other resins include phenol resin, benzocyclobutene resin, fluorene resin, liquid crystal polymer, polyethersulfone, polyarylate, polyetherimide, polyphenylsulfone, polycarbonate, acrylonitrile-butadiene-styrene resin, and polyphenylene sulfide.

[0112] As described above, the resin contained in the curable liquid composition may be a precursor of each of the resins described above.

[0113] The weight average molecular weight (Mw) of the resin is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 5,000 to 50,000. The number average molecular weight (Mn) of the resin is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, and even more preferably from 4,000 to 25,000. The polydispersity (Mw / Mn) of the resin is preferably from 1.0 to 3.5, more preferably from 2.0 to 3.0.

[0114] The resins may be used alone or in combination of two or more. The resin content is preferably from 1.0 to 99.0 mass %, more preferably from 5.0 to 98.0 mass %, and even more preferably from 5.0 to 50.0 mass %, based on the total solid content of the liquid curable composition.

[0115] (inorganic filler) The curable liquid composition may contain an inorganic filler. The inorganic filler is preferably an inorganic filler. Examples of inorganic fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chion-doped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride. The inorganic filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).

[0116] The shape of the inorganic filler may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred.

[0117] The average particle size of the inorganic filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less. The lower limit of the average particle size of the inorganic filler is preferably more than 0 nm, more preferably 5 nm or more, even more preferably 10 nm or more, and particularly preferably 50 nm or more. The average particle size of the inorganic filler is also preferably 5 to 300 nm, more preferably 10 to 150 nm, and even more preferably 50 to 150 nm. The average particle size of the inorganic filler is a value calculated by the following particle size measurement method. Particle size measurement method: A rectangular area of ​​3 μm × 10 μm in a cross section along the normal direction of the surface of a composition layer formed using the liquid curable composition is observed with a scanning electron microscope, and the long diameters of all inorganic fillers observed within the area are measured at five different locations on the film. The average value of the long diameters of all inorganic fillers measured in each step is taken as the average particle size of the inorganic fillers.

[0118] The particle size measurement method will now be described in detail. The liquid curable composition is applied to a substrate (preferably a glass substrate) to form a composition layer. The thickness of the composition layer is preferably 3 μm or more. In addition, to form the composition layer, after applying the liquid curable composition, a drying treatment may be carried out as necessary. A cross section of the resulting composition layer was cut out along the normal direction of the surface (the surface opposite the substrate side), and a rectangular area of ​​3 μm × 10 μm on the cross section was observed using a scanning electron microscope. The major axis of all inorganic fillers observed within the area was measured. The scanning electron microscope used was a Hitachi High-Tech S-4800. The magnification during observation was 50,000 times. The above operation is carried out at five different locations in the composition layer, and the average value (arithmetic mean value) of the major axes of all the inorganic fillers measured in each operation is taken as the average particle size of the inorganic filler. The above-mentioned major axis refers to the length of the longest line segment among the line segments connecting any two points on the outline of the external shape of the inorganic filler in the observed image. Furthermore, when the inorganic filler aggregates to form aggregates in the observed image, the major axis of each inorganic filler constituting the aggregate is measured.

[0119] Examples of inorganic fillers include NSS-3N (manufactured by Tokuyama Corporation, silicon dioxide), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, solid content concentration 50% by mass MEK (methyl ethyl ketone) slurry), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), and PMA-ST. (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), Y50SP-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).

[0120] The inorganic filler may be surface-modified with a surface treatment agent. Examples of the surface modifier include a silane coupling agent, a titanate coupling agent, a disilazane compound, and a basic compound. The surface modifier may have a reactive group, for example, the reactive groups that the above-mentioned resins may have.

[0121] The inorganic fillers may be used alone or in combination of two or more. The content of the inorganic filler is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, based on the total solid content of the liquid curable composition, and is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and even more preferably 75.0% by mass or less, based on the total solid content of the liquid curable composition.

[0122] (Compounds having reactive groups) The curable liquid composition may contain a compound having a reactive group. The compound having a reactive group is a compound different from the above-mentioned resin, and is a compound having a reactive group. Furthermore, the compound having a reactive group is preferably a compound different from the surface modifier. Examples of the reactive group possessed by the compound having a reactive group include reactive groups that can be possessed by the above-mentioned resins, and a polymerizable group is preferred. That is, the liquid curable composition preferably contains a compound having a polymerizable group (hereinafter also referred to as a "polymerizable compound") as the compound having a reactive group. The compound having a reactive group may have one or more reactive groups, or may have two or more reactive groups. The number of reactive groups that the compound having a reactive group has is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6.

[0123] When the curable liquid composition contains a polymerizable compound (preferably a compound having a group with an ethylenically unsaturated double bond), the curable liquid composition preferably further contains a photopolymerization initiator, which will be described later.

[0124] A polymerizable compound is a compound having one or more polymerizable groups in one molecule. As the polymerizable compound, a compound having a group with an ethylenically unsaturated double bond is preferred, a compound having a (meth)acryloyl group, a vinyl group or a styryl group is more preferred, and a compound having a (meth)acryloyl group is even more preferred.

[0125] The number of polymerizable groups that the polymerizable compound has is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. Examples of the polymerizable compound include a polymerizable compound having one polymerizable group in one molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two polymerizable groups in one molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more polymerizable groups in one molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound"). The polymerizable compound is preferably a bifunctional polymerizable compound or a trifunctional or higher functional polymerizable compound.

[0126] Examples of bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Inc.), and SR209 (manufactured by Sartomer Inc.).

[0127] Examples of the tri- or higher functional polymerizable compound include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton. The term "(tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and the term "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0128] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0129] Examples of the polymerizable compound include urethane (meth)acrylate (preferably tri- or higher functional urethane (meth)acrylate). The number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, more preferably 8 or more. The upper limit is preferably 20 or less. Examples of trifunctional or higher urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0130] The compound having a reactive group may have liquid crystal properties.

[0131] The compound having a reactive group is also preferably a low molecular weight compound. The molecular weight of the compound having a reactive group is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. The molecular weight of the compound having a reactive group is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.

[0132] The compound having a reactive group may be used alone or in combination of two or more. The content of the compound having a reactive group is preferably from 1 to 95 mass %, more preferably from 10 to 90 mass %, and even more preferably from 30 to 80 mass %, based on the total solid content of the liquid curable composition.

[0133] (thermal polymerization initiator) The liquid curable composition preferably contains a thermal polymerization initiator. The thermal polymerization initiator can be selected depending on the type of polymerizable compound, but a thermal radical polymerization initiator is preferred. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Furthermore, a photopolymerization initiator, which will be described later, may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0134] Examples of the thermal polymerization initiator include known azo compounds and known peroxide compounds. Examples of the azo compounds include azobis compounds. The azo compounds may be compounds having a cyano group or may be compounds not having a cyano group. Examples of the peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. As the thermal polymerization initiator, commercially available products can be used, and examples thereof include V-40, V-601, and VF-096 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and Perhexyl O, Perhexyl D, Perhexyl I, Perhexa 25O, Perhexa 25Z, Percumyl D, Percumyl D-40, Percumyl D-40MB, Percumyl H, Percumyl P, and Percumyl ND manufactured by NOF Corporation. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0135] The thermal polymerization initiators may be used alone or in combination of two or more. The content of the thermal polymerization initiator is preferably from 0.05 to 10 mass %, more preferably from 0.1 to 10 mass %, and even more preferably from 0.1 to 5 mass %, based on the total solid content of the liquid curable composition.

[0136] (Photopolymerization initiator) The liquid curable composition may contain a photopolymerization initiator. The photopolymerization initiator is a compound different from the various components described above. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0137] Examples of the photopolymerization initiator include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure). As the photopolymerization initiator, an oxime ester compound or an aminoacetophenone compound is preferred, and an oxime ester compound is more preferred.

[0138] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.).

[0139] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series, manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0140] Examples of photopolymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819). Examples of the photopolymerization initiator include those described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0141] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably from 0.01 to 10.0 mass %, more preferably from 0.1 to 5.0 mass %, and even more preferably from 0.1 to 3.0 mass %, based on the total solid content of the liquid curable composition.

[0142] (thermal base generator) The curable liquid composition may contain a thermal base generator. When the liquid curable composition contains a resin precursor, the reaction of the resin precursor is accelerated by including a thermal base generator in the liquid curable composition.

[0143] The thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating. The onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), and more preferably an ammonium salt compound or an iminium salt compound. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion or a sulfate anion, and more preferably a carboxylate anion. The anion constituting the ammonium salt compound preferably further has an aromatic ring. Examples of the aromatic ring include A in formula (A1) described below. a1 Examples of aromatic rings that constitute aromatic ring groups represented by the following formula are given.

[0144] The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The base may be linear, branched, or cyclic, and is preferably cyclic.

[0145] Examples of the thermal base generator include those described in WO 2018 / 038002.

[0146] The temperature at which the thermal base generator generates a base is preferably the heating temperature in step 4 in the method for producing a laminate described below. The temperature at which the thermal base generator generates a base is, for example, preferably 50 to 400°C, and more preferably 100 to 250°C. The temperature at which the thermal base generator generates a base can be measured by a known measurement method or a literature value. For example, the base generation temperature can be determined by the peak temperature of the lowest exothermic peak when the compound to be measured is heated to 250°C at 5°C / min in a pressure-resistant capsule using differential scanning calorimetry.

[0147] The thermal base generator may be used alone or in combination of two or more. The content of the thermal base generator is preferably from 0.01 to 10.0 mass %, more preferably from 0.1 to 5.0 mass %, based on the total solid content of the liquid curable composition. The mass ratio of the content of the thermal base generator to the content of the resin is preferably from 0.0005 to 1.0, more preferably from 0.001 to 0.1, and even more preferably from 0.001 to 0.05.

[0148] (plasticizer) The curable liquid composition may contain a plasticizer. The plasticizer is a compound different from the various components described above, and preferably does not have a reactive group.

[0149] The molecular weight of the plasticizer is preferably 200-1,000, more preferably 250-800, and even more preferably 300-600. When the plasticizer has a molecular weight distribution, the above-mentioned molecular weight refers to the weight average molecular weight.

[0150] The boiling point of the plasticizer is preferably from 230 to 500°C, more preferably from 280 to 480°C, further preferably from 300 to 450°C, and particularly preferably from 350 to 450°C. The boiling point is the boiling point under normal pressure (760 mmHg). In this specification, the boiling point of a compound is a value determined by the following measurement method. When a compound is distilled under normal pressure (760 mmHg), the boiling point is the temperature of the evaporated gas at the point where condensation begins (measured from 23 to 300°C, temperature rise rate 1°C / min). The distillation of the compound was carried out using a Liebig condenser. If distillation did not begin at 300°C under normal pressure, distillation was carried out under reduced pressure. Similar distillation was carried out at pressures of 100 mmHg, 50 mmHg, and 5 mmHg, in that order (measurement from 23 to 300°C, temperature increase rate 1°C / min, distillation at the next pressure if distillation did not begin at 300°C). The boiling point at normal pressure was calculated using the nomograph described in Science of Petroleum, Vol. II, p. 1281 (1938) based on the temperature and pressure at which condensation of the evaporated gas began. If distillation did not begin at 300°C under 5 mmHg, the boiling point at normal pressure was deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line was drawn between the boiling point at reduced pressure (line A) and the degree of vacuum (line C). The value at the intersection of the line drawn in step 1 and line B was read (step 2). This was deemed to be the boiling point at normal pressure.

[0151] The viscosity of the plasticizer at 25° C. is preferably from 0.01 to 500 mPa·s, more preferably from 0.05 to 300 mPa·s, and even more preferably from 0.1 to 100 mPa·s. The viscosity can be measured using a Brookfield viscometer.

[0152] Examples of the plasticizer include polycarboxylic acid esters, phosphoric acid esters, polyether esters, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and benzyl benzoate, with polycarboxylic acid esters being preferred.

[0153] Examples of polycarboxylic acid esters include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacate esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate). Examples of polycarboxylic acid esters include ethylphthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetylcitrate, 2-ethylhexyl benzyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0154] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0155] The polyether esters are preferably organic acid esters of polyalkylene glycol. Examples of organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid). Specific examples of polyether esters include triethylene glycol bis-2-ethylhexanoate.

[0156] Examples of alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers include hexaethylene glycol monomethyl ether (mPEG6-OH), pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.

[0157] The plasticizers may be used alone or in combination of two or more. The content of the plasticizer is preferably 5.0 to 50.0 mass %, more preferably 10.0 to 30.0 mass %, based on the total solid content of the liquid curable composition.

[0158] (surfactant) The curable liquid composition may contain a surfactant.

[0159] Examples of surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Silicone-based surfactants are preferred as surfactants. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain fluorine atoms.

[0160] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21, etc.). The fluorosurfactant may be a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorosurfactant may be a block polymer. The fluorine-based surfactant may be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group with an ethylenically unsaturated double bond in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0161] As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having seven or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred in terms of improving environmental friendliness.

[0162] Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, and F-555- A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC); EXP.MFS-324, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS- 579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Corporation); PolyFox Examples include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS); and U-120E (manufactured by Unichem).

[0163] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0164] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups having siloxane bonds in the side chains. Preferred silicone surfactants are polymers having repeating units with hydrophilic groups in the side chains and repeating units with groups having siloxane bonds in the side chains. The polymers may be either random copolymers or block copolymers.

[0165] Commercially available silicone surfactants include, for example, EXP.S-309-2, EXP.S-315, EXP.S-503-2, EXP.S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266. , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125 , KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicones Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Perform BYK Materials; BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0166] The surfactant may also be a nonionic surfactant other than those mentioned above. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A No. 2009-237362.

[0167] The surfactants may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.01 to 3.0 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.1 to 0.8 mass %, based on the total solid content of the liquid curable composition.

[0168] (rust inhibitor) The curable liquid composition may contain a rust inhibitor. Examples of the rust inhibitor include heterocyclic compounds, such as triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds, and triazole compounds, benzotriazole compounds, and tetrazole compounds are preferred. Examples of heterocyclic compounds include compounds described in WO 2022 / 039027.

[0169] The rust inhibitors may be used alone or in combination of two or more. The content of the rust inhibitor is preferably from 0.01 to 3.0 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.1 to 0.8 mass %, based on the total solid content of the liquid curable composition.

[0170] (Other additives) The curable liquid composition may contain additives other than those described above. Examples of other additives include silane coupling agents, photoacid generators, curing agents, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen donor compounds, impurities, sensitizers, alkoxysilane compounds, maleimide compounds, and hydrosilylation agents.

[0171] Examples of the silane coupling agent include the components described in paragraphs 0299 ​​to 0300 of JP-A No. 2021-128183. Examples of the aliphatic thiol compound, the thermally crosslinkable compound, the polymerization inhibitor, and the hydrogen donor compound include various components described in WO 2022 / 039027. Examples of the sensitizer and alkoxysilane compound include the components described in paragraphs 0097 to 0119 of WO 2018 / 179640. Examples of maleimide compounds (compounds having a maleimide ring) include known maleimide compounds and the maleimide compounds described in WO 2022 / 102756. Examples of hydrosilylation agents include platinum catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum group metal catalysts such as platinum bisacetoacetate; and palladium-based catalysts and rhodium-based catalysts. The hydrosilylation agent is preferably used as a curing agent when a silicone resin or a precursor thereof is used as the resin.

[0172] [Process 2] Fig. 2 is a schematic cross-sectional view for explaining step 2, showing a cross section along the thickness direction of the mold member 10, the cured product 30, and the laminate 20. Specifically, Fig. 2 shows the state in which the liquid curable composition L (see Fig. 1B) filled in the recess 12 of the mold member 10 has cured to obtain the cured product 30. The method for curing the liquid curable composition L is determined appropriately depending on the types of components contained in the liquid curable composition, and examples thereof include a method of heating the liquid curable composition L, and, if the liquid curable composition L is photosensitive, a method of exposing the liquid curable composition L to light. Alternatively, both heating and exposure may be performed. When exposure is performed, the mold member 10 and / or the laminate 20 only needs to be made of a light-transmitting material.

[0173] When the liquid curable composition L is cured by heating, the heating temperature of the liquid curable composition L is preferably 80°C or higher, more preferably 100°C or higher, and even more preferably 140°C or higher, from the viewpoint of accelerating curing, and is preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 180°C or lower, from the viewpoint of suppressing thermal deterioration of the substrate 10 in the laminate 20. The heating time for the curable liquid composition L is preferably from 1 to 180 minutes, more preferably from 10 to 120 minutes, and even more preferably from 20 to 90 minutes.

[0174] When the liquid curable composition L is cured by exposure to light, the light source used for exposure may be one that irradiates light in a wavelength range to which the various photosensitive components in the liquid curable composition L (e.g., resin, polymerizable compound, photopolymerization initiator, photoacid generator, etc.) are sensitive (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.). Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 200 mJ / cm 2 is preferred, and 10 to 200 mJ / cm 2 is more preferred.

[0175] [Step 3] Fig. 3 is a schematic cross-sectional view illustrating step 3, showing a cross section along the thickness direction of the mold member 10, the cured product 30, and the laminate 20. Specifically, Fig. 3 shows a state in which only the mold member 10 has been peeled off from a structure composed of the mold member 10, the cured product 30, and the laminate 20. In step 3, it is preferable that only the mold member 10 is peeled off while the bond between the laminate 20 and the cured product 30 is maintained.

[0176] After the mold member 10 is peeled off, the cured product 30 has a first hole 34 and a second hole 36 formed therein. The first hole 34 continues from the surface of the cured product 30 on which the molding member 10 was placed to the surface of the first wiring 24 (i.e., the first hole 34 is a hole that penetrates the cured product 30). If the cured product 30 remains on the surface of the first wiring 24 after the molding member 10 is peeled off, the cured product remaining on the surface of the first wiring 24 can be removed by a known treatment (for example, plasma treatment) to expose the surface of the first wiring 24. The second hole portion 36 is formed from the surface of the cured product 30 on the side where the molding member 10 was placed toward the second wiring 26 , and is a hole that does not penetrate the cured product 30 .

[0177] It is believed that the mold member 10 becomes easy to peel from the cured product 30 due to shrinkage caused by the curing of the liquid curable composition L in step 2, etc. Here, when the substrate 22 in the laminate 20 is a resin substrate and the mold member 10 is made of a material other than resin (for example, metal or glass), the bonding strength between the laminate 20 and components (for example, resin, etc.) that may be contained in the cured product 30 is improved. Therefore, it is easy to peel only the mold member 10 from the cured product 30 while maintaining the bond between the laminate 20 and the cured product 30. Furthermore, to make it easier to peel the cured product 30 from the mold member 10, the above-mentioned release layer may be provided on the surface of the mold member 10.

[0178] The method for peeling the mold member 10 from the cured product 30 is not particularly limited, and any known method can be used.

[0179] <Cured product> After the mold member 10 is peeled off, the cured product 30 has a pattern corresponding to the mold member 10 formed thereon. Specifically, the first holes 34 in the cured product 30 preferably have a shape corresponding to the first protrusions 14 of the mold member 10 and have the above-mentioned pattern having vias. When the first hole 34 has a pattern having vias, the diameter of the first hole 34 is preferably 0.1 to 100 μm, more preferably 1 to 50 μm. The depth of the first hole 34 is preferably 1 to 500 μm, more preferably 3 to 100 μm. In the example of FIG. 3, the number of first holes 34 is one, but the present invention is not limited to this, and the number of first holes 34 may be two or more.

[0180] The second hole 36 in the cured product 30 has a shape corresponding to the second protrusion 16 of the mold member 10, and is preferably the linear groove described above. When the second holes 36 are linear grooves, the diameter (width) of the second holes 36 is preferably 0.01 to 100 μm, more preferably 0.1 to 20 μm. The depth of the second holes 36 is preferably 0.01 to 50 μm, more preferably 1 to 20 μm. 3 shows an example in which the number of second holes 36 is three, but the present invention is not limited to this and the number of second holes 36 may be two or less, or four or more. When the number of second holes 36 is two or more, the distance between adjacent second holes 36 is preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm.

[0181] [Step 4] 4A and 4B are schematic cross-sectional views for explaining step 4, showing cross sections along the thickness direction of the cured product 30, the metal layer 40 (connection portion 44, wiring portion 46), and the laminate 20.

[0182] FIG. 4A is a diagram showing a state in which a metal layer 40 has been formed by filling the first hole 34 and the second hole 36 (both see FIG. 3) of the cured product 30 with metal.

[0183] The method for forming the metal layer 40 is not particularly limited, but for example, plating can be used. An example of a method for forming the metal layer 40 by plating will be described below. First, a power supply layer (for example, a layer made of copper) is provided by a method such as sputtering on the entire side of the cured product 30 on which the first hole portion 34 and the second hole portion 36 are formed. Next, a metal layer 40 is formed by performing an electrolytic plating process (for example, electrolytic copper plating) using the power supply layer. The method for forming the metal layer 40 is not limited to this, and may be, for example, electroless plating as a wet process, or sputtering as a dry process.

[0184] FIG. 4B is a diagram showing a state in which a connection portion 44 connected to the first wiring 24 and a wiring portion 46 are formed by polishing the surface of the metal layer 40 (see FIG. 4A). The polishing treatment is not particularly limited, and for example, mechanical polishing treatment, chemical mechanical polishing treatment, etc. can be adopted. In step 4, a method of performing a polishing process has been described as an example, but the polishing process is an optional process and may be performed as needed. Also, instead of the polishing process, a known etching process or the like may be performed to form the connection portion 44 and the wiring portion 46 from the metal layer 40.

[0185] Through the above-described steps 1 to 4, the wiring substrate 100 shown in FIG. 4B is obtained. The wiring substrate 100 is used, for example, in semiconductor devices, such as various semiconductor devices including semiconductor packages used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0186] [Other steps] The method for manufacturing a wiring board of the present invention may include steps other than steps 1 to 4 (hereinafter also referred to as "other steps"). Other steps include, for example, a step of exposing the surface of the first wiring 24, a post-curing step of the cured product 30, and the like. The step of exposing the surface of the first wiring 24 is carried out after step 3 and before step 4, when the cured material 30 remains on the surface of the first wiring 24. As the step of exposing the surface of the first wiring 24, a known treatment such as a plasma treatment can be used, for example. The post-curing step of the cured product 30 is a step of curing uncured components that may be contained in the cured product 30, and is carried out, for example, after step 3 and before step 4. [Example]

[0187] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0188] [Preparation of Liquid Curable Composition 1] The various components were mixed in the amounts shown below (amounts based on solid content) to prepare liquid curable composition 1. Liquid curable composition 1 was a liquid composition at 23°C, and had a viscosity of 1.0 Pa s at 23°C measured by the method described above. ---------------------------------------------------------------------------------- Composition of liquid curable composition 1 ---------------------------------------------------------------------------------- Polyimide precursor A-1 (see formula below) 25.0 parts by mass SR205NS (Sartomer) 68.4 parts by weight Perhexa 25O (NOF Corporation) 3.0 parts by mass Compound G-1 (see formula below, thermal base generator) 1.7 parts by mass HAT (5-amino-1H-tetrazole, rust inhibitor) 0.3 parts by mass Compound J-1 (see formula below) 1.6 parts by mass ----------------------------------------------------------------------------------

[0189] Polyimide precursor A-1 [ka]

[0190] Compound G-1 [ka]

[0191] Compound J-1 [ka]

[0192] <Method for synthesizing polyimide precursor A-1> 4,4'-Oxydiphthalic anhydride (dried at 140°C for 12 hours, 20.0 g, 64.5 mmol), 2-hydroxyethyl methacrylate (16.8 g, 129 mmol), hydroquinone (0.05 g), pyridine (20.4 g, 258 mmol), and diethylene glycol dimethyl ether (100 g) were mixed and stirred at 60°C for 18 hours to obtain a reaction mixture (a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate). The resulting diester was then chlorinated using thionyl chloride (SOCl2), to obtain a reaction mixture. Next, a solution of 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) in N-methylpyrrolidone (100 mL) was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. After reacting the reaction mixture at 0°C for 1 hour, ethanol (70 g) was added and the mixture was stirred at room temperature for 1 day. The resulting reaction solution was added to water (5 L) and stirred at 5,000 rpm for 15 minutes to obtain a crude polymer precipitate. The precipitate collected by filtration from the mixture was stirred in water (3 L) for 30 minutes and collected by filtration again. The resulting precipitate was dried under reduced pressure at 45°C for 3 days to obtain polyimide precursor A-1. The weight average molecular weight (Mw) of the polyimide precursor A-1 was 18,000, and the acid value was 0 mgKOH / g.

[0193] The acid value of the resin was determined according to JIS K0070 by dissolving 0.1 g of the synthesized resin in 20 ml of N-methyl-2-pyrrolidone (NMP) and titrating with KOH using thymolphthalein as an indicator.

[0194] [Preparation of Liquid Curable Composition 2] Liquid curable composition 2 was prepared by mixing various components in the amounts shown below (amounts based on solid content). Liquid curable composition 2 was a liquid composition at 23° C., and had a viscosity of 1.0 Pa·s at 23° C. as measured by the method described above. ---------------------------------------------------------------------------------- Composition of liquid curable composition 2 ---------------------------------------------------------------------------------- Polyimide precursor A-1 (see formula above) 15.0 parts by mass SR205NS (Sartomer) 53.4 parts by weight Perhexa 25O (NOF Corporation) 3.0 parts by mass Compound G-1 (see formula above) 1.7 parts by mass HAT (5-amino-1H-tetrazole, rust inhibitor) 0.3 parts by mass ·Compound J-1 (see formula above) 1.6 parts by mass Silica filler (YA050C-MJE, particle size 50 nm, manufactured by Admatechs Co., Ltd.) 25.0 parts by mass ----------------------------------------------------------------------------------

[0195] [Preparation of Liquid Curable Composition 3] Liquid curable composition 3 was prepared by mixing various components in the amounts shown below (amounts based on solid content). Liquid curable composition 3 was a liquid composition at 23° C., and had a viscosity of 1.0 Pa·s at 23° C. as measured by the method described above. ---------------------------------------------------------------------------------- Composition of liquid curable composition 3 ---------------------------------------------------------------------------------- Polysilsesquioxane A-1 (see synthesis method below) 23.0 parts by mass Polysilsesquioxane A-2 (see synthesis method below) 23.0 parts by mass SR205NS (Sartomer) 50.7 parts by weight Perhexa 25O (NOF Corporation) 3.0 parts by mass HAT (5-amino-1H-tetrazole, rust inhibitor) 0.3 parts by mass ----------------------------------------------------------------------------------

[0196] <Method for synthesizing polysilsesquioxane A-1> Polysilsesquioxane A-1 was synthesized by the following method. Styrylmethoxysilane (0.15 mol), hexyltrimethoxysilane (0.15 mol), and 75.0 g of methyl isobutyl ketone were mixed in a 300 mL three-neck flask and heated to an external temperature of 80°C while stirring. 18.0 g of 0.1% by mass aqueous potassium hydroxide solution was added dropwise over 5 minutes, and the mixture was heated and stirred for 5 hours. During heating, the reaction was carried out while refluxing methanol was removed from the system using a Dean-Stark apparatus. After stopping the stirring and cooling to room temperature (25°C) in a water bath, 150 g of methyl isobutyl ketone and 150 g of 5% by mass saline were added to extract the organic phase. The organic phase was washed once with 150 g of 5% by mass saline and twice with 150 g of pure water, dried over 45 g of magnesium sulfate, and concentrated at 50°C under a reduced pressure of 35 mmHg to obtain polysilsesquioxane A-1. The weight average molecular weight (Mw) was 43,700 and the number average molecular weight (Mn) was 8,900.

[0197] <Method for synthesizing polysilsesquioxane A-2> Polysilsesquioxane A-2 was synthesized in the same manner as polysilsesquioxane A-1, except that phenylmethoxysilane (0.15 mol) was used instead of styrylmethoxysilane. The weight-average molecular weight (Mw) was 10,500 and the number-average molecular weight (Mn) was 4,400.

[0198] [Example 1] A mold was prepared as a mold member for forming a patterned cured product, with a recessed portion on the surface and a first protrusion on the bottom of the recessed portion. Here, the first protrusion on the mold was cylindrical with a diameter of 5 μm and a height of 25 μm. The previously prepared liquid curable composition 1 was filled into the recesses of the mold so that the recesses were completely filled with the liquid curable composition 1. Next, an electrode-patterned polyimide film was placed on the mold so that the liquid curable composition 1 filled into the recesses was completely covered, and the polyimide film was pressed against the mold at a pressure of 0.5 MPa using a laminator. At this time, the land electrodes of the polyimide film were aligned with the first convex portions of the mold before lamination. In this state, the liquid curable composition 1 filled in the recesses of the mold was cured by heating at 150°C for 30 minutes, yielding a cured product. The mold was then removed, and a post-curing treatment was carried out at 200°C for 100 minutes. Residue remaining in the first holes of the cured product corresponding to the first protrusions of the mold was then removed by plasma treatment, yielding a patterned cured product. Next, a 0.5 μm thick copper layer was formed as a power supply layer by sputtering on the entire side of the patterned cured product where the first hole was formed, and then electrolytic copper plating was performed using the power supply layer to form conductive vias in the first hole.Then, the surface was polished using a polishing device to produce the wiring board of Example 1 including the conductive vias. When the electrical continuity of the wiring board of Example 1 was checked, it was confirmed that there was electrical continuity at the via portion.

[0199] [Example 2] A wiring board of Example 2 including conductive vias was produced in the same manner as in Example 1, except that liquid curable composition 2 was used instead of liquid curable composition 1. When the electrical continuity of the wiring board of Example 2 was checked, it was confirmed that there was electrical continuity at the via portion.

[0200] [Example 3] A wiring board of Example 3 including conductive vias was produced in the same manner as in Example 1, except that liquid curable composition 3 was used instead of liquid curable composition 1. When the electrical continuity of the wiring board of Example 3 was checked, it was confirmed that there was electrical continuity at the via portion.

[0201] As described above, according to the method for manufacturing a wiring board of the present invention, it was possible to easily form via portions that exhibit good conductivity, and it was confirmed that wiring boards can be manufactured more easily and accurately (Examples 1 to 3). [Explanation of symbols]

[0202] 10. Mold material 12 recess 12b Bottom 14 First convex part 16 Second convex part 20 laminate 22 PCB 24 1st wiring 26 2nd wiring 30 Cured product 34 1st hole 36 2nd hole 40 metal layer 44 Connection 46 Wiring section 100 wiring board L. Liquid curable composition

Claims

1. A method for manufacturing a wiring substrate, a step 1 of filling a liquid curable composition into a recess of a mold member having a surface on which a recess is arranged and a first protrusion on the bottom surface of the recess, and placing a laminate including a substrate and wiring on the mold member so that the first protrusion and the wiring face each other; Step 2: curing the liquid curable composition filled in the recesses obtained in Step 1 to obtain a cured product; Step 3: peeling the mold member from the cured product; and step 4 of filling a first hole portion, which is provided on the surface of the cured material at a position corresponding to the first convex portion and which continues from the surface of the cured material to the surface of the wiring, with metal to form a connection portion that connects to the wiring.

2. The method for producing a wiring substrate according to claim 1 , wherein the liquid curable composition contains a resin.

3. 3. The method for manufacturing a wiring board according to claim 2, wherein the resin comprises at least one selected from the group consisting of a polyimide precursor, a silicone resin, an epoxy resin, a polyimide resin, a polyamide resin, a maleimide resin, and a polyphenylene ether resin.

4. a second protrusion having a height lower than that of the first protrusion on a bottom surface of the recess; 3. The method for manufacturing a wiring board according to claim 1 or 2, wherein in step 4, a wiring portion is formed by filling a metal into a second hole portion that is provided on the surface of the cured material at a position corresponding to the second convex portion and does not penetrate the cured material.

5. The method for manufacturing a wiring board according to claim 1 or 2, wherein in step 4, the metal is filled by plating.

Images