Method for manufacturing circuit board

Abstract

The present invention addresses the problem of providing a method for manufacturing a circuit board provided with a fine and thin insulating layer. The solution of the invention is a method for manufacturing a circuit board. The method for manufacturing a circuit board includes, in this order, a step for forming a resin pattern by discharging a resin composition onto a base material using a jet dispenser, a step for forming an insulating pattern by curing the resin pattern, and a step for forming a conductor layer on the base material and the insulating pattern by an electrolytic plating method, and a step for forming a conductor pattern by removing a portion of the conductor layer. The resin composition contains a thermosetting resin, an organic solvent, an inorganic filler, and a thermoplastic resin. The resin composition satisfies the relationships X > = 30 and X / Y + X / Z < 10, where X (mass%) is the mass ratio of the organic solvent, Y (mass%) is the mass ratio of the inorganic filler, and Z (mass%) is the mass ratio of the thermoplastic resin, when the total components in the resin composition are 100 mass%.

Description

Manufacturing method of circuit board Technical Field

[0001] This invention relates to a method for manufacturing a circuit board. Background Technology

[0002] Printed wiring boards and other circuit boards are widely used in various electronic devices. As a manufacturing method for circuit boards, there are known methods based on a build-up approach where insulating and conductive layers are alternately stacked on an inner substrate. One example of this build-up approach is a method where an insulating layer is used to cover the conductive layer after the conductive layer has been fabricated. Examples of methods for covering the conductive layer with an insulating layer include lamination, spin coating, curtain coating, dip coating, spray coating, and slot coating. However, in these methods, because the insulating layer uniformly covers the entire conductive layer, it is impossible to form the insulating layer only at specific locations on the conductive layer.

[0003] On the other hand, as a method for manufacturing circuit boards in which a conductive layer is formed only in specific locations, a method of dispensing conductive material using a jet dispenser is known. For example, patent documents 1 and 2 disclose methods for manufacturing circuit boards that include the step of dispensing conductive material using a jet dispenser.

[0004] Prior art literature: Patent literature Patent literature 1: Japanese Patent No. 6864046 Patent literature 2: Japanese Patent No. 6668586. Summary of the Invention

[0005] The technical problem to be solved by the present invention: The inventors have been working to develop a new method for forming an insulating layer using a jet dispensing machine when forming an insulating layer only at specific locations on a conductor layer. However, the inventors have found that for the resin composition used to form the insulating layer, the lower the viscosity of the resin composition, the more difficult it is to form a fine insulating layer. Furthermore, the inventors have also found that the higher the viscosity of the resin composition, the thicker the insulating layer is formed, and the more difficult it is to thin the insulating layer. Therefore, the inventors have discovered a trade-off between the fineness and thinness of the insulating layer in the formation of the insulating layer using a jet dispensing machine.

[0006] The present invention was made in view of the above circumstances, and its object is to provide: a method for manufacturing a circuit board having a fine and thin insulating layer; and a semiconductor device having a circuit board manufactured by the method.

[0007] Means for Solving Technical Problems The inventors conducted in-depth research to solve the aforementioned problems. As a result, the inventors discovered that the aforementioned problems could be solved using the following method for manufacturing a circuit board, thus completing the present invention: The method for manufacturing the circuit board sequentially includes: (I) a step of forming a resin pattern by discharging a resin composition onto a substrate using a jet dispensing machine; (II) a step of forming an insulating pattern by curing the resin pattern; (III) a step of forming a conductor layer on the substrate and the insulating pattern using an electrolytic plating method; and (IV) a step of forming a conductor pattern by removing a portion of the conductor layer. The resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler material, and (D) a thermoplastic resin. When all components in the resin composition are set to 100% by mass, and the content of (B) the organic solvent is set to X% by mass, the content of (C) the inorganic filler material is set to Y% by mass, and the content of (D) the thermoplastic resin is set to Z% by mass, the relationship X ≥ 30 and X / Y + X / Z < 10 is satisfied.

[0008] That is, the present invention includes the following: <1> A method for manufacturing a circuit board, the method comprising, in sequence: (I) a step of forming a resin pattern by discharging a resin composition onto a substrate using a jet dispensing machine; (II) a step of forming an insulating pattern by curing the resin pattern; (III) a step of forming a conductor layer on the substrate and the insulating pattern using an electrolytic plating method; and (IV) a step of forming a conductor pattern by removing a portion of the conductor layer, wherein the resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler material, and (D) a thermoplastic resin, wherein when all components in the resin composition are set to 100% by mass, and the content of (B) the organic solvent is set to X (mass%), the content of (C) the inorganic filler material is set to Y (mass%), and the content of (D) the thermoplastic resin is set to Z (mass%), the relationship X ≥ 30 and X / Y + X / Z < 10 is satisfied. <2> according to <1> In the manufacturing method described above, the viscosity of the resin composition, measured using an E-type viscometer at 25°C and 100 rpm, is 350 mPa·s or more and 1500 mPa·s or less. <3> according to <1> or <2> The manufacturing method wherein (A) the thermosetting resin comprises at least one of epoxy resin and maleimide resin; <4> according to <3> The manufacturing method wherein (A) the thermosetting resin comprises a curing agent; <5> according to <1> ~ <4> In any one of the manufacturing methods, (B) the organic solvent comprises an organic solvent with a boiling point of 100°C or higher and 200°C or lower, and when the total amount of organic solvent in the resin composition is set to 100% by mass, the content of the organic solvent with a boiling point of 100°C or higher and 200°C or lower is 50% by mass or higher. <6> according to <1> ~ <5> In any one of the manufacturing methods, wherein (C) the average particle size of the inorganic filler material is 0.Below 4μm; <7> according to <1> ~ <6> In any one of the manufacturing methods, wherein (C) the inorganic filler material comprises silicon dioxide; <8> according to <1> ~ <7> In any one of the manufacturing methods, when the components in the resin composition other than the organic solvent are set to 100% by mass, (C) the content of the inorganic filler material is 20% by mass or more and 70% by mass or less. <9> according to <1> ~ <8> The manufacturing method described in any one of the following, wherein (D) the thermoplastic resin contains an aromatic ring; <10> according to <1> ~ <9> In any one of the manufacturing methods, when the components other than organic solvents in the resin composition are set to 100% by mass, the content of (D) thermoplastic resin is 15% by mass or more and 40% by mass or less. <11> according to <1> ~ <10> The manufacturing method according to any one of the following methods includes a step of roughening the insulating pattern after step (II) and before step (III), wherein step (III) sequentially includes: a step of forming a seed layer on the substrate and the insulating pattern by wet plating, and a step of forming a conductor layer containing a single metal layer of copper on the seed layer by electrolytic plating. <12> according to <1> ~ <10> The manufacturing method according to any one of the following, wherein step (III) sequentially comprises: a step of forming a plated seed layer on the substrate and the insulating pattern by dry plating, and a step of forming a conductor layer containing a single metal layer of copper on the plated seed layer by electrolytic plating, wherein the plated seed layer comprises a conductive seed layer and a diffusion barrier layer between the conductive seed layer and the substrate and the insulating pattern, wherein the conductive seed layer contains a copper-containing metal and the diffusion barrier layer contains a titanium-containing metal; <13> according to <1> ~ <12> In any one of the manufacturing methods, the line width of the insulating pattern is 300 μm or less; <14> according to <1> ~ <13> In any one of the manufacturing methods, the thickness of the insulating pattern is less than 15 μm; <15> according to <1> ~ <14> The manufacturing method described in any one of the following methods further satisfies the relationship X / Y + X / Z > 4; <16> according to <1> ~ <15> In any one of the manufacturing methods, the circuit board is a semiconductor packaging substrate; <17> A semiconductor device, wherein the semiconductor device comprises utilizing <1> ~ <16> The circuit board manufactured by any one of the manufacturing methods described above.

[0009] Effects of the Invention According to the present invention, a method for manufacturing a circuit board having a fine and thin insulating layer can be provided; and a semiconductor device having a circuit board manufactured by the method can be provided. Detailed Implementation

[0010] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented in any way without departing from the scope of the claims and their equivalents.

[0011] [Explanation of terms] In this specification, the term "optionally having substituents" as used with respect to a compound or group refers to both the case where the hydrogen atoms of the compound or group are not substituted by substituents and the case where some or all of the hydrogen atoms of the compound or group are substituted by substituents.

[0012] In this specification, the term "substituent" refers to halogen atoms, alkyl, alkenyl, cycloalkyl, alkoxy, cycloalkoxy, aryl, aryloxy, aralkyl, arylalkoxy, monovalent heterocyclic group, alkylidene group, amino, silyl, carboxyl, sulfonyl, cyano, nitro, hydroxyl, mercapto, and oxo group, unless otherwise specified.

[0013] In this specification, the term "aromatic ring" refers to a ring that follows Hückel's rule, containing 4n+2 electrons (n ​​being an integer greater than or equal to 1) in its π-electron system. This includes monocyclic aromatic rings and fused aromatic rings composed of two or more monocyclic aromatic rings. An aromatic ring can be an aromatic carbon ring containing only carbon atoms as ring-forming atoms, or an aromatic heterocycle containing heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms. In this specification, the term "heteroatom" refers to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and silicon atoms.

[0014] In this specification, the term "(meth)acryloyl" includes acryloyl, methacryloyl, and combinations thereof. Additionally, the term "(meth)acrylate compound" refers to a compound having a (meth)acryloyl group, including acrylate compounds, methacrylate compounds, and combinations thereof. However, (meth)acrylate compounds do not include (meth)acrylic acid. It should be noted that the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof.

[0015] In this specification, the term "non-volatile component" in relation to a resin composition refers to the component constituting the resin composition other than the organic solvents described later. Furthermore, the term "resin component" in relation to a resin composition refers to the component constituting the non-volatile component of the resin composition other than the inorganic fillers described later.

[0016] [Resin Composition] Before describing in detail the method for manufacturing the circuit board of the present invention, the resin composition for forming the resin pattern in step (I) of the manufacturing method will be described.

[0017] The resin composition forming the resin pattern comprises (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin. Furthermore, this resin composition is characterized in that, when all components of the resin composition are set to 100% by mass, and the content of (B) the organic solvent is set to X (mass%), the content of (C) the inorganic filler is set to Y (mass%), and the content of (D) the thermoplastic resin is set to Z (mass%), the relationship X ≥ 30 and X / Y + X / Z < 10 is satisfied. According to the manufacturing method of a circuit board using a resin composition satisfying the above relationship, a circuit board having a fine and thin insulating layer can be manufactured.

[0018] As described above, the resin composition forming the resin pattern satisfies the relationship X ≥ 30. That is, relative to 100% by mass of all components in the resin composition, the content of (B) organic solvent in the resin composition is 30% by mass or more. The preferred numerical range of X will be explained in detail in the section on <(B) organic solvent> described later.

[0019] As described above, the resin composition forming the resin pattern satisfies the relationship X / Y + X / Z < 10. The value of "X / Y + X / Z" is preferably 9.7 or less, more preferably 9.4 or less, and even more preferably 9.1 or less or 9 or less. When the value of "X / Y + X / Z" is within the above range, a finer and thinner insulating layer can be formed in the circuit board. The lower limit of the value of "X / Y + X / Z" is not particularly limited and can be 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, 4 or more, etc. Preferably, the lower limit of the value of "X / Y + X / Z" is greater than 4. That is, in the preferred embodiment, the resin composition forming the resin pattern further satisfies the relationship X / Y + X / Z > 4. Furthermore, the lower limit of the value of "X / Y + X / Z" can be greater than 4, for example, it can be 4.5 or more, 5 or more, 5.5 or more, 6 or more.

[0020] In the resin composition forming the resin pattern, the value of "X / Y" is not particularly limited as long as the value shown in "X / Y+X / Z" is within the specified range. In one embodiment, the value of "X / Y" is preferably 9.5 or less, more preferably 9 or less, further preferably 8.5 or less, even more preferably 8 or less, even more preferably 7.5 or less, even more preferably 7 or less, particularly preferably 6.5 or less, and even more preferably 6 or less, 5.5 or less, 5 or less, 4.5 or less, or 4 or less. The lower limit of the value of "X / Y" is not particularly limited and can be 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, etc.

[0021] In the resin composition forming the resin pattern, the value of "X / Z" is not particularly limited as long as the value shown in "X / Y+X / Z" is within the specified range. In one embodiment, the value of "X / Z" is preferably 9.5 or less, more preferably 9 or less, further preferably 8.5 or less, even more preferably 8 or less, even more preferably 7.5 or less, even more preferably 7 or less, particularly preferably 6.5 or less, and even more preferably 6 or less. The lower limit of the value of "X / Z" is not particularly limited and can be 0.1 or more, 0.5 or more, 1 or more, 1.5 or more, 2 or more, 2.5 or more, etc.

[0022] The resin composition for forming the resin pattern may further include (E) a curing accelerator and (F) other additives as needed. The components contained in the resin composition for forming the resin pattern are described in detail below.

[0023] <(A) Thermosetting Resin> The resin composition forming the resin pattern includes (A) thermosetting resin as component (A). The (A) thermosetting resin can react with heat to form bonds and undergo curing. Therefore, by curing a resin composition containing (A) thermosetting resin, (B) organic solvent, (C) inorganic filler, and (D) thermoplastic resin, an insulating layer containing the cured resin composition can be obtained. One type of (A) thermosetting resin can be used alone, or two or more types can be used in combination.

[0024] Examples of thermosetting resins (A) include: epoxy resins, reactive ester resins, phenolic resins, cyanate ester resins, benzoxazine resins, carbodiimide resins, acid anhydride resins, amine resins, thiol resins, and resins with free radical polymerizable groups.

[0025] In one embodiment, (A) the thermosetting resin comprises an epoxy resin. As the epoxy resin, a curable resin having epoxy groups can be used. Examples of epoxy resins include: xylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol phenolic varnish-type epoxy resin, phenol phenolic varnish-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, and cresol phenolic varnish-type epoxy resin. Epoxy resins include phenolic alkyl epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, butadiene-structured epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexane-diethanol-type epoxy resins, naphthyl ether-type epoxy resins, tris(hydroxymethyl)-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and phenolphthalimidine-type epoxy resins, etc. Epoxy resins can be used alone or in combination of two or more types.

[0026] From the viewpoint of obtaining a cured product with excellent heat resistance, epoxy resins preferably include epoxy resins containing aromatic rings. Regarding aromatic rings, as described above. Examples of epoxy resins containing aromatic rings include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy resin containing aromatic rings, and other epoxy resins containing aromatic rings. Glycidyl ester type epoxy resin, cresol phenolic varnish type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin containing aromatic rings, butadiene-structured epoxy resin containing aromatic rings, alicyclic epoxy resin containing aromatic rings, heterocyclic epoxy resin, spirocyclic epoxy resin containing aromatic rings, cyclohexanediol type epoxy resin containing aromatic rings, naphthalene ether type epoxy resin, tris(hydroxymethyl) type epoxy resin containing aromatic rings, tetraphenylethane type epoxy resin containing aromatic rings, etc.

[0027] For (A) thermosetting resin, epoxy resin is preferably an epoxy resin containing two or more epoxy groups per molecule. The proportion of epoxy resin containing two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, and typically 100% by mass or less, relative to 100% by mass of the epoxy resin.

[0028] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter referred to as "solid epoxy resins").

[0029] As a liquid epoxy resin, it is preferred to have a liquid epoxy resin containing two or more epoxy groups in one molecule.

[0030] The preferred liquid epoxy resin is selected from at least one of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, and epoxy resin with butadiene structure.

[0031] Specific examples of liquid epoxy resins include: DIC's "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "828EL", "828", "825", and "EPIKOTE828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "152" (phenolic varnish type epoxy resin); Mitsubishi Chemical... The following epoxy resins are listed: "630", "630LSD", and "604" (glycidylamine type epoxy resin); "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX-1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; Nagase. ChemteX's "EX-252" and "EX-721" (glycidyl ester type epoxy resins); Daicel's "EHPE3150CE", ENEOS's "THI-DE", Lissenok's "ShofreeCDMDG", and SYMRISE's "LDO" (alicyclic epoxy resins); Daicel's "CELLOXIDE 2021P", "CELLOXIDE 2081P", "CELLOXIDE 2000", and "CELLOXIDE" 8000 (alicyclic epoxy resin with an ester skeleton); Daicel's "PB-3600"; Nippon Soda's "JP-100" and "JP-200" (epoxy resins with a butadiene structure); Nippon Steel Chemical Materials' "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Mitsubishi Chemical's "YX8000" and "YX8034" (hydrogenated bisphenol A type epoxy resin); Mitsubishi Chemical's "YL9028", "YL9029", and "YL9113" (epoxy resins with a siloxane skeleton); Shin-Etsu Silicones' "KR-470", "X-40-2678", and "X-40-2669" (epoxy resins with a siloxane skeleton), etc.

[0032] As a solid epoxy resin, it is preferable to have a solid epoxy resin containing two or more epoxy groups in one molecule, more preferably to have a solid epoxy resin containing three or more epoxy groups in one molecule, and even more preferably to have a solid epoxy resin containing three or more epoxy groups and an aromatic ring in one molecule.

[0033] As a solid epoxy resin, the preferred types are xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthalene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with biphenyl-type epoxy resin being more preferred.

[0034] Specific examples of solid epoxy resins include: DIC's "HP-4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol phenolic varnish type epoxy resin); DIC's "N-695" (cresol phenolic varnish type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resin); and DIC's "EXA-7311" and "EX..." A-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000 (naphthalene ether type epoxy resin); EPPN-502H (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC7000L (naphthalene phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-3000H, NC-3000, NC-3000L, NC-3000FH, NC-3100 (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; ESN475V, ESN4100V (naphthalene ether type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd. Epoxy resins of various types; Nippon Steel Chemical Materials Co., Ltd.'s "ESN485" (naphthol type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthyl type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bi-xylenol type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX8800" (anthracite type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX7700" (phenol aralkyl type epoxy resin); Osaka Gas Chemical Co., Ltd.'s "PG-100"... "CG-500"; "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "EHPE3150" manufactured by Daicel Co., Ltd.; "DE-102" and "DE-103" manufactured by ENEOS Co., Ltd.; "DCPD-DE" (alicyclic epoxy resin) manufactured by Nippon Materials Technology Co., Ltd., etc.

[0035] When using liquid epoxy resin and solid epoxy resin in combination as (A) thermosetting resin, the mass ratio of liquid epoxy resin to solid epoxy resin is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and even more preferably 1:0.2 to 1:5.

[0036] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. or more, more preferably 80 g / eq. or more, even more preferably 110 g / eq. or more, preferably 5000 g / eq. or less, more preferably 3000 g / eq. or less, even more preferably 2000 g / eq. or less, and even more preferably 1000 g / eq. or less. When the epoxy equivalent of the epoxy resin is within the above range, a cured body with sufficient crosslinking density of the resin composition can be obtained. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K 7236.

[0037] The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, preferably 5000 or less, more preferably 3000 or less, and even more preferably 1500 or less. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0038] From the viewpoint of significantly achieving the desired effect of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of epoxy resin in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.3% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0039] From the viewpoint of significantly achieving the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2.5% by mass or more, even more preferably 3.5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.

[0040] When the thermosetting resin (A) comprises an epoxy resin, the resin composition preferably comprises at least one thermosetting resin selected from reactive ester resins, phenolic resins, cyanate ester resins, benzoxazine resins, carbodiimide resins, acid anhydride resins, amine resins, and thiol resins as the thermosetting resin (A). Hereinafter, reactive ester resins, phenolic resins, cyanate ester resins, benzoxazine resins, carbodiimide resins, acid anhydride resins, amine resins, and thiol resins are sometimes collectively referred to as "curing agents".

[0041] As described above, when the thermosetting resin (A) comprises an epoxy resin, the resin composition preferably includes a curing agent as the thermosetting resin (A). More preferably, the thermosetting resin (A) comprises at least one of an active ester resin and a phenolic resin.

[0042] As reactive ester resins, compounds with two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and heterocyclic hydroxyl compounds, are generally preferred. Reactive ester resins can react with epoxy resins to cure the resin composition when combined with them, and are therefore sometimes called "reactive ester-based curing agents." This reactive ester resin is preferably a resin obtained through the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxyl compounds and / or thiols. This reactive ester resin is preferably an reactive ester resin obtained from carboxylic acid compounds and hydroxyl compounds, and more preferably an reactive ester resin obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds. Examples of carboxylic acid compounds include, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, and linear phenolic resins. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene. Active ester resins can be used alone or in combination of two or more types.

[0043] Specifically, the active ester resin is preferably selected from at least one of dicyclopentadiene-type active ester resins, naphthalene-type active ester resins containing a naphthalene structure, active ester resins containing acetylated linear phenolic resins, and active ester resins containing benzoylated linear phenolic resins, with at least one of dicyclopentadiene-type and naphthalene-type active ester resins being more preferred. As a dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferred.

[0044] Commercially available reactive ester resins include, for example, reactive ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", and "EXB-8000H" (manufactured by DIC Corporation); and reactive ester resins containing a naphthalene structure such as "EXB-8100L-65T" and "EXB-8150-60T". Examples of active ester resins containing phosphorus include "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); examples of active ester resins containing phosphorus include "EXB9401" (manufactured by DIC Corporation); examples of active ester resins that are acetylated linear phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins that are benzoylated linear phenolic resins include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and examples of active ester resins containing styrene and naphthalene structures include "PC1300-02-65MA" (manufactured by Air Water Corporation).

[0045] As phenolic resins, resins having one or more, preferably two or more, hydroxyl groups (phenolic hydroxyl groups) bonded to aromatic rings such as benzene rings or naphthalene rings in one molecule can be used. When combined with epoxy resins, phenolic resins can react with the epoxy resins to cure the resin composition; therefore, they are sometimes called "phenolic curing agents." From the viewpoint of heat resistance and water resistance, phenolic resins with a phenolic structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic resins are preferred, and phenolic resins containing a triazine skeleton are more preferred. Among these, linear phenolic resins containing a triazine skeleton are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. A single phenolic resin can be used alone, or two or more can be used in combination.

[0046] Specific examples of phenolic resins include: "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "S" manufactured by Nippon Steel Chemical Materials Co., Ltd. "N-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Company; "GDP-6115L", "GDP-6115H", "ELPC 75" manufactured by Qunrong Chemical Company, etc.

[0047] The active group equivalent of the curing agent is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, preferably 3000 g / eq. or less, more preferably 1000 g / eq. or less, further preferably 500 g / eq. or less, and even more preferably 300 g / eq. or less. The active group equivalent is the mass of the curing agent per equivalent of active groups. Furthermore, the active group of the curing agent refers to a group capable of reacting with the epoxy groups of the epoxy resin, and varies depending on the type of curing agent. For example, the active group of phenolic resins is a phenolic hydroxyl group. Additionally, for example, the active group equivalent of phenolic resins represents the phenolic hydroxyl group equivalent, indicating the mass of resin per equivalent of phenolic hydroxyl groups.

[0048] The weight-average molecular weight (Mw) of the curing agent is preferably 100 or more, more preferably 250 or more, even more preferably 400 or more, preferably 5000 or less, more preferably 3000 or less, and even more preferably 1500 or less. The weight-average molecular weight of the curing agent is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0049] When the number of epoxy groups in the epoxy resin is set to 1, the number of active groups in the curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. "Number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the epoxy resin in the resin composition by the epoxy equivalent. Similarly, "number of active groups in the curing agent" refers to the sum of all values ​​obtained by dividing the mass of the curing agent in the resin composition by the active group equivalent.

[0050] From the viewpoint of significantly achieving the desired effect of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of the curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less.

[0051] From the viewpoint of significantly achieving the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of the curing agent in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less.

[0052] In one embodiment, (A) the thermosetting resin comprises a resin having a free radical polymerizable group (hereinafter sometimes referred to as a "free radical polymerizable resin"). The free radical polymerizable resin may contain an olefinically unsaturated bond. Therefore, the free radical polymerizable resin may have a free radical polymerizable group containing an olefinically unsaturated bond. Examples of free radical polymerizable groups include, for example, unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; α,β-unsaturated carbonyl groups such as acryloyl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl). The free radical polymerizable resin preferably contains two or more free radical polymerizable groups per molecule.

[0053] Examples of free radical polymerizable resins include: maleimide-based free radical polymerizable resins (hereinafter sometimes referred to as "maleimide resins"), (meth)acrylic acid-based free radical polymerizable resins, styrene-based free radical polymerizable resins, allyl-based free radical polymerizable resins, etc. Among these, the free radical polymerizable resin preferably includes maleimide resin.

[0054] Maleimide resin is a resin having, for example, one or more, preferably two or more, maleimide groups in one molecule. Maleimide resin can be an aliphatic maleimide resin containing an aliphatic amine skeleton, or an aromatic maleimide resin containing an aromatic amine skeleton. Commercially available maleimide resins include, for example: Shin-Etsu Chemical Industry Co., Ltd.'s "SLK-2600" and "SLK-6895-T90"; Designer Molecules Inc.'s "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", and "BMI-2500" (maleimide resins containing a dimeric diamine structure); Designer Molecules Inc.'s "BMI-6100" (aromatic maleimide resin); Nippon Kayaku Co., Ltd.'s "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aryl maleimide resin); KI Chemical Co., Ltd.'s "BMI-70" and "BMI-80"; and Daiwa Chemical Industry Co., Ltd.'s "BMI-2300" and "BMI-TMH", etc. Alternatively, the maleimide resin disclosed in Japanese Invention Association Publication No. 2020-500211 (maleimide resin containing an indane skeleton) can also be used as the maleimide resin.

[0055] The free radical polymerizable group equivalent of the resin is preferably 20 g / eq. or more, more preferably 50 g / eq. or more, even more preferably 70 g / eq. or more, even more preferably 90 g / eq. or more, preferably 3000 g / eq. or less, more preferably 2500 g / eq. or less, even more preferably 2000 g / eq. or less, even more preferably 1500 g / eq. or less. The free radical polymerizable group equivalent indicates the mass of the free radical polymerizable resin per 1 equivalent of free radical polymerizable groups.

[0056] The weight-average molecular weight (Mw) of the free radical polymerizable resin is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and even more preferably 3,000 or less. The lower limit is not particularly limited; for example, it can be 150 or more. The weight-average molecular weight of the free radical polymerizable resin is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0057] From the viewpoint of significantly achieving the desired effect of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of free radical polymerizable resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 13% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0058] From the viewpoint of significantly achieving the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of free radical polymerizable resin in the resin composition is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 33% by mass or more or 35% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0059] From the viewpoint of significantly achieving the desired effects of the present invention, (A) the thermosetting resin preferably comprises at least one of epoxy resin and maleimide resin.

[0060] From the viewpoint of significantly achieving the desired effect of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of (A) thermosetting resin in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, even more preferably 10% by mass or more, even more preferably 13% by mass or more or 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 31% by mass or less or 30% by mass or less.

[0061] From the viewpoint of significantly achieving the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of (A) thermosetting resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 35% by mass or more, particularly more preferably 40% by mass or more or 43% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, 63% by mass or less or 61% by mass or less.

[0062] <(B) Organic Solvent> The resin composition that forms the resin pattern includes (B) organic solvent as component (B). (B) organic solvent does not include substances that belong to component (A) above. (B) organic solvent may be used alone or in combination of two or more.

[0063] Examples of organic solvents (B) include aromatic solvents and non-aromatic solvents.

[0064] Aromatic solvents are solvents containing aromatic rings within their molecules. Examples of aromatic solvents include: benzene (boiling point 80℃), toluene (boiling point 110℃), o-xylene (boiling point 144℃), m-xylene (boiling point 139℃), p-xylene (boiling point 138℃), ethylbenzene (boiling point 136℃), etc. 6-8 Aromatic hydrocarbons; C9 aromatic hydrocarbons including 1,2,3-trimethylbenzene (boiling point 176℃), 1,3,5-trimethylbenzene (boiling point 165℃), 1,2,4-trimethylbenzene (boiling point 169℃), 4-ethyltoluene (boiling point 161℃), 3-ethyltoluene (boiling point 160℃), 2-ethyltoluene (boiling point 166℃), isopropylbenzene (boiling point 152℃), n-propylbenzene (boiling point 159℃), indene (boiling point 176℃), etc.; n-butylbenzene (boiling point 183℃), isobutylbenzene (boiling point 172℃), sec-butylbenzene (boiling point 173℃), tert-butylbenzene (boiling point 169℃), 1,2- The following are listed: diethylbenzene (boiling point 184℃), 1,3-diethylbenzene (boiling point 181℃), 1,4-diethylbenzene (boiling point 183℃), 3-ethyl-o-xylene (boiling point 194℃), 4-ethyl-o-xylene (boiling point 190℃), 2-ethyl-p-xylene (boiling point 187℃), 1-methyl-isopropylbenzene (boiling point 178℃), 1-methyl-3-isopropylbenzene (boiling point 175℃), 1-methyl-4-isopropylbenzene (boiling point 177℃), 1,2,3,5-tetramethylbenzene (boiling point 198℃), naphthalene (boiling point 218℃), 1,2,3,4-tetrahydronaphthalene (boiling point 207℃), etc. 10 Aromatic hydrocarbons; C10 of 1,3-dimethyl-4-isopropylbenzene (boiling point 199℃), 1-ethyl-4-isopropylbenzene (boiling point 197℃), etc. 11 Aromatic hydrocarbons, 1,4-diisopropylbenzene (boiling point 210℃), etc., C 12 Aromatic hydrocarbon solvents such as aromatic hydrocarbons; aromatic ketone solvents such as acetophenone (boiling point 202℃); aromatic alcohol solvents such as benzyl alcohol (boiling point 205℃) and phenylethanol (boiling point 219-221℃); aromatic ether solvents such as anisole (boiling point 154℃), phenethyl ether (boiling point 169℃), and phenylethylene glycol (boiling point 244℃); aromatic ester solvents such as methyl benzoate (boiling point 198-200℃) and ethyl benzoate (boiling point 211-213℃), etc.

[0065] Non-aromatic solvents are solvents that do not contain an aromatic ring within their molecules. Examples of non-aromatic solvents include glycol solvents, glycol ether solvents, glycol ether ester solvents, aliphatic hydrocarbon solvents, aliphatic ketone solvents, aliphatic ester solvents, aliphatic ether solvents, aliphatic alcohol solvents, nitrile solvents, amide solvents, and urea solvents.

[0066] Examples of diol solvents include ethylene glycol (boiling point 197℃), diethylene glycol (boiling point 244℃), propylene glycol (boiling point 188℃), dipropylene glycol (boiling point 232℃), and propylene glycol (boiling point 211-217℃).

[0067] Examples of glycol ether solvents include: ethylene glycol monomethyl ether (also known as methyl cellosolve) (boiling point 124℃), ethylene glycol monoethyl ether (also known as cellosolve) (boiling point 135℃), ethylene glycol monopropyl ether (also known as propyl cellosolve) (boiling point 151℃), ethylene glycol monobutyl ether (also known as butyl cellosolve) (boiling point 171℃), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve) (boiling point 160℃), ethylene glycol monotert-butyl ether (also known as tert-butyl cellosolve) (boiling point 152℃), and ethylene glycol monohexyl ether (boiling point 208℃); diethylene glycol monomethyl ether (also known as methyl carbitol) (boiling point 193℃), and diethylene glycol monoethyl ether (also known as carbitol). Carbitols include: ethylene glycol monopropyl ether (boiling point 196℃), diethylene glycol monopropyl ether (also known as propyl carbitol) (boiling point 212-216℃), diethylene glycol monobutyl ether (DB) (also known as butyl carbitol) (boiling point 230℃); propylene glycol monomethyl ether (PGM) (boiling point 120℃), propylene glycol monoethyl ether (boiling point 132℃), propylene glycol monopropyl ether (boiling point 150℃), propylene glycol monobutyl ether (boiling point 170℃); dipropylene glycol monomethyl ether (boiling point 188℃), dipropylene glycol monoethyl ether (boiling point 198℃), dipropylene glycol monopropyl ether (boiling point 210℃), dipropylene glycol monobutyl ether (boiling point 215℃), etc.

[0068] Examples of glycol ether ester solvents include: ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate) (boiling point 145℃), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate) (boiling point 156℃), ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate) (boiling point 191℃), etc.; carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) (boiling point 217℃), diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate) (boiling point 247℃); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEA) (boiling point 146℃), propylene glycol monoethyl ether acetate (boiling point 160℃); and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate (boiling point 200℃), etc.

[0069] Examples of aliphatic hydrocarbon solvents include: n-pentane (boiling point 36℃), n-hexane (boiling point 69℃), 2-methylpentane (also known as isohexane) (boiling point 60-62℃), n-heptane (boiling point 98℃), n-octane (boiling point 125℃), cyclopentane (boiling point 49℃), cyclohexane (boiling point 81℃), methylcyclohexane (boiling point 101℃), and ethylcyclohexane (boiling point 132℃).

[0070] Examples of aliphatic ketone solvents include: acetone (boiling point 56℃), methyl ethyl ketone (MEK) (boiling point 79℃), diethyl ketone (boiling point 101℃), 2-pentanone (boiling point 101℃), methyl isobutyl ketone (boiling point 116℃), 2-hexanone (boiling point 127℃), 2-heptanone (MAK) (boiling point 151℃), diisobutyl ketone (boiling point 168℃), and other aliphatic acyclic ketones; and cyclopentanone (boiling point 131℃), cyclohexanone (Anone) (boiling point 155℃), 2-methylcyclohexanone (boiling point 162℃), and other aliphatic cyclic ketones.

[0071] Aliphatic ester solvents are non-aromatic solvents with ester structures that do not belong to the glycol ether ester solvent family. Examples include: methyl acetate (boiling point 57℃), ethyl acetate (boiling point 77℃), n-propyl acetate (boiling point 96℃), isopropyl acetate (boiling point 89℃), n-butyl acetate (boiling point 126℃), isobutyl acetate (boiling point 118℃), sec-butyl acetate (boiling point 112℃), tert-butyl acetate (boiling point 97℃), n-amyl acetate (boiling point 149℃), and isoamyl acetate (boiling point 142℃). Alkyl esters of fatty acids, such as ethyl propionate (boiling point 99℃), propyl propionate (boiling point 122℃), and isopropyl propionate (boiling point 108℃); alkyl esters of hydroxy acids, such as methyl lactate (boiling point 144-145℃), ethyl lactate (boiling point 151-155℃), and butyl lactate (boiling point 185-187℃); alkyl esters of keto acids, such as methyl acetoacetate (boiling point 170℃) and ethyl acetoacetate (boiling point 184℃); and lactones, such as γ-butyrolactone (GBL) (boiling point 204℃).

[0072] Aliphatic ether solvents are non-aromatic solvents with ether structures that do not belong to glycol ether solvents or glycol ether ester solvents. Examples include aliphatic noncyclic ethers such as diethyl ether (boiling point 34℃), diisopropyl ether (boiling point 68℃), and methyl tert-butyl ether (boiling point 55℃); and aliphatic cyclic ethers such as tetrahydrofuran (boiling point 66℃), 1,4-dioxane (boiling point 101℃), and 1,3-dioxolane (boiling point 75℃).

[0073] Aliphatic alcohol solvents are non-aromatic solvents with an alcohol structure that do not belong to the diol or glycol ether solvent systems. Examples include: methanol (boiling point 64℃), ethanol (boiling point 78℃), n-propanol (boiling point 97℃), isopropanol (boiling point 82℃), n-butanol (boiling point 117℃), isobutanol (boiling point 108℃), sec-butanol (boiling point 99℃), tert-butanol (boiling point 82℃), and n-pentanol (boiling point 138℃). Aliphatic acyclic alcohols such as isoamyl alcohol (boiling point 131℃), sec-amyl alcohol (boiling point 119℃), tert-amyl alcohol (boiling point 102℃), neoamyl alcohol (boiling point 113℃), n-hexanol (boiling point 157℃), n-heptanol (boiling point 175℃), isoheptanol (boiling point 159℃), n-octanol (boiling point 195℃), and 2-ethylhexanol (boiling point 184℃); and aliphatic cyclic alcohols such as cyclohexanol (boiling point 161℃).

[0074] Examples of nitrile solvents include acetonitrile (boiling point 82℃) and propionitrile (boiling point 97℃).

[0075] Examples of amide solvents include noncyclic amides such as N,N-dimethylformamide (DMF) (boiling point 153℃) and N,N-dimethylacetamide (DMA) (boiling point 165℃); and cyclic amides such as N-methyl-2-pyrrolidone (NMP) (boiling point 202℃).

[0076] Examples of urea solvents include acyclic ureas such as tetramethylurea (boiling point 176℃) and cyclic ureas such as 1,3-dimethyl-2-imidazolinone (DMI) (boiling point 220℃) and N,N'-dimethylpropylene urea (DMPU) (boiling point 246℃).

[0077] (B) The organic solvent preferably comprises an organic solvent with a boiling point of 100°C or higher and 200°C or lower. The organic solvent with a boiling point of 100°C or higher and 200°C or lower can be an aromatic solvent, a non-aromatic solvent, or a mixture of aromatic and non-aromatic solvents (mixed solvent). One organic solvent with a boiling point of 100°C or higher and 200°C or lower can be used alone, or two or more can be used in combination. In the case where (B) the organic solvent comprises an organic solvent with a boiling point of 100°C or higher and 200°C or lower, unintended drying of the resin composition before discharge is particularly effective in suppressing this, thus particularly preventing poor discharge of the resin composition, and is therefore preferred. Furthermore, in the case where (B) the organic solvent comprises an organic solvent with a boiling point of 100°C or higher and 200°C or lower, the discharged resin composition can be dried rapidly, thus making it particularly easy to maintain the shape of the discharged resin composition (i.e., the shape of the resin pattern), and is particularly advantageous for forming fine and thin resin patterns, and is therefore preferred.

[0078] From the viewpoint of significantly achieving the desired effects of the present invention, when the total amount of organic solvents in the resin composition is set to 100% by mass, the content of organic solvents in the resin composition with a boiling point of 100°C or higher and 200°C or lower is preferably 50% by mass or higher, more preferably 52% by mass or higher, and even more preferably 53% by mass or higher, 54% by mass or higher, or 55% by mass or higher. In a preferred embodiment, the lower limit of this content may be 60% by mass or higher, 65% by mass or higher, 70% by mass or higher, 75% by mass or higher, 80% by mass or higher, 85% by mass or higher, or 90% by mass or higher. The upper limit of this content may be 100% by mass, or less than 100% by mass or less than 95% by mass.

[0079] When all components in the resin composition are set to 100% by mass, the content of (B) organic solvent in the resin composition (i.e., the value represented by content X in the above formula) is 30% by mass or more. From the viewpoint of significantly achieving the desired effect of the present invention, the lower limit of this content X is preferably 32% by mass or more, more preferably 34% by mass or more, and even more preferably 36% by mass or more. Furthermore, from the viewpoint of significantly achieving the desired effect of the present invention, the upper limit of this content X is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less.

[0080] <(C) Inorganic Filler Material> The resin composition forming the resin pattern includes (C) inorganic filler material as component (C). The (C) inorganic filler material is contained in the resin composition in a particle state and is contained in the cured product (insulating pattern) while maintaining this particle morphology. The (C) inorganic filler material can be used alone or in combination of two or more.

[0081] Inorganic compounds can be used as inorganic filler materials. Examples of inorganic filler materials include: silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide and alumina are preferred, with silicon dioxide being particularly preferred. Examples of silicon dioxide include: amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Furthermore, spherical silicon dioxide is preferred.

[0082] Commercially available inorganic filler materials include, for example: "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Yatuma Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "CellSpheres" and "MG-005" manufactured by Pacific Cement Co., Ltd.; and "Hipresica FH" manufactured by Ube Exsymo Co., Ltd.

[0083] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of the inorganic filler material is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.4 μm or less, or 0.3 μm or less. The lower limit of this average particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, and even more preferably 0.05 μm or more. The average particle size of the inorganic filler material can be measured by laser diffraction / scattering based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler material can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median diameter can be used for measurement. The sample for measurement can be a sample obtained by weighing 100 mg of the inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. For the sample for measurement, the volume-based particle size distribution of the inorganic filler material is measured using a laser diffraction particle size distribution measuring device with the light source wavelength set to blue and red in a flow cell manner. The average particle size is calculated based on the obtained particle size distribution as the median diameter. Examples of laser diffraction particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0084] From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​the inorganic filler material is preferably 0.1 m². 2 / g or more, preferably 1m 2 / g or more, further preferably 10m 2 / g or more, and more preferably 20m 2 / g or more, 25m 2 / g or more or 30m 2 / g or more. The upper limit of this specific surface area is preferably 100m². 2 / g or less, preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area of ​​inorganic fillers can be obtained by the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas onto the sample surface, and then calculating the specific surface area using the BET multi-point method.

[0085] Inorganic filler materials are preferably surface-treated with appropriate surface treatment agents. Surface treatment can improve the moisture resistance and dispersibility of inorganic filler materials. Examples of surface treatment agents include: vinyl silane coupling agents, epoxy silane coupling agents, styrene silane coupling agents, (meth)acrylic acid silane coupling agents, amino silane coupling agents, isocyanurate silane coupling agents, urea silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, anhydride silane coupling agents, and other silane coupling agents; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silazane compounds. A single surface treatment agent can be used, or two or more can be used in combination.

[0086] Commercially available surface treatment agents include, for example: "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0087] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment using surface treatment agents is preferably within a specific range. Specifically, 100% by mass of the inorganic filler material is preferably surface treated with 0.2% to 5% by mass of a surface treatment agent.

[0088] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler material. From the viewpoint of improving the dispersibility of the inorganic filler material, the carbon content per unit surface area of ​​the inorganic filler material is preferably 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m³. 2 That's all. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, the upper limit of the carbon content per unit surface area of ​​the inorganic filler material is preferably 1 mg / m². 2 The following is more preferably 0.8 mg / m³ 2The following is a further preferred value: 0.5 mg / m³ 2 The carbon content per unit surface area of ​​inorganic filler materials can be determined after cleaning the surface-treated inorganic filler materials with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the surface-treated inorganic filler materials, and the materials are ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler materials can be determined using a carbon analyzer. A suitable carbon analyzer is the "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd.

[0089] From the viewpoint of significantly achieving the desired effects of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of the inorganic filler (C) in the resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, further more preferably 35% by mass or more, even more preferably 39% by mass or more or 40% by mass or more, and even more preferably 45% by mass or more. Wherein, according to the method of having the content of the inorganic filler (C) at 35% by mass or more (and further at 39% by mass or more, 40% by mass or more, or 45% by mass or more), the dielectric loss tangent of the insulating layer can be particularly reduced in the fine and thin insulating layer, and is therefore preferred. Generally, if the content of the inorganic filler in the resin composition increases (for example, the content of the inorganic filler is 50% by mass or more relative to 100% by mass of the non-volatile component in the resin composition), the mechanical strength of the cured resin composition may sometimes decrease, and therefore, the reliability of the insulating layer containing the cured resin composition may sometimes decrease. Furthermore, if the content of inorganic filler in the resin composition increases, the viscosity of the resin composition may become extremely high. As mentioned earlier, the higher the viscosity of the resin composition, the thicker the insulating layer will be formed, making it difficult to achieve a thin insulating layer. In contrast, the resin composition used in the circuit board manufacturing method of the present invention, by satisfying the above-mentioned relationship of "X≥30 and X / Y+X / Z<10", can achieve a fine and thin insulating layer even when containing more inorganic filler, compared with conventional resin compositions used in jet dispensing machines, resulting in a cured product exhibiting excellent mechanical strength. Furthermore, the resin composition used in the circuit board manufacturing method of the present invention, compared with conventional resin compositions used in jet dispensing machines, by containing more inorganic filler, can particularly reduce the dielectric loss tangent of the insulating layer in a fine and thin insulating layer, thus significantly contributing to the miniaturization and high performance of electronic devices. However, the scope of the present invention in the form of a higher content of inorganic filler does not narrow or exclude the scope of the form of a lower content of inorganic filler. From the viewpoint of more significantly achieving the desired effect of the present invention, the upper limit of the content of the inorganic filler material (C) is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, 69% by mass or less, 68% by mass or less or 67% by mass, further more preferably 66% by mass or less, 65% by mass or less, 64% by mass or less or 63% by mass, and even more preferably 62% by mass or less, 61% by mass or less, or 60% by mass or less.

[0090] When all components in the resin composition are set to 100% by mass, the content of (C) inorganic filler material in the resin composition (i.e., the value of content Y in the above formula) is not particularly limited as long as the values ​​shown in "X / Y+X / Z" are within the specified range. In one embodiment, the lower limit of this content Y is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and even more preferably 20% by mass or more or 25% by mass or more. In another embodiment, the upper limit of this content Y is preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0091] <(D) Thermoplastic Resin> The resin composition that forms the resin pattern includes (D) thermoplastic resin as component (D). The (D) thermoplastic resin as component (D) does not contain any substances belonging to components (A) to (C) above. One type of (D) thermoplastic resin may be used alone, or two or more types may be used in combination.

[0092] Examples of thermoplastic resins (D) include: polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyether-imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, etc. Preferably, the thermoplastic resin (D) includes at least one of polyimide resins and phenoxy resins.

[0093] Polyimide resins can be resins with an imide structure. Polyimide resins are generally obtained through an imidization reaction of a diamine compound with an acid anhydride, or an imidization reaction of a diisocyanate compound with an acid anhydride. Specific examples of polyimide resins include linear polyimides (the polyimide described in Japanese Patent Application Publication No. 2006-37083) obtained by reacting difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride, and modified polyimides containing a polysiloxane backbone (the polyimides described in Japanese Patent Application Publication Nos. 2002-12667 and 2000-319386, etc.). Commercially available polyimide resins can be used, such as "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rika Co., Ltd. Polyimide resins can be used alone or in combination of two or more.

[0094] In a preferred embodiment, the polyimide resin comprises a structural unit (hereinafter also referred to as "structural unit (1)") as shown in formula (1). The number of structural units (1) contained in each molecule of polyimide resin is 1 or more, without particular limitation, but may be 100 or less, 50 or less, or 30 or less.

[0095] [Chemical Formula 1] .

[0096] (In formula (1), R1 is a tetravalent group as shown in formula (1-1) below, and R2 is a divalent group as shown in formula (1-2) below).

[0097] [Chemical Formula 2] .

[0098] (In equation (1-1), Ar) 11 Ar 12 Ar 13 and Ar 14 Each independently represents an aromatic ring optionally having substituents, L 11 L 12 and L 13 Each of these groups independently represents a divalent linker, and nc1 represents an integer greater than or equal to 0.

[0099] [Chemical Formula 3] .

[0100] (In equation (1-2), Ar) 21 Ar 22 Ar 23 and Ar 24 Each independently represents an aromatic ring optionally having substituents, L 21 L 22 and L 23 Each of these groups independently represents a divalent linker, and nc2 represents an integer greater than 1.

[0101] In equation (1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each independently represents an aromatic ring optionally having substituents. Ar 11 Ar 12 Ar 13 and Ar 14 The aromatic ring represented (hereinafter also referred to as "aromatic ring C") is preferably an aromatic ring with 6 to 100 carbon atoms, more preferably an aromatic ring with 6 to 50 carbon atoms, even more preferably an aromatic carbon ring with 6 to 100 carbon atoms, and even more preferably an aromatic carbon ring with 6 to 50 carbon atoms.

[0102] As Ar11 Ar 12 Ar 13 and Ar 14 Examples of aromatic rings include: monocyclic aromatic rings such as benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; fused rings formed by the condensation of two or more monocyclic aromatic rings such as naphthyl rings, anthracene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, borazine rings, and phthalazine rings; and fused rings formed by the condensation of one or more monocyclic non-aromatic rings on one or more monocyclic aromatic rings, such as indanium rings, fluorene rings, and tetrahydronaphthalene rings. 11 Ar 12 Ar 13 and Ar 14 The aromatic rings represented are preferably each independently an aromatic carbon ring having 6 to 14 carbon atoms with substituents, and more preferably a benzene ring.

[0103] In equation (1-1), Ar 11 Ar 12 Ar 13 and Ar 14 When representing an aromatic ring with substituents, the number of substituents is not limited. Examples of such substituents (hereinafter also referred to as "substituent S") can be independently listed as follows: halogen atom, alkyl, cycloalkyl, alkoxy, cycloalkoxy, aryl, aryloxy, arylalkyl, arylalkoxy, monovalent heterocyclic group, alkylidene group, amino, silyl, acyl, acyloxy, carboxyl, sulfonyl, cyano, nitro, hydroxyl, mercapto, and oxo.

[0104] In equation (1-1), L 11 L 12 and L 13 Each independently represents a divalent linker. L 11 L 12 and L 13 The divalent linking group is preferably a divalent group formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50 atoms, respectively). Examples of divalent linking groups include: -SO2-, -CO-, -COO-, -O-, -S-, -O-C6H4-O- (where -C6H4- represents phenylene), -O-C6H4-C(CH3)2-C6H4-O-, and -COO-(CH2). m-OCO- (where m represents an integer from 1 to 20), -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO-, alkylene, alkenylene, ynylene, arylene, heteroarylene, -NR 0 -(Here, R) 0 (representing hydrogen atoms, alkyl groups with 1 to 3 carbon atoms) and -C(=O)-NR 0 -

[0105] As L 11 L 12 and L 13 The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5 or 1 to 4. As L 11 L 12 and L 13 The number of carbon atoms in the alkenyl group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 5. As L 11 L 12 and L 13 The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 10. As L 11 L 12 and L 13 The number of carbon atoms in the heteroaryl group is preferably 2 to 20, more preferably 3 to 10, 4 to 10 or 5 to 10.

[0106] L 11 L 12 and L 13 The divalent linker indicated preferably does not contain an aromatic ring. In one embodiment, L 11 The divalent linker and L are represented 13 The divalent linking groups represented are identical to each other, L 11 The divalent linker and L are represented 12 The divalent linking groups represented are different from each other. In a preferred embodiment, L 11 and L 13 For -O-, L 12 It is optionally an alkylene group having substituents. In a more preferred embodiment, L 11 and L 13 For -O-, L 12 It is a dimethylmethylene group.

[0107] In equation (1-1), nc1 represents an integer greater than or equal to 0. In a preferred embodiment, nc1 represents an integer greater than or equal to 1. There is no particular upper limit to the integer represented by nc1, for example, it can be 50, 40, 30 or 20.

[0108] Among the tetravalent groups shown in formula (1-1), L is preferred.11 and L 13 It is -O-, and L 12 It is optionally an alkylene group having a substituent. More preferably, it is Ar. 11 Ar 12 Ar 13 and Ar 14 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, L 11 and L 13 It is -O-, and L 12 It is optionally an alkylene group having substituents. Furthermore, Ar is more preferably preferred. 11 Ar 12 Ar 13 and Ar 14 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, L 11 and L 13 For -O-, L 12 It is a dimethylmethylene group.

[0109] In equation (1-2), Ar 21 Ar 22 Ar 23 and Ar 24 Each independently represents an aromatic ring optionally having substituents. Ar 21 Ar 22 Ar 23 and Ar 24 The aromatic ring represented and the examples of substituents optionally present on the aromatic ring are the same as those of the aromatic ring C and substituent S described above. Therefore, in a preferred embodiment, Ar 21 Ar 22 Ar 23 and Ar 24 Each is an aromatic carbon ring with 6 to 14 carbon atoms, which can be independently selected and have substituents.

[0110] In equation (1-2), L 21 L 22 and L 23 Each independently represents a divalent linker. L 21 L 22 and L 23 Examples of divalent linking groups represented by L 11 L 12 and L 13 The divalent linking groups represented are the same. Therefore, in a preferred embodiment, L 21 and L 23 For -O-, L 22In a more preferred embodiment, L is an alkylene group optionally having a substituent. 21 and L 23 For -O-, L 22 It is a dimethylmethylene group.

[0111] In equation (1-2), nc2 represents an integer greater than or equal to 1. In a preferred embodiment, nc2 represents an integer greater than or equal to 2. There is no particular upper limit to the integer represented by nc2; for example, it can be 60, 50, 40, or 30.

[0112] Among the divalent groups shown in formula (1-2), L is preferred. 21 and L 23 It is -O-, and L 22 It is optionally an alkylene group having a substituent. More preferably, it is Ar. 21 Ar 22 Ar 23 and Ar 24 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, L 21 and L 23 It is -O-, and L 22 It is optionally an alkylene group having substituents. Furthermore, Ar is more preferably preferred. 21 Ar 22 Ar 23 and Ar 24 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, L 21 and L 23 For -O-, L 12 It is a dimethylmethylene group.

[0113] Among the tetravalent group shown in formula (1-1) and the divalent group shown in formula (1-2), Ar is preferred. 11 Ar 12 Ar 13 and Ar 14 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally having substituents, and Ar 21 Ar 22 Ar 23 and Ar 24 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally having substituents. Furthermore, L is preferred. 11 and L 13 For -O-, L 12 For optional alkylene groups with substituents, L 21 and L 23 It is -O-, and L 22 It can be an alkylene group with optional substituents.

[0114] The aforementioned structural unit (1) can be obtained, for example, according to known methods for manufacturing polyimide resins, typically by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound to imide, or by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound to imide. It should be noted that polyimide resins may contain a portion of polyamic acid structures that can be generated during the imideation process.

[0115] Structural unit (1) can be obtained, for example, by reacting 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (the compound shown in formula (I) below; also referred to as "BPADA") with 4,4'-[1,4-phenylenebis[(1-methylethylene)-4,1-phenyleneoxy]]bisaniline (the compound shown in formula (II) below; also referred to as "BPPAN"). That is, in one embodiment, R1 in structural unit (1) is the skeleton from BPADA, and R2 in structural unit (1) is the skeleton from BPPAN.

[0116] [Chemical Formula 4] .

[0117] In addition, the polyimide resin may further comprise the structural unit shown in formula (2) below (hereinafter also referred to as "structural unit (2)"). Therefore, in one embodiment, the polyimide resin further comprises the structural unit shown in formula (2) below. The number of structural units (2) contained in each molecule of polyimide resin is 0 or more, without particular limitation, but may be 100 or less, 50 or less, or 30 or less.

[0118] [Chemical Formula 5] .

[0119] (In formula (2), R3 represents a tetravalent aliphatic group or a tetravalent aromatic group with a substituent, and R4 represents a divalent aliphatic group or a divalent aromatic group with a substituent. Where R3 and R1 are the same, R4 and R2 are different; where R4 and R2 are the same, R3 and R1 are different.)

[0120] In formula (2), R3 represents a tetravalent aliphatic group with substituents or a tetravalent aromatic group with substituents.

[0121] The tetravalent aliphatic group represented by R3 contains at least a carbon atom, and is preferably a tetravalent group formed by one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50 atoms, respectively). More preferably, the tetravalent aliphatic group represented by R3 is a tetravalent aliphatic group with 1 to 100 carbon atoms, and even more preferably, a tetravalent aliphatic group with 1 to 50 carbon atoms. When R3 represents a tetravalent aliphatic group with a substituent, the examples of the substituent are the same as those of the substituent S.

[0122] The tetravalent aromatic group represented by R3 is preferably a tetravalent aromatic group with 6 to 100 carbon atoms, more preferably a tetravalent aromatic group with 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are similar to those in formula (1-1) where Ar... 11 Ar 12 Ar 13 and Ar 14 The examples of aromatic rings represented are the same. In formula (2), when R3 represents a tetravalent aromatic group with a substituent, the examples of the substituent are the same as those of the substituent S.

[0123] As R3 represents a tetravalent aromatic group, examples include the group obtained by removing two anhydride groups from a tetracarboxylic dianhydride having optionally substituent aromatic groups. Specific examples of tetracarboxylic dianhydrides having optionally substituent aromatic groups include: BPADA, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride.

[0124] In formula (2), R4 represents a divalent aliphatic group with substituents or a divalent aromatic group with substituents.

[0125] R4 represents a divalent aliphatic group that contains at least a carbon atom, preferably a divalent group formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50). In formula (2), R4 represents a divalent aliphatic group that has 1 to 100 carbon atoms, and more preferably a divalent aliphatic group that has 1 to 50 carbon atoms. In formula (2), when R4 represents a divalent aliphatic group having a substituent, the examples of the substituent are the same as the examples of the substituent S, for example, an alkyl group having 1 to 6 carbon atoms. Therefore, in one embodiment, R4 is a divalent aliphatic group that optionally has a substituent, one of which is an alkyl group having 1 to 6 carbon atoms. Furthermore, in one embodiment, R4 is a divalent aliphatic group that optionally has a substituent, and is a divalent group obtained by removing two amino groups from isophorone diamine.

[0126] When R4 represents a divalent aliphatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine.

[0127] When R4 represents a divalent aliphatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound selected from 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, and 1,5-diamino-2-methylpentane, which has a branched aliphatic group with optional substituents.

[0128] When R4 represents an optional divalent aliphatic group with substituents, it can be selected from 5-amino-1,3,3-trimethylcyclohexylmethylamine (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6The group obtained by removing two amino groups from a diamine compound having an optional aliphatic group, such as decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-diadamantane, and 1,6-diaminoadamantane. These diamine compounds are characterized in that their aliphatic group comprises an alicyclic carbocyclic ring.

[0129] The divalent aromatic group represented by R4 is preferably a divalent aromatic group with 6 to 100 carbon atoms, more preferably a divalent aromatic group with 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. In formula (2), when R4 represents a divalent aromatic group having a substituent, the example of the substituent is the same as the example of substituent S.

[0130] When R4 represents a divalent aromatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound selected from 4,4'-diaminodiphenyl ether, 1,4-phenylene diamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane that has an aromatic group with optional substituents.

[0131] Where R3 and R1 are the same, R4 and R2 are different; where R4 and R2 are the same, R3 and R1 are different. In one embodiment, R3 and R1 are the same.

[0132] The aforementioned structural unit (2) can be obtained, for example, by a known method for manufacturing polyimide resins. Structural unit (2) can be obtained, for example, by reacting BPADA with isophorone diamine. That is, in such a structural unit (2), R3 is a backbone from BPADA, and R4 is a backbone from isophorone diamine. If R3 and R1 are the same, then R3 and R1 are backbones from BPADA.

[0133] The end structure of polyimide resin is not particularly limited. For example, the end structure of polyimide resin can be an anhydride group or a carboxyl or amino group derived from its raw material compound (e.g., an acid such as BPADA, an amine such as BPPAN). When the raw material compound further contains maleic anhydride, the end structure of the polyimide resin can be a maleimide group.

[0134] The glass transition temperature (Tg) of the polyimide resin is preferably 140°C or higher, more preferably 145°C or higher, and even more preferably 150°C or higher, 160°C or higher, or 170°C or higher. There is no particular upper limit, and it can be 300°C or lower, etc. The glass transition temperature (Tg) of the polyimide resin can be determined by thermomechanical analysis (TMA).

[0135] The content of structural unit (1) in the polyimide resin is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, 30% by mass or more, or 40% by mass or more. The upper limit of this content ratio can be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less. Here, the content ratio (mass percentage) of structural unit (1) can be calculated based on the proportion of each material used in the synthesis of the polyimide resin (by mass). Alternatively, the molecular weight of the polyimide resin and the formula weight of the structural unit (1) can be determined, and the ratio of the formula weight of the structural unit (1) to the molecular weight can be calculated. When the polyimide resin is a polymer, the content ratio of structural unit (1) estimated from the degree of polymerization is preferably within the above-mentioned range.

[0136] The content of structural unit (2) in the polyimide resin can be 0% by mass (i.e., without structural unit (2)), and there is no upper limit as long as it does not hinder the effect of the present invention. When the polyimide resin is a resin that further contains structural unit (2), the content of structural unit (2) in the polyimide resin can be, for example, 1% or more by mass, 5% or more by mass, 10% or more by mass, 20% or more by mass, or 30% or more by mass, and 95% or less by mass, 90% or less by mass, 80% or less by mass, 70% or less by mass, or 60% or less by mass. Here, the content of structural unit (2) is calculated in the same way as the content of structural unit (1).

[0137] The weight-average molecular weight (Mw) of the polyimide resin is preferably 1,000 or more, preferably 200,000 or less, more preferably 150,000 or less or 100,000 or less, further preferably 80,000 or less or 60,000 or less, and even more preferably 40,000 or less or 30,000 or less. In one embodiment, the upper limit of the weight-average molecular weight (Mw) of the polyimide resin may be 5,000 or less or 3,000 or less. The weight-average molecular weight of the polyimide resin is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0138] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include: Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (a phenoxy resin containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (a phenoxy resin containing a bisphenol acetophenone backbone); Nippon Steel Chemical Materials' "FX280" and "FX293"; and Mitsubishi Chemical's "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30," etc. Phenoxy resins can be used alone or in combination of two or more.

[0139] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd. A single polyvinyl acetal resin can be used alone, or two or more resins can be used in combination.

[0140] Examples of polyolefin resins include: low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers. Polyolefin resins can be used alone or in combination of two or more types.

[0141] Examples of polybutadiene resins include: resins containing a hydrogenated polybutadiene backbone, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, polybutadiene resins containing urethane groups, and polyphenylene ether-polybutadiene resins. Polybutadiene resins can be used alone or in combination of two or more types.

[0142] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Other examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Risenok Co., Ltd. Polyamide-imide resins can be used alone or in combination of two or more types.

[0143] Specific examples of polysulfone resins include Solvay Performance Polymers' polysulfone "P1700" and "P3500". Polysulfone resins can be used alone or in combination of two or more types.

[0144] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC Co., Ltd. Specific examples of polyetherimide resins include "Ultem" manufactured by GE Co., Ltd.

[0145] Examples of polycarbonate resins include: hydroxyl-containing polycarbonate resins, phenolic hydroxyl-containing polycarbonate resins, carboxyl-containing polycarbonate resins, anhydride-containing polycarbonate resins, isocyanate-containing polycarbonate resins, and urethane-containing polycarbonate resins. Specific examples of polycarbonate resins include: Mitsubishi Gas Chemical's "FPC0220," Asahi Kasei's "T6002" and "T6001" (polycarbonate diol), and Kuraray's "C-1090," "C-2090," and "C-3090" (polycarbonate diol). Polycarbonate resins can be used alone or in combination of two or more types.

[0146] Specific examples of polyetheretherketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0147] Examples of polyester resins include: polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin. A single polyester resin can be used alone, or two or more resins can be used in combination.

[0148] From the viewpoint of significantly maximizing the effects of the present invention, (D) the thermoplastic resin preferably contains an aromatic ring. This aromatic ring can be an aromatic carbide ring or an aromatic heterocycle. Furthermore, the aromatic ring can be a monocyclic aromatic ring, a fused aromatic ring formed by the condensation of two or more monocyclic aromatic rings, or a fused aromatic ring in which one or more monocyclic non-aromatic rings are condensed onto one or more monocyclic aromatic rings. Preferably, the aromatic ring contained in (D) the thermoplastic resin is an aromatic carbide ring. The number of carbon atoms in the aromatic carbide ring is preferably 6 or more and 10 or less.

[0149] (D) When the thermoplastic resin contains aromatic rings, the number of aromatic rings is, for example, 1 or more, preferably 2 or more. (D) When the thermoplastic resin contains 2 or more aromatic rings, these 2 or more aromatic rings may be the same or different.

[0150] From the viewpoint of achieving more significant effects of the present invention, (D) thermoplastic resin more preferably contains aromatic rings, and these aromatic rings are all aromatic carbon rings. That is, in a more preferred embodiment, (D) thermoplastic resin contains aromatic carbon rings but does not contain aromatic heterocycles. In such an embodiment, (D) thermoplastic resin may contain non-aromatic rings or may not contain non-aromatic rings. The non-aromatic ring may be a non-aromatic carbon ring in which only carbon atoms are used as cyclizing atoms, or it may be a non-aromatic heterocycle in which, in addition to carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and other heteroatoms are used as cyclizing atoms.

[0151] When the resin composition comprises a thermoplastic resin other than a polyimide resin, the weight-average molecular weight (Mw) of the thermoplastic resin other than the polyimide resin is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, 15,000 or more, or 20,000 or more, preferably 200,000 or less, more preferably 150,000 or less, or 100,000 or less, and further preferably 80,000 or less, or 60,000 or less. The weight-average molecular weight of the thermoplastic resin other than the polyimide resin is the weight-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0152] From the viewpoint of significantly achieving the desired effects of the present invention, when the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of (D) thermoplastic resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more or 16% by mass or more, further more preferably 17% by mass or more or 18% by mass or more, preferably 50% by mass or less, more preferably 46% by mass or less or 45% by mass or less, further preferably 40% by mass or less, further more preferably 35% by mass or less, 33% by mass or less or 31% by mass or less. In this case, where the content of (D) thermoplastic resin is 15% by mass or more and 40% by mass or less, it is particularly easy to maintain the shape of the discharged resin composition (i.e., the shape of the resin pattern), and thus it is particularly advantageous to form fine and thin resin patterns, which is therefore preferred. Furthermore, in a configuration where the content of the (D) thermoplastic resin is 15% by mass or more and 40% by mass or less, separation between components in the resin composition before discharge or sedimentation of inorganic filler materials is particularly effective, and is therefore preferred. Furthermore, in a configuration where the content of the (D) thermoplastic resin is 15% by mass or more and 40% by mass or less, excessive softness of the resin pattern (and insulating pattern) is particularly effective, and is therefore preferred.

[0153] From the viewpoint of significantly achieving the desired effect of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of (D) thermoplastic resin in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, 37% by mass or more, or 39% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, further more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, particularly preferably 65% ​​by mass or less, particularly more preferably 60% by mass or less, or 57% by mass or less.

[0154] When all components in the resin composition are set to 100% by mass, the content of (D) thermoplastic resin in the resin composition (i.e., the value of content Z in the above formula) is not particularly limited as long as the value shown in "X / Y+X / Z" is within the specified range. In one embodiment, the lower limit of this content Z is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and even more preferably 7% by mass or more or 8% by mass or more. In another embodiment, the upper limit of this content Z is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, 23% by mass or less, or 21% by mass or less.

[0155] <(E) Curing Accelerator> The resin composition forming the resin pattern may contain (E) curing accelerator as an optional component. The (E) curing accelerator, as component (E), does not contain substances belonging to components (A) to (D) above. The (E) curing accelerator functions as a catalyst for the thermosetting resin reaction of (A), thus promoting the curing of the resin composition. One (E) curing accelerator may be used alone, or two or more may be used in combination.

[0156] Examples of curing accelerators include: imidazole-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and urea-based curing accelerators.

[0157] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethylimidazolium Imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc.; and adducts of the imidazole compounds with epoxy resins; etc. The imidazole-based curing accelerator is preferably at least one of 2-phenyl-4-methylimidazolium, 2-ethyl-4-methylimidazolium, and 1-benzyl-2-phenylimidazolium. Commercially available imidazole-based curing accelerators can be used, such as: Mitsubishi Chemical's "P200-H50"; and Shikoku Chemical Industry's "Curezol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2MZA-PW", "2PHZ", "2P4MZ", "2PHZ-PW", "1B2PZ", and "1B2PZ-10M".

[0158] Phosphorus-based curing accelerators include, for example, phosphonium salts and phosphine. Examples of phosphonium salts include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, n-butylphosphonium tetraphenylborate, bis(tetrabutylphosphonium)pyromellitic acid tetraphosphate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, di-tert-butylmethylphosphonium tetraphenylborate, etc., and aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, etc. Aromatic phosphonium salts such as phosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[0159] Examples of phosphine species include: tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, and other aliphatic phosphines; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri( Aromatic phosphines such as 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; and aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants.

[0160] As a phosphorus-based curing accelerator, commercially available products can be used, such as "TBP-DA" manufactured by Beixing Chemical Industry Co., Ltd.

[0161] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, and 2,4,6-tris(dimethylaminomethyl)phenol, with 4-dimethylaminopyridine being preferred. Commercially available amine-based curing accelerators can be used, such as "PN-50," "PN-23," and "MY-25" manufactured by Ajinomoto Fine-Techno.

[0162] Examples of guanidine-based curing accelerators include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0163] Examples of organometallic curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone; organocopper complexes such as copper(II) acetylacetone; organozinc complexes such as zinc(II) acetylacetone; organoiron complexes such as iron(III) acetylacetone; organonickel complexes such as nickel(II) acetylacetone; and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0164] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

[0165] When the resin composition contains a (E) curing accelerator, and the non-volatile component (i.e., the component other than the organic solvent) in the resin composition is set to 100% by mass, the content of the (E) curing accelerator in the resin composition is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, 0.08% by mass or less, or 0.06% by mass or less.

[0166] When the resin composition contains (E) curing accelerator, and the resin component in the resin composition is set to 100% by mass, the content of (E) curing accelerator in the resin composition is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.07% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0167] <(F) Other Additives> The resin composition forming the resin pattern may be combined with components (A) to (E) above to further include (F) other additives as optional components. The (F) other additives, as components (F), do not contain substances belonging to components (A) to (E) above.

[0168] Other additives (F) include, for example: peroxide-based free radical polymerization initiators, azo-based free radical polymerization initiators, and other free radical polymerization initiators; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds and organozinc compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; thickeners such as Benton (swellable clay) and montmorillonite; defoamers such as organosilicon-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; and benzotriazole-based ultraviolet absorbers. UV absorbers such as urea-silanes; adhesive enhancers such as triazole-based, tetraazole-based, and triazine-based adhesive enhancers; antioxidants such as hindered phenolic antioxidants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate esters, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); stabilizers such as borate ester stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (F) Other additives may be used alone or in combination of two or more.

[0169] [Method for Manufacturing Resin Composition] A resin composition forming a resin pattern can be manufactured, for example, by mixing the above-mentioned components. The components can be mixed partially or entirely simultaneously, or sequentially. During the mixing of the components, a suitable temperature can be set, thus heating and / or cooling can be performed temporarily or continuously. Furthermore, stirring or agitation can be performed during the mixing of the components. Moreover, degassing can be performed under low-pressure conditions such as vacuum.

[0170] [Characteristics of the Resin Composition] The resin composition forming the resin pattern comprises (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin (and, if necessary, (E) a curing accelerator and (F) other additives). Furthermore, this resin composition is characterized in that, when all components in the resin composition are set to 100% by mass, and the content of (B) the organic solvent is set to X (mass%), the content of (C) the inorganic filler is set to Y (mass%), and the content of (D) the thermoplastic resin is set to Z (mass%), the relationship X ≥ 30 and X / Y + X / Z < 10 is satisfied. According to the manufacturing method of a circuit board using a resin composition satisfying the above relationship, a circuit board having a fine and thin insulating layer can be manufactured.

[0171] As described above, a circuit board with a fine insulating layer can be manufactured using a method for manufacturing a circuit board using a resin composition that satisfies the relationship X≥30 and X / Y+X / Z<10. For example, as described later in the section <Experimental Example 3: Discharge Test Using a Jet Dispenser>, the nozzle diameter was fixed at 50 μm, the distance between the nozzle and the glass plate was fixed at 500 μm, and the supply pressure of the resin composition was fixed at 0.02 MPa. Only one drop of resin composition was dispensed using a jet dispensing machine. The dispensed resin composition was heated at 180°C for 50 minutes to obtain a cured product. The linewidth (maximum width of the cured product in the direction parallel to the plane of the glass plate) of the cured product obtained by the above operation is preferably 300 μm or less, more preferably 270 μm or less, and even more preferably 250 μm or less. There is no particular limitation on the lower limit of the linewidth of the cured product, for example, it can be 50 μm (the same size as the nozzle diameter) or more.

[0172] As described above, a circuit board with a thin insulating layer can be manufactured using a method for manufacturing a circuit board using a resin composition that satisfies the relationship X≥30 and X / Y+X / Z<10. For example, as described later in the section <Experimental Example 3: Discharge Test Using a Jet Dispenser>, the nozzle diameter was fixed at 50 μm, the distance between the nozzle and the glass plate was fixed at 500 μm, and the supply pressure of the resin composition was fixed at 0.02 MPa. Only one drop of resin composition was dispensed using a jet dispensing machine. The dispensed resin composition was heated at 180°C for 50 minutes to obtain a cured product. The thickness of the cured product obtained by the above operation (the maximum width of the cured product perpendicular to the plane of the glass plate) is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 7 μm or less, 6 μm or less, or 5 μm or less. There is no particular limitation on the lower limit of the thickness of the cured product, and it can be 1 μm or more, etc.

[0173] The resin composition forming the resin pattern can have a specific range of viscosity. For example, as described in the <Experimental Example 1: Viscosity Measurement> section, when measuring for 2 minutes using an E-type viscometer at a measurement temperature of 25°C, a rotor of 1.34° × R24, an amount of resin composition of 1.2 ml, and a rotation speed of 100 rpm, the viscosity of the resin composition is preferably 350 mPa·s or more, more preferably 500 mPa·s or more, even more preferably 600 mPa·s or more, even more preferably 700 mPa·s or more, preferably 1500 mPa·s or less, even more preferably 1300 mPa·s or less, even more preferably 1200 mPa·s or less, even more preferably 1100 mPa·s or less, and even more preferably 1000 mPa·s or less.

[0174] The resin composition forming the resin pattern can have a specific range of surface tension. For example, as described in the <Experimental Example 2: Measurement of Surface Tension> section, the surface tension was measured five times using the pendant-drop method at a measurement temperature of 25°C. When the average value of the five measurements is taken as the surface tension of the resin composition, the surface tension of the resin composition is preferably 20 mN / m or more, more preferably 25 mN / m or more, even more preferably 27 mN / m or more, and preferably 30 mN / m or less.

[0175] Resin compositions that form resin patterns can produce cured products exhibiting low dielectric loss tangents. For example, as described in the section "Experimental Example 4: Determination of Dielectric Loss Tangent (Df)," when the measurement was performed at 5.8 GHz and 23°C, the dielectric loss tangent (Df) of the cured product obtained by heat curing the resin composition at 200°C for 90 minutes was preferably 0.006 or less, more preferably 0.005 or less, and even more preferably 0.004 or less. The lower limit value of the dielectric loss tangent can be 0.0001 or more, etc.

[0176] The resin composition forming a resin pattern can result in a cured product exhibiting excellent mechanical strength. Therefore, the cured product of the resin composition forming a resin pattern can possess high rigidity and toughness. For example, a resin composition is applied to a support to form a resin composition layer with a dried thickness of 40 μm. The dried resin composition layer is then cured at 200°C for 90 minutes to obtain a cured product. When this cured product is punctured by a needle with a diameter of 1 mm at a speed of 50 mm / min, the fracture strength (puncture strength) of the cured product punctured by the needle is preferably 4 N or more, more preferably 4.5 N or more, and even more preferably 5 N or more, 5.5 N or more, or 6 N or more. A higher upper limit for the puncture strength is preferable; for example, it can be 50 N or less. The puncture strength can be measured according to the method described in the <Test Example 5: Stab Test> section below.

[0177] [Method for Manufacturing Circuit Board] The circuit board includes an insulating pattern obtained by curing a resin pattern formed from the above-described resin composition. Specifically, the method for manufacturing the circuit board of the present invention is characterized by sequentially comprising the following steps: (I) a step of forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispensing machine; (II) a step of forming an insulating pattern by curing the resin pattern; (III) a step of forming a conductor layer on the substrate and the insulating pattern using an electrolytic plating method; and (IV) a step of forming a conductor pattern by removing a portion of the conductor layer. According to the method for manufacturing the circuit board of the present invention, a circuit board having a fine and thin insulating layer can be manufactured.

[0178] <Process (I)> In process (I), the above resin composition is discharged onto the substrate by using a jet dispensing machine to form a resin pattern.

[0179] As for the jet dispensing machine used in step (I), there are no particular limitations as long as it can dispense the resin composition, and any known jet dispensing machine can be used. Examples of jet dispensing machines include: piezoelectric jet dispensing machines that use piezoelectric elements, bubble-type (thermal) jet dispensing machines that use heating elements, electromagnetic jet dispensing machines that use solenoid valves, and air-type jet dispensing machines that use air pressure.

[0180] The "substrate" used in process (I) is a component that becomes the substrate of a circuit board, and examples include: glass epoxy board, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. Furthermore, the substrate may have a conductive layer on one or both sides. Additionally, the conductive layer of the substrate may be patterned. A substrate with a conductive layer (circuit) formed on one or both sides is sometimes called an "inner layer circuit substrate." Furthermore, intermediate components for which an insulating layer and / or a conductive layer should be further formed during the manufacture of the circuit board are also included in the term "substrate." When the circuit board is a component-integrated circuit board, an inner layer substrate with integrated components may also be used.

[0181] In step (I), a resin pattern is formed using the resin composition, such that the main surface of the substrate can obtain the desired conductor pattern, by selectively expelling the resin composition from areas other than the conductor pattern forming portion. More specifically, via steps (II) and (III) described later, the resin pattern is formed by expelling the resin composition in step (I) in such a way that the main surface is exposed with the desired conductor pattern. For example, when using an inner layer circuit substrate as the substrate, the exposed conductor layer (circuit) of the inner layer circuit substrate can be used as a plating electrode, and the conductor pattern can be formed by electrolytic plating.

[0182] In step (I), the resin pattern can be dried as needed. There are no particular limitations on the drying conditions of the resin pattern; conditions typically used when forming the insulating layer of a circuit board can be used. The drying of the resin pattern can be carried out, for example, by vacuuming, depressurization, heating, hot air blowing, or a combination thereof.

[0183] When drying the resin pattern by vacuuming and / or reducing pressure, the air pressure is preferably set to 500 Pa or less, more preferably 200 Pa or less. The vacuum drying time is not particularly limited, but is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 10 minutes.

[0184] When drying the resin pattern by heating, the heating and drying temperature is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, preferably less than 200°C, more preferably less than 150°C, even more preferably less than 140°C, less than 130°C, or less than 120°C. Furthermore, the heating and drying time at this temperature is preferably 1 minute to 30 minutes, more preferably 1 minute to 10 minutes, and even more preferably 1 minute to 5 minutes.

[0185] From the viewpoint of thinning the circuit board, the thickness of the resin pattern formed by process (I) (the maximum width of the resin pattern perpendicular to the main surface of the substrate) is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less or 5 μm or less. The lower limit of the resin pattern thickness is not particularly limited; for example, it can be 1 μm or more.

[0186] <Step (II)> In step (II), an insulating pattern is formed by curing the resin pattern formed in step (I). The curing of the resin pattern can be performed, for example, by heat curing. The heat curing conditions for the resin pattern are not particularly limited, and conditions commonly used when forming an insulating layer on a circuit board can be used.

[0187] For example, the thermosetting conditions of the resin pattern vary depending on the composition of the resin composition forming the resin pattern, but in one embodiment, the curing temperature is preferably 140°C to 250°C, more preferably 150°C to 240°C, and even more preferably 160°C to 230°C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0188] Before heat curing the resin pattern, the resin pattern can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin pattern, the resin composition layer can be preheated at a temperature of 50°C to 140°C, preferably 60°C to 135°C, more preferably 70°C to 130°C for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0189] After step (II) and before step (III), the insulating pattern can be roughened as needed. The steps and conditions for roughening are not particularly limited, and known steps and conditions commonly used in forming the insulating layer of a circuit board can be employed. Both dry and wet roughening processes can be performed. Examples of dry roughening processes include plasma treatment and dry sandblasting. Examples of wet roughening processes include a method that sequentially performs swelling treatment using a swelling solution, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing solution.

[0190] In plasma processing as a dry roughening process, there are no particular restrictions on the method of plasma generation. Examples include microwave plasma generated by microwaves, high-frequency plasma using high frequencies, atmospheric pressure plasma generated under atmospheric pressure, and vacuum plasma generated under vacuum.

[0191] The plasma-generating gas is not particularly limited as long as it can roughen the insulating pattern; for example, a gas containing fluorine atoms, N2, or O2 is preferred. Examples of fluorine-containing gases include F2, CF4, C2F6, and SF6. In this case, in addition to fluorine-containing gases, N2, and O2, other gases such as Ar may also be included.

[0192] The time for the plasma roughening treatment is not particularly limited, but it is preferably 30 seconds or more, more preferably 60 seconds or more, 90 seconds or more, or 120 seconds or more. From the viewpoint that it is easy to achieve an insulating layer with low surface roughness after the roughening treatment, the upper limit of the roughening treatment time is preferably 10 minutes or less, more preferably 5 minutes or less.

[0193] As a dry roughening process, dry sandblasting can also be used to grind the object being processed by ejecting abrasive material from a nozzle. Dry sandblasting can be performed using commercially available dry sandblasting equipment. When using water-soluble abrasive material, by washing with water after dry sandblasting, the abrasive will not remain on the substrate and insulating pattern, thus effectively roughening the insulating pattern.

[0194] In wet roughening treatment, examples of swelling solutions used for swelling treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as alkaline solutions. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Amtech Japan. Swelling treatment using a swelling solution can be performed, for example, by immersing the insulating pattern in a swelling solution at 30°C to 90°C for 1 to 20 minutes.

[0195] In wet roughening treatment, an alkaline permanganate aqueous solution is preferably used as the oxidizing agent solution for roughening. Examples include solutions in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Roughening treatment using the oxidizing agent solution preferably involves immersing the insulating pattern in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "ConcentrateCompact CP" and "Dosingsolution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0196] In wet roughening treatment, an acidic aqueous solution is preferred as the neutralizing liquid used for neutralization treatment. Commercially available examples include "Reduction solution Securiganth P" manufactured by Ammet Japan Co., Ltd. Neutralization treatment using the neutralizing liquid can be performed by immersing the treated surface of the insulating pattern, which has undergone roughening treatment with an oxidizing agent, in the neutralizing liquid at 30°C to 80°C for 5 to 30 minutes.

[0197] When combining dry and wet roughening treatments, either the dry roughening treatment or the wet roughening treatment can be performed first.

[0198] The linewidth of the insulating pattern formed in step (II) also depends on the design of the desired conductor pattern, but is preferably 300 μm or less, more preferably 270 μm or less, and even more preferably 250 μm or less. There is no particular limitation on the lower limit of the linewidth of the insulating pattern, for example, it can be 50 μm or more.

[0199] From the viewpoint of thinning the circuit board, the thickness of the insulating pattern formed in process (II) is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the insulating pattern thickness is not particularly limited; for example, it can be 1 μm or more.

[0200] <Step (III)> In step (III), a conductor layer is formed on the substrate and the insulating pattern formed in step (II) using an electroplating method. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer formed in step (III) comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. More preferably, the conductor layer formed in step (III) comprises a copper-containing metal.

[0201] The conductor layer formed in step (III) can be a single metal layer or an alloy layer. Examples of alloy layers include those formed from alloys of two or more metals selected from the aforementioned metals (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of pattern formation in conductor layer formation, the conductor layer formed in step (III) is preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy. More preferably, it is a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy. Even more preferably, it is a single metal layer of copper.

[0202] The conductor layer formed in process (III) can be a single-layer structure or a multi-layer structure consisting of two or more single metal layers or alloy layers containing different types of metals or alloys.

[0203] In step (III), the conductor layer is formed using an electroplating method. Specifically, electroplating can be performed on the substrate and the insulating pattern formed in step (II) to form a conductor layer for forming the desired conductor pattern.

[0204] Typically, an aqueous solution of a metal salt is used as the electroplating solution. There are no restrictions on the metal salt, as long as it can form an electroplated layer. When copper is used as the metal, examples of copper salts include copper sulfate pentahydrate, copper halides such as copper chloride, copper acetate, copper nitrate, copper tetrafluoroborate, alkyl sulfonate, aryl sulfonate, aminosulfonate, copper perchlorate, and copper gluconate, with copper sulfate being preferred. The concentration of the metal salt in the electroplating solution can be, for example, 50 g / L or more and 400 g / L or less. A saturation concentration is more preferable. Furthermore, the electroplating solution may contain acids such as sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and hydrochloric acid; a halide ion supplier; a brightener; and additives such as a surfactant.

[0205] In a preferred embodiment, step (III) includes the step of forming a plated seed layer on the substrate and the insulating pattern formed in step (II). When step (III) includes the step of forming a plated seed layer, a conductor layer is formed on the formed plated seed layer by electrolytic plating.

[0206] The seed layer can be formed by either dry or wet plating. Examples of dry plating include physical vapor deposition (PVD) methods such as sputtering, ion plating, and vacuum evaporation, as well as chemical vapor deposition (CVD) methods such as thermal CVD and plasma CVD. Examples of wet plating include electroless plating.

[0207] The plated seed layer includes at least a conductive seed layer. The conductive seed layer is the layer that functions as an electrode in the electroplating process. There are no particular limitations on the conductive material constituting the conductive seed layer, as long as it exhibits sufficient conductivity; preferred examples include copper, palladium, gold, platinum, silver, aluminum, and their alloys.

[0208] The seed layer may also include a diffusion barrier layer between the conductive seed layer and the substrate and the insulating pattern formed in step (II). The diffusion barrier layer is a layer that prevents the conductive material constituting the conductive seed layer from diffusing into the insulating pattern (insulating layer) and causing insulation breakdown. There are no particular limitations on the material constituting the diffusion barrier layer, as long as it can suppress and prevent the diffusion of the conductive material constituting the conductive seed layer. Preferred examples include titanium, tungsten, tantalum, and their alloys. When the seed layer includes a diffusion barrier layer, the conductive seed layer can be formed on the diffusion barrier layer after the diffusion barrier layer is formed on the substrate and the insulating pattern formed in step (II).

[0209] The thickness of the seed layer is preferably 1000 nm (1 μm) or less, more preferably 800 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less. In the method of the present invention, the thickness of the seed layer can be even thinner. For example, the thickness of the seed layer can be 250 nm or less, 200 nm or less, 150 nm or less, 140 nm or less, 120 nm or less, or 100 nm or less. When the seed layer includes a diffusion barrier layer, the "thickness of the seed layer" in the present invention refers to the average thickness of the entire seed layer, including both the conductive seed layer and the diffusion barrier layer.

[0210] <Step (IV)> In step (IV), a conductor pattern is formed by removing a portion of the conductor layer formed in step (III). There are no particular limitations on the location of the conductor layer removed in step (IV). For example, a conductor pattern can be formed by removing a conductor layer formed on an insulating pattern. Alternatively, for example, a portion of the conductor layer can be selectively removed before forming a multilayer circuit board, depending on the desired circuit board design.

[0211] In step (IV), the method for removing a portion of the conductor layer is not particularly limited as long as that portion can be removed, but it is preferred to remove it by grinding.

[0212] Examples of polishing conditions as part of the conductor layer include: chemical mechanical polishing (CMP) methods using a chemical mechanical polishing (CMP) apparatus; mechanical polishing methods such as belt polishing, polishing, ceramic polishing, grinding using a surface grinder, and surface grinding using a rotating grinding wheel; etc. Furthermore, various types of abrasive grains can be used depending on the condition of the target polishing surface. Additionally, the degree of polishing as part of the conductor layer can be adjusted, for example, by ending polishing at the moment the surface of the insulating pattern is exposed.

[0213] From the viewpoint of thinning the circuit board, the thickness of the conductor pattern obtained in process (IV) is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the conductor pattern thickness is not particularly limited; for example, it can be 1 μm or more.

[0214] After step (IV), the conductor pattern can be annealed as needed. Annealing improves the adhesion between the insulation pattern and the conductor pattern. Annealing can be performed, for example, by heating at 150°C to 210°C for 20 to 180 minutes.

[0215] In a preferred embodiment, the method for manufacturing the circuit board of the present invention is characterized by including a roughening process for the insulating pattern after step (II) and before step (III), wherein step (III) sequentially includes: a step of forming a seed layer on the substrate and the insulating pattern by wet plating, and a step of forming a conductor layer comprising a single metal layer of copper on the seed layer by electrolytic plating; the method for manufacturing the circuit board according to the embodiment can manufacture circuit boards having finer and thinner insulating layers. Therefore, the method for manufacturing the circuit board in the embodiment significantly contributes to the miniaturization and high performance of electronic devices.

[0216] In another preferred embodiment, the method for manufacturing the circuit board of the present invention is characterized in that step (III) sequentially includes: a step of forming a plated seed layer on the substrate and the insulating pattern by dry plating, and a step of forming a conductor layer containing a single metal layer of copper on the plated seed layer by electrolytic plating, wherein the plated seed layer includes a conductive seed layer and a diffusion barrier layer between the conductive seed layer and the substrate and the insulating pattern, wherein the conductive seed layer contains a copper-containing metal and the diffusion barrier layer contains a titanium-containing metal; the method for manufacturing the circuit board according to the described embodiment can manufacture circuit boards having finer and thinner insulating layers. Therefore, the method for manufacturing the circuit board in the described embodiment significantly contributes to the miniaturization and high performance of electronic devices.

[0217] In the manufacturing method of the circuit board, each of the above-mentioned processes may be performed only once or may be repeated two or more times. For example, processes (I) to (IV) may be repeated to form a circuit board with a multilayer structure, such as a multilayer printed wiring board having multiple insulating patterns (insulating layers) and conductor patterns (conductor layers).

[0218] A semiconductor chip packaging substrate can be manufactured by bonding a semiconductor chip to a circuit board manufactured by the above-described manufacturing method.

[0219] The bonding conditions between the circuit board and the semiconductor chip can be any condition that allows the terminal electrodes of the semiconductor chip and the circuit wiring (conductor pattern) of the circuit board to be conductively connected. For example, the conditions used in flip-chip mounting of semiconductor chips can be used. Alternatively, bonding between the semiconductor chip and the circuit board can be achieved, for example, via an insulating adhesive.

[0220] As an example of a bonding method, a method of pressing a semiconductor chip onto a circuit board can be cited. As for the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0221] Another example of a bonding method is the bonding of semiconductor chips to a circuit board using reflow soldering. Reflow soldering conditions can range from 120°C to 300°C.

[0222] Examples of semiconductor packaging substrates include fan-in and fan-out packages.

[0223] As described above, the circuit board manufacturing method of the present invention can manufacture a circuit board having a fine and thin insulating layer. Furthermore, as described above, the resin composition used in the circuit board manufacturing method of the present invention can produce a cured product exhibiting a low dielectric loss tangent and excellent mechanical strength. Therefore, the circuit board manufacturing method of the present invention is suitable for forming an insulating layer of a printed wiring board (and further, an interlayer insulating layer of a printed wiring board). Additionally, the circuit board manufacturing method of the present invention is suitable for forming an insulating layer of a rewiring substrate for a semiconductor packaging substrate (and further, a semiconductor package). In other words, the circuit board manufacturing method of the present invention can be used as a method for manufacturing a printed wiring board or a method for manufacturing a semiconductor packaging substrate.

[0224] [Semiconductor Device] One embodiment of the present invention relates to a semiconductor device comprising a circuit board manufactured by the manufacturing method described above. Examples of such semiconductor devices include various semiconductor devices for use in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes). Embodiments

[0225] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" indicate amounts, and unless otherwise specified, refer to "parts by mass" and "% by mass" of the resin, respectively. In addition, unless otherwise specified, the temperature and pressure conditions are room temperature (25°C) and atmospheric pressure (1 atm).

[0226] <Synthesis Example 1: Synthesis of Polyimide Resin D1> In 400g of N,N-dimethylacetamide (DMAc) as a solvent, 49.6g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 50.4g of 4,4'-[1,4-phenylenebis[(1-methylethylene)-4,1-phenyleneoxy]]diphenylamine (BPPAN) as a solvent, and 40g of toluene as a solvent were mixed. The resulting monomer composition was stirred and reacted at room temperature and atmospheric pressure for 3 hours. A solution of polyamic acid was thus obtained.

[0227] Next, the polyamic acid solution was heated and maintained at approximately 160°C while azeotropically removing the condensed water and toluene under a nitrogen stream. It was confirmed that a predetermined amount of water accumulated in the moisture metering receiver and that no more water flow was observed. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, it was cooled. This yielded a varnish containing 20% ​​by mass of polyimide resin D1 as a non-volatile component.

[0228] Based on the above reaction pathway, it is presumed that polyimide resin D1 contains the structural unit shown in formula (D1a). Furthermore, based on the above reaction pathway, it is presumed that polyimide resin D1 contains a first backbone from BPADA and a second backbone from BPPAN.

[0229] [Chemical Formula 6] .

[0230] In addition, the glass transition temperature (Tg) of polyimide resin D1 (TMA method) is 210°C. The glass transition temperature (Tg) was measured using a Rigaku TMA apparatus, with a heating rate of 5°C / min from 25°C to 250°C.

[0231] <Synthetic Example 2: Synthesis of Polymer D2 Containing a Triazine Ring> In a 100 mL three-necked flask, 0.384 g (1.00 mmol) of 2-anilino-4,6-bis(4-aminoanilino)-1,3,5-triazine and 2 mL of N-methyl-2-pyrrolidone (NMP) were added and dissolved. 0.444 g (1.00 mmol) of bis(4,6-dimethoxy-1,3,5-triazine-2-yl)isophthalate was added, and the reaction was carried out at room temperature for 6 hours. The resulting reaction solution was poured into 200 mL of methanol, and the precipitated polymer was separated by filtration. The filtered polymer was washed with methanol and dried under reduced pressure at room temperature to obtain polymer D2 containing a triazine ring. The obtained polymer D2 containing a triazine ring has a number-average molecular weight (Mn) of 25,000 and a weight-average molecular weight (Mw) of 51,000. Furthermore, polymer D2 containing a triazine ring contains the structural unit shown in the following formula.

[0232] [Chemical Formula 7] .

[0233] <Examples 1-11, Comparative Examples 1-4: Preparation of Resin Compositions> Each component was weighed according to the mass parts recorded in Tables 1-3 below, and uniformly dispersed using a high-speed rotary mixer to obtain a varnish-like resin composition (resin varnish). Details of each component recorded in Tables 1-3 below are described below.

[0234] (A) Thermosetting Resins: "ZX-1059": A mixture of liquid bisphenol A and bisphenol F epoxy resins, manufactured by Nippon Steel Chemical Materials Co., Ltd., with an epoxy equivalent of approximately 165 g / eq. "NC-3000": A liquid biphenyl-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 257 g / eq. "LA-3018-50P": A phenolic resin containing a triazine skeleton, manufactured by DIC Corporation, containing a 50% by weight propylene glycol monomethyl ether solution after removing organic solvents, with hydroxyl groups... Equivalent to approximately 151 g / eq. • "HPC-8000-65T": Active ester resin, manufactured by DIC Corporation, a toluene solution with a composition of 65% by mass after removing organic solvents, active ester equivalent to approximately 223 g / eq. • "Maleimide Resin 1": Maleimide resin containing an aliphatic skeleton having the structure shown in the following formula (a portion of which may contain unsaturated bonds), manufactured by Shin-Etsu Chemical Industry Co., Ltd. "SLK6895-T90", a toluene solution with a composition of 90% by mass after removing organic solvents.

[0235] [Chemical Formula 8] .

[0236] (B) Organic solvents: “MEK”: Methyl ethyl ketone, manufactured by Fujifilm and Kohden Chemical Co., Ltd., boiling point 79°C; “Cyclohexanone”: Cyclohexanone, manufactured by Pure Chemicals Co., Ltd., boiling point 155°C.

[0237] (C) Inorganic Filler Material • "Inorganic Filler Material 1": Spherical silica particles with an average particle size of 0.3 μm and a specific surface area of ​​30.7 m² were surface-treated with 3.0 parts by weight of a silane coupling agent containing N-phenyl-3-aminopropyl groups ("KBM-573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) to 100 parts by weight of "UFP30" manufactured by Denka Co., Ltd. 2 / g.

[0238] (D) Thermoplastic resin • “YX6954BH30”: A phenoxy resin containing a bisphenol acetophenone backbone and free of heterocyclic compounds, manufactured by Mitsubishi Chemical Corporation, with a composition of 30% by mass of methyl ethyl ketone (MEK): cyclohexanone = 1:1 after removing organic solvents • “Polyimide resin D1”: Polyimide resin D1 obtained in Synthesis Example 1 • “Polymer D2 containing a triazine ring”: Polymer D2 containing a triazine ring obtained in Synthesis Example 2

[0239] (E) Curing accelerator "2P4MZ": 2-Phenylon-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd.

[0240] <Experimental Example 1: Viscosity Measurement> The viscosity of the resin compositions obtained in each example and comparative example was measured. Specifically, an E-type viscometer (RE80 type viscometer manufactured by Toki Sangyo Co., Ltd.) was used, and the measurement was performed for 2 minutes at a measurement temperature of 25°C, a rotor of 1.34°×R24, a volume of 1.2 ml of varnish-like resin composition, and a rotation speed of 100 rpm.

[0241] <Experimental Example 2: Measurement of Surface Tension> The surface tension of the resin compositions obtained in each example and comparative example was measured. Specifically, the surface tension was measured using a contact angle meter (DMs-401, Kyowa Interface Science Co., Ltd.) at a measurement temperature of 25°C using the pendant drop method. Five measurements were performed, and the average of the five measurements was taken as the surface tension of the resin composition.

[0242] <Experimental Example 3: Discharge Test Using a Jet Dispensing Machine> The varnish-like resin compositions obtained in the various examples and comparative examples were fed into a jet dispensing machine (VERMES Microdispensing, MDS3280) for discharge tests. Specifically, a flat glass plate was prepared. On the flat surface of the glass plate, the nozzle diameter was fixed at 50 μm, the distance between the nozzle and the glass plate was fixed at 500 μm, and the supply pressure of the resin composition was fixed at 0.02 MPa. The coating frequency was adjusted appropriately, and each resin composition was discharged.

[0243] Typically, under conditions of low coating frequency (i.e., weak discharge conditions), the resin composition cannot be discharged. Conversely, under conditions of high coating frequency (i.e., strong discharge conditions), the discharged resin composition droplets become larger.

[0244] In this test example, the coating frequency of each resin composition was varied to achieve the minimum coating frequency required for discharge. Furthermore, in this test example, the resin composition was discharged onto a glass plate with only one droplet discharged from each composition.

[0245] Next, the discharged resin composition was dried in an oven at 130°C for 5 minutes. Then, the resin composition was heated at 180°C for 50 minutes to thermally cure it. Through this process, evaluation sample A, containing the cured resin composition, was obtained.

[0246] In the obtained evaluation specimen A, the linewidth (maximum width of evaluation specimen A in the direction parallel to the glass plate plane) was measured using a digital microscope (Keyence VHX-X1F). Next, evaluation specimen A was subjected to grinding using an ion milling machine (Hitachi High-Tech IM4000) to obtain a cross-section perpendicular to the glass plate plane. The cross-section of the ground evaluation specimen A was observed using a digital microscope (Keyence VHX-X1F), and the thickness of evaluation specimen A (maximum width of evaluation specimen A in the direction perpendicular to the glass plate plane) was measured. The linewidth and thickness of each evaluation specimen A were evaluated according to the following evaluation criteria.

[0247] [Evaluation criteria for the diameter of sample A] "○": The line width of sample A is less than 300 μm. "×": The line width of sample A exceeds 300 μm.

[0248] [Evaluation criteria for the thickness of sample A] "○": The thickness of sample A is less than 15 μm. "×": The thickness of sample A exceeds 15 μm.

[0249] <Experimental Example 4: Determination of Dielectric Loss Tangent (Df)> As a support, a PET film (Toray Industries, Ltd., "LUMIRROR R80", thickness: 38 μm, softening point: 130°C) that had been released using an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. On this support, the varnish-like resin composition obtained in each example and comparative example was uniformly coated using a die coater to a thickness of 15 μm after drying. The coating was then dried in an oven at 130°C for 5 minutes to form a resin composition layer.

[0250] The resin composition layer was heated at 200°C for 90 minutes to thermally cure it. The support was then peeled off to obtain the cured product. The cured product was cut into pieces 2 mm wide and 80 mm long to obtain evaluation specimens (evaluation specimen B). For evaluation specimen B, the dielectric loss tangent (Df) was measured using an Agilent Technologies HP8362B resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on five specimens, and the average value was calculated.

[0251] <Experimental Example 5: Stab Test> As a support, a PET film (Toray Industries, Ltd., "LUMIRROR R80", thickness: 38 μm, softening point: 130°C) that had been released using an alkyd resin release agent (Lintec Corporation, "AL-5") was prepared. On this support, the varnish-like resin composition obtained in each example and comparative example was uniformly coated using a die coater to a thickness of 40 μm after drying. The coating was then dried in an oven at 130°C for 5 minutes to form a resin composition layer.

[0252] The resin composition layer was heated at 200°C for 90 minutes to thermally cure it. The support was then peeled off to obtain the cured product. The cured product was cut into test pieces with sides of approximately 30 mm, and puncture resistance was tested using a universal testing machine (AND Corporation's "Tensiron RTC1250A"). Specifically, the test piece was mounted on the aforementioned apparatus, and a needle with a load of 50 N and a diameter of 1 mm was brought into contact with the test piece at a speed of 50 mm / min. The maximum point load at fracture was measured.

[0253] [Table 1] .

[0254] [Table 2] .

[0255] [Table 3] .

Claims

1. A method for manufacturing a circuit board, the method comprising, in sequence: (I) a step of forming a resin pattern by discharging a resin composition onto a substrate using a jet dispensing machine; (II) a step of forming an insulating pattern by curing the resin pattern; (III) a step of forming a conductor layer on the substrate and the insulating pattern using an electrolytic plating method; and (IV) a step of forming a conductor pattern by removing a portion of the conductor layer, wherein the resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler material, and (D) a thermoplastic resin, wherein when all components in the resin composition are set to 100% by mass, the content of (B) the organic solvent is set to X% by mass, the content of (C) the inorganic filler material is set to Y% by mass, and the content of (D) the thermoplastic resin is set to Z% by mass, the relationship X ≥ 30 and X / Y + X / Z < 10 is satisfied.

2. The manufacturing method according to claim 1, wherein, The viscosity of the resin composition, measured using an E-type viscometer at 25°C and 100 rpm, is 350 mPa·s or more and 1500 mPa·s or less.

3. The manufacturing method according to claim 1, wherein, (A) Thermosetting resins include at least one of epoxy resins and maleimide resins.

4. The manufacturing method according to claim 3, wherein, (A) Thermosetting resins contain curing agents.

5. The manufacturing method according to claim 1, wherein, (B) The organic solvents include organic solvents with a boiling point of 100°C or higher and 200°C or lower. When the total amount of organic solvents in the resin composition is set to 100% by mass, the content of organic solvents with a boiling point of 100°C or higher and 200°C or lower is 50% by mass or higher.

6. The manufacturing method according to claim 1, wherein, (C) The average particle size of the inorganic filler is less than 0.4 μm.

7. The manufacturing method according to claim 1, wherein, (C) The inorganic filler material contains silicon dioxide.

8. The manufacturing method according to claim 1, wherein, When the components in the resin composition other than the organic solvent are set to 100% by mass, the content of (C) inorganic filler material is 20% by mass or more and 70% by mass or less.

9. The manufacturing method according to claim 1, wherein, (D) Thermoplastic resins contain aromatic rings.

10. The manufacturing method according to claim 1, wherein, When the components other than organic solvents in the resin composition are set at 100% by mass, the content of (D) thermoplastic resin is 15% by mass or more and 40% by mass or less.

11. The manufacturing method according to claim 1, wherein, After step (II) and before step (III), there is a step of roughening the insulating pattern. Step (III) sequentially includes: a step of forming a seed layer on the substrate and the insulating pattern by wet plating, and a step of forming a conductor layer containing a single metal layer of copper on the seed layer by electrolytic plating.

12. The manufacturing method according to claim 1, wherein, Step (III) sequentially includes: a step of forming a plated seed layer on the substrate and the insulating pattern by dry plating, and a step of forming a conductor layer containing a single metal layer of copper on the plated seed layer by electrolytic plating, wherein the plated seed layer includes a conductive seed layer and a diffusion barrier layer between the conductive seed layer and the substrate and the insulating pattern, wherein the conductive seed layer contains a copper-containing metal and the diffusion barrier layer contains a titanium-containing metal.

13. The manufacturing method according to claim 1, wherein, The line width of the insulating pattern is less than 300 μm.

14. The manufacturing method according to claim 1, wherein, The thickness of the insulating pattern is less than 15 μm.

15. The manufacturing method according to claim 1, wherein, Further satisfy the relationship X / Y+X / Z>4.

16. The manufacturing method according to claim 1, wherein, The circuit board is a semiconductor packaging substrate.

17. A semiconductor device, wherein, The circuit board is manufactured using the manufacturing method according to any one of claims 1 to 16.