Circuit board manufacturing method

Abstract

To provide a method for manufacturing a circuit board equipped with a fine and thin insulating layer. [Solution] A method for manufacturing a circuit board, comprising in this order: forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispenser; forming an insulating pattern by curing the resin pattern; forming a conductive layer on the substrate and the insulating pattern by electroplating; and forming a conductive pattern by removing a part of the conductive layer; wherein the resin composition is a resin composition comprising a thermosetting resin, an organic solvent, an inorganic filler, and a thermoplastic resin; and when the total components in the resin composition are considered to be 100% by mass, the mass percentage of the organic solvent is X (mass%), the mass percentage of the inorganic filler is Y (mass%), and the mass percentage of the thermoplastic resin is Z (mass%), the relationship X≧30 and X / Y+X / Z<10 is satisfied.

Description

[Technical Field]

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

[0002] Circuit boards, such as printed circuit boards, are widely used in various electronic devices. A known manufacturing method for circuit boards involves a build-up method in which insulating layers and conductive layers are alternately stacked on an inner layer substrate. One example of a build-up method involves creating a conductive layer and then covering it with an insulating layer, followed by repeated stacking. Methods for covering the conductive layer with an insulating layer include lamination, spin coating, curtain coating, dip coating, spray coating, and slit coating. However, these methods have the problem that the insulating layer uniformly covers the entire conductive layer, making it impossible to form an insulating layer only on specific locations on the conductive layer.

[0003] On the other hand, a known method for manufacturing a circuit board in which a conductive layer is formed only in specific locations involves dispensing a conductive material using a jet dispenser. For example, the techniques disclosed in Patent Documents 1 and 2 are examples of circuit board manufacturing methods that include the step of dispensing a conductive material using a jet dispenser. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 6864046 [Patent Document 2] Patent No. 6668586 [Overview of the project] [Problems that the invention aims to solve]

[0005] The inventors have been working on developing a novel method for forming an insulating layer only at specific locations on a conductive layer using a jet dispenser. However, the inventors have found that the lower the viscosity of the resin composition used to form the insulating layer, the more difficult it tends to be to form a fine insulating layer. Furthermore, the inventors have found that the higher the viscosity of the resin composition, the thicker the insulating layer becomes, making it difficult to thin the insulating layer. Therefore, the inventors have found that there is a trade-off between miniaturization and thinning of the insulating layer when forming an insulating layer using a jet dispenser.

[0006] The present invention has been made in view of the above, and aims to provide a method for manufacturing a circuit board having a fine and thin insulating layer; and a semiconductor device comprising a circuit board manufactured by the said manufacturing method. [Means for solving the problem]

[0007] The inventors diligently studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by a method for manufacturing a circuit board, comprising in this order: (I) forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispenser; (II) forming an insulating pattern by curing the resin pattern; (III) forming a conductive layer on the substrate and the insulating pattern by electroplating; and (IV) forming a conductive pattern by removing a part of the conductive layer; wherein the resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin; and when the total components in the resin composition are taken as 100% by mass, the content of (B) the organic solvent is X (mass%), the content of (C) the inorganic filler is Y (mass%), and the content of (D) the thermoplastic resin is Z (mass%), such that X≧30 and X / Y+X / Z<10, and thus the inventors have completed the present invention. In other words, the present invention includes the following:

[0008] <1> (I) A step of forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispenser. (II) A step of forming an insulating pattern by curing the resin pattern, (III) A step of forming a conductive layer on the substrate and the insulating pattern by electroplating, (IV) A step of forming a conductor pattern by removing a portion of the conductor layer, A method for manufacturing a circuit board, comprising the following in this order: The resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin, When the total components in the resin composition are considered to be 100% by mass, (B) the content of the organic solvent is X (by mass%), (C) the content of the inorganic filler is Y (by mass%), and (D) the content of the thermoplastic resin is Z (by mass%), X ≥ 30 and X / Y + X / Z < 10 A method for manufacturing a circuit board that satisfies the relationship. <2> In the aforementioned resin composition, the viscosity of the resin composition, measured using an E-type viscometer under the conditions of 25°C and 100 rpm, is 350 mPa·s or more and 1500 mPa·s or less. <1> The manufacturing method described above. <3> (A) The thermosetting resin comprises at least one of epoxy resin and maleimide resin. <1> or <2> The manufacturing method described above. <4> (A) The thermosetting resin contains a curing agent, <3> The manufacturing method described above. <5> (B) The organic solvent includes an organic solvent with a boiling point of 100°C or higher and 200°C or lower. The content of organic solvents with a boiling point between 100°C and 200°C is 50% by mass or more, when the total amount of organic solvents in the resin composition is taken as 100% by mass. <1> ~ <4> A manufacturing method described in any one of the following items. <6> (C) The average particle size of the inorganic filler is 0.4 μm or less. <1> ~ <5> A manufacturing method described in any one of the following items. <7> (C) The inorganic filler contains silica, <1> ~ <6> A manufacturing method described in any one of the following items. <8> (C) The inorganic filler content is 20% by mass or more and 70% by mass or less, when the components other than organic solvents in the resin composition are taken as 100% by mass. <1> ~ <7> A manufacturing method described in any one of the following items. <9> (D) Thermoplastic resin containing an aromatic ring, <1> ~ <8> A manufacturing method described in any one of the following items. <10> (D) The content of thermoplastic resin is 15% by mass or more and 40% by mass or less, when the content of components other than organic solvents in the resin composition is taken as 100% by mass. <1> ~ <9> A manufacturing method described in any one of the following items. <11> After process (II) and before process (III), The process includes a step of roughening the aforementioned insulating pattern, Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by wet plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, It includes in this order, <1> ~ <10> A manufacturing method described in any one of the following items. <12> Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by dry plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, This includes them in this order, The plated seed layer includes a conductive seed layer made of a metal containing copper, and a diffusion barrier layer made of a metal containing titanium between the conductive seed layer, the substrate, and the insulating pattern. <1> ~ <10> A manufacturing method described in any one of the following items. <13> The line width of the aforementioned insulating pattern is 300 μm or less. <1> ~ <12> A manufacturing method described in any one of the following items. <14> The thickness of the insulating pattern is 15 μm or less. <1> ~ <13> A manufacturing method described in any one of the following items. <15> moreover, X / Y + X / Z > 4 Satisfying the relationship, <1> ~ <14> A manufacturing method described in any one of the following items. <16> The circuit board is a semiconductor package substrate. <1> ~ <15> A manufacturing method described in any one of the following items. <17> <1> ~ <16> A semiconductor device comprising a circuit board manufactured by the manufacturing method described in any one of the items. [Effects of the Invention]

[0009] According to the present invention, a method for manufacturing a circuit board having a fine and thin insulating layer; and a semiconductor device comprising a circuit board manufactured by the manufacturing method; can be provided. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0011] [Explanation of terms] In this specification, the term “may have substituents” with respect to a compound or group means both cases where the hydrogen atoms of the compound or group are not substituted with substituents, and cases where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0012] In this specification, the term "substituent" means, unless otherwise specified, a halogen atom, alkyl group, alkenyl group, cycloalkyl group, alkoxy group, cycloalkyloxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, monovalent heterocyclic group, alkylidene group, amino group, silyl group, carboxyl group, sulfo group, cyano group, nitro group, hydroxyl group, mercapto group, and oxo group.

[0013] In this specification, the term "aromatic ring" means a ring that obeys Hückel's rule, where the number of electrons in the π-electron system on the ring is 4n+2 (where n is an integer greater than or equal to 1), and includes monocyclic aromatic rings and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings. An aromatic ring can be an aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. In this specification, the term "heteroatom" means an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, or silicon atoms.

[0014] In this specification, the term "(meth)acryloyl group" includes acryloyl groups, methacryloyl groups, and combinations thereof. The term "(meth)acrylate compound" refers to a compound having a (meth)acryloyl group and includes acrylate compounds, methacrylate compounds, and combinations thereof. However, (meth)acrylic acid is not included in (meth)acrylate compounds. The term "(meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof.

[0015] In this specification, "non-volatile components" as used in reference to a resin composition refer to components of the resin composition other than the organic solvents described later. Furthermore, "resin components" as used in reference to a resin composition refer to components 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, we will first describe the resin composition used to form the resin pattern in step (I) of the manufacturing method.

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

[0018] As mentioned above, the resin composition that forms the resin pattern is X≧30 The following relationship is satisfied: That is, the content of (B) organic solvent in the resin composition is 30% by mass or more, relative to 100% by mass of all components in the resin composition. The preferred numerical range for X will be explained in detail in the section <(B) Organic Solvent> below.

[0019] As mentioned above, the resin composition that forms the resin pattern is X / Y + X / Z < 10 The following relationship is satisfied. The numerical value represented by "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 numerical value represented by "X / Y+X / Z" is within the above range, a finer and thinner insulating layer can be formed on the circuit board. The lower limit of the numerical value represented by "X / Y+X / Z" is not particularly limited, but 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. Among these, it is preferable that the lower limit of the numerical value represented by "X / Y+X / Z" is greater than 4. That is, in a preferred embodiment, the resin composition that forms the resin pattern is further X / Y + X / Z > 4 The following relationship is satisfied. Also, the lower limit of the numerical value expressed as "X / Y + X / Z" can be greater than 4, for example, 4.5 or greater, 5 or greater, 5.5 or greater, or 6 or greater.

[0020] In a resin composition that forms a resin pattern, the numerical value represented by "X / Y" is not particularly limited, as long as the numerical value represented by "X / Y + X / Z" falls within a predetermined range. In one embodiment, the numerical value represented by "X / Y" is preferably 9.5 or less, more preferably 9 or less, even more 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, particularly 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 numerical value represented by "X / Y" is not particularly limited, but 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 a resin composition that forms a resin pattern, the numerical value represented by "X / Z" is not particularly limited, as long as the numerical value represented by "X / Y + X / Z" falls within a predetermined range. In one embodiment, the numerical value represented by "X / Z" is preferably 9.5 or less, more preferably 9 or less, even more 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 particularly more preferably 6 or less. The lower limit of the numerical value represented by "X / Z" is not particularly limited, but 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 that forms the resin pattern may optionally further contain (E) a curing accelerator and (F) other additives. The components of the resin composition that forms the resin pattern will be described in detail below.

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

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

[0025] In one embodiment, (A) the thermosetting resin includes an epoxy resin. As the epoxy resin, a curable resin having epoxy groups may be used. Examples of epoxy resins include bixylenol-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, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, and phenolphthaleimidine-type epoxy resin. Epoxy resins may be used individually or in combination of two or more types.

[0026] From the viewpoint of obtaining a cured product with excellent heat resistance, it is preferable that the epoxy resin contains an aromatic ring. The aromatic ring is as described above. Examples of epoxy resins containing an aromatic ring 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, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisquilenol type epoxy resin, and glycidylamine type epoxy resin having an aromatic ring. Examples include resins, glycidyl ester type epoxy resins having aromatic rings, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins containing aromatic rings, epoxy resins having a butadiene structure containing aromatic rings, alicyclic epoxy resins containing aromatic rings, heterocyclic epoxy resins, spiro ring-containing epoxy resins containing aromatic rings, cyclohexanedimethanol type epoxy resins containing aromatic rings, naphthylene ether type epoxy resins, trimethylol type epoxy resins containing aromatic rings, and tetraphenylethane type epoxy resins containing aromatic rings.

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

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

[0029] As the liquid epoxy resin, a liquid epoxy resin containing two or more epoxy groups per molecule is preferred.

[0030] The liquid epoxy resin is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resins having a butadiene structure.

[0031] Specific examples of liquid epoxy resins include DIC's "HP-4032", "HP-4032-D", "HP-4032-SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "828EL", "828", "825", "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "807", "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "152" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630", "630LSD", 604 (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyrol type epoxy resin); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material's "ZX-1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's "EX-252" and "EX-721" (glycidyl ester Stellate epoxy resins: "EHPE3150CE" from Daicel Corporation, "THI-DE" from ENEOS Corporation, "Showfree CDMDG" from Resonaq Corporation, "LDO" from Symrise Corporation (alicyclic epoxy resins): "Celoxide 2021P", "Celoxide 2081P", "Celoxide 2000", "Celoxide 8000" from Daicel Corporation (alicyclic epoxy resins with an ester skeleton): "PB-3600" from Daicel Corporation, "JP-100", "JP-200" from Nippon Soda Co., Ltd. (epoxy resins with a butadiene structure) Examples of resins include: "ZX-1658" and "ZX-1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) from Nippon Steel Chemical & Material; "YX8000" and "YX8034" (hydrogenated bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; "YL9028," "YL9029," and "YL9113" (epoxy resins with a siloxane skeleton) from Mitsubishi Chemical Corporation; and "KR-470," "X-40-2678," and "X-40-2669" (epoxy resins with a siloxane skeleton) from Shin-Etsu Silicone Co., Ltd.

[0032] As for the solid epoxy resin, a solid epoxy resin containing two or more epoxy groups per molecule is preferred, a solid epoxy resin containing three or more epoxy groups per molecule is more preferred, and a solid epoxy resin containing three or more epoxy groups and an aromatic ring per molecule is even more preferred.

[0033] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene 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 novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC's "EXA-731" 1", EXA-7311-G3", EXA-7311-G4", EXA-7311-G4S", HP-6000 (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC-3000H", NC-3000, NC-3000L, NC-3000FH", NC-3100 (biphenyl type epoxy resin); Nippon Steel Chemical & Material Co., Ltd.'s "ESN4 75V", "ESN4100V" (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical's "YX7700" (phenol aralkyl type epoxy resin); Osaka Gas Chemical's "PG-100" and "CG-500"; Mitsubishi Chemical's "YX7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "1010" (bisphenol A type epoxy resin); Mitsubishi Chemical's "1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku's "WHR991S" (phenolphthaleimidine type epoxy resin);Examples include "EHPE3150" from Daicel Corporation, "DE-102" and "DE-103" from ENEOS Corporation, and "DCPD-DE" (alicyclic epoxy resin) from Nippon Materials Technology Co., Ltd.

[0035] (A) When a combination of liquid epoxy resin and solid epoxy resin is used as the thermosetting resin, the ratio of their amounts (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20 by mass, 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 5,000 g / eq. or less, more preferably 3,000 g / eq. or less, even more preferably 2,000 g / eq. or less, and even more preferably 1,000 g / eq. or less. When the epoxy equivalent of the epoxy resin is within the above range, the crosslinking density of the cured resin composition can result in a cured product with sufficient crosslinking density. The epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[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 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight on a polystyrene basis, measured by gel permeation chromatography (GPC).

[0038] From the viewpoint of significantly achieving the desired effects of the present invention, the epoxy resin content 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, when the non-volatile components (i.e., components other than organic solvents) in the resin composition are taken as 100% by mass.

[0039] From the viewpoint of significantly achieving the desired effects of the present invention, the epoxy resin content 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, when the total resin component in the resin composition is considered to be 100% by mass.

[0040] (A) When the thermosetting resin includes an epoxy resin, the resin composition preferably includes, as (A) the thermosetting resin, at least one thermosetting resin selected from the group consisting of active ester resins, phenolic resins, cyanate ester resins, benzoxazine resins, carbodiimide resins, acid anhydride resins, amine resins, and thiol resins. Hereinafter, active ester resins, phenolic resins, cyanate ester resins, benzoxazine resins, carbodiimide resins, acid anhydride resins, amine resins, and thiol resins may be collectively referred to as "curing agents".

[0041] As mentioned above, when (A) the thermosetting resin includes an epoxy resin, the resin composition preferably includes a curing agent as (A) the thermosetting resin. In particular, it is more preferable that (A) the thermosetting resin includes at least one of an active ester resin and a phenolic resin.

[0042] As the active ester resin, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. When combined with an epoxy resin, the active ester resin can react with the epoxy resin to cure the resin composition, and is therefore sometimes called an "active ester curing agent." The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. The active ester resin is preferably obtained from a carboxylic acid compound and a hydroxy compound, and more preferably from a carboxylic acid compound and a phenol compound and / or a naphthol compound. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds 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-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene. The active ester resin may be used alone or in combination of two or more types.

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

[0044] Commercially available activated ester resins include, for example, activated 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 activated ester resins containing a naphthalene structure such as "EXB-8100L-65T", "EXB-8150-60T", and "EXB-8150 Examples include "-62T", "EXB-9416-70BK", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); as an active ester resin that is an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin that is a benzoylated phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and as an active ester resin containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Corporation).

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

[0046] Specific examples of phenolic resins include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" from Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" from Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-3" from Nippon Steel Chemical & Material Co., Ltd. Examples include "75", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" from DIC Corporation; and "GDP-6115L", "GDP-6115H", "ELPC75" from Gun-ei Chemical Co., Ltd.

[0047] The active group equivalent of the curing agent is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, preferably 3,000 g / eq. or less, more preferably 1,000 g / eq. or less, even more 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 group. The active group of the curing agent refers to a group that can react with the epoxy group of the epoxy resin, and this varies depending on the type of curing agent. For example, the active group of phenolic resin is a phenolic hydroxyl group. For example, the active group equivalent of phenolic resin refers to the phenolic hydroxyl group equivalent, and represents the mass of the resin per equivalent of a phenolic hydroxyl group.

[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 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. The weight-average molecular weight of the curing agent is the weight-average molecular weight on a polystyrene basis, measured 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 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 curing agent in the resin composition by the active group equivalent.

[0050] From the viewpoint of significantly achieving the desired effects of the present invention, 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, when the non-volatile components (i.e., components other than organic solvents) in the resin composition are taken as 100% by mass.

[0051] From the viewpoint of significantly achieving the desired effects of the present invention, 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, when the resin component in the resin composition is considered to be 100% by mass.

[0052] In one embodiment, (A) the thermosetting resin includes a resin having radical polymerizable groups (hereinafter sometimes referred to as "radical polymerizable resin"). The radical polymerizable resin may contain ethylenically unsaturated bonds. Therefore, the radical polymerizable resin may have radical polymerizable groups containing ethylenically unsaturated bonds. Examples of radical polymerizable groups include unsaturated hydrocarbon groups such as vinyl groups, allyl groups, 1-propenyl groups, 3-cyclohexenyl groups, 3-cyclopentenyl groups, 2-vinylphenyl groups, 3-vinylphenyl groups, and 4-vinylphenyl groups; and α,β-unsaturated carbonyl groups such as acryloyl groups, methacryloyl groups, and maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl groups). It is preferable that the radical polymerizable resin contains two or more radical polymerizable groups in one molecule.

[0053] Examples of radical polymerizable resins include maleimide-based radical polymerizable resins (hereinafter sometimes referred to as "maleimide resins"), (meth)acrylic-based radical polymerizable resins, styrene-based radical polymerizable resins, and allyl-based radical polymerizable resins. Among these, it is preferable that the radical polymerizable resin contains maleimide resin.

[0054] Maleimide resin is a resin having, for example, one or more, preferably two or more, maleimide groups in one molecule. The maleimide resin may be an aliphatic maleimide resin containing an aliphatic amine skeleton, or an aromatic maleimide resin containing an aromatic amine skeleton. Examples of commercially available maleimide resins include "SLK-2600" and "SLK-6895-T90" from Shin-Etsu Chemical Co., Ltd., "BMI-1500," "BMI-1700," "BMI-3000J," "BMI-689," and "BMI-2500" (dimer amine structure-containing maleimide resins) from Designer Molecules Inc., "BMI-6100" (aromatic maleimide resin) from Designer Molecules Inc., "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide resins) from Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" from K.I. Chemicals Co., Ltd., and "BMI-2300" and "BMI-TMH" from Yamato Chemical Industries, Ltd. Alternatively, a maleimide resin (indane ring skeleton-containing maleimide resin) disclosed in the Japan Institute of Invention and Innovation, Technical Report No. 2020-500211 may be used as the maleimide resin.

[0055] The radical polymerizable group equivalent of the radical polymerizable 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 3,000 g / eq. or less, more preferably 2,500 g / eq. or less, even more preferably 2,000 g / eq. or less, and even more preferably 1,500 g / eq. or less. The radical polymerizable group equivalent represents the mass of the radical polymerizable resin per equivalent of one radical polymerizable group.

[0056] The weight-average molecular weight (Mw) of the 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, but may be, for example, 150 or more. The weight-average molecular weight of the radical polymerizable resin is the weight-average molecular weight on a polystyrene basis, measured by gel permeation chromatography (GPC).

[0057] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the 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, when the non-volatile components (i.e., components other than organic solvents) in the resin composition are taken as 100% by mass.

[0058] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the 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, when the total resin components in the resin composition are considered as 100% by mass.

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

[0060] From the viewpoint of significantly achieving the desired effects of the present invention, 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, and still 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, and even more preferably 31% by mass or less or 30% by mass or less.

[0061] From the viewpoint of significantly achieving the desired effects of the present invention, 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, and especially 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 solvents> The resin composition forming the resin pattern contains (B) an organic solvent as component (B). The organic solvent (B) excludes those corresponding to component (A) described above. The organic solvent (B) may be used alone or in combination of two or more types.

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

[0064] Aromatic solvents are solvents that contain an aromatic ring within their molecule. Examples of aromatic solvents include benzene (boiling point 80°C), toluene (boiling point 110°C), o-xylene (boiling point 144°C), m-xylene (boiling point 139°C), p-xylene (boiling point 138°C), ethylbenzene (boiling point 136°C), etc. 6-8Aromatic hydrocarbons; C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene (boiling point 176°C), 1,3,5-trimethylbenzene (boiling point 165°C), 1,2,4-trimethylbenzene (boiling point 169°C), 4-ethyltoluene (boiling point 161°C), 3-ethyltoluene (boiling point 160°C), 2-ethyltoluene (boiling point 166°C), isopropylbenzene (boiling point 152°C), n-propylbenzene (boiling point 159°C), indan (boiling point 176°C); n-butylbenzene (boiling point 183°C), isobutylbenzene (boiling point 172°C), sec-butylbenzene (boiling point 173°C), tert-butylbenzene (boiling point 169°C), 1, C2-diethylbenzene (boiling point 184°C), 1,3-diethylbenzene (boiling point 181°C), 1,4-diethylbenzene (boiling point 183°C), 3-ethyl-o-xylene (boiling point 194°C), 4-ethyl-o-xylene (boiling point 190°C), 2-ethyl-p-xylene (boiling point 187°C), 1-methyl-2-isopropylbenzene (boiling point 178°C), 1-methyl-3-isopropylbenzene (boiling point 175°C), 1-methyl-4-isopropylbenzene (boiling point 177°C), 1,2,3,5-tetramethylbenzene (boiling point 198°C), naphthalene (boiling point 218°C), 1,2,3,4-tetrahydronaphthalene (boiling point 207°C), etc. 10 Aromatic hydrocarbons; such as 1,3-dimethyl-4-isopropylbenzene (boiling point 199°C), 1-ethyl-4-isopropylbenzene (boiling point 197°C), etc. 11 Aromatic hydrocarbons, such as 1,4-diisopropylbenzene (boiling point 210°C), and C 12 Examples include aromatic hydrocarbon solvents such as aromatic hydrocarbons; aromatic ketone solvents such as acetophenone (boiling point 202°C); aromatic alcohol solvents such as benzyl alcohol (boiling point 205°C) and phenethyl alcohol (boiling point 219-221°C); aromatic ether solvents such as anisole (boiling point 154°C), phenethole (boiling point 169°C), and phenyl glycol (boiling point 244°C); and aromatic ester solvents such as methyl benzoate (boiling point 198-200°C) and ethyl benzoate (boiling point 211-213°C).

[0065] Non-aromatic solvents are solvents that do not contain aromatic rings 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 glycol-based solvents include ethylene glycol (boiling point 197°C), diethylene glycol (boiling point 244°C), propylene glycol (boiling point 188°C), dipropylene glycol (boiling point 232°C), and trimethylene glycol (boiling point 211-217°C).

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

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

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

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

[0071] Aliphatic ester solvents are non-aromatic solvents having an ester structure that do not fall under the category of glycol ether ester solvents. Examples include methyl acetate (boiling point 57°C), ethyl acetate (boiling point 77°C), n-propyl acetate (boiling point 96°C), isopropyl acetate (boiling point 89°C), n-butyl acetate (boiling point 126°C), isobutyl acetate (boiling point 118°C), sec-butyl acetate (boiling point 112°C), tert-butyl acetate (boiling point 97°C), n-pentyl acetate (boiling point 149°C), isopentyl acetate (boiling point 142°C), and propio. Examples include fatty acid alkyl esters such as ethyl phosphate (boiling point 99°C), propyl propionate (boiling point 122°C), and isopropyl propionate (boiling point 108°C); alkyl hydroxy acids such as methyl lactate (boiling point 144-145°C), ethyl lactate (boiling point 151-155°C), and butyl lactate (boiling point 185-187°C); alkyl keto acids such as methyl acetoacetate (boiling point 170°C) and ethyl acetoacetate (boiling point 184°C); and lactones such as γ-butyrolactone (GBL) (boiling point 204°C).

[0072] Aliphatic ether solvents are non-aromatic solvents having an ether structure that do not fall under glycol ether solvents or glycol ether ester solvents. Examples include aliphatic acyclic ethers such as diethyl ether (boiling point 34°C), diisopropyl ether (boiling point 68°C), and methyl tert-butyl ether (boiling point 55°C); and aliphatic cyclic ethers such as tetrahydrofuran (boiling point 66°C), 1,4-dioxane (boiling point 101°C), and 1,3-dioxolane (boiling point 75°C).

[0073] Aliphatic alcohol solvents are non-aromatic solvents having an alcohol structure that does not fall under glycol solvents or glycol ether solvents. Examples include methanol (boiling point 64°C), ethanol (boiling point 78°C), n-propanol (boiling point 97°C), isopropanol (boiling point 82°C), n-butyl alcohol (boiling point 117°C), isobutyl alcohol (also known as isobutanol) (boiling point 108°C), sec-butyl alcohol (boiling point 99°C), tert-butyl alcohol (boiling point 82°C), n-pentyl alcohol (boiling point 138°C), iso Examples include aliphatic acyclic alcohols such as pentyl alcohol (boiling point 131°C), sec-pentyl alcohol (boiling point 119°C), tert-pentyl alcohol (boiling point 102°C), neopentyl alcohol (boiling point 113°C), n-hexyl alcohol (boiling point 157°C), n-heptyl alcohol (boiling point 175°C), isoheptyl alcohol (boiling point 159°C), n-octyl alcohol (boiling point 195°C), and 2-ethylhexyl alcohol (boiling point 184°C); and aliphatic cyclic alcohols such as cyclohexanol (boiling point 161°C).

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

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

[0076] Examples of urea-based solvents include acyclic ureas such as tetramethylurea (boiling point 176°C); and cyclic ureas such as 1,3-dimethyl-2-imidazolidinone (DMI) (boiling point 220°C) and N,N'-dimethylpropyleneurea (DMPU) (boiling point 246°C).

[0077] (B) The organic solvent preferably contains an organic solvent having a boiling point of 100°C or higher and 200°C or lower. The organic solvent having a boiling point of 100°C or higher and 200°C or lower may be an aromatic solvent, a non-aromatic solvent, or a mixture of an aromatic solvent and a non-aromatic solvent (mixed solvent). The organic solvent having a boiling point of 100°C or higher and 200°C or lower may be used alone or in combination of two or more types. In the embodiment in which (B) the organic solvent contains an organic solvent having a boiling point of 100°C or higher and 200°C or lower, unintended drying of the resin composition before discharge can be particularly suppressed, and thus, discharge defects of the resin composition can be particularly suppressed, which is preferable. Furthermore, in the embodiment in which (B) the organic solvent contains an organic solvent having a boiling point of 100°C or higher and 200°C or lower, the discharged resin composition can be dried quickly, and therefore, the shape of the discharged resin composition (i.e., the shape of the resin pattern) can be particularly easily maintained, and thus, fine and thin resin patterns can be formed particularly advantageously, which is preferable.

[0078] From the viewpoint of significantly achieving the desired effects of the present invention, the content of the organic solvent having a boiling point of 100°C or higher and 200°C or lower in the resin composition is preferably 50% by mass or higher or 51% 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, when the total amount of organic solvent in the resin composition is considered to be 100% by mass. In a preferred embodiment, the lower limit of the 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 the content may be 100% by mass, less than 100% by mass, or 95% by mass or lower.

[0079] When the total components in the resin composition are considered to be 100% by mass, the content of (B) organic solvent in the resin composition (i.e., the value indicated by content X in the above relational formula) is 30% by mass or more. The lower limit of 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, from the viewpoint of significantly achieving the desired effects of the present invention. The upper limit of 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, from the viewpoint of significantly achieving the desired effects of the present invention.

[0080] <(C) Inorganic filler> The resin composition forming the resin pattern includes (C) an inorganic filler as component (C). The inorganic filler (C) is included in the resin composition in granular form and is included in the cured product (insulating pattern) while maintaining its granular form. The inorganic filler (C) may be used alone or in combination of two or more types.

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

[0082] Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation; and "Highpresica FH" from Ube Eximo Co., Ltd.

[0083] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of the inorganic filler is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.4 μm or less or 0.3 μm or less. The lower limit of the 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 can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size can be measured by taking the median diameter as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The measurement sample was prepared using a laser diffraction-scattering particle size distribution analyzer with blue and red light source wavelengths, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size was calculated as the median diameter from the obtained particle size distribution. Examples of laser diffraction particle size distribution analyzers include the "LA-960" manufactured by Horiba, Ltd.

[0084] From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​the inorganic filler is preferably 0.1 m². 2 / g or more, comfortably 1m 2 / g or more, more preferably 10m 2 / g or more, more preferably 20m 225 m or more per g 2 30 m or more per g 2 per g. The upper limit of the specific surface area is preferably 100 m 2 per g or less, more preferably 80 m 2 per g or less, still more preferably 60 m 2 per g or less, 50 m 2 per g or less or 40 m 2 per g or less. The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0085] The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include silane coupling agents such as vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, acid anhydride-based silane coupling agents; non-silane coupling - alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; silazane compounds, etc. The surface treatment agent may be used alone or in combination of two or more.

[0086] Examples of commercially available products of the surface treatment agent include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0087] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0088] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, the upper limit of the amount of carbon per unit surface area of ​​the inorganic filler is 1 mg / m², from the viewpoint of preventing an increase in the melt viscosity of the resin composition. 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following is even more preferable. The amount of carbon per unit surface area of ​​the inorganic filler can be measured after washing the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) after surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0089] From the viewpoint of significantly achieving the desired effects of the present invention, the content of (C) inorganic filler in the resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, even 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, when the non-volatile components (i.e., components other than organic solvents) in the resin composition are taken as 100% by mass. In particular, the embodiment in which the content of (C) inorganic filler is 35% by mass or more (furthermore, 39% by mass or more, 40% by mass or more or 45% by mass or more) is preferred because it can particularly lower the dielectric loss tangent of the insulating layer in a fine and thin insulating layer. Generally, when the content of inorganic filler in the resin composition is increased (for example, when the content of inorganic filler relative to 100% by mass of non-volatile components in the resin composition is 50% by mass or more), the mechanical strength of the cured product of the resin composition may be inferior, and therefore the reliability of the insulating layer containing the cured product of the resin composition may decrease. Furthermore, increasing the inorganic filler content in the resin composition can drastically increase its viscosity. As mentioned above, higher viscosity results in a thicker insulating layer, making it difficult to thin the insulating layer. In contrast, the resin composition used in the circuit board manufacturing method of the present invention satisfies the above-mentioned relationship "X≧30 and X / Y+X / Z<10," allowing for a fine and thin insulating layer even when containing a larger amount of inorganic filler compared to conventional resin compositions for jet dispensers, and furthermore, yielding a cured product with excellent mechanical strength. Moreover, in the embodiment of the resin composition used in the circuit board manufacturing method of the present invention that contains a larger amount of inorganic filler compared to conventional resin compositions for jet dispensers, the dielectric loss tangent of the insulating layer can be made particularly low in the fine and thin insulating layer, thus significantly contributing to the miniaturization and performance improvement of electronic devices. However, the technical scope of the present invention in embodiments with a high inorganic filler content does not narrow or exclude the technical scope of embodiments with a low inorganic filler content.The upper limit of the content of the (C) inorganic filler is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, 69% by mass or less, 68% by mass or less, or 67% by mass or less, even more preferably 66% by mass or less, 65% by mass or less, 64% by mass or less, or 63% by mass or less, and even more preferably 62% by mass or less, 61% by mass or less, or 60% by mass or less.

[0090] When the total components in the resin composition are considered to be 100% by mass, the content of (C) inorganic filler in the resin composition (i.e., the value indicated by content Y in the above relational expression) is not particularly limited as long as the numerical value expressed as "X / Y + X / Z" above is within a predetermined range. In one embodiment, the lower limit of content Y is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more or 25% by mass or more. Also in one embodiment, the upper limit of content Y is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0091] <(D) Thermoplastic resin> The resin composition forming the resin pattern includes a thermoplastic resin (D) as component (D). The thermoplastic resin (D) as component (D) does not include components (A) to (C) described above. The thermoplastic resin (D) may be used alone or in combination of two or more types.

[0092] Examples of thermoplastic resins (D) include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like. In particular, it is preferable that the thermoplastic resin (D) contains at least one of polyimide resin and phenoxy resin.

[0093] Polyimide resins can be resins having an imide structure. Polyimide resins can generally be obtained by imidation reactions between diamine compounds and acid anhydrides, or between diisocyanate compounds and acid anhydrides. Specific examples of polyimide resins include, for example, linear polyimides obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimide described in Japanese Patent Publication No. 2006-37083), and modified polyimides containing a polysiloxane skeleton (polyimides described in Japanese Patent Publication No. 2002-12667 and Japanese Patent Publication No. 2000-319386, etc.). Commercially available polyimide resins may also be used, for example, "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika Co., Ltd. Polyimide resins may be used alone or in combination of two or more types.

[0094] In one preferred embodiment, the polyimide resin contains structural units represented by the following formula (1) (hereinafter also referred to as "structural unit (1)"). The number of structural units (1) contained in one molecule of polyimide resin is 1 or more, and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less.

[0095] [ka]

[0096] (In formula (1), R1 is a tetravalent group represented by the following formula (1-1): R2 is a divalent group represented by the following formula (1-2).

[0097] [ka]

[0098] (In formula (1-1), Ar 11 Ar 12 Ar 13 and Ar14 Each of these independently represents an aromatic ring which may have substituents, L 11 , L 12 and L 13 Each of these independently represents a divalent linking group. nc1 represents a non-negative integer.

[0099] [ka]

[0100] (In formula (1-2), Ar 21 Ar 22 Ar 23 and Ar 24 Each of these independently represents an aromatic ring which may have substituents, L 21 , L 22 and L 23 Each of these independently represents a divalent linking group. nc2 represents an integer greater than or equal to 1.

[0101] In formula (1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each of these independently represents an aromatic ring that may or may not have substituents. 11 Ar 12 Ar 13 and Ar 14 The aromatic ring represented by (hereinafter also referred to as "aromatic ring C") is preferably an aromatic ring having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and even more preferably an aromatic carbon ring having 6 to 100 carbon atoms, and even more preferably 6 to 50 carbon atoms.

[0102] Ar 11 Ar 12 Ar 13 and Ar 14Examples of aromatic rings represented by Ar 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; condensed rings formed by the fusion of two or more monocyclic aromatic rings such as naphthalene 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, sinnoline rings, and phthalazine rings; and condensed rings formed by the fusion of one or more monocyclic aromatic rings with one or more monocyclic non-aromatic rings such as indan rings, fluorene rings, and tetraline rings. 11 Ar 12 Ar 13 and Ar 14 The aromatic rings represented are preferably, independently, aromatic carbon rings having 6 to 14 carbon atoms, which may have substituents, and more preferably, benzene rings.

[0103] In formula (1-1), Ar 11 Ar 12 Ar 13 and Ar 14 When represents an aromatic ring having substituents, the number of substituents is not limited. Examples of such substituents (hereinafter also referred to as "substituents S") include, independently of each other, halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, monovalent heterocyclic groups, alkylidene groups, amino groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, sulfo groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, and oxo groups.

[0104] In formula (1-1), L 11 , L 12 and L 13 Each of these independently represents a divalent linking group. 11 , L 12 and L 13The divalent linking group represented by is preferably a divalent group consisting of one or more skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms (for example, 1 to 3000, 1 to 1000, 1 to 100, and 1 to 50 atoms). Examples of divalent linking groups include -SO2-, -CO-, -COO-, -O-, -S-, -O-C6H4-O- (where -C6H4- represents a phenylene group), -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 group, alkenylene group, alkynylene group, arylene group, heteroarylene group, -NR 0 -(Here, R 0 ) represents a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. ) and -C(=O)-NR 0 - are listed.

[0105] L 11 , L 12 and L 13 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 5 or 1 to 4. 11 , L 12 and L 13 The number of carbon atoms in the alkenylene group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 5. 11 , L 12 and L 13 The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 10. 11 , L 12 and L 13 The number of carbon atoms in the heteroarylene 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 linking group represented by preferably does not contain an aromatic ring. In one embodiment, L 11 The divalent linking group and L13 The divalent linking group represented by is the same as each other, and L 11 The divalent linking group represented by and L 12 The divalent linking group represented by are different from each other. In a preferred embodiment, L 11 and L 13 is -O-, and L 12 is an alkylene group which may have a substituent. In a more preferred embodiment, L 11 and L 13 is -O-, and L 12 is a dimethylmethylene group.

[0107] In formula (1-1), nc1 represents an integer of 0 or more. In a preferred embodiment, nc1 represents an integer of 1 or more. The upper limit of the integer represented by nc1 is not particularly limited, and can be, for example, 50, 40, 30 or 20.

[0108] In the tetravalent group represented by formula (1-1), L 11 and L 13 is -O-, and moreover, L 12 is preferably an alkylene group which may have a substituent. Also, Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and L 11 and L 13 is -O-, and moreover, L 12 is preferably an alkylene group which may have a substituent. Also, Ar 11 , Ar 12 , Ar 13 and Ar 14 are each independently an aromatic carbocyclic ring having 6 to 14 carbon atoms which may have a substituent, and L 11 and L 13 is -O-, and L 12 is more preferably a dimethylmethylene group.

[0109] In formula (1-2), Ar 21 , Ar 22 , Ar23 and Ar 24 Each of these independently represents an aromatic ring that may or may not have substituents. 21 Ar 22 Ar 23 and Ar 24 Examples of the aromatic ring represented by and the substituents that the aromatic ring may have are the same as those described above for the aromatic ring C and substituent S. Therefore, in one preferred embodiment, Ar 21 Ar 22 Ar 23 and Ar 24 Each of these is independently an aromatic carbon ring having 6 to 14 carbon atoms, which may have substituents.

[0110] In formula (1-2), L 21 , L 22 and L 23 Each of these independently represents a divalent linking group. 21 , L 22 and L 23 An example of a divalent linking group represented by is L 11 , L 12 and L 13 This is similar to the divalent linking group represented by . Therefore, in a preferred embodiment, L 21 and L 23 is -O-, L 22 is an alkylene group which may have substituents, and in a more preferred embodiment, L 21 and L 23 is -O-, L 22 This 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. The upper limit of the integer represented by nc2 is not particularly limited, but could be, for example, 60, 50, 40, or 30.

[0112] In the divalent group represented by formula (1-2), L 21 and L 23 is -O- and L 22 It is preferable that is an alkylene group which may have substituents. Also, Ar21 Ar 22 Ar 23 and Ar 24 However, each is independently an aromatic carbon ring having 6 to 14 carbon atoms, which may have substituents, L 21 and L 23 is -O- and L 22 It is more preferable that is an alkylene group which may have substituents. Also, Ar 21 Ar 22 Ar 23 and Ar 24 However, each is independently an aromatic carbon ring having 6 to 14 carbon atoms, which may have substituents, L 21 and L 23 is -O-, L 12 It is even more preferable that the group is a dimethylmethylene group.

[0113] In the tetravalent group represented by formula (1-1) and the divalent group represented by formula (1-2), Ar 11 Ar 12 Ar 13 and Ar 14 However, each is independently an aromatic carbon ring having 6 to 14 carbon atoms, which may have substituents, and Ar 21 Ar 22 Ar 23 and Ar 24 However, each is preferably an aromatic carbon ring having 6 to 14 carbon atoms, which may have substituents. 11 and L 13 is -O-, L 12 L is an alkylene group which may have substituents. 21 and L 23 is -O- and L 22 It is preferable that the alkylene group may have substituents.

[0114] The above structural unit (1) can be obtained, for example, by a known method for producing polyimide resins, typically by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound to imidize it, or by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound to imidize it. It is acceptable for the polyimide resin to partially contain polyamic acid structures that may be formed during the imidization process.

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

[0116] [ka]

[0117] Furthermore, the polyimide resin may also contain structural units represented by the following formula (2) (hereinafter also referred to as "structural unit (2)"). Therefore, in one embodiment, the polyimide resin further contains structural units represented by the following formula (2). The number of structural units (2) contained in one molecule of polyimide resin is 0 or more and is not particularly limited, but can be 100 or less, 50 or less, or 30 or less.

[0118] [ka]

[0119] (In formula (2), R3 represents a tetravalent aliphatic group which may have substituents or a tetravalent aromatic group which may have substituents. R4 represents a divalent aliphatic group or a divalent aromatic group, which may have substituents. However, if R3 is the same as R1, R4 is different from R2, and if R4 is the same as R2, R3 is different from R1.

[0120] In formula (2), R3 represents an optionally substituted tetravalent aliphatic group or an optionally substituted tetravalent aromatic group.

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

[0122] The tetravalent aromatic group represented by R3 is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. An example of an aromatic ring included in the aromatic group is Ar in formula (1-1). 11 Ar 12 Ar 13 and Ar 14 The example of the aromatic ring represented is the same as that of the example

[0123] The tetravalent aromatic group represented by R3 can be a group obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride having an aromatic group that may have substituents. Specific examples of tetracarboxylic dianhydrides having an aromatic group that may have substituents include BPADA, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride.

[0124] In formula (2), R4 represents an optionally substituted divalent aliphatic group or an optionally substituted divalent aromatic group.

[0125] The divalent aliphatic group represented by R4 is a divalent group comprising at least carbon atoms, and preferably consisting of one or more skeleton atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50). In formula (2), the divalent aliphatic group represented by R4 is more preferably a divalent aliphatic group having 1 to 100 carbon atoms, and even more preferably 1 to 50 carbon atoms. In formula (2), when R4 represents a substituted divalent aliphatic group, the examples of the substituents are the same as the examples of substituent S, for example, an alkyl group having 1 to 6 carbon atoms. Therefore, in one embodiment, R4 is a divalent aliphatic group which may have substituents, and one of the substituents is an alkyl group having 1 to 6 carbon atoms. In another embodiment, R4 is a divalent aliphatic group which may have substituents, and is a divalent group obtained by removing two amino groups from isophoronediamine.

[0126] When R4 represents a divalent aliphatic group which may have substituents, it may be a group obtained by removing two amino groups from a diamine compound having a linear aliphatic group which may have substituents, 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 which may have substituents, it may be a group obtained by removing two amino groups from a diamine compound having a branched aliphatic group which may have substituents, 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.

[0128] When R4 represents a divalent aliphatic group which may have substituents, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 The group may be a diamine compound having an aliphatic group which may have substituents, selected from decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-biadamantyl, and 1,6-diaminoadamantane, from which two amino groups have been removed. These diamine compounds are characterized in that their aliphatic group contains an alicyclic carbocyclic ring.

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

[0130] If R4 represents a divalent aromatic group which may have substituents, it may be a group obtained by removing two amino groups from a diamine compound having an aromatic group which may have substituents, selected from 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0131] However, if R3 is the same as R1, R4 is different from R2, and if R4 is the same as R2, R3 is different from R1. In one embodiment, R3 is the same as R1.

[0132] The structural unit (2) described above can be obtained, for example, by a known method for producing polyimide resins. Structural unit (2) can be obtained, for example, by reacting BPADA with isophorone diamine. That is, in such structural unit (2), R3 is a skeleton derived from BPADA, and R4 is a skeleton derived from isophorone diamine. When R3 is the same as R1, R3 and R1 are skeletons derived from BPADA.

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

[0134] The glass transition temperature Tg (°C) of 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, but it can be 300°C or lower. The glass transition temperature Tg (°C) of polyimide resin can be measured 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 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 of structural unit (1) (mass percentage) can be calculated from the proportion of the amount (parts by mass) of each material used in the synthesis of the polyimide resin. Alternatively, the molecular weight of the polyimide resin and the formula weight of structural unit (1) may be specified, and the content of structural unit (1) may be calculated as the ratio of the formula weight of structural unit (1) to the molecular weight. When the polyimide resin is a polymer, it is preferable that the content of structural unit (1) estimated from the degree of polymerization falls within the above range.

[0136] The content of structural unit (2) in the polyimide resin may be 0% by mass (i.e., no structural unit (2)), and there is no upper limit as long as it does not hinder the effects of the present invention. If the polyimide resin is a resin that further contains structural unit (2), the content of structural unit (2) in the polyimide resin may be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. 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, even more 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 in terms of polystyrene, measured by gel permeation chromatography (GPC).

[0138] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and others. Phenoxy resins may be used individually or in combination of two or more types.

[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 S-Rec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc., manufactured by Sekisui Chemical Co., Ltd. Polyvinyl acetal resins may be used individually or in combination of two or more types.

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

[0141] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins. Polybutadiene resins may be used individually or in combination of two or more types.

[0142] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Resonaq Corporation. Polyamide-imide resins may be used individually or in combination of two or more types.

[0143] Specific examples of polysulfone resins include Solvay Advanced Polymers' polysulfones "P1700" and "P3500." Polysulfone resins may be used individually 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 Corporation. Specific examples of polyetherimide resins include "Ultem" manufactured by GE Corporation.

[0145] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" from Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) from Asahi Kasei Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) from Kuraray Co., Ltd. Polycarbonate resins may be used individually or in combination of two or more types.

[0146] Specific examples of polyether ether ketone resins include "Sumiproi 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, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin. Polyester resins may be used individually or in combination of two or more types.

[0148] From the viewpoint of significantly obtaining the effects of the present invention, it is preferable that the thermoplastic resin (D) contains an aromatic ring. The aromatic ring may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. Furthermore, the aromatic ring may be a monocyclic aromatic ring, a condensed aromatic ring formed by the condensation of two or more monocyclic aromatic rings, or a condensed aromatic ring formed by the condensation of one or more monocyclic aromatic rings with one or more monocyclic non-aromatic rings. Among these, the aromatic ring contained in the thermoplastic resin (D) is preferably an aromatic carbocyclic ring. The number of carbon atoms in the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

[0149] (D) If the thermoplastic resin contains aromatic rings, the number of aromatic rings is, for example, one or more, preferably two or more. (D) If the thermoplastic resin contains two or more aromatic rings, the two or more aromatic rings may be the same or different.

[0150] From the viewpoint of obtaining the effects of the present invention more significantly, it is more preferable that the thermoplastic resin (D) contains aromatic rings, and that all of the aromatic rings are aromatic carbocyclic rings. That is, in a more preferred embodiment, the thermoplastic resin (D) contains aromatic carbocyclic rings but does not contain aromatic heterocyclic rings. In such an embodiment, the thermoplastic resin (D) may contain non-aromatic rings or may not contain non-aromatic rings. The non-aromatic ring may be a non-aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or it may be a non-aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc., in addition to carbon atoms as ring constituent atoms.

[0151] When the resin composition contains a thermoplastic resin other than polyimide resin, the weight-average molecular weight (Mw) of the thermoplastic resin other than polyimide resin is preferably 5,000 or more, more preferably 8,000 or more, even more 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 even more preferably 80,000 or less, or 60,000 or less. The weight-average molecular weight of the thermoplastic resin other than polyimide resin is the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography (GPC).

[0152] From the viewpoint of significantly achieving the desired effects of the present invention, the content of (D) thermoplastic 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 or 16% by mass or more, even 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, even more preferably 40% by mass or less, even more preferably 35% by mass or less, 33% by mass or less or 31% by mass or less. In particular, the embodiment in which the content of (D) thermoplastic resin is 15% by mass or more or 40% by mass or less is preferred because 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 a fine and thin resin pattern. Furthermore, in the embodiment in which the content of the (D) thermoplastic resin is 15% by mass or more and 40% by mass or less, separation of components contained in the resin composition before discharge and sedimentation of inorganic fillers can be particularly suppressed, which is preferable. Furthermore, in the embodiment in which the content of the (D) thermoplastic resin is 15% by mass or more and 40% by mass or less, excessive flexibility of the resin pattern (and insulating pattern) can be particularly suppressed, which is preferable.

[0153] From the viewpoint of significantly achieving the desired effects of the present invention, the content of (D) thermoplastic resin in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, 37% by mass or more, or 39% by mass or more, when the total resin component in the resin composition is considered as 100% by mass, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, even 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, and especially more preferably 60% by mass or less or 57% by mass or less.

[0154] When the total components in the resin composition are considered to be 100% by mass, the content of (D) thermoplastic resin in the resin composition (i.e., the value indicated by content Z in the above relational formula) is not particularly limited as long as the numerical value expressed as "X / Y + X / Z" falls within a predetermined range. In one embodiment, the lower limit of content Z is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, or 8% by mass or more. Also in one embodiment, the upper limit of content Z is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, 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 optionally contain (E) a curing accelerator. The (E) curing accelerator does not include those corresponding to components (A) to (D) described above. The (E) curing accelerator functions as a catalyst for the reaction of the (A) thermosetting resin and can therefore accelerate the curing of the resin composition. The (E) curing accelerator may be used alone or in combination of two or more types.

[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-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Nilimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-F Examples include imidazole compounds such as phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of the imidazole compounds with epoxy resins. Among these, at least one of 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole is preferred as the imidazole-based curing accelerator.Commercial imidazole-based curing accelerators may be used, for example, "P200-H50" from Mitsubishi Chemical Corporation; and "Curesol 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" from Shikoku Chemicals, Inc.

[0158] Examples of phosphorus-based curing accelerators include phosphonium salts and phosphines. Examples of phosphonium salts include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, n-butylphosphonium tetraphenylborate, bis(tetrabutylphosphonium) pyromelitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, and propyltriphenylphosphonium bromide. Aromatic phosphonium salts such as bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate are examples.

[0159] Examples of phosphines include aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, and tris(2,5-dimethylphenyl)phosphine. Tris(2,6-dimethylphenyl)phosphine, tris(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-B Examples include aromatic phosphines such as s(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 and triphenylborane; and aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products.

[0160] As a phosphorus-based curing accelerator, commercially available products may be used, such as "TBP-DA" manufactured by Hokko 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 may also be used, such as "PN-50," "PN-23," and "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd.

[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]deca-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. Examples include ro[4.4.0]deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene being preferred.

[0163] Examples of metal-based hardening 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 organocalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate; organocuponex complexes such as copper(II) acetylacetonate; organozinc complexes such as zinc(II) acetylacetonate; organoiron complexes such as iron(III) acetylacetonate; organonickel complexes such as nickel(II) acetylacetonate; and organomanganese complexes such as manganese(II) acetylacetonate. 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 aliphatic dimethylureas such as 1,1-dimethylurea, 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-dimethyl Aromatic dimethylureas such as toluene urea, 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), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], etc.

[0165] If the resin composition contains (E) a curing accelerator, the content of (E) the 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, when the non-volatile components (i.e., components other than organic solvents) in the resin composition are taken as 100% by mass.

[0166] If the resin composition contains (E) a curing accelerator, the content of (E) the 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, when the total amount of resin components in the resin composition is 100% by mass.

[0167] <(F) Other additives> The resin composition forming the resin pattern may further contain, in combination with components (A) to (E) described above, any additional component (F) or other additives. This additional additive (F) as component (F) does not include any components corresponding to components (A) to (E) described above.

[0168] (F) Other additives include, for example, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organic fillers such as rubber particles; organometallic compounds such as organocenium 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 bentonite and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; and benzotriazole-based ultraviolet absorbers. Examples include ultraviolet absorbers such as; adhesion improvers such as urea silane; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (E) Other additives may be used individually or in combination of two or more types.

[0169] [Method for producing resin compositions] A resin composition for forming a resin pattern can be manufactured, for example, by mixing the components described above. The components described above may be mixed some or all at once, or sequentially. The temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or throughout the process. Stirring or shaking may also be performed during the mixing of each component. Furthermore, degassing may be performed under low-pressure conditions such as under vacuum.

[0170] [Properties of resin compositions] The resin composition that forms the resin pattern comprises (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin (and optionally (E) a curing accelerator and (F) other additives). Furthermore, when the total components in the resin composition are considered to be 100% by mass, the content of (B) the organic solvent is X (by mass%), the content of (C) the inorganic filler is Y (by mass%), and the content of (D) the thermoplastic resin is Z (by mass%), X ≥ 30 and X / Y + X / Z < 10 The method is characterized by satisfying the relationship described above. According to the method for manufacturing a circuit board using a resin composition that satisfies the relationship described above, a circuit board having a fine and thin insulating layer can be manufactured.

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

[0172] As mentioned above, a circuit board manufacturing method using a resin composition that satisfies the relationship X≧30 and X / Y+X / Z<10 can be used to manufacture a circuit board with a thin insulating layer. For example, as described in the section "Test Example 3: Dispensing Test using a Jet Dispenser" below, the nozzle diameter is fixed at 50 μm, the distance between the nozzle and the glass plate is 500 μm, and the supply pressure of the resin composition is fixed at 0.02 MPa, and only one drop of the resin composition is dispensed using a jet dispenser. The dispensed resin composition is heated at 180°C for 50 minutes to obtain a cured product. The thickness of the cured product obtained by this 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 lower limit to the thickness of the cured product, and it can be 1 μm or more, etc.

[0173] The resin composition forming the resin pattern may have a viscosity within a specific range. For example, as described in the section <Test Example 1: Viscosity Measurement>, when measured for 2 minutes using an E-type viscometer under the conditions of a measurement temperature of 25°C, a rotor of 1.34° × R24, a resin composition volume 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, 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 may have a surface tension within a specific range. For example, as described in the section <Test Example 2: Measurement of Surface Tension>, five measurements are taken using the pendant drop method at a measurement temperature of 25°C. When the average of these 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] The resin composition forming the resin pattern can result in a cured product exhibiting a low dielectric loss tangent. For example, as described in <Test Example 4: Measurement of Dielectric Loss Tangent (Df)>, when measured at 5.8 GHz and 23°C, the dielectric loss tangent (Df) of a cured product obtained by heat-curing the resin composition at 200°C for 90 minutes is preferably 0.006 or less, more preferably 0.005 or less, and even more preferably 0.004 or less. The lower limit of the dielectric loss tangent can be 0.0001 or more, etc.

[0176] The resin composition used to form the resin pattern can yield a cured product exhibiting excellent mechanical strength. Therefore, the cured product of the resin composition used to form the resin pattern can have high rigidity and toughness. For example, a resin composition is applied to a support so that the thickness after drying is 40 μm to form a resin composition layer. Then, the dried resin composition layer is cured at 200°C for 90 minutes to obtain a cured product. When a needle with a diameter of 1 mm is pierced into the cured product at a speed of 50 mm / min, the strength at which the cured product breaks (piercing strength) is preferably 4 N or more, more preferably 4.5 N or more, even more preferably 5 N or more, 5.5 N or more, or 6 N or more. The upper limit of the piercing strength is preferably higher, and may be, for example, 50 N or less. The piercing strength can be measured according to the method described in the section <Test Example 5: Piercing (Stab) Test> described later.

[0177] [Manufacturing method for circuit boards] The circuit board includes an insulating pattern obtained by curing a resin pattern formed with the above-described resin composition. More specifically, the method for manufacturing the circuit board of the present invention is as follows: (I) A step of forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispenser. (II) A step of forming an insulating pattern by curing the resin pattern, (III) A step of forming a conductive layer on the substrate and the insulating pattern by electroplating, (IV) A step of forming a conductor pattern by removing a portion of the conductor layer, The present invention is characterized by including these elements in this order. According to the method for manufacturing a circuit board of the present invention, a circuit board having a fine and thin insulating layer can be manufactured.

[0178] <Process (I)> In step (I), a resin pattern is formed by dispensing the above-mentioned resin composition onto a substrate using a jet dispenser.

[0179] The jet dispenser used in step (I) is not particularly limited as long as it can dispense the resin composition, and any known jet dispenser may be used. Examples of jet dispensers include piezoelectric jet dispensers using piezoelectric elements, bubble jet (thermal) jet dispensers using heating elements, electromagnetic jet dispensers using solenoid valves, and air-type jet dispensers using air pressure.

[0180] The "substrate" used in process (I) refers to a material that serves as the substrate for a circuit board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides. The conductive layer on the substrate may also be patterned. A substrate in which a conductive layer (circuit) is formed on one or both sides is sometimes called an "internal layer circuit substrate." Intermediate products on which an insulating layer and / or a conductive layer is to be further formed when manufacturing a circuit board are also included in the term "substrate." If the circuit board is a component-embedded circuit board, an internal layer substrate with embedded components may be used.

[0181] In step (I), the resin pattern formed by the resin composition is formed by selectively extruding the resin composition to areas other than the conductor pattern formation area so that the main surface of the substrate can obtain a desired conductor pattern. Specifically, the resin pattern is formed by extruding the resin composition in step (I) so that the main surface is exposed with the desired conductor pattern, after going through steps (II) and (III) described later. For example, when an inner layer circuit substrate is used as the substrate, the conductor layer (circuit) of the exposed inner layer circuit substrate may be used as a plating electrode, and a conductor pattern may be formed by electroplating.

[0182] In step (I), the resin pattern may be dried as needed. There are no particular restrictions on the drying conditions for the resin pattern, and conditions commonly used when forming the insulating layer of a circuit board may be used. The drying of the resin pattern can be carried out, for example, by vacuum, reduced pressure, heating, hot air blowing, or a combination thereof.

[0183] When drying the resin pattern under vacuum and / or reduced pressure, the air pressure is preferably 500 Pa or less, and more preferably 200 Pa or less. The vacuum drying time is not particularly limited, but is preferably 30 seconds to 30 minutes, and 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. The heating and drying time while maintaining 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] The thickness of the resin pattern formed in step (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, from the viewpoint of thinning the circuit board. The lower limit of the resin pattern thickness is not particularly limited, but can be, for example, 1 μm or more.

[0186] <Process (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 carried out, for example, by thermal curing. The conditions for thermal curing of the resin pattern are not particularly limited, and conditions that are normally used when forming an insulating layer of a circuit board may be used.

[0187] For example, the thermal curing conditions for 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 can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0188] Prior to heat-curing the resin pattern, the resin pattern may be preheated at a temperature lower than the curing temperature. For example, prior to heat-curing the resin pattern, the resin composition layer may 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 5 minutes or more, 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 may be roughened as needed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a circuit board can be adopted. Either dry or wet roughening treatment may be performed. Examples of dry roughening treatments include plasma treatment and dry sandblasting. Examples of wet roughening treatments include swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution, performed in that order.

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

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

[0192] The duration of the plasma roughening treatment is not particularly limited, but is preferably 30 seconds or more, more preferably 60 seconds or more, 90 seconds or more, or 120 seconds or more. The upper limit of the roughening treatment duration is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of easily achieving an insulating layer with low surface roughness after the roughening treatment.

[0193] As a dry roughening treatment, dry sandblasting may also be used, in which an abrasive material is sprayed from a nozzle to polish the object to be treated. Dry sandblasting can be carried out using commercially available dry sandblasting equipment. When a water-soluble abrasive material is used as the abrasive material, the insulating pattern can be effectively roughened without any abrasive residue remaining on the substrate and insulating pattern by rinsing with water after the dry sandblasting treatment.

[0194] In the wet roughening treatment, examples of swelling solutions used for the swelling treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as the alkaline solution. Examples of commercially available swelling solutions include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Attec Japan. The swelling treatment with the swelling solution may be carried out, 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 preferred as the oxidizing agent solution used for roughening. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be used. The roughening treatment with the oxidizing agent solution is preferably carried out by immersing the insulating pattern in the 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. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Attec Japan.

[0196] In the wet roughening treatment, as the neutralizing solution used for the neutralization treatment, an acidic aqueous solution is preferable. As commercially available products, for example, "Reduction Solution Securigan P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The neutralization treatment with the neutralizing solution may be performed by immersing the treatment surface of the insulating pattern, which has been roughened with an oxidizing agent, in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes.

[0197] When performing a combination of dry roughening treatment and wet roughening treatment, the dry roughening treatment may be performed first, or the wet roughening treatment may be performed first.

[0198] The line width of the insulating pattern formed in step (II) 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. The lower limit of the line width of the insulating pattern is not particularly limited, and may be, for example, 50 μm or more.

[0199] From the perspective of thinning the circuit board, the thickness of the insulating pattern formed in step (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 thickness of the insulating pattern is not particularly limited, and may be, for example, 1 μm or more.

[0200] <Step (III)> In step (III), a conductor layer is formed on the base material and the insulating pattern formed in step (II) by an electrolytic plating method. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer formed in step (III) contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Among them, it is more preferable that the conductor layer formed in step (III) is made of a metal containing copper.

[0201] The conductive layer formed in step (III) may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductive layer formation, cost, and ease of patterning, the conductive 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. A single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, is more preferable, and a single metal layer of copper is even more preferable.

[0202] The conductive layer formed in step (III) may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal or alloy layers made of different types of metals or alloys are stacked.

[0203] In step (III), the conductive layer is formed by electroplating. Specifically, electroplating is performed on the substrate and the insulating pattern formed in step (II) to form a conductive layer for creating the desired conductive pattern.

[0204] Generally, 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 electroplating layer. When copper is used as the metal, examples of copper salts include copper sulfate such as copper sulfate pentahydrate, copper halides such as copper chloride, copper acetate, copper nitrate, copper tetrafluoroborate, copper alkylsulfonate, copper arylsulfonate, copper sulfamate, copper perchlorate, and copper gluconate, with copper sulfate being preferred. The concentration of the metal salt in the electroplating solution may be, for example, 50 g / L or more and 400 g / L or less. It is more preferable that the concentration of the metal salt in the electroplating solution be at saturation. The electroplating solution may also contain additives such as acids such as sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and hydrochloric acid; halide ion suppliers; brighteners; and surfactants.

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

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

[0207] The plating seed layer includes at least a conductive seed layer. The conductive seed layer is a layer that functions as an electrode in the electroplating method. The conductive material constituting the conductive seed layer is not particularly limited as long as it exhibits sufficient conductivity, but preferred examples include copper, palladium, gold, platinum, silver, aluminum, and their alloys.

[0208] The plated 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 dielectric breakdown. The material constituting the diffusion barrier layer is not particularly limited as long as it can suppress and prevent the diffusion of the conductive material constituting the conductive seed layer, but preferred examples include titanium, tungsten, tantalum and their alloys. When the plated seed layer includes a diffusion barrier layer, the conductive seed layer can be formed on the diffusion barrier layer after forming the diffusion barrier layer on the substrate and the insulating pattern formed in step (II).

[0209] The thickness of the plating 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 plating seed layer may be even thinner. For example, the thickness of the plating seed layer may 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 plating seed layer includes a diffusion barrier layer, the "thickness of the plating seed layer" in the present invention refers to the average thickness of the entire plating seed layer, including not only the conductive seed layer but also the diffusion barrier layer.

[0210] <Process (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 restrictions on the location of the conductor layer to be removed in step (IV). For example, a conductor pattern may be formed by removing a conductor layer formed on an insulating pattern. Alternatively, for example, prior to the formation of a multilayer circuit board, a portion of the conductor layer may be selectively removed according to the desired circuit board design.

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

[0212] Polishing conditions for a portion of the conductive layer include chemical mechanical polishing (CMP) using a chemical mechanical polishing (CMP) apparatus; mechanical polishing methods such as belt polishing, buff polishing, ceramic polishing, grinding with a surface grinder, and surface grinding with a rotating grinding wheel; and various grit sizes of abrasives may be used depending on the desired state of the polished surface. Furthermore, the degree of polishing of a portion of the conductive layer can be determined, for example, by ending the polishing when the surface of the insulating pattern is exposed.

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

[0214] After step (IV), the conductor pattern may be annealed as needed. Annealing can improve the adhesion between the insulating 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 one preferred embodiment, the method for manufacturing the circuit board of the present invention is as follows: After process (II) and before process (III), The process includes a step of roughening the aforementioned insulating pattern, Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by wet plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, The method is characterized by including these elements in this order. According to the circuit board manufacturing method in this embodiment, it is possible to manufacture a circuit board having an even finer and thinner insulating layer. Therefore, the circuit board manufacturing method in this embodiment contributes significantly to the miniaturization and performance improvement of electronic devices.

[0216] In another preferred embodiment, the method for manufacturing the circuit board of the present invention is as follows: Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by dry plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, This includes them in this order, The plated seed layer is characterized by comprising a conductive seed layer made of a metal containing copper, and a diffusion barrier layer made of a metal containing titanium between the conductive seed layer, the substrate, and the insulating pattern. According to the method for manufacturing a circuit board in this embodiment, it is possible to manufacture a circuit board having an even finer and thinner insulating layer. Therefore, the method for manufacturing a circuit board in this embodiment makes a significant contribution to the miniaturization and performance improvement of electronic devices.

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

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

[0219] As the bonding conditions between the circuit board and the semiconductor chip, any conditions under which the terminal electrodes of the semiconductor chip and the circuit wiring (conductor pattern) of the circuit board can be conductively connected can be adopted. For example, the conditions used in flip-chip mounting of the semiconductor chip can be adopted. Also, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0220] As an example of the bonding method, a method of pressing the semiconductor chip onto the circuit board can be mentioned. As 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] Also, as another example of the bonding method, a method of reflowing and bonding the semiconductor chip to the circuit board can be mentioned. The reflow conditions may be in the range of 120°C to 300°C.

[0222] Examples of the semiconductor package substrate include, for example, a fan-in (Fan-In) type package, a fan-out (Fan-Out) type package, and the like.

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

[0224] [Semiconductor device] A semiconductor device according to one embodiment of the present invention comprises a circuit board manufactured by the manufacturing method described above. Examples of such semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). [Examples]

[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 "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions were room temperature (25°C) and atmospheric pressure (1 atm).

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

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

[0228] From the above reaction pathway, it was estimated that polyimide resin D1 contains a structural unit represented by the following formula (D1a). Furthermore, from the above reaction pathway, it was estimated that polyimide resin D1 contains a first skeleton derived from BPADA and a second skeleton derived from BPPAN.

[0229] [ka]

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

[0231] <Synthesis Example 2: Synthesis of Triazine Ring-Containing Polymer D2> 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 dissolved. To this, 0.444 g (1.00 mmol) of bis(4,6-dimethoxy-1,3,5-triazine-2-yl) isophthalate was added, and the mixture was reacted at room temperature for 6 hours. The resulting reaction solution was poured into 200 mL of methanol, and the precipitated polymer was filtered off. The filtered polymer was washed with methanol and then dried under reduced pressure at room temperature to obtain triazine ring-containing polymer D2. The obtained triazine ring-containing polymer D2 had a number-average molecular weight (Mn) of 25,000 and a weight-average molecular weight (Mw) of 51,000. Furthermore, triazine ring-containing polymer D2 contains structural units represented by the following formula.

[0232] [ka]

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

[0234] (A) Thermosetting resin • "ZX-1059": A mixture of liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent weight approximately 165 g / eq. • "NC-3000": Liquid biphenyl-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight approximately 257 g / eq. • "LA-3018-50P": Triazine skeleton-containing phenolic resin, manufactured by DIC Corporation. The component, excluding organic solvents, is a 50% by mass propylene glycol monomethyl ether solution, with a hydroxyl group equivalent of approximately 151 g / eq. • "HPC-8000-65T": Activated ester resin, manufactured by DIC Corporation. A toluene solution containing 65% by mass of the active ester equivalent, excluding organic solvents. Approximately 223 g / eq of active ester. • "Maleimide Resin 1": An aliphatic skeleton-containing maleimide resin having a structure represented by the following formula (may contain some unsaturated bonds), "SLK6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd., and a toluene solution with 90% by mass of the components excluding the organic solvent.

[0235] [ka]

[0236] (B) Organic solvents • "MEK": Methyl ethyl ketone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., boiling point 79°C • "Cyclohexanone": Cyclohexanone, manufactured by Junsei Chemical Co., Ltd., boiling point 155°C

[0237] (C) Inorganic filler • "Inorganic filler 1": 100 parts by mass of Denka's "UFP30", and a silane coupling agent having an N-phenyl-3-aminopropyl group (Shin-Etsu Chemical Co., Ltd.'s "KBM-57"). 3) Spherical silica surface-treated with 3.0 parts by mass, average particle size 0.3 μm, specific surface area 30.7 m² 2 / g

[0238] (D) Thermoplastic resin • "YX6954BH30": A phenoxy resin containing a bisphenol acetophenone skeleton and no heterocyclic rings, manufactured by Mitsubishi Chemical Corporation. The component, excluding organic solvents, is a 30% by mass methyl ethyl ketone (MEK):cyclohexanone = 1:1 solution. • "Polyimide resin D1": Polyimide resin D1 obtained in Synthesis Example 1 • "Triadine ring-containing polymer D2": Triazine ring-containing polymer D2 obtained in Synthesis Example 2

[0239] (E) Curing accelerator • "2P4MZ": 2-phenyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.

[0240] <Test 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 viscometer manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity for 2 minutes under the following conditions: measurement temperature 25°C, rotor 1.34° × R24, amount of varnish-like resin composition 1.2 ml, and rotation speed 100 rpm.

[0241] <Test 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, manufactured by Kyowa Interface Science Co., Ltd.) at a measurement temperature of 25°C using the pendant drop method. Five measurements were taken, and the average of the five measurements was taken as the surface tension of the resin composition.

[0242] <Test Example 3: Dispensing Test using a Jet Dispenser> The varnish-like resin compositions obtained in each example and comparative example were dispensed into a jet dispenser (VERMES Microdispensing's "MDS3280") and a dispensing test was conducted. In detail, a glass plate with a flat surface 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 as appropriate to dispense each resin composition.

[0243] Generally, when the coating frequency is low (i.e., the discharge conditions are weak), the resin composition cannot be discharged. Also, generally, when the coating frequency is high (i.e., the discharge conditions are strong), the droplets of the discharged resin composition become larger.

[0244] In this test, the coating frequency was changed for each resin composition, and the discharge test was performed at the lowest coating frequency at which discharge was possible. In this test, the resin composition was discharged onto a glass plate so that only one droplet of each resin composition was discharged.

[0245] Next, the extruded 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 heat-cur it. Through this procedure, evaluation sample A consisting of the cured resin composition was obtained.

[0246] Using a digital microscope (Keyence VHX-X1F), the line width of the obtained evaluation sample A (the maximum width of evaluation sample A parallel to the plane of the glass plate) was measured. Next, evaluation sample A was polished using an ion mill (Hitachi High-Tech IM4000) to obtain a cross-section perpendicular to the plane of the glass plate. The cross-section of evaluation sample A after polishing was observed using a digital microscope (Keyence VHX-X1F), and the thickness of evaluation sample A (the maximum width of evaluation sample A perpendicular to the plane of the glass plate) was measured. The line width and thickness of each evaluation sample A were evaluated according to the following evaluation criteria.

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

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

[0249] <Test Example 4: Measurement of Dielectric Loss Tangent (Df)> As a support, a PET film (Toray Industries, Ltd., "Lumirror R80", thickness: 38 μm, softening point: 130°C) treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. The varnish-like resin composition obtained in each example and comparative example was uniformly applied to the support using a die coater so that the thickness of the dried resin composition layer was 15 μm, and the resin composition layer was formed by drying in an oven at 130°C for 5 minutes.

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

[0251] <Test Example 5: Stab Test> As a support, a PET film (Toray Industries, Ltd., "Lumirror R80", thickness: 38 μm, softening point: 130°C) treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. The varnish-like resin composition obtained in each example and comparative example was uniformly applied to the support using a die coater so that the thickness of the dried resin composition layer was 40 μm, and the resin composition layer was formed by drying in an oven at 130°C for 5 minutes.

[0252] The resin composition layer was heated at 200°C for 90 minutes to heat-cur it, and then the support was peeled off to obtain a cured product. The obtained cured product was cut into test pieces approximately 30 mm on each side, and puncture resistance tests were performed using a universal material testing machine (AND Corporation's "TensironRTC1250A"). Specifically, after mounting the test piece in the device, a 1 mm diameter needle with a load of 50 N was brought into contact with the test piece at a speed of 50 mm / min, and the maximum point load at which fracture occurred was measured.

[0253] [Table 1]

[0254] [Table 2]

[0255] [Table 3]

Claims

1. (I) A step of forming a resin pattern by dispensing a resin composition onto a substrate using a jet dispenser. (II) A step of forming an insulating pattern by curing the resin pattern, (III) A step of forming a conductive layer on the substrate and the insulating pattern by electroplating, (IV) A step of forming a conductor pattern by removing a portion of the conductor layer, A method for manufacturing a circuit board, comprising the following in this order: The resin composition is a resin composition comprising (A) a thermosetting resin, (B) an organic solvent, (C) an inorganic filler, and (D) a thermoplastic resin, When the total components in the resin composition are assumed to be 100% by mass, (B) the content of the organic solvent is X (by mass%), (C) the content of the inorganic filler is Y (by mass%), and (D) the content of the thermoplastic resin is Z (by mass%), X ≥ 30 and X / Y + X / Z < 10 A method for manufacturing a circuit board that satisfies the relationship.

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

3. (A) The manufacturing method according to claim 1, wherein the thermosetting resin comprises at least one of an epoxy resin and a maleimide resin.

4. (A) The manufacturing method according to claim 3, wherein the thermosetting resin includes a curing agent.

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

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

7. (C) The manufacturing method according to claim 1, wherein the inorganic filler contains silica.

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

9. (D) The manufacturing method according to claim 1, wherein the thermoplastic resin contains an aromatic ring.

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

11. After process (II) and before process (III), The process includes a step of roughening the aforementioned insulating pattern, Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by wet plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, The manufacturing method according to claim 1, comprising the following in this order.

12. Process (III) is A step of forming a plating seed layer on the substrate and the insulating pattern by dry plating, A step of forming a conductive layer consisting of a single copper metal layer on the aforementioned plated seed layer by electroplating, This includes them in this order, The manufacturing method according to claim 1, wherein the plating seed layer comprises a conductive seed layer made of a metal containing copper, and a diffusion barrier layer made of a metal containing titanium between the conductive seed layer, the substrate, and the insulating pattern.

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

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

15. moreover, X / Y + X / Z > 4 A manufacturing method according to claim 1 that satisfies the relationship.

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

17. A semiconductor device comprising a circuit board manufactured by the manufacturing method described in any one of claims 1 to 16.

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