Resin composition and semiconductor package substrate using the same

Abstract

To provide a resin composition which is capable of being handled as a solution dissolved in an organic solvent, exhibiting a low coefficient of linear thermal expansion, a high glass transition temperature, superior mechanical properties including elongation at break and modulus, superior dielectric properties including dielectric constant and dielectric loss tangent, and excellent resolution limit.SOLUTION: The resin composition contains (A) a polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure, and (B) an organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and further to a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate, which are obtained using the resin composition. [Background technology]

[0002] Conventionally, polyimide resins, which have excellent heat resistance, insulating properties, mechanical properties, etc., have been used for surface protection films, interlayer insulating films, etc. of semiconductor elements. For example, Patent Documents 1 and 2 describe polyimide resins having fluorine atoms introduced into their molecular structure. Patent Document 3 describes a polyimide having an alicyclic structure introduced, and Patent Document 4 describes a polyimide having a multi-branched structure introduced. Furthermore, Patent Document 5 describes a polyimide film utilizing a porous membrane. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 4-328126 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-071783 [Patent Document 3] Patent No. 7267567 [Patent Document 4] Japanese Patent Application Laid-Open No. 2006-131706 [Patent Document 5] Japanese Patent Application Laid-Open No. 2003-201363 Summary of the Invention [Problem to be solved by the invention]

[0004] Although the fluorine-atom-introduced polyimide resins described in Patent Documents 1 and 2 have the effect of reducing polymer density and improving solubility in solvents, organic compounds containing fluorine atoms are toxic, and therefore materials with a low fluorine atom content are desirable. Furthermore, the polyimide described in Patent Document 3 has a dielectric constant of 2.7 at its lowest, and the polyimide described in Patent Document 4 has a dielectric constant of 2.8 at its lowest, which are unsatisfactory performance. The polyimide film described in Patent Document 5 has problems such as insufficient strength as a protective film and poor insulation due to moisture intrusion into the cavity during high-temperature, high-humidity testing.

[0005] In recent years, 5G and 6G communication applications have required even lower dielectric properties, such as lower dielectric constants and dielectric loss, as well as limiting resolution (via processability using etching masks). Furthermore, the number of layers used for package rewiring has increased from the conventional two to four or even five or more layers. As a result, stresses caused by heat and impact can cause warping in the substrate, and to prevent warping of the laminated substrate, a low coefficient of linear thermal expansion (CTE) is becoming increasingly important. Furthermore, from the perspective of the heat resistance of the packaged semiconductor chips, low-temperature curing or no-curing materials are desired.

[0006] The polyimide resins described in Patent Documents 1 to 5 have low solubility in solvents. Therefore, in the resin compositions, polyimide precursors such as polyamic acid are used. After forming an insulating layer, the polyimide precursor is cyclized to form the insulating layer. In this case, a high-temperature curing reaction is required to imidize the polyimide precursor, which may adversely affect the packaged semiconductor chip. Furthermore, the imidization reaction after forming the insulating layer is difficult to proceed because the water generated by the imidization reaction is difficult to remove, and some polyamic acid structures remain even after the curing reaction. This results in the problem that the dielectric constant and dielectric loss tangent of the cured product are not sufficiently small. Therefore, polyimide resins that are soluble in organic solvents are desired.

[0007] The present invention has been made in view of the above-mentioned problems, and aims to provide a resin composition, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate, which can be handled as a solution dissolved in an organic solvent, and which has a low linear thermal expansion coefficient, a high glass transition temperature, excellent mechanical properties such as elongation at break and elastic modulus, excellent dielectric properties such as dielectric constant and dielectric loss tangent, and excellent limiting resolution. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a resin composition containing a polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure, and (B) an organic solvent, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) a polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure, and (B) an organic solvent, A resin composition comprising: [2] The resin composition according to [1], wherein the component (A) further has a structure derived from a tetracarboxylic dianhydride. [3] The resin composition according to [1] or [2], wherein the hydroxy structure is a hydroxycarbonyl group or a phenolic hydroxy group. [4] The resin composition according to any one of [1] to [3], which is in the form of a varnish. [5] The resin composition according to any one of [1] to [4], wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3): [ka] (In formula (A-1), each A independently represents a tetravalent organic group.) [ka] (In formula (A-2), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.) [ka] In formula (A-3), X's each independently represent a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of the groups is a hydroxy group or a hydroxycarbonyl group. [6] The resin composition according to [5], wherein A in formula (A-1) is a tetravalent group represented by the following formula (X-4): [ka] (In formula (X-4), ring Ar 1 , ring Ar 2 and ring Ar 3 each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. 1 and L 2 each independently represents -O- or an alkylene group having 1 to 4 carbon atoms; nc represents an integer of 0 or more; * represents a bond. [7] The resin composition according to [5] or [6], wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5): [ka] (In formula (A-4), each A independently represents a tetravalent organic group. Xa and Xb independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.) [ka] In formula (A-5), each A independently represents a tetravalent organic group. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of the groups is a hydroxy group or a hydroxycarbonyl group. [8] The resin composition according to [7], wherein the sum (m+n) of m defined in the following formula (1) and n defined in the following formula (2) is 90 to 100, where M is the number of repetitions of the structural unit represented by formula (A-4), N is the number of repetitions of the structural unit represented by formula (A-5), and L is the number of repetitions of the other structural unit, if any.

number

number

[10] The resin composition according to [8] or [9], wherein n=1 to 50.

[11] The resin composition according to any one of [7] to

[10] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1): [ka] [ka]

[12] The resin composition according to any one of [7] to

[10] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-2) and a structural unit represented by the following formula (A-5-1): [ka] [ka]

[13] The resin composition according to any one of [7] to

[10] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-3) and a structural unit represented by the following formula (A-5-2): [ka] [ka]

[14] The resin composition according to any one of [7] to

[10] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-3): [ka] [ka]

[15] The resin composition according to any one of [1] to

[14] , wherein the component (B) is an organic solvent composed of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.

[16] The resin composition according to any one of [1] to

[15] , wherein the component (B) is an ester-based organic solvent.

[17] The resin composition according to any one of [1] to

[15] , wherein the component (B) includes at least one selected from γ-butyrolactone, cyclopentanone, cyclohexanone, propylene glycol, and propylene glycol monomethyl ether acetate.

[18] The resin composition according to any one of [1] to

[17] , further comprising (C) an inorganic filler.

[19] The resin composition according to any one of [1] to

[18] , further comprising (D) a surfactant.

[20] The resin composition according to any one of claims [1] to

[19] , further comprising (E) an adhesion aid.

[21] A semiconductor package substrate comprising an insulating layer formed from a dried product of the resin composition according to any one of [1] to

[20] .

[22] A semiconductor device comprising the semiconductor package substrate according to

[21] .

[23] (I) forming an insulating layer containing a dried product of the resin composition according to any one of [1] to

[20] on a circuit board; (II) forming a photoresist layer on an insulating layer containing a dried resin composition and irradiating the photoresist layer with actinic rays; (III) developing the photoresist layer to form a mask layer; (IV) a step of transferring the photoresist pattern to an underlying insulating layer containing a dried resin composition by dry etching; (V) stripping the photoresist layer; A method for manufacturing a semiconductor package substrate, comprising: [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate, which can be handled as a solution dissolved in an organic solvent, and which has a low linear thermal expansion coefficient, a high glass transition temperature, excellent mechanical properties such as elongation at break and elastic modulus, excellent dielectric properties such as dielectric constant and dielectric loss tangent, and excellent limiting resolution. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating step (I) in one embodiment of a method for manufacturing a semiconductor package substrate. [Figure 2] FIG. 2 is a schematic cross-sectional view illustrating step (II) in one embodiment of the method for manufacturing a semiconductor package substrate. [Figure 3] FIG. 3 is a schematic cross-sectional view illustrating step (III) in one embodiment of the method for manufacturing a semiconductor package substrate. [Figure 4] FIG. 4 is a schematic cross-sectional view illustrating step (IV) in one embodiment of the method for manufacturing a semiconductor package substrate. [Figure 5] FIG. 5 is a schematic cross-sectional view illustrating step (V) in one embodiment of the method for manufacturing a semiconductor package substrate. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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 implemented with any modifications within the scope of the claims and their equivalents.

[0013] In the following description, unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0014] In the following description, "dielectric constant" refers to "relative dielectric constant" unless otherwise specified.

[0015] In the following description, unless otherwise specified, the term "optionally substituted" used in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with substituents and a case where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0016] [Resin composition] The resin composition of the present invention contains (A) a polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure, and (B) an organic solvent.

[0017] By incorporating components (A) and (B) into the resin composition, it is possible to obtain a resin composition that can be handled as a solution dissolved in an organic solvent and has a low linear thermal expansion coefficient, a high glass transition temperature, excellent mechanical properties such as elongation at break and modulus of elasticity, excellent dielectric properties such as dielectric constant and dielectric dissipation factor, and excellent limiting resolution. The resin composition may further contain optional components in addition to components (A) and (B). Examples of optional components include (C) inorganic filler, (D) surfactant, (E) adhesion aid, (F) crosslinking agent, (G) polymerization initiator, and (H) other additives.

[0018] The resin composition is preferably in a varnish form. Being in a varnish form allows the resin composition to be uniformly applied in the manufacturing method of a semiconductor package substrate described below. Furthermore, the resin composition can be made into a varnish by adjusting the content of the component (B) described below.

[0019] Each component contained in the resin composition will be described in detail below.

[0020] <(A) Polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure> The resin composition contains, as component (A), a polyimide polymer having a structure derived from a diamine having an indane structure (A) and a structure derived from a diamine having a hydroxy structure. When component (A) has a structure derived from a diamine having an indane structure, the dielectric loss tangent Df of the dried product can be reduced. When component (A) has a structure derived from a diamine having a hydroxy structure, the polarity of component (A) is increased, thereby improving solubility in organic solvents. Furthermore, component (A) may have a structure derived from a diamine that does not fall into either a diamine having an indane structure or a diamine having a hydroxy structure, as long as the effects of the present invention are not impaired. One type of component (A) may be used alone, or two or more types may be used in combination.

[0021] The indane structure represents a skeleton shown in the following formula (a1-1): The indane structure is preferably a trimethylindane structure shown in the following formula (a1-2). [ka]

[0022] Examples of diamines having an indane structure include diamine (1), diamine (3), and diamines (6) to (12) represented by the following formulae, with diamine (1) or diamine (3) being preferred, and diamine (1) being more preferred. [ka]

[0023] Examples of the hydroxy structure include an alcoholic hydroxy group, a phenolic hydroxy group, and a hydroxycarbonyl group, with a phenolic hydroxy group or a hydroxycarbonyl group being preferred, and a hydroxycarbonyl group being more preferred. Examples of diamines having a hydroxy structure include diamine (2), diamine (4), and diamines (13) to (20) represented by the following formulae, with diamine (2) or diamine (4) being preferred, and diamine (2) being more preferred. [ka]

[0024] Component (A) may have a polyamic acid and / or polyamic acid ester structure in addition to a polyimide structure, as long as the effects of the present invention are not impaired. The polyamic acid and / or polyamic acid ester structure may be present when the imidization reaction does not proceed completely in step (ii) of the <Production Method of Component (A)> described below.

[0025] The component (A) preferably further has a structure derived from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydrides and aromatic tetracarboxylic acid dianhydrides, with aromatic tetracarboxylic acid dianhydrides being preferred.

[0026] Examples of the aliphatic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, and bicyclo[2.2.1]heptane-2-exo-3-exo-5-ene- 6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 2-(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthyl)succinic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Examples of suitable bis(2-aminopropyl)ether include 1,4-butanediol-bis(3-aminopropyl)ether, N,N'-1,4-phenylenebis[octahydro-1,3-dioxo-5-isobenzofurancarboxamide], decahydro-dimethanonaphthalenetetracarboxylic dianhydride, bis[2-(3-aminopropoxy)ethyl]ether, 1,4-butanediol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis(3-aminopropoxy)ethane, triethylene glycol-bis(3-aminopropyl)ether, polyethylene glycol-bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane, and 1,4-butanediol-bis(3-aminopropyl)ether.

[0027] Examples of aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3', Examples of the tetracarboxylic dianhydride include 4,4'-para-terphenyltetracarboxylic dianhydride, 3,3',4,4'-meta-terphenyltetracarboxylic dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, with 4,4'-oxydiphthalic dianhydride or 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride being preferred, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride being more preferred. One type of tetracarboxylic dianhydride may be used alone, or two or more types may be used in combination.

[0028] When the component (A) has a structure derived from a tetracarboxylic dianhydride with an asymmetric structure represented by the following formula (P-1) and a structure derived from a diamine with an asymmetric structure represented by the following formula (Q-1), the structural units of the polyimide polymer may be four types of positional isomers represented by the following formulas (PQ-1) to (PQ-4). [ka]

[0029] In the following description, polyimide polymers may be described using structural formulas. Unless otherwise specified, the expression of any one of formulas (PQ-1) to (PQ-4) is considered to encompass all structures of formulas (PQ-1) to (PQ-4). That is, a "polyimide polymer having a structural unit represented by formula (PQ-1)" means a "polyimide polymer having one or more structural units selected from formulas (PQ-1) to (PQ-4)." In the case of a polyimide polymer having two or more structural units selected from formulas (PQ-1) to (PQ-4), this term also includes polyimide polymers in which the two or more structural units are copolymerized in any of the following ways: random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0030] The component (A) is preferably a polyimide polymer having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3). [ka] (In formula (A-1), each A independently represents a tetravalent organic group.) [ka] (In formula (A-2), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.) [ka] In formula (A-3), X's each independently represent a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of the groups is a hydroxy group or a hydroxycarbonyl group.

[0031] In formula (A-1), each A independently represents a tetravalent organic group. A is preferably a tetravalent organic group having 6 to 40 carbon atoms. The lower limit of the number of carbon atoms in A is more preferably 8 or more, 10 or more, or 12 or more, even more preferably 18 or more or 21 or more, and particularly preferably 24 or more. The upper limit of the number of carbon atoms in the tetravalent organic group is more preferably 36 or less, even more preferably 32 or less, and particularly preferably 28 or less.

[0032] A is preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms.

[0033] A is preferably a tetravalent organic group having an aromatic ring. The term "aromatic ring" refers to a ring conforming to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4r+2 (r is a natural number), and includes monocyclic aromatic rings and fused aromatic rings in which two or more monocyclic aromatic rings are fused. The aromatic ring is preferably a monocyclic aromatic ring. The aromatic ring may be an aromatic carbocycle having only carbon atoms as ring-constituting atoms, or an aromatic heterocycle having heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. The aromatic ring is preferably an aromatic carbocycle. The number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, and even more preferably 6 or more, with the upper limit being preferably 24 or less, more preferably 18 or less or 14 or less, and even more preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0034] Examples of the monocyclic aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a furazan ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a pyridazine ring. Examples of fused aromatic rings in which two or more monocyclic aromatic rings are fused include a naphthalene ring, an anthracene ring, a phenanthrene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a pyridothiazole ring, a benzotriazole ring, an imidazopyridine ring, a triazopyridine ring, a purine ring, etc. As the aromatic ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0035] A is preferably a tetravalent group represented by the following formula (X-4). [ka] (In formula (X-4), ring Ar 1 , ring Ar 2 and ring Ar 3 L each independently represents an aromatic ring which may have a substituent. 1 and L 2 each independently represents a divalent linking group; nc represents an integer of 0 or more; * represents a bond.

[0036] In formula (X-4), ring Ar 1 , ring Ar 2 and ring Ar 3 Each of the rings independently represents an aromatic ring which may have a substituent. Preferred embodiments of the aromatic ring are as described above, and an aromatic carbocyclic ring having 6 to 10 carbon atoms is preferred, a benzene ring or a naphthalene ring is more preferred, and a benzene ring is even more preferred. In addition, the ring Ar 1 , ring Ar 2 and ring Ar3 Examples of the substituent that the aromatic ring in the formula (I) may have include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy groups; halogen-substituted alkyl groups such as trifluoromethyl; cycloalkyloxy groups; aryl groups; arylalkyl groups; monovalent heterocyclic groups; alkylidene groups; amino groups; silyl groups; acyl groups; acyloxy groups; carboxy groups; sulfo groups; cyano groups; nitro groups; mercapto groups; and oxo groups, with alkyl groups being preferred. The above-mentioned substituents may further have a substituent. The substituents may be contained alone or in combination of two or more. When nc is an integer of 2 or more, formula (X-4) contains two or more rings Ar 2 exists, but the two or more rings Ar 2 may be the same or different from each other.

[0037] In formula (X-4), L 1 and L 2 each independently represents a divalent linking group. 1 and L 2 is preferably a divalent group consisting of one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms. 1 and L 2 The upper limit of the number of skeletal atoms in is preferably 3000 or less, 1000 or less, 100 or less, or 50 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less.

[0038] Examples of the divalent linking group include -SO2-, -CO-, -COO-, -O-, -S-, -O-C6H4-O- (wherein -C6H4- represents a phenylene group), -O-C6H4-C(CH3)2-C6H4-O-, and -COO-(CH2). q-OCO- (wherein q represents an integer of 1 to 20), -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO-, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -C(=O)-, -C(=O)-O-, -NR 0 -(where R 0 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and —C(═O)—NR 0 -, etc. H represents a hydrogen atom, C represents a carbon atom, N represents a nitrogen atom, O represents an oxygen atom, S represents a sulfur atom, "-" represents a single bond, and "=" represents a double bond.

[0039] The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 2,2-propylidene group (dimethylmethylene group), and the like. A methylene group or a 2,2-propylidene group is preferred, and a 2,2-propylidene group is more preferred.

[0040] The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms.

[0041] The arylene group and heteroarylene group are preferably an arylene group or heteroarylene group having 6 to 20 carbon atoms, and more preferably an arylene group or heteroarylene group having 6 to 10 carbon atoms.

[0042] L 1 and L 2 The divalent linking group represented by the formula (I) preferably does not contain an aromatic ring.

[0043] Among the above, L 1 and L 2The divalent linking group represented by is preferably -O- or an alkylene group having 1 to 4 carbon atoms, more preferably -O-, a methylene group, or a 2,2-propylidene group, and even more preferably -O- or a 2,2-propylidene group.

[0044] When nc is an integer of 2 or more, formula (X-4) contains two or more L 2 There are two or more L 2 may be the same or different from each other.

[0045] In formula (X-4), nc represents an integer of 0 or more. nc is preferably 1 or more, and more preferably 2 or more. The upper limit of nc is not particularly limited, but may be, for example, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, or 3 or less.

[0046] Examples of A include aromatic groups in which the bond is at the ortho position, and alicyclic aliphatic groups. Examples of such groups include the following groups (i) to (xiii). In the formula, * represents a bond. A is preferably group (ii), group (vii), group (viii), group (ix), group (x), group (xi), or group (xii), more preferably group (ii) or group (ix), and even more preferably group (ix). [ka]

[0047] The tetravalent organic group may have a substituent. Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy groups; halogen-substituted alkyl groups such as trifluoromethyl; cycloalkyloxy groups; aryl groups; arylalkyl groups; monovalent heterocyclic groups; alkylidene groups; amino groups; silyl groups; acyl groups; acyloxy groups; carboxy groups; sulfo groups; cyano groups; nitro groups; mercapto groups; and oxo groups, with alkyl groups being preferred. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituent may be contained alone or in combination of two or more kinds.

[0048] In formula (A-2), Xa and Xb each independently represent a single bond, a group represented by formula (X-1), a group represented by formula (X-2), or a group represented by formula (X-3). Xa and Xb may be bonded to a five-membered ring or a benzene ring.

[0049] Examples of the group represented by formula (X-1) include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

[0050] Examples of the group represented by formula (X-2) include groups represented by the following formulae (2-1) to (2-6). [ka]

[0051] Examples of the group represented by formula (X-3) include groups represented by the following formulae (3-1) to (3-3). [ka]

[0052] Among them, Xa is preferably a group represented by formula (X-1) or a group represented by formula (X-2), more preferably a 1,4-phenylene group or a group represented by formula (2-1), and even more preferably a group represented by formula (2-1). Xb is preferably a single bond or a group represented by formula (X-3), more preferably a single bond or a group represented by formula (3-1), and even more preferably a group represented by formula (3-1).

[0053] In formula (A-2), x represents an integer of 0 to 5. x is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

[0054] In formula (A-3), X's each independently represent a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. The bonding position of X may be any of the ortho-position, meta-position, and para-position based on the position of the bond to other structural units, but from the viewpoint of significantly achieving the effects of the present invention, the meta-position or para-position is preferred.

[0055] The number of carbon atoms in the alkylene group which may have a halogen atom as a substituent is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group, a 1,2-propylene group, a 1,3-propylene group, a 1,1-propylidene group, and a 2,2-propylidene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, or a bromine atom being more preferred, a fluorine atom or a chlorine atom being even more preferred, and a fluorine atom being particularly preferred.

[0056] Examples of the alkylene group having a halogen atom as a substituent include a difluoromethylene group, a tetrafluoroethylene group, a 1,2-difluoroethylene group, and a hexafluoro-2,2-propylidene group.

[0057] The number of carbon atoms in the arylene group is preferably 6 to 15, more preferably 6 to 10, and even more preferably 6. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C6H4-C6H4-).

[0058] Examples of divalent groups formed from these combinations include divalent groups formed from a combination of an ester bond and an alkylene group having 1 to 20 carbon atoms, and divalent groups formed from a combination of an ester bond and an arylene group having 6 to 20 carbon atoms. Examples of such groups include a carbonyloxymethylene group, a carbonyloxyethylene group, a carbonyloxypropylene group, a carbonyloxyphenylene group, a carbonyloxynaphthylene group, and a carbonyloxybiphenylene group.

[0059] Among these, X is preferably an alkylene group having 1 to 3 carbon atoms which may have a halogen atom as a substituent, more preferably a methylene group, a 2,2-propylidene group or a hexafluoro-2,2-propylidene group, still more preferably a methylene group or a hexafluoro-2,2-propylidene group, and still more preferably a methylene group.

[0060] In formula (A-3), Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group. 1 and Y 2 may be the same or different, and are preferably the same. 1 and Y 2 are each independently preferably a hydroxy group or a hydroxycarbonyl group, more preferably a hydroxycarbonyl group. 1 and Y 2 The bonding position of Y may be any of the ortho, meta, and para positions based on the position of the bond to other structural units, but the ortho position is preferred from the viewpoint of significantly achieving the effects of the present invention.1 and Y 2 The bonding position of may be any of the ortho-position, meta-position, and para-position based on the substitution position of X. However, from the viewpoint of significantly obtaining the effects of the present invention, the meta-position or para-position is preferable, and the meta-position is more preferable.

[0061] In formula (A-3), Y 1 and Y 2 At least one of Y is a hydroxy group or a hydroxycarbonyl group. 1 and Y 2 and Y are preferably both a hydroxy group or a hydroxycarbonyl group. 1 and Y 2 More preferably, both of the groups are hydroxycarbonyl groups.

[0062] The structural unit represented by formula (A-1), the structural unit represented by formula (A-2), and the structural unit represented by formula (A-3) may be bonded in any order. The structural unit represented by formula (A-1) is preferably bonded to the structural unit represented by formula (A-2) or the structural unit represented by formula (A-3).

[0063] In addition to the structural units represented by formula (A-1), (A-2), and (A-3), component (A) may contain other structures as long as the effects of the present invention are not impaired. Examples of other structures include polyamic acid and / or polyamic acid ester structures represented by formula (A-6) or (A-7) below, and structures derived from diamines that do not fall into the category of diamines having an indane structure or diamines having a hydroxy structure. The polyamic acid and / or polyamic acid ester structure represented by formula (A-6) or (A-7) below may be present when the imidization reaction does not proceed completely in step (ii) of the <Production Method of Component (A)> described below. [ka] (In formula (A-6) and formula (A-7), each A independently represents a tetravalent organic group. R1 and R 2 each independently represents a hydrogen atom or a monovalent organic group.

[0064] The component (A) is preferably a polyimide polymer having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5). [ka] (In formula (A-4), each A independently represents a tetravalent organic group. Xa and Xb independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) [ka] (In the formula, * represents a bond.) [ka] In formula (A-5), each A independently represents a tetravalent organic group. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of the groups is a hydroxy group or a hydroxycarbonyl group.

[0065] In formula (A-4) and formula (A-5), A each independently represents a tetravalent organic group and is the same as A in formula (A-1).

[0066] In formula (A-4), Xa and Xb each independently represent a single bond, a group represented by formula (X-1), a group represented by formula (X-2), or a group represented by formula (X-3), and are the same as Xa and Xb in formula (A-2).

[0067] In formula (A-4), x represents an integer of 0 to 5 and is the same as x in formula (A-2).

[0068] In formula (A-5), X's each independently represent a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof, and are the same as X's in formula (A-3). The bonding position of X may be any of the ortho-position, meta-position, and para-position based on the bonding position of the nitrogen atom of the polyimide, but is preferably the meta-position or para-position from the viewpoint of significantly achieving the effects of the present invention.

[0069] In formula (A-5), Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of Y in formula (A-5) is a hydroxy group or a hydroxycarbonyl group. 1 and Y 2 is Y in formula (A-3) 1 , and Y 2 is the same as Y 1 and Y 2 The bonding position of Y may be any of the ortho, meta, and para positions based on the bonding position of the nitrogen atom of the polyimide, but the ortho position is preferred from the viewpoint of significantly achieving the effects of the present invention. 1 and Y 2 The bonding position of may be any of the ortho-position, meta-position, and para-position based on the substitution position of X. However, from the viewpoint of significantly obtaining the effects of the present invention, the meta-position or para-position is preferable, and the meta-position is more preferable.

[0070] The structural units represented by formula (A-4) and the structural units represented by formula (A-5) may be bonded in any order, and examples of the bonding form include random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0071] In addition to the structural units represented by formula (A-4) and formula (A-5), component (A) may contain other structures as long as the effects of the present invention are not impaired. Examples of other structures include polyamic acid and / or polyamic acid ester structures represented by formula (A-8), formula (A-9), formula (A-10), or formula (A-11) below, and polyimide structures derived from diamines that do not fall into the category of diamines having an indane structure or diamines having a hydroxy structure. The polyamic acid and / or polyamic acid ester structures represented by formula (A-8), formula (A-9), formula (A-10), or formula (A-11) below may be present when the imidization reaction does not proceed completely in step (ii) of the <Production Method of Component (A)> described below. [ka] (In formula (A-8) and formula (A-9), each A independently represents a tetravalent organic group. Xa and Xb independently represent a single bond, a group represented by formula (X-1) above, a group represented by formula (X-2) above, or a group represented by formula (X-3) above. R 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group, and x represents an integer of 0 to 5. [ka] In formula (A-10) and formula (A-11), each A independently represents a tetravalent organic group. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y 1 and Y 2 At least one of R is a hydroxy group or a hydroxycarbonyl group. 1 and R 2each independently represents a hydrogen atom or a monovalent organic group.

[0072] When the number of repetitions of the structural unit represented by formula (A-4) is M, the number of repetitions of the structural unit represented by formula (A-5) is N, and if other structural units are present, the number of repetitions of the other structural units is L, the sum (m+n) of m defined by the following formula (1) and n defined by the following formula (2) is preferably 90 to 100. When m+n is 90 or more, the heating temperature can be lowered when the resin composition is heated to form an insulating layer.

number

number

[0073] When the component (A) contains a structural unit represented by the above formula (A-8), (A-9), (A-10), or (A-11), the number of repetitions of the structural unit is included in L in the calculation.

[0074] m+n is more preferably 95 or greater, or 96 or greater, even more preferably 97 or greater, and particularly preferably 98 or greater.

[0075] From the viewpoint of reducing the dielectric loss tangent Df of the dried product, m is preferably 50 to 99. The lower limit of m is more preferably 60 or more, further preferably 70 or more or 80 or more, and particularly preferably 85 or more. The upper limit of m is more preferably 95 or less, further preferably 90 or less.

[0076] From the viewpoints of improving the solubility of the polyimide polymer in organic solvents, improving adhesion to substrates, and increasing the glass transition temperature, n is preferably 1 to 50. The lower limit of n is more preferably 5 or more, even more preferably 10 or more, and particularly preferably 15 or more. The upper limit of n is more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less.

[0077] Specific examples of the component (A) include polyimide polymers having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1). [ka] [ka]

[0078] Further, other specific examples of the component (A) include polyimide polymers having a structural unit represented by the following formula (A-4-2) and a structural unit represented by the following formula (A-5-1). [ka] [ka]

[0079] Further, other specific examples of the component (A) include polyimide polymers having a structural unit represented by the following formula (A-4-3) and a structural unit represented by the following formula (A-5-2). [ka] [ka]

[0080] Further, other specific examples of the component (A) include polyimide polymers having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-3). [ka] [ka]

[0081] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight of component (A) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 14,000 or more or 16,000 or more, and particularly preferably 20,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 200,000 or less or 100,000 or less, and particularly preferably 50,000 or less or 30,000 or less. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0082] From the viewpoints of limiting resolution and physical properties of the dried product, the content of component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more, when all components of the resin composition are taken as 100% by mass, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0083] From the viewpoints of limiting resolution and physical properties of the dried product, the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, when the non-volatile components of the resin composition are taken as 100% by mass, and the upper limit is preferably 99.6% by mass or less, more preferably 99% by mass or less or 95% by mass or less, and even more preferably 90% by mass or less or 80% by mass or less.

[0084] From the viewpoints of limiting resolution and physical properties of the dried product, the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more or 70% by mass or more, even more preferably 80% by mass or more, 90% by mass or more, or 95% by mass or more, when the resin component of the resin composition is taken as 100% by mass. The upper limit is preferably 99.9% by mass or less, more preferably 99.8% by mass or less or 99.7% by mass or less, and even more preferably 99.6% by mass or less. The "resin component" refers to non-volatile components other than the inorganic filler described below.

[0085] <Method of manufacturing component (A)> There are no particular restrictions on the method for producing component (A). Component (A) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine.

[0086] The tetracarboxylic dianhydride can be any of the tetracarboxylic dianhydrides described above. The diamine can be any of the diamines (1) to (20) described above. In addition, when component (A) also has a structure derived from a diamine that does not fall into either a diamine having an indane structure or a diamine having a hydroxy structure, diamines represented by the following formulas (1a) to (20a) can also be used. [ka]

[0087] Specifically, for example, component (A) is (i) a step of charging a diamine, a tetracarboxylic dianhydride, and an organic solvent into a reaction vessel and heating the mixture; (ii) adding a solvent that forms an azeotrope with water to the reaction vessel and heating and refluxing; The composition can be produced by a production method including the steps of:

[0088] In step (i), a diamine and a tetracarboxylic dianhydride are reacted to produce a polyamic acid. The organic solvent used in step (i) is preferably an ester-based organic solvent, more preferably a lactone-based organic solvent, and particularly preferably γ-butyrolactone. In step (i), for example, a separable flask can be used as a reaction vessel, and an oil bath can be used for heating. The heating temperature is preferably 50 to 55°C, and the heating time is preferably 15 to 20 hours.

[0089] In step (ii), a polyimide polymer is produced by the imidization reaction of the polyamic acid produced in step (i). By adding a solvent that forms an azeotrope with water in step (ii), the water produced by the imidization reaction can be removed from the reaction system by azeotropy, allowing the imidization reaction to proceed effectively. The reaction temperature in step (ii) is preferably 150 to 180°C, and the heating time is preferably 5 to 8 hours. Examples of solvents that form an azeotrope with water include toluene and benzene, and toluene is preferred.

[0090] The reaction in step (ii) may be carried out without a catalyst, but it is preferable to add a base catalyst or an acid catalyst. The addition of a catalyst can increase the yield of the imidization reaction, resulting in a dried product with better dielectric properties. The amount of catalyst added is preferably 0.1 to 5% by mass, where the total amount of the diamine and tetracarboxylic dianhydride is taken as 100% by mass.

[0091] Examples of base catalysts include pyridine, triethylamine, tributylamine, N,N-dimethylaminopyridine (DMAP), N-methylimidazole (MIMZ), etc. Examples of acid catalysts include acetic acid, oxalic acid, benzoic acid, 3,5-dihydroxybenzoic acid, etc., with benzoic acid being preferred.

[0092] <(B) Organic solvent> The resin composition contains an organic solvent (B) as component (B). Component (B) may be used singly or in combination of two or more. Examples of component (B) include organic solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From the viewpoint of safety, component (B) is preferably an organic solvent composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably an organic solvent composed of carbon, oxygen, and hydrogen atoms.

[0093] Examples of component (B) include glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, amide-based organic solvents, urea-based organic solvents, sulfur-based organic solvents, etc. From the viewpoint of safety, component (B) is preferably an ester-based organic solvent, ketone-based organic solvent, glycol-based organic solvent, glycol ether-based organic solvent, or glycol ether ester-based organic solvent, and more preferably an ester-based organic solvent.

[0094] Examples of glycol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol.

[0095] Examples of glycol ether organic solvents include cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monoethyl ether ( carbitols such as diethylene glycol monopropyl ether (also known as propyl carbitol) and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers such as propylene glycol monomethyl ether (PGM), propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; and dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.

[0096] Examples of glycol ether ester organic solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), and ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate); carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate.

[0097] Examples of ketone organic solvents include aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone, and 2-methylcyclohexanone; and aromatic ketones such as acetophenone.

[0098] Ester-based organic solvents are organic solvents having an ester structure that do not fall under the category of glycol ether ester-based organic solvents, and examples thereof include fatty acid alkyl esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; hydroxy acid alkyl esters such as methyl lactate, ethyl lactate, and butyl lactate; keto acid alkyl esters such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents.

[0099] Ether-based organic solvents are organic solvents having an ether structure that do not fall under the category of glycol ether-based organic solvents or glycol ether ester-based organic solvents, and examples thereof include aliphatic acyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenetole.

[0100] Alcohol-based organic solvents are organic solvents having an alcohol structure that does not fall under the category of glycol-based organic solvents and glycol ether-based organic solvents, and examples thereof include aliphatic acyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, sec-pentyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, and 2-ethylhexyl alcohol; aliphatic cyclic alcohols such as cyclohexanol; and aromatic alcohols such as benzyl alcohol and phenethyl alcohol.

[0101] Examples of aliphatic hydrocarbon organic solvents include n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

[0102] Examples of aromatic organic solvents include C benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. 6-8 Aromatic hydrocarbons: C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, and 2-ethyltoluene; C1 aromatic hydrocarbons such as 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, and 1,2,3,5-tetramethylbenzene 10 Examples thereof include aromatic hydrocarbons; aromatic heterocyclic compounds such as pyridine, furan, and thiophene.

[0103] Examples of amide-based organic solvents include aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide; lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; and phosphoric acid amides such as hexamethylphosphoramide.

[0104] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0105] An example of the sulfur-based organic solvent is dimethyl sulfoxide.

[0106] Among these, γ-butyrolactone, cyclopentanone, cyclohexanone, propylene glycol, or propylene glycol monomethyl ether acetate is preferred, and γ-butyrolactone is more preferred.

[0107] In order to obtain a varnish having an appropriate viscosity from the resin composition, the content of component (B) is preferably 10% by mass or more, more preferably 20% by mass or more or 30% by mass or more, even more preferably 40% by mass or more or 50% by mass or more, and particularly preferably 60% by mass or more, when the total amount of all components in the resin composition is 100% by mass. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0108] From the viewpoint of significantly obtaining the effects of the present invention, the total content of the (A) component and the (B) component in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more or 30% by mass, even more preferably 40% by mass or more or 50% by mass or more, and particularly preferably 60% by mass or more, 70% by mass or more, or 80% by mass or more, when all components of the resin composition are taken as 100% by mass.

[0109] From the viewpoint of obtaining a varnish having an appropriate viscosity from the resin composition, the mass ratio of component (B) to component (A) [component (B) / component (A)] is preferably 0.5 or more, more preferably 1.0 or more or 1.5 or more, and even more preferably 2.0 or more or 2.5 or more. The upper limit is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 4 or less.

[0110] <(C) Inorganic filler> The resin composition may contain an inorganic filler (C) as an optional component. The inorganic filler (C) is usually contained in the resin composition in the form of particles. By including the component (C) in the resin composition, the linear thermal expansion coefficient of the dried product can be further reduced and the glass transition temperature can be further increased.

[0111] Inorganic compounds can be used as the (C) inorganic filler material. Examples of (C) inorganic fillers include silica, alumina, aluminosilicate, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0112] (C) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," "SO-C1," "SC2300-SVJ," "SC2050-SXF," and "180nmSX-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "CellSpheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0113] The average particle size of the (C) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less or 0.5 μm or less. The lower limit of the average particle size of the (C) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.15 μm or more or 0.2 μm or more. The average particle size of the (C) inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used 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 the mixture ultrasonically for 10 minutes. The wavelength of the light source used in the laser diffraction particle size distribution analyzer can be blue or red, and the measurement can be performed using a flow cell system. Examples of the laser diffraction particle size distribution analyzer include the "LA-960" manufactured by Horiba, Ltd.

[0114] The specific surface area of the (C) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more or 3m 2 / g or more, particularly preferably 5m 2 / g or more, 10m 2 / g or more or 15m 2 The upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 / g or less or 30m 2 The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0115] The inorganic filler (C) is preferably surface-treated with a surface treatment agent, which can improve the moisture resistance and dispersibility of the inorganic filler (C).Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; 3-methyltriethoxysilane; Methacrylic silane coupling agents such as acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane amino-based silane coupling agents such as 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; 3-ureidopropyltrialkoxysilane, etc. ureido-based silane coupling agents such as mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; silane coupling agents such as acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; non-silane coupling alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane. The surface treatment agent may be used alone or in combination of two or more in any ratio.

[0116] The (C) inorganic filler more preferably contains an inorganic filler that has been surface-treated with a surface treatment agent selected from a vinyl silane coupling agent and an amino silane coupling agent, and particularly preferably contains an inorganic filler that has been surface-treated with an amino silane coupling agent.

[0117] When the resin composition contains (C) an inorganic filler, the content of component (C) is 0% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, when the total amount of all components in the resin composition is 100% by mass, from the viewpoint of further reducing the linear thermal expansion coefficient of the dried product. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less, even more preferably 15% by mass or less, or 12% by mass or less, and particularly preferably 10% by mass or less.

[0118] When the resin composition contains (C) an inorganic filler, the content of component (C) is, from the viewpoint of further reducing the linear thermal expansion coefficient of the dried product, 0% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more or 5% by mass or more, and even more preferably 10% by mass or more or 20% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less or 50% by mass or less, and even more preferably 40% by mass or less or 30% by mass or less.

[0119] When the resin composition contains an inorganic filler (C), the total content of the components (A), (B), and (C) in the resin composition is, from the viewpoint of significantly obtaining the effects of the present invention, preferably 15% by mass or more, more preferably 20% by mass or more or 30% by mass, even more preferably 40% by mass or more or 50% by mass or more, and particularly preferably 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, when all components of the resin composition are taken as 100% by mass.

[0120] When the resin composition contains an inorganic filler (C), from the viewpoint of further reducing the linear thermal expansion coefficient of the dried product, the mass ratio of component (C) to component (A) [component (C) / component (A)] has a lower limit of 0 or more, preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more. The upper limit is preferably 2 or less, more preferably 1 or less or 0.8 or less, and even more preferably 0.6 or less or 0.4 or less.

[0121] <(D) Surfactant> The resin composition may contain (D) a surfactant as an optional component. However, component (D) excludes components (A) to (C). By including component (D) in the resin composition, a more uniform coating film can be formed when the resin composition is applied.

[0122] The (D) surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, polyether-based surfactants, and poly(meth)acrylate-based surfactants. Among these, polyether-based surfactants are preferred as the (D) component. The (D) surfactants may be used alone or in combination of two or more.

[0123] Examples of the fluorosurfactant include fluorosurfactants composed of a compound having a fluoroalkyl group or a fluoroalkylene chain at least at any one of the terminal, main chain, and side chain. Specific examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis(1,1,2,2-tetrafluoropentyl) ether, hexa ... perfluoroalkyl-N-ethylsulfonylglycine salts, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl)phosphate, and monoperfluoroalkylethyl phosphate esters.

[0124] Commercially available fluorine-based surfactants include "Megafac (registered trademark) F-142D", "Megafac (registered trademark) F-172", "Megafac (registered trademark) F-173", "Megafac (registered trademark) F-183", "Megafac (registered trademark) F-444", "Megafac (registered trademark) F-445", "Megafac (registered trademark) F-470", "Megafac (registered trademark) F-475", "Megafac (registered trademark) F-477", "Megafac (registered trademark) F-555", and "Megafac (registered trademark) F-559" (all trade names, manufactured by DIC Corporation), "Ftop (registered trademark) EF301", "Ftop (registered trademark) 303", and "Ftop (registered trademark) 352" (all trade names, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), "Florald (registered trademark) FC-430", "Florald (registered trademark) FC-431" (all trade names, manufactured by Sumitomo 3M Limited), and "Asahiguard (registered trademark) Examples of such polyolefin resins include "AG710" (trade name, manufactured by Asahi Glass Co., Ltd.), "Surflon (registered trademark) S-382", "Surflon (registered trademark) SC-101", "Surflon (registered trademark) SC-102", "Surflon (registered trademark) SC-103", "Surflon (registered trademark) SC-104", "Surflon (registered trademark) SC-105", and "Surflon (registered trademark) SC-106" (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.), "BM-1000", "BM-1100" (all trade names, manufactured by Yusho Co., Ltd.), "NBX-15", "FTX-218", and "DFX-218" (all trade names, manufactured by Neos Corporation).

[0125] Commercially available silicone surfactants include, for example, "SH28PA," "SH7PA," "SH21PA," "SH30PA," and "ST94PA" (all trade names, manufactured by Dow Corning Toray Co., Ltd.), "BYK-301," "BYK-307," "BYK-331," "BYK-333," and "BYK-345" (all trade names, manufactured by BYK-Chemie Japan K.K.).

[0126] Commercially available polyether surfactants include, for example, "KP-341," "KP-360A," "KP-101," "KP-106," "KP-109," "KP-110," "KP-112," "KP-118," "KP-120," "KP-121," "KP-124," "KP-125," "KP-126," "KP-301," and "KP-306" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), with "KP-341" being preferred.

[0127] When the resin composition contains a surfactant (D), the content of the component (D) is, from the viewpoint of forming a more uniform coating film when the resin composition is applied, 0% by mass or more, preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more or 0.0015% by mass or more, and particularly preferably 0.002% by mass or more, when the total components of the resin composition is taken as 100% by mass. The upper limit is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably 0.005% by mass or less.

[0128] When the resin composition contains a surfactant (D), the content of the component (D) is, from the viewpoint of forming a more uniform coating film when the resin composition is applied, 0% by mass or more, preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more or 0.003% by mass or more, particularly preferably 0.005% by mass or more or 0.006% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, particularly preferably 0.009% by mass or less or 0.008% by mass or less.

[0129] When the resin composition contains a surfactant (D), the content of the component (D) is, from the viewpoint of forming a more uniform coating film when the resin composition is applied, 0% by mass or more, preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more or 0.003% by mass or more, particularly preferably 0.005% by mass or more or 0.007% by mass or more, based on 100% by mass of the resin components of the resin composition. The upper limit is preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0130] When the resin composition contains a surfactant (D), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the lower limit of the mass ratio of the component (D) to the component (A) [component (D) / component (A)] is preferably 10 -5 More preferably, 2×10 -5 More preferably, 5 × 10 -5 The upper limit is preferably 10 -2 Less than or equal to 10, more preferably -3 Less than 5 × 10, more preferably -4 Below 2 × 10, particularly preferably -4 The following is the result.

[0131] <(E) Adhesion aid> The resin composition may contain an adhesion aid (E) as an optional component. However, the components (A) to (D) are excluded from the component (E). By including the adhesion aid (E) in the resin composition, the adhesive strength between the substrate and the dried resin composition can be improved. The component (E) may be used alone or in combination of two or more.

[0132] As the adhesion promoter (E), a compound that improves the adhesive strength between the substrate and the insulating layer formed using the resin composition can be used. Examples of such compounds include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, and benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,5-Dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3- Mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2- Mercaptoethyl tripropoxysilane, 2-mercaptoethyl tripropoxysilane, 2-mercaptoethyl ethoxydipropoxysilane, 2-mercaptoethyl dimethoxypropoxysilane, 2-mercaptoethyl methoxydipropoxysilane, 4-mercaptobutyl trimethoxysilane, 4-mercaptobutyl triethoxysilane, 4-mercaptobutyl tripropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, aminotriazine ring and ethoxysilyl Silane coupling agents such as compounds having a hydroxyl group; aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate; 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1H-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 3,5-diphenyl-1,2,Examples of the adhesion aid include triazole-based adhesion aids such as 4-triazole. Among these, the adhesion aid (E) is preferably a silane coupling agent or a triazole-based adhesion aid, and more preferably a triazole-based adhesion aid. Furthermore, among the triazole-based adhesion aids, 3,5-diamino-1,2,4-triazole is preferred.

[0133] (E) The adhesion aid may be a commercially available product. Examples of commercially available products include "KBM403" (3-glycidoxypropyltriethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "LS1375" (3-mercaptopropylmethyldimethoxysilane), and "LS3610" (N-(3-triethoxysilylpropyl)urea) manufactured by Shin-Etsu Chemical Co., Ltd.; "Sila-Ace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; and "SIM6475.0" (3-mercaptopropyltriethoxysilane) and "SIM6474.0" manufactured by Azmax Corporation. " (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea); "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Chemical Industry Co., Ltd.; and 3,5-diamino-1,2,4-triazole manufactured by Tokyo Chemical Industry Co., Ltd.

[0134] When the resin composition contains an adhesion aid (E), the content of the component (E) is 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, when the total amount of all components in the resin composition is 100% by mass, from the viewpoint of improving the adhesion strength between the substrate and the dried product of the resin composition. The upper limit is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less.

[0135] When the resin composition contains an adhesion aid (E), the content of the component (E) is, from the viewpoint of improving the adhesive strength between the substrate and the dried resin composition, 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.4% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.6% by mass or less.

[0136] When the resin composition contains an adhesion aid (E), the content of the component (E) is, from the viewpoint of improving the adhesive strength between the substrate and the dried resin composition, 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.4% by mass or more, when the nonvolatile components of the resin composition are taken as 100% by mass. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.6% by mass or less.

[0137] <(F) Crosslinking agent> The resin composition may optionally contain a crosslinking agent (F). However, the component (F) does not include components (A) to (E). By including the crosslinking agent (F) in the resin composition, when the resin composition is dried to form an insulating layer, radicals are generated from the thermal radical polymerization initiator (described below), which promotes the crosslinking reaction of the crosslinking agent (F), thereby further improving the mechanical strength and chemical stability of the dried resin composition. Furthermore, when the dried resin composition is irradiated with actinic rays, radicals are generated from the photoradical polymerization initiator (described below) upon exposure to the actinic rays, which promotes the crosslinking reaction of the crosslinking agent (F), thereby further improving the mechanical strength and chemical stability of the dried resin composition. The component (F) may be used alone or in combination of two or more.

[0138] As component (F), a compound capable of causing a crosslinking reaction to proceed upon heating or irradiation with actinic rays can be used. The lower limit of the number of reactive sites that cause a crosslinking reaction per molecule of component (F) (hereinafter sometimes referred to as the "number of functional groups") is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit of the number of functional groups is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less or 4 or less. Examples of functional groups include an ethylenically unsaturated bond, an epoxy group, a hydroxyl group, an amino group, a cyano group, a carboxyl group, and a formyl group, with an ethylenically unsaturated bond or an epoxy group being preferred.

[0139] Component (F) is more preferably a compound having an ethylenically unsaturated bond, and even more preferably a compound having an ethylenically unsaturated bond in which at least one carbon atom at the α-position of the ethylenically unsaturated bond is a carbon atom of a carbonyl group or a carbon atom of an aromatic group. The carbon atom at the α-position of the ethylenically unsaturated bond refers to the first carbon atom adjacent to the carbon atom bonded by the carbon-carbon double bond.

[0140] An ethylenically unsaturated bond refers to a carbon-carbon double bond. Therefore, component (F) contains a group having an ethylenically unsaturated bond (hereinafter, occasionally referred to as an "ethylenically unsaturated group"). The ethylenically unsaturated group is typically a monovalent group, such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, or a (meth)acryloyl group. From the viewpoint of radical polymerization reactivity, a (meth)acryloyl group or a phenylethynyl group is preferred, a (meth)acryloyl group is more preferred, and a methacryloyl group is even more preferred. The term "(meth)acryloyl group" encompasses a methacryloyl group, an acryloyl group, and a combination thereof. Because component (F) contains an ethylenically unsaturated bond, it is capable of radical polymerization. However, for radical polymerization under general conditions, a compound having a carbonyl group or an aromatic group at at least one α-position of the ethylenically unsaturated bond is preferred. The lower limit for the number of ethylenically unsaturated bonds per molecule of component (F) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and the upper limit is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less or 4 or less. Furthermore, when component (F) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

[0141] The component (F) is preferably a compound represented by the following formula (B-1). [ka] (In the formula, R 1b each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; Z 1b each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom; A 1b represents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms, where nb represents an integer of 2 to 6.

[0142] R 1b are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group. Among these, R 1b is preferably a hydrogen atom or a methyl group.

[0143] Z 1b each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom.

[0144] As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferred, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferred. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, with a methylene group being preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 20. [ka]

[0145] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 12 carbon atoms. Examples of such arylene groups include a phenylene group and a naphthylene group. The arylene group may also contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 4. [ka]

[0146] As the linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, a linear or branched alkenylene group having 2 to 10 carbon atoms is preferred, and a linear or branched alkenylene group having 2 to 6 carbon atoms is more preferred. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 10. The alkenylene group is preferably a propenylene group. [ka]

[0147] Among them, Z 1b As the alkyl group, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferred, and a methylene group is more preferred.

[0148] A 1brepresents a linear, cyclic, or branched nb-valent organic group having 1 to 10 carbon atoms. Examples of the nb-valent organic group include an nb-valent hydrocarbon group which may contain an oxygen atom, an nb-valent group derived from bisphenol, an nb-valent group derived from fluorene, an nb-valent group derived from tricyclodecane, and an nb-valent group derived from an isocyanuric group. Examples of the nb-valent hydrocarbon group which may contain an oxygen atom include an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom, and an nb-valent aromatic hydrocarbon group which may contain an oxygen atom, with an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom being preferred. A 1b Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0149] nb represents an integer of 2 to 6, preferably an integer of 3 to 6, more preferably an integer of 3 to 5, further preferably 3 or 4, and particularly preferably 3.

[0150] The component (F) is preferably a compound represented by the following formula (B-2). [ka] (In the formula, R 2b each independently represents a hydrogen atom or a methyl group.

[0151] R 2b represents a hydrogen atom or a methyl group, and a methyl group is preferred.

[0152] Specific examples of the component (F) include the following compounds (CL-1) to (CL-13), and the component (F) is preferably the compound (CL-1), the compound (CL-2), or the compound (CL-12), although the component (F) is not limited to these. [ka] [ka] [ka]

[0153] The compound having an ethylenically unsaturated bond may be a commercially available product, such as NK Ester D-TMP, TMPT, A-TMPT, 4G, 9G, 14G, 23G, or DCP manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., or SR209, CN2301, or CN2304 manufactured by Sartomer Japan.

[0154] From the viewpoints of the limiting resolution of the resin composition and the mechanical strength of the cured product of the resin composition, the component (F) is preferably a crosslinking agent having two or more epoxy groups. Examples of such crosslinking agents include aromatic epoxy compounds such as bixylenol-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, bisphenol AF-type epoxy compounds, trisphenol-type epoxy compounds, naphthol novolac-type epoxy compounds, phenol novolac-type epoxy compounds, tert-butyl-catechol-type epoxy compounds, naphthalene-type epoxy compounds, naphthol-type epoxy compounds, anthracene-type epoxy compounds, cresol novolac-type epoxy compounds, biphenyl-type epoxy compounds, and naphthylene ether-type epoxy compounds; aliphatic epoxy compounds such as epoxy compounds having a butadiene structure, cyclohexane-type epoxy compounds, cyclohexanedimethanol-type epoxy compounds, trimethylol-type epoxy compounds, and tetraphenylethane-type epoxy compounds; alicyclic epoxy compounds; heterocyclic epoxy compounds; glycidyl ether-type epoxy compounds; and glycidylamine-type epoxy compounds. Among these, aromatic epoxy compounds are preferred from the viewpoint of achieving the effects of the present invention more significantly, and among aromatic epoxy compounds, naphthalene-type epoxy compounds are preferred.

[0155] Specific examples of aromatic epoxy compounds include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy compounds) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; and "ZX105" manufactured by Nippon Steel Chemical & Material Co., Ltd. 9 (a mixture of bisphenol A and bisphenol F epoxy compounds); DIC's "HP4032H" (a naphthalene-type epoxy compound); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy compounds); DIC's "N-690" (a cresol novolac-type epoxy compound); DIC's "N-695" (a cresol novolac-type epoxy compound); Nippon Kayaku's "EPPN-502H" (a trisphenol-type epoxy compound); Nippon Kayaku's "NC7000L" " (naphthol novolac type epoxy compound); "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy compounds) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6121" (biphenyl type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX4000H", "YX4000", and "YX4000HK" manufactured by Mitsubishi Chemical Corporation (bixylenol-type epoxy compound); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene-type epoxy compound); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF-type epoxy compound); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene-type epoxy compound); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A-type epoxy compound); and "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane-type epoxy compound).

[0156] The epoxy equivalent of the crosslinking agent having two or more epoxy groups is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. Within this range, the crosslink density of the cured product of the epoxy resin composition is sufficient, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0157] From the viewpoint of significantly achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of the crosslinking agent having two or more epoxy groups is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0158] In addition to the above-mentioned compounds having an ethylenically unsaturated bond and crosslinking agents having two or more epoxy groups, component (F) may also be nitrogen-containing compounds containing an average of two or more methylol groups and / or alkoxymethyl groups per molecule, such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds, as well as condensates thereof, and phenol compounds containing an average of two or more methylol groups or alkoxymethyl groups per molecule.

[0159] When the resin composition contains a crosslinking agent (F), the content of the component (F) is, from the viewpoint of significantly achieving the effects of the present invention, 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, 2% by mass or more, or 3% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 20% by mass or less, more preferably 18% by mass or less, 16% by mass or less, even more preferably 14% by mass or less, 12% by mass or less, or 10% by mass or less, and particularly preferably 8% by mass or less, 6% by mass or less, or 4% by mass or less.

[0160] When the resin composition contains a (F) crosslinking agent, from the viewpoint of significantly achieving the effects of the present invention, the lower limit of the mass ratio of the (F) component to the (A) component [(F) component / (A) component] is 0 or more, preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.03 or more. The upper limit is preferably 1 or less, 0.2 or less, more preferably 0.17 or less or 0.15 or less, even more preferably 0.1 or less or 0.05 or less, and particularly preferably 0.04 or less.

[0161] <(G) Polymerization initiator> The resin composition may contain a polymerization initiator (G) as an optional component. However, the component (G) excludes components (A) to (F). By including the polymerization initiator (G) in the resin composition, when the resin composition is dried to form an insulating layer or when the dried resin composition is irradiated with actinic rays, the polymerization initiator reacts with the crosslinking agent (F) to further improve the mechanical strength and chemical stability of the dried resin composition. The component (G) may be used alone or in combination of two or more.

[0162] (G) Examples of the polymerization initiator include a photoradical polymerization initiator and a thermal radical polymerization initiator.

[0163] Examples of the photoradical polymerization initiator include an intramolecular cleavage-type photoradical polymerization initiator and a hydrogen abstraction-type photoradical polymerization initiator, with the intramolecular cleavage-type photoradical polymerization initiator being preferred. The intramolecular cleavage-type photoradical polymerization initiator is a type of photoradical polymerization initiator that generates radicals by intramolecular cleavage, and the hydrogen abstraction-type photoradical polymerization initiator is a type of photoradical polymerization initiator that generates radicals by exchanging hydrogen or electrons between two molecules.

[0164] Examples of the intramolecular cleavage type photoradical polymerization initiator include an α-aminoketone-based photoradical polymerization initiator, a phosphine oxide-based photoradical polymerization initiator, an α-hydroxyketone-based photoradical polymerization initiator, an oxime ester-based photoradical polymerization initiator, a benzyl-based photoradical polymerization initiator, a benzyl ketal-based photoradical polymerization initiator, a benzoin-based photoradical polymerization initiator, a peroxide-based photoradical polymerization initiator, and a titanocene-based photoradical polymerization initiator. From the viewpoint of photosensitivity, an oxime ester-based photoradical polymerization initiator is preferred.

[0165] Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone-based photoradical polymerization initiators, acetophenone-based photoradical polymerization initiators, thioxanthone-based photoradical polymerization initiators, and aromatic bisimidazole-based photoradical polymerization initiators.

[0166] Examples of the α-aminoketone-based photoradical polymerization initiator include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and N-phenylglycine.

[0167] Examples of phosphine oxide-based photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L).

[0168] Examples of the α-hydroxyketone-based photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0169] Examples of the oxime ester-based photoradical polymerization initiator include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02), 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-1 , 2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, etc., and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01) or [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) is preferred.

[0170] Examples of the benzyl-based photoradical polymerization initiator include benzyl.

[0171] Examples of the benzyl ketal-based photoradical polymerization initiator include benzyl dimethyl ketal (2,2-dimethoxy-2-phenylacetophenone) and benzyl-β-methoxyethyl acetal.

[0172] Examples of the benzoin-based photoradical polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0173] Examples of the peroxide-based photoradical polymerization initiator include benzoyl perchloride.

[0174] Examples of the titanocene-based photoradical polymerization initiator include bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanocene.

[0175] Examples of the benzophenone-based photoradical polymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone.

[0176] Examples of the acetophenone-based photoradical polymerization initiator include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0177] Examples of the thioxanthone-based photoradical polymerization initiator include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone.

[0178] Examples of aromatic bisimidazole-based photoradical polymerization initiators include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

[0179] Commercially available photoradical polymerization initiators can be used, including, for example, "Irgacure-OXE01," "Irgacure-OXE02," "Irgacure-OXE04," and "IrgacureTPO" manufactured by BASF, "Omnirad907," "Omnirad369," "Omnirad379," "Omnirad379EG," "Omnirad819," and "OmniradTPO" manufactured by IGM, and "N-1919" manufactured by ADEKA.

[0180] From the viewpoint of obtaining a cured product with excellent adhesion, the thermal radical polymerization initiator preferably has a one-hour half-life temperature of 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. The upper limit is preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 180°C or lower. The one-hour half-life indicates the time it takes for the amount of the thermal radical polymerization initiator to be reduced to half, which is one hour, and the one-hour half-life temperature indicates the decomposition temperature of the thermal radical polymerization initiator at which the one-hour half-life is obtained.

[0181] The thermal radical polymerization initiator may be a compound capable of generating radicals upon heating, such as a peroxide-based thermal radical polymerization initiator, an azo compound-based thermal radical polymerization initiator, a persulfate compound-based thermal radical polymerization initiator, or a redox-based thermal radical polymerization initiator.

[0182] Examples of the peroxide-based thermal radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide; tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, and 1,4-bis(1-tert-butyl) dialkyl peroxide compounds such as 2,5-dimethyl-2,5-di(tert-butylperoxy-1-methylethyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,2-di(tert-butylperoxy)butane, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, and 2,3-dimethyl-2,3-diphenylbutane; dilauroyl peroxide diacyl peroxide compounds such as didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl) peroxydicarbonate; tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, and tert- Examples of the peroxyester compounds include hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-butylperoxymaleic acid, and n-butyl-4,4-di(tert-butylperoxy)valerate.

[0183] The peroxide-based thermal radical polymerization initiator is preferably either a hydroperoxide compound or a dialkyl peroxide compound, and more preferably a dialkyl peroxide compound.

[0184] Examples of the azo compound-based thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 1,1'-azobis(cyclohexanecarbonitrile), and dimethyl-2,2'-azobisisobutyrate, with 2,2'-azobisisobutyronitrile being preferred.

[0185] Examples of the persulfate compound-based thermal radical polymerization initiator include potassium persulfate.

[0186] Commercially available thermal radical initiators can be used. Examples of commercially available thermal radical initiators include "Perhexyl I", "Perbutyl 355", "Perbutyl L", "Perbutyl I", "Perbutyl E", "Perhexyl Z", "Perhexa 25Z", "Perbutyl A", "Perhexa 22", "Perbutyl Z", "Perhexa V", "Perbutyl P", "Percumyl D", "Perhexyl D", "Perhexa 25B", "Perbutyl C", "Perbutyl D", "Permenta H", "Perhexyne 25B", "Percumyl P", "Perocta H", "Percumyl H", "Perbutyl H", and "Nofumer BC", all manufactured by NOF Corporation.

[0187] When the resin composition contains a (G) polymerization initiator, the content of the (G) component is, from the viewpoint of significantly achieving the effects of the present invention, 0% by mass or more, preferably 0.01% by mass or more or 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, when the non-volatile components of the resin composition are taken as 100% by mass. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0188] <(H) Other Additives> The resin composition may further contain (H) other additives to the extent that the object of the present invention is not impaired. Examples of (H) other additives include thermoplastic resins; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters; and curing agents such as phenolic curing agents and cyanate ester-based curing agents. Furthermore, the components (A) to (G) may also function as thermoplastic resins, colorants, polymerization inhibitors, thickeners, defoamers, flame retardants, or curing agents. In this case, the component in question is considered to be one of components (A) to (G), not component (H).

[0189] <Method of manufacturing resin composition> The resin composition can be produced by mixing the essential components (A) and (B) and the optional components (C) to (H), and kneading or stirring the mixture, if necessary, using a kneading device such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or a stirring device such as a super mixer or a planetary mixer.

[0190] Alternatively, the resin composition may be prepared by mixing the above-mentioned components (A) and (B) to prepare a resin composition (hereinafter, the resin composition prepared by mixing the components (A) and (B) is referred to as a "polyimide varnish"), and then adding optional components (C) to (H) to the polyimide varnish as necessary. Alternatively, the polyimide varnish may be used as a resin composition directly without adding components (C) to (H).

[0191] The component (A) of the present invention is highly soluble in the organic solvent (B), and precipitates are unlikely to form even if the polyimide varnish is stored for a long period after preparation. Therefore, the components (C) to (H) can be added to a polyimide varnish that has been stored for a long period after preparation to prepare a resin composition.

[0192] <Physical properties and applications of resin compositions> In one embodiment, the resin composition of the present invention exhibits the property that it can be handled as a solution dissolved in an organic solvent. The time until a precipitate forms when the polyimide varnish is stored at 5°C is preferably 10 hours or more, more preferably 1 month or more. The upper limit is not particularly limited, but it can be within 1 year, for example. The time until a precipitate forms when the polyimide varnish is stored at 5°C can be measured according to the method described in the Examples below.

[0193] In one embodiment, the dried resin composition of the present invention exhibits a low coefficient of linear thermal expansion. The coefficient of linear thermal expansion (ppm / °C) in the planar direction in the temperature range of 25°C to 150°C is preferably 83 ppm / °C or less, more preferably 65 ppm / °C or less, even more preferably 60 ppm / °C or less or 50 ppm / °C or less, and particularly preferably 40 ppm / °C or less. The lower limit is not particularly limited, but may be 1 ppm / °C or more, or 10 ppm / °C or more, for example. The coefficient of linear thermal expansion can be measured according to the method described in the Examples below.

[0194] In one embodiment, the dried product of the resin composition of the present invention exhibits the characteristic of a high glass transition temperature. The glass transition temperature is preferably 181°C or higher, more preferably 185°C or higher, even more preferably 190°C or higher or 195°C or higher, and particularly preferably 200°C or higher, 205°C or higher, or 210°C or higher. The upper limit is not particularly limited, but may be 300°C or lower, for example. The glass transition temperature can be measured according to the method described in the Examples below.

[0195] In one embodiment, the dried resin composition of the present invention exhibits a high elongation at break. The elongation at break at 25°C is preferably 5% or more, more preferably 20% or more, 30% or more, or 35% or more, even more preferably 40% or more, 45% or more, and particularly preferably 50% or more. The upper limit is not particularly limited, but may be 200% or less. The elongation at break can be measured according to the method described in the Examples below.

[0196] In one embodiment, the dried product of the resin composition of the present invention exhibits a high modulus of elasticity. The modulus of elasticity at 25°C is preferably 1.8 GPa or more, more preferably 2.0 GPa or more or 2.2 GPa or more, even more preferably 2.4 GPa or more, and particularly preferably 2.6 GPa or more. The upper limit is not particularly limited, but may be 10 GPa or less, for example. The modulus of elasticity can be measured according to the method described in the Examples below.

[0197] In one embodiment, the dried resin composition of the present invention exhibits a low dielectric constant (Dk). The dielectric constant at 23°C is preferably less than 3.0, more preferably less than 2.9 or less than 2.8, even more preferably less than 2.7, and particularly preferably less than 2.6. The lower limit is not particularly limited, but may be 1.0 or more. The dielectric constant can be measured according to the method described in the Examples below.

[0198] In one embodiment, the dried product of the resin composition of the present invention exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent at 23°C is preferably 0.01 or less, more preferably 0.008 or less or 0.005 or less, even more preferably 0.004 or less, and particularly preferably 0.003 or less. The resin composition of the present invention contains a polyimide polymer, thereby enabling the dielectric loss tangent to be low. The lower limit is not particularly limited, but may be 0.0001 or more, 0.001 or more, for example. The dielectric loss tangent can be measured according to the method described in the examples below.

[0199] In one embodiment, the dried product of the resin composition of the present invention exhibits excellent limiting resolution. For example, exposure, development, and transfer are performed using a quartz glass mask and photoresist that draws circular holes (vias) with opening diameters of 0.5 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, and 5.0 μm in the exposure pattern. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably less than 2.0 μm, more preferably less than 1.0 μm, and even more preferably less than 0.8 μm. The lower limit is not particularly limited, but can be 0.5 μm or greater. The limiting resolution can be measured according to the method described in the Examples below.

[0200] In one embodiment, the resin composition of the present invention is characterized by a good balance of the above properties.

[0201] The uses of the resin composition of the present invention are not particularly limited, and it can be used in a wide range of applications where resin compositions are used, such as silicon wafers, circuit boards (printed wiring boards, semiconductor package substrates, laminates, multilayer printed wiring boards, etc.), solder resists, buffer coating films, underfill materials, die bonding materials, semiconductor encapsulants, semiconductor chip packages, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, system-in-packages, hole-filling resins, component-embedding resins, and display applications. In these applications, the dried product of the resin composition can function as, for example, an insulating layer or a sealing layer. Among these, the resin composition can be suitably used as a resin composition for an insulating layer of a printed wiring board or a semiconductor package substrate (a printed wiring board or a semiconductor package substrate having an insulating layer made of a dried resin composition), a resin composition for an interlayer insulating layer (a printed wiring board or a semiconductor package substrate having an interlayer insulating layer made of a dried resin composition), a resin composition for plating (a printed wiring board or a semiconductor package substrate having plating formed on a dried resin composition), and a resin composition for solder resist (a printed wiring board or a semiconductor package substrate having a solder resist made of a dried resin composition), a resin composition for a rewiring formation layer of a wafer-level package (a wafer-level package having a rewiring formation layer made of a dried resin composition), a resin composition for a rewiring formation layer of a fan-out wafer-level package (a fan-out wafer-level package having a rewiring formation layer made of a dried resin composition), a resin composition for a rewiring formation layer of a fan-out panel-level package (a fan-out panel-level package having a rewiring formation layer made of a dried resin composition), a resin composition for a buffer coat (a semiconductor device having a buffer coat made of a dried resin composition), and a resin composition for an insulating layer for a display (a display having an insulating layer made of a dried resin composition).

[0202] [Semiconductor package substrate] The semiconductor package substrate of the present invention includes an insulating layer formed from a dried product of the resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coating film, or a solder resist.

[0203] Specifically, the semiconductor package substrate of the present invention can be manufactured using the above-mentioned resin composition, and the dried resin composition is used as an insulating layer. (I) forming an insulating layer containing a dried product of the resin composition of the present invention on a circuit board; (II) forming a photoresist layer on an insulating layer containing a dried resin composition, and irradiating the photoresist layer with actinic rays through a mask pattern; (III) developing the photoresist layer to form a mask layer; (IV) transferring the photoresist pattern to an underlying insulating layer containing a dried resin composition by dry etching; (V) stripping the photoresist layer; The method for manufacturing a semiconductor package substrate preferably includes steps (I) to (V) in the following order: step (I), step (II), step (III), step (IV), and step (V).

[0204] <Process (I)> In step (I), an insulating layer containing a dried product of the resin composition of the present invention is formed on a circuit board. Fig. 1 is a schematic cross-sectional view illustrating step (I) in one embodiment of a method for producing a semiconductor package substrate. An example of a method for forming an insulating layer containing a dried product of the resin composition is a method in which the resin composition is directly applied onto a circuit board.

[0205] When the resin composition is applied directly onto a circuit board, an insulating layer containing the dried resin composition can be formed on the circuit board by drying and volatilizing component (B).

[0206] Examples of methods for applying the resin composition include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0207] The resin composition may be applied in several batches, in one batch, or by a combination of different methods. Among these, the die coating method is preferred because it provides excellent uniformity. Furthermore, to avoid contamination, it is preferable to carry out the application process in an environment where foreign matter is less likely to be generated, such as a clean room.

[0208] After applying the resin composition, it is dried, if necessary, in a hot air oven or far-infrared oven. Drying conditions are preferably 120°C to 200°C for 10 to 180 minutes. Because the resin composition of the present invention contains a polyimide polymer, the heating temperature can be lowered. When the resin composition contains a crosslinking agent (F), the resin composition may be cured by a crosslinking reaction during drying. The product obtained by drying is referred to as a "dried product," even if a curing reaction such as a crosslinking reaction occurs during drying. In this way, an insulating layer containing the dried product of the resin composition is formed on the circuit board.

[0209] Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. The term "circuit board" refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of a support substrate such as those described above. Furthermore, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the term "circuit board." The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0210] <Process (II)> In step (II), a photoresist layer is formed on the insulating layer containing the dried resin composition, and the resulting layer is irradiated with actinic rays. Fig. 2 is a schematic cross-sectional view illustrating step (II) in one embodiment of the method for producing a semiconductor package substrate. As in step (I), a method for forming a photoresist layer on the insulating layer containing the dried resin composition includes applying a photoresist directly onto the insulating layer containing the dried resin composition on the circuit board.

[0211] Next, an exposure step is performed in which actinic rays are irradiated to predetermined portions of the photoresist layer through a mask pattern. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The dose of ultraviolet rays is 10 mJ / cm. 2 ~1000mJ / cm 2 The exposure method may be either a contact exposure method in which a mask pattern (not shown) is brought into close contact with the circuit board, or a non-contact exposure method in which exposure is performed using parallel light without contact, and either method may be used. In this case, the photoresist used may be either a positive type or a negative type.

[0212] In step (II), vias can be formed using a via pattern such as a round hole pattern as the mask pattern. The via diameter (opening diameter) is preferably 20 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The lower limit is not particularly limited, but can be 0.05 μm or more, 0.10 μm or more, etc. Examples of photoresists that can be used include PMER P-CY1000 and TCIR-ZR8800 manufactured by Tokyo Ohka Kogyo Co., Ltd., and the FPPR-PET series, FPPR-HW series, and FSMR series manufactured by Fuji Yakuhin Kogyo Co., Ltd.

[0213] <Process (III)> In step (III), a mask layer is formed by developing the photoresist layer. Fig. 3 is a schematic cross-sectional view illustrating step (III) in one embodiment of a method for manufacturing a semiconductor package substrate. A method for developing the photoresist layer involves irradiating the photoresist layer with active light in step (II), followed by a development step of removing unexposed portions of the photoresist layer with a developer when a negative photoresist is used, or a development step of removing exposed portions of the photoresist layer with a developer when a positive photoresist is used, thereby forming a pattern. Development is preferably performed by wet development.

[0214] In the case of the wet development, a developer that is safe, stable, and easy to operate, such as an alkaline solution, an aqueous developer, or an organic solvent, is used. Among these, a development process using an alkaline solution, such as an alkaline aqueous solution, is preferred. The developer may be used alone or in combination of two or more. Furthermore, known methods such as spraying, shaking immersion, brushing, and scraping may be appropriately used as the development method.

[0215] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. Of these, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0216] These alkaline aqueous solutions may contain surfactants, antifoaming agents, etc. to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected depending on the developability of the photoresist layer, but is preferably 20°C to 50°C.

[0217] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanols having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

[0218] The concentration of the organic solvent in the developer is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of the organic solvent can be adjusted according to the developability. The organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0219] In forming a pattern, two or more development methods may be used in combination as needed. Development methods include dipping, bathing, spraying, high-pressure spraying, brushing, and slapping, with the high-pressure spraying method being preferred for improving resolution. When using a spraying method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0220] <Process (IV)> In step (IV), the photoresist pattern is transferred to an underlying insulating layer containing a dried resin composition by dry etching. Figure 4 is a schematic cross-sectional view illustrating step (IV) in one embodiment of a method for manufacturing a semiconductor package substrate. For dry etching, vacuum discharge plasma such as inductively coupled plasma (ICP) or capacitively coupled plasma (CCP) can be used. More preferably, plasma of a gas reactive with the etching target is generated, and a bias is applied to the circuit board to attract reactive ions in the plasma to the substrate surface, thereby accelerating etching. This method, also known as reactive ion etching (RIE), allows for faster and anisotropic transfer of the mask pattern to an insulating layer containing a dried resin composition. Furthermore, because the components of the dried resin composition are exhausted as gases through a chemical reaction, accumulation of the components of the dried resin composition in the vacuum chamber can be suppressed, thereby maintaining long-term operational stability of the etching process.

[0221] The etching gas can be selected from halogen-based gases such as O2 gas, Cl-based gas, F-based gas, Br-based gas, and I-based gas depending on the material to be etched. Examples of F-based gases include CF4 gas and C4F6 gas, while examples of Cl-based gases include BCl3 gas, CCl4 gas, HCl gas, PCl3 gas, and SCl2 gas. Two or more of these gases may be mixed together. Rare gases such as He (helium), Ne (neon), Ar (argon), and Xe (xenon) or inert gases such as N2 may be added to the halogen-based gas. The flow rate of the etching gas is preferably 10 to 5,000 sccm, more preferably 100 to 1,000 sccm. The pressure within the etching chamber is preferably 1 to 100 Pa, more preferably 10 to 50 Pa. The bias output and etching time need to be optimized depending on the film thickness of the insulating layer containing the dried resin composition, but the bias output is preferably 100 to 200 W, and the etching time is preferably 1 second to 10 minutes.

[0222] <Process (V)> In step (V), the photoresist layer is peeled off from the insulating layer containing the dried resin composition. FIG. 5 is a schematic cross-sectional view illustrating step (V) in one embodiment of a method for manufacturing a semiconductor package substrate. An organic solvent is preferably used for the peeling. Examples of organic solvents include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone. If the photoresist remains after peeling using an organic solvent, it can be removed by dipping, bathing, spraying, high-pressure spraying, brushing, slapping, or the like.

[0223] [Semiconductor Devices] Examples of semiconductor devices on which the above-mentioned semiconductor package substrate is mounted include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0224] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0225] [Synthesis of polyimide polymers, production of polyimide varnish] <Comparative Example 1-1: Synthesis of Polyimide Polymer (A1) and Production of Polyimide Varnish (AB1)> 96.4 g of acid anhydride (1) (4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 539 g of γ-butyrolactone and stirring at room temperature. 83.4 g of diamine (1) represented by the following structural formula was then added, and the separable flask was heated in an oil bath until the internal temperature reached 55°C and polymerized for 20 hours. Next, 179.8 g of toluene and 5.4 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150°C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. The reaction solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80°C for 40 hours to obtain 175 g of polyimide polymer (A1). [ka] [ka]

[0226] The molecular weight of the polyimide polymer (A1) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000. 1 H-NMR measurement confirmed that the polymer had a structural unit represented by the following formula (A-4-1): The copolymerization ratio was m=100 (structural unit represented by formula (A-4-1)). [ka]

[0227] The obtained polyimide polymer (A1) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB1).

[0228] <Example 1-1: Synthesis of polyimide polymer (A2), production of polyimide varnish (AB2)>

[0229] 86.9 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 482.4 g of γ-butyrolactone and stirring at room temperature. 71.5 g of diamine (1) represented by the following structural formula and 2.4 g of diamine (2) (MBAA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 160.8 g of toluene and 4.8 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 158 g of polyimide polymer (A2). [ka] [ka] [ka]

[0230] The molecular weight of the polyimide polymer (A2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,400. 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1). The copolymerization ratios were m=95.1 (structural unit represented by formula (A-4-1)) and n=4.9 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0231] The obtained polyimide polymer (A2) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB2).

[0232] <Example 1-2: Synthesis of polyimide polymer (A3), production of polyimide varnish (AB3)> 86.9 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 470.1 g of γ-butyrolactone and stirring at room temperature. 67.7 g of diamine (1) represented by the following structural formula and 4.8 g of diamine (2) (MBAA) were added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 156.7 g of toluene and 4.7 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 151 g of polyimide polymer (A3). [ka] [ka] [ka]

[0233] The molecular weight of the polyimide polymer (A3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,700. 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1). The copolymerization ratios were m=89.7 (structural unit represented by formula (A-4-1)) and n=10.3 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0234] The obtained polyimide polymer (A3) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB3).

[0235] <Example 1-3: Synthesis of polyimide polymer (A4), production of polyimide varnish (AB4)> 93.1 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 503.7 g of γ-butyrolactone and stirring at room temperature. 64.5 g of diamine (1) represented by the following structural formula and 10.3 g of diamine (2) (MBAA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 167.9 g of toluene and 5.1 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 165 g of polyimide polymer (A4). [ka] [ka] [ka]

[0236] The molecular weight of the polyimide polymer (A4) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 20,800 in weight average molecular weight (Mw). 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1). The copolymerization ratios were m=80.1 (structural unit represented by formula (A-4-1)) and n=19.9 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0237] The obtained polyimide polymer (A4) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB4).

[0238] <Example 1-4: Synthesis of polyimide polymer (A5), production of polyimide varnish (AB5)> 93.4 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 486.0 g of γ-butyrolactone and stirring at room temperature. 48.4 g of diamine (1) represented by the following structural formula and 20.5 g of diamine (2) (MBAA) were added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 162.0 g of toluene and 4.9 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 160 g of polyimide polymer (A5). [ka] [ka] [ka]

[0239] The molecular weight of the polyimide polymer (A5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000. 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1). The copolymerization ratios were m=61.5 (structural unit represented by formula (A-4-1)) and n=38.5 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0240] The obtained polyimide polymer (A5) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB5).

[0241] <Example 1-5: Synthesis of polyimide polymer (A6), production of polyimide varnish (AB6)> 109.1 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 496.2 g of γ-butyrolactone and stirring at room temperature. 50.3 g of diamine (3) (PIDA) represented by the following structural formula and 6.0 g of diamine (2) (MBAA) were added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 165.4 g of toluene and 5.0 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropic distillation of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 161 g of polyimide polymer (A6). [ka] [ka] [ka]

[0242] The molecular weight of the polyimide polymer (A6) was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 16,300. 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-2) and a structural unit represented by the following formula (A-5-1). The copolymerization ratios were m=90.1 (structural unit represented by formula (A-4-2)) and n=9.9 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0243] The obtained polyimide polymer (A6) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was designated as polyimide varnish (AB6).

[0244] <Example 1-6: Synthesis of polyimide polymer (A7), production of polyimide varnish (AB7)> 87.6 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 485.9 g of γ-butyrolactone and stirring at room temperature. 68.2 g of diamine (1) represented by the following structural formula and 6.2 g of diamine (4) (6FAP) were added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 162.0 g of toluene and 4.9 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 142 g of polyimide polymer (A7). [ka] [ka] [ka]

[0245] The molecular weight of the polyimide polymer (A7) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 14,900. 1 H-NMR measurement confirmed that the copolymer had a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-3). The copolymerization ratios were m=90.8 (structural unit represented by formula (A-4-1)) and n=9.2 (structural unit represented by formula (A-5-3)). [ka] [ka]

[0246] The obtained polyimide polymer (A7) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was used as polyimide varnish (AB7).

[0247] <Example 1-7: Synthesis of polyimide polymer (A8), production of polyimide varnish (AB8)> 66.7 g of acid anhydride (2) (4,4'-oxydiphthalic dianhydride, ODPA) represented by the following structural formula was placed in a 1 L separable flask, followed by 479.9 g of γ-butyrolactone and stirring at room temperature. 87.1 g of diamine (1) represented by the following structural formula and 6.2 g of diamine (2) (MBAA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 55°C and polymerized for 20 hours. Next, 160.0 g of toluene and 4.8 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150°C. Dehydration imidization by azeotropic distillation of toluene and water was carried out for 5 hours. The reaction solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80°C for 40 hours to obtain 157 g of polyimide polymer (A8). [ka] [ka] [ka]

[0248] The molecular weight of the polyimide polymer (A8) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 32,000. 1H-NMR measurement confirmed that the copolymer had the structural unit represented by the following formula (A-4-3) and the structural unit represented by the following formula (A-5-2). The copolymerization ratios were m = 89.8 (structural unit represented by formula (A-4-3)) and n = 10.2 (structural unit represented by formula (A-5-2)). [ka] [ka]

[0249] The obtained polyimide polymer (A8) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was used as polyimide varnish (AB8).

[0250] Comparative Example 1-2: Synthesis of Polyimide Polymer (A9) and Production of Polyimide Varnish (AB9) 116.3 g of acid anhydride (1) (BPADA) represented by the following structural formula was placed in a 1 L separable flask, followed by 488.9 g of γ-butyrolactone and stirring at room temperature. 40.3 g of diamine (5) represented by the following structural formula and 6.4 g of diamine (2) (MBAA) were added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 163.0 g of toluene and 4.9 g of benzoic acid were added, and the internal temperature was heated to 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 163 g of polyimide polymer (A9). [ka] [ka] [ka]

[0251] The molecular weight of the polyimide polymer (A9) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 35,700. 1 H-NMR measurement confirmed that the copolymer had the structural unit represented by the following formula (A'-4-4) and the structural unit represented by the following formula (A-5-1). The copolymerization ratios were 1 = 90.0 (structural unit represented by formula (A'-4-4)) and n = 10.0 (structural unit represented by formula (A-5-1)). [ka] [ka]

[0252] The obtained polyimide polymer (A9) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was used as polyimide varnish (AB9).

[0253] Comparative Example 1-3: Synthesis of Polyimide Polymer (A10) and Production of Polyimide Varnish (AB10) 99.3 g of acid anhydride (2) (ODPA) represented by the following structural formula was placed in a 1 L separable flask, 498.4 g of γ-butyrolactone was added, and the mixture was stirred at room temperature. 57.7 g of diamine (5) represented by the following structural formula and 9.2 g of diamine (2) (MBAA) were then added, and the separable flask was heated in an oil bath until the internal temperature reached 55 ° C. and polymerized for 20 hours. Next, 166.1 g of toluene and 5.0 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 ° C. Dehydration imidization by azeotropy of toluene and water was carried out for 5 hours. After the reaction, the solution was crystallized in 5 L of pure water, and the resulting solid was filtered and dried under reduced pressure at 80 ° C. for 40 hours to obtain 165 g of polyimide polymer (A10). [ka] [ka] [ka]

[0254] The molecular weight of the polyimide polymer (A10) was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 40,100. 1 H-NMR measurement confirmed that the copolymer had structural units represented by the following formula (A'-4-5) and structural units represented by the following formula (A-5-2). The copolymerization ratios were 1 = 89.2 (structural units represented by formula (A'-4-5)) and n = 10.8 (structural units represented by formula (A-5-2)). [ka] [ka]

[0255] The obtained polyimide polymer (A10) was dissolved in γ-butyrolactone to prepare a 25% by mass solution, which was used as polyimide varnish (AB10).

[0256] <γ-butyrolactone solubility> The prepared polyimide varnishes (AB1) to (AB10) were subjected to a storage test at 5° C. for one month, and the solubility was evaluated according to the following criteria. The results are shown in Table 1. ◯: No precipitates after 1 month. △: No precipitates were observed after 10 hours, but precipitates were observed after 1 month. ×: Precipitation was observed after 10 hours.

[0257] The measurement results of the obtained polyimide polymer and polyimide varnish are shown in Table 1. [Table 1]

[0258] [Production of resin composition] <Example 2-1> A resin composition was produced by blending 400 parts by mass of the polyimide varnish (AB2) produced in Example 1-1, 0.01 parts by mass of "KP-341" as the component (D), and 0.5 parts by mass of "DATA" as the component (E).

[0259] <Example 2-2> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB3) was used instead of polyimide varnish (AB2).

[0260] <Example 2-3> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB4) was used instead of polyimide varnish (AB2).

[0261] <Example 2-4> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB5) was used instead of polyimide varnish (AB2).

[0262] <Example 2-5> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB6) was used instead of polyimide varnish (AB2).

[0263] <Example 2-6> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB7) was used instead of polyimide varnish (AB2).

[0264] <Example 2-7> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB8) was used instead of polyimide varnish (AB2).

[0265] <Example 2-8> A resin composition was produced by blending 400 parts by mass of the polyimide varnish (AB3) produced in Example 1-2, 10 parts by mass of "180nmSX-C1" as the (C) component, 0.01 parts by mass of "KP-341" as the (D) component, and 0.5 parts by mass of "DATA" as the (E) component.

[0266] <Example 2-9> A resin composition was produced in the same manner as in Example 2-8, except that the blending amount of "180nmSX-C1" was changed to 30 parts by mass.

[0267] <Example 2-10> A resin composition was produced in the same manner as in Example 2-8, except that the blending amount of "180nmSX-C1" was changed to 50 parts by mass.

[0268] <Example 2-11> A resin composition was produced in the same manner as in Example 2-8, except that the blending amount of "180nmSX-C1" was changed to 70 parts by mass.

[0269] <Comparative Example 2-1> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB1) was used instead of polyimide varnish (AB2).

[0270] <Comparative Example 2-2> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB9) was used instead of polyimide varnish (AB2).

[0271] <Comparative Example 2-3> A resin composition was produced in the same manner as in Example 2-1, except that polyimide varnish (AB10) was used instead of polyimide varnish (AB2).

[0272] In Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3, a high-speed rotary mixer or a high-pressure dispersing device was used to mix the components. The amounts of the components in the resin compositions produced in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3, as well as the measurement results described below, are shown in Table 2. [Table 2]

[0273] The abbreviations in the table are as follows: (C) Inorganic filler 180nmSX-C1: Spherical silica (manufactured by Admatechs Co., Ltd., specific surface area 20m) surface-treated with an amino-silane coupling agent 2 / g, average particle size 0.2μm) (D) Surfactant KP-341: Polyether surfactant (Shin-Etsu Chemical Co., Ltd.) (E) Adhesion aid DATA (3,5-diamino-1,2,4-triazole): A compound represented by the following structural formula [ka]

[0274] <Preparation of film for measuring physical properties> The resin compositions produced in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3 were coated onto a release-treated PET film (product name NS-80A, manufactured by Fujimori Kogyo Co., Ltd.) using a blade to a film thickness of 140 μm. The solution on the PET film was heated at 80°C for 20 minutes using a heater to obtain a resin composition layer. The resin composition layer was peeled from the PET film, attached to a metal frame using heat-resistant tape, and heated at 190°C for 2 hours to produce a film for measuring physical properties.

[0275] <Measurement of coefficient of linear thermal expansion (CTE)> The film for measuring physical properties was cut into a 5 mm wide, 15 mm long specimen. This specimen was subjected to thermomechanical analysis using a tensile load method using a thermomechanical analyzer (Rigaku Corporation, Thermo Plus TMA8310). Specifically, the specimen was loaded into the thermomechanical analyzer and subjected to two consecutive measurements under the conditions of a 1 g load and a heating rate of 5°C / min (the first measurement was performed at 200°C, and the second measurement was performed at 260°C). The linear thermal expansion coefficient (ppm / °C) in the planar direction over the temperature range from 25°C to 150°C was calculated in the second measurement and evaluated according to the following criteria. The results are shown in Table 2. ○: 65ppm / ℃ or less △: More than 65 ppm / ℃ and less than 83 ppm / ℃ ×: Greater than 83 ppm / ℃

[0276] <Measurement of glass transition temperature Tg> The film for physical property measurement was cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") using the tensile load method. Specifically, the test pieces were loaded into the thermomechanical analyzer and measured twice consecutively under the conditions of a 1 g load and a heating rate of 5°C / min (the first time the temperature was raised to 200°C, and the second time it was raised to 260°C). The glass transition temperature Tg (°C) was calculated from the results of the second measurement and evaluated according to the following criteria. The results are shown in Table 2. ○: 185℃ or higher △: 181℃ or higher but less than 185℃ ×: Less than 181℃

[0277] <Measurement of elongation at break and elastic modulus> The film for measuring physical properties was cut into a No. 1 dumbbell shape to obtain a test piece. The test piece was subjected to tensile strength measurement using an Orientec tensile testing machine "RTC-1250A" to determine the elongation at break and modulus of elasticity at 25°C. The measurement was carried out in accordance with JIS K7127. Three measurements were carried out, and the average value was used as the measurement result, and evaluation was carried out according to the following criteria (units: elongation at break = %, modulus of elasticity = GPa). The results are shown in Table 2. Elongation at break ○: 35% or more △: 5% or more and less than 35% ×: Less than 5% Elastic modulus ○: 1.8GPa or more ×: Less than 1.8GPa

[0278] <Measurement of dielectric properties (dielectric constant, dielectric loss tangent)> The resin compositions produced in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3 were coated onto a release-treated PET film (product name NS-80A, manufactured by Fujimori Kogyo Co., Ltd.) using a blade to a film thickness of 140 μm. The solution on the PET film was heated at 80°C for 15 minutes using a heater to form a film having a resin composition layer. The resin composition layer was peeled from the PET film, and the resin composition layer was attached to a metal frame using heat-resistant tape, and then irradiated with 1000 mJ / cm. 2 The film was then irradiated with ultraviolet light for 1 hour and heated at 190°C for 2 hours to prepare a film for measuring dielectric properties.

[0279] A test piece measuring 2 mm in width and 80 mm in length was cut from the dielectric property measurement film. The dielectric constant Dk and dielectric loss tangent Df of the cut test piece were measured using an Agilent Technologies HP8362B measuring device by the cavity resonance perturbation method at a measurement frequency of 2.8 GHz and a measurement temperature of 23°C, and evaluated according to the following criteria. The results are shown in Table 2. ·Dielectric constant Dk ○: Less than 3.0 ×: 3.0 or higher ·Dielectric tangent Df ○: 0.01 or less ×: Greater than 0.01

[0280] <Evaluation of limiting resolution (minimum aperture diameter of transferred via pattern)> As shown in Figure 1, the resin compositions produced in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-3 were first spin-coated onto a 6-inch wafer at a rotation speed of 500 to 3000 rpm, and the film thickness was adjusted to 4.0 µm. This resin composition layer was heated at 190°C for 2 hours, and then a photoresist (PMER P-BZ4000, manufactured by TOK Corporation) that served as an etching mask was applied to the top of the resin composition layer by spin-coating, followed by heating at 105°C for 5 minutes to produce a laminate.

[0281] The laminate was exposed to ultraviolet light (wavelength 365 nm, intensity 40 mW / cm) using an exposure machine with NA = 0.05. 2 The exposure was performed at a dose of 50 mJ / cm. 2 to 1000mJ / cm 2 The optimum value was set in the range of 0.5 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, and 5.0 μm. A quartz glass mask was used for the exposure pattern, which draws round holes (vias) with opening diameters of 0.5 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, and 5.0 μm.

[0282] Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C was used as a developer and sprayed onto the entire surface of the photoresist of the laminate for 30 seconds at a spray pressure of 0.1 MPa, followed by paddle development for the required time, and finally a spray rinse with water at a spray pressure of 0.1 MPa for 30 seconds.

[0283] Furthermore, the upper photoresist pattern was transferred to the lower resin composition layer by etching for 300 seconds using a plasma etching device (NE-550, manufactured by ULVAC) with the oxygen gas:CF4 gas ratio maintained at 10:90.

[0284] The diameters of the bottoms of vias with openings of 0.5 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, and 5.0 μm in the etching transfer pattern were observed and measured using a scanning electron microscope (SEM) at 1000x magnification. The smallest size that can be opened is defined as the limiting resolution, and evaluation was performed according to the following criteria. The results are shown in Table 2. ○: Less than 1.0 μm △: 1.0 μm or more and less than 2.0 μm ×:2.0μm or more

[0285] <Overall rating> In the evaluation of the γ-butyrolactone solubility, the coefficient of linear thermal expansion (CTE), the glass transition temperature (Tg), the elongation at break, the modulus of elasticity, the dielectric constant, the dielectric loss tangent, and the limiting resolution, points were assigned with ○ being 100 points, △ being 50 points, and × being 0 points, and the average points were calculated to evaluate the degree to which the above properties were excellent and balanced.

[0286] Polyimide polymers (A2) to (A8) having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure are soluble in the organic solvent γ-butyrolactone, and the polyimide varnishes of Examples 1-1 to 1-7 containing these polyimide polymers were less likely to produce precipitates when stored at 5°C. Furthermore, Examples 2-1 to 2-11 had small linear thermal expansion coefficients and excellent stress relaxation performance during film layering. They also had excellent mechanical properties such as elongation at break and modulus of elasticity, and limiting resolution, and particularly excellent dielectric properties such as dielectric constant and dielectric loss tangent. On the other hand, polyimide polymers (A1) and (A10), which do not have the structure specified in the present application, have poor solubility in γ-butyrolactone, and the polyimide varnishes of Comparative Examples 1-1 and 1-3 containing these polyimide polymers quickly produced precipitates when stored at 5°C. In Comparative Examples 2-2 and 2-3, in which the polyimide polymer did not have a structure derived from a diamine having an indane structure, the glass transition temperature, dielectric constant, dielectric loss tangent, and limiting resolution were not satisfactory. Furthermore, in Examples 2-1 to 2-11, the "overall evaluation" value, which comprehensively evaluates the γ-butyrolactone solubility, linear thermal expansion coefficient, glass transition temperature, elongation at break, modulus of elasticity, dielectric constant, dielectric loss tangent, and limiting resolution, was high, and the various physical properties were well-balanced and excellent. On the other hand, in Comparative Examples 2-1 to 2-3, the "overall evaluation" value was low, and many of the physical properties were unsatisfactory. [Explanation of symbols]

[0287] 10. Insulating layer containing dried resin composition 11. Insulating layer containing dried resin composition after pattern formation 20 Circuit Board 30 photoresist layer 31 Mask Layer

Claims

1. (A) a polyimide polymer having a structure derived from a diamine having an indane structure and a structure derived from a diamine having a hydroxy structure, and (B) an organic solvent, A resin composition comprising:

2. The resin composition according to claim 1 , wherein the component (A) further has a structure derived from a tetracarboxylic dianhydride.

3. The resin composition according to claim 1, wherein the hydroxy structure is a hydroxycarbonyl group or a phenolic hydroxy group.

4. The resin composition according to claim 1 , which is in the form of a varnish.

5. The resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-1), a structural unit represented by the following formula (A-2), and a structural unit represented by the following formula (A-3): 【Chemical 1】 (In formula (A-1), each A independently represents a tetravalent organic group.) 【Chemistry 2】 (In formula (A-2), Xa and Xb each independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below, and x represents an integer of 0 to 5.) 【Chemistry 3】 (In the formula, * represents a bond.) 【Chemistry 4】 (In formula (A-3), each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y １ and Y ２ each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y １ and Y ２ At least one of the groups is a hydroxy group or a hydroxycarbonyl group.

6. The resin composition according to claim 5, wherein A in formula (A-1) is a tetravalent group represented by the following formula (X-4): 【Chemistry 5】 (In formula (X-4), ring Ar １ , Ring Ar ２ and ring Ar ３ each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. １ and L ２ each independently represents -O- or an alkylene group having 1 to 4 carbon atoms; nc represents an integer of 0 or more; * represents a bond.

7. The resin composition according to claim 5, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4) and a structural unit represented by the following formula (A-5): 【Chemistry 6】 (In formula (A-4), each A independently represents a tetravalent organic group. Xa and Xb independently represent a single bond, a group represented by formula (X-1) below, a group represented by formula (X-2) below, or a group represented by formula (X-3) below. x represents an integer of 0 to 5.) 【Chemistry 7】 (In the formula, * represents a bond.) 【Chemistry 8】 (In formula (A-5), each A independently represents a tetravalent organic group. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 6 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y １ and Y ２ each independently represents a hydrogen atom, a hydroxy group, or a hydroxycarbonyl group; Y １ and Y ２ At least one of the groups is a hydroxy group or a hydroxycarbonyl group.

8. The resin composition according to claim 7, wherein the sum (m+n) of m defined in the following formula (1) and n defined in the following formula (2) is 90 to 100, where M is the number of repetitions of the structural unit represented by formula (A-4), N is the number of repetitions of the structural unit represented by formula (A-5), and L is the number of repetitions of the other structural unit, if any: [Equation 1] [Equation 2]

9. The resin composition according to claim 8, wherein m is 50 to 99.

10. The resin composition according to claim 8, wherein n=1 to 50.

11. The resin composition according to claim 7, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-1): 【Chemistry 9】 【Chemistry 10】

12. The resin composition according to claim 7, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-2) and a structural unit represented by the following formula (A-5-1): 【Chemistry 11】 【Chemistry 12】

13. The resin composition according to claim 7, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-3) and a structural unit represented by the following formula (A-5-2): 【Chemistry 13】 【Chemistry 14】

14. The resin composition according to claim 7, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-4-1) and a structural unit represented by the following formula (A-5-3): 【Chemistry 15】 【Chemistry 16】

15. The resin composition according to claim 1, wherein the component (B) is an organic solvent composed of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.

16. The resin composition according to claim 1, wherein the component (B) is an ester-based organic solvent.

17. 2. The resin composition according to claim 1, wherein the component (B) comprises at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, cyclohexanone, propylene glycol, and propylene glycol monomethyl ether acetate.

18. The resin composition according to claim 1 , further comprising (C) an inorganic filler.

19. The resin composition according to claim 1 , further comprising (D) a surfactant.

20. The resin composition according to claim 1 , further comprising (E) an adhesion aid.

21. A semiconductor package substrate comprising an insulating layer formed from a dried product of the resin composition according to any one of claims 1 to 20.

22. A semiconductor device comprising the semiconductor package substrate of claim 21.

23. (I) forming an insulating layer containing a dried product of the resin composition according to any one of claims 1 to 20 on a circuit board; (II) forming a photoresist layer on an insulating layer containing a dried resin composition and irradiating the photoresist layer with actinic rays; (III) developing the photoresist layer to form a mask layer; (IV) transferring the photoresist pattern to an underlying insulating layer containing a dried resin composition by dry etching; (V) stripping the photoresist layer; A method for manufacturing a semiconductor package substrate, comprising:

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