Photosensitive composition, transfer film, laminate production method, laminate, and semiconductor package

Abstract

The present invention addresses the problem of providing a photosensitive composition that has excellent resolution and is capable of forming a film having excellent migration resistance. This photosensitive composition comprises a polyimide precursor, a polymerizable compound which is a compound different from the polyimide precursor, and a compound represented by formula (1). The polymerizable compound includes a compound having two or more polymerizable groups. The acid value of the polyimide precursor is 75 mgKOH / g or less.

Description

Photosensitive composition, transfer film, laminate manufacturing method, laminate, semiconductor package

[0001] The present invention relates to a photosensitive composition, a transfer film, a method for producing a laminate, a laminate, and a semiconductor package.

[0002] In display devices (e.g., organic electroluminescence (EL) display devices and liquid crystal display devices) equipped with a touch panel such as a capacitance-type input device, conductive patterns such as an electrode pattern corresponding to a sensor in the viewing area, and wiring for peripheral wiring and lead-out wiring are provided inside the touch panel. An insulating film is used for the purpose of forming and protecting such electrode patterns and conductive patterns. Similarly, in multilayer printed wiring boards and build-up substrates for semiconductor packages, insulating films are provided between each layer for the purpose of insulating and protecting the wiring between the wiring.

[0003] As a composition capable of forming the insulating film described above, for example, Patent Document 1 discloses a negative photosensitive resin composition containing an alkali-soluble resin and two or more predetermined oxime ester-based photopolymerization initiators.

[0004] International Publication No. 2021 / 006315

[0005] The present inventors have investigated films formed from the above-mentioned negative-type photosensitive resin compositions and found that the resolution does not satisfy the desired level and there is room for improvement. Furthermore, films obtained from photosensitive compositions are also required to have excellent migration resistance.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition that can form a film with excellent migration resistance and excellent resolution. Another object of the present invention is to provide a transfer film, a method for manufacturing a laminate, a laminate, and a semiconductor package related to the photosensitive composition.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A photosensitive composition comprising: a polyimide precursor; a polymerizable compound different from the polyimide precursor; and a compound represented by formula (1) described below, wherein the polymerizable compound comprises a compound having two or more polymerizable groups, and wherein the polyimide precursor has an acid value of 75 mgKOH / g or less. [2] The photosensitive composition according to [1], wherein the polyimide precursor has an acid value of 10 mgKOH / g or less. [3] The photosensitive composition according to [1] or [2], wherein the dissolution rate of the polyimide precursor in 200 mL of a 2.38 mass % aqueous trimethylammonium hydroxide solution at 23°C is 100 mg / min or less. [4] The photosensitive composition according to any one of [1] to [3], wherein the polyimide precursor has a polymerizable group. [5] The photosensitive composition according to any one of [1] to [4], wherein the weight-average molecular weight of the polyimide precursor is 10,000 to 50,000. [6] The photosensitive composition according to any one of [1] to [5], wherein the content of the polyimide precursor is 10.0 to 90.0 mass % based on the total solid content of the photosensitive composition. [7] The photosensitive composition according to any one of [1] to [6], wherein the weight-average molecular weight of the polymerizable compound is 150 to 1,000. [8] The photosensitive composition according to any one of [1] to [7], wherein the content of the polymerizable compound is 3.0 to 50.0 mass % based on the total solid content of the photosensitive composition. [9] The photosensitive composition according to any one of [1] to [8], wherein the mass ratio of the content of the polymerizable compound to the content of the polyimide precursor is 0.20 or more.

[10] The photosensitive composition according to any one of [1] to [9], further comprising a chain transfer agent.

[11] The photosensitive composition according to

[10] , wherein the content of the chain transfer agent is 0.01 to 5.0 mass% based on the total solid content of the photosensitive composition.

[12] The photosensitive composition according to any one of [1] to

[11] , further comprising a polymerization inhibitor.

[13] The photosensitive composition according to

[12] , wherein the content of the polymerization inhibitor is 0.01 to 5.0 mass% based on the total solid content of the photosensitive composition.

[14] The photosensitive composition according to any one of [1] to

[13] , further comprising a sensitizer.

[15] The photosensitive composition according to

[14] , wherein the content of the sensitizer is 0.01 to 5.0% by mass, based on the total solid content of the photosensitive composition.

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

[15] , further comprising a filler.

[17] The photosensitive composition according to

[16] , wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

[18] The photosensitive composition according to

[16] or

[17] , wherein the average particle size of the filler is 100 nm or less.

[19] The photosensitive composition according to any one of

[16] to

[18] , wherein the content of the filler is 30.0% by mass or more, based on the total solid content of the photosensitive composition.

[20] The photosensitive composition according to any one of

[16] to

[19] , wherein the content of the filler is 90.0 mass % or less based on the total solid content of the photosensitive composition.

[21] A transfer film having a temporary support and a photosensitive composition layer formed using the photosensitive composition according to any one of [1] to

[20] .

[22] A method for producing a laminate, comprising: Step 1: forming a photosensitive composition layer on a substrate using the photosensitive composition according to any one of [1] to

[20] ; Step 2: forming a pattern including vias in the photosensitive composition layer; and Step 3: subjecting the pattern to at least one of heating and exposure.

[23] A laminate produced by the method for producing a laminate according to

[22] .

[24] A semiconductor package comprising the laminate according to

[23] .

[0009] The present invention provides a photosensitive composition that can form a film having excellent migration resistance and excellent resolution. The present invention also provides a transfer film, a method for producing a laminate, a laminate, and a semiconductor package, all of which are related to the photosensitive composition.

[0010] FIG. 2 is a schematic diagram illustrating an example of a layer structure of a transfer film.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] The term "step" in this specification includes not only an independent step, but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

[0014] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, the temperature when performing each of the above steps may be 25° C. unless otherwise specified. Furthermore, in this specification, unless otherwise specified, room temperature is 25° C.

[0015] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0016] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, such as g-rays, h-rays, and i-rays, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). Furthermore, in the present invention, light refers to actinic rays or radiation. In this specification, "exposure" refers to not only exposure using far ultraviolet rays typified by mercury lamps and excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.

[0017] In this specification, the "solid content" of the photosensitive composition refers to the components that form a film formed using the photosensitive composition. Typically, when the photosensitive composition contains a solvent (e.g., an organic solvent and water), it refers to all components excluding the solvent. Furthermore, liquid components that form a film are also considered to be solid content.

[0018] In this specification, unless otherwise specified, the content ratio of each repeating unit of the polymer is a molar ratio. In this specification, unless otherwise specified, the molecular weight when there is a molecular weight distribution is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​obtained by gel permeation chromatography (GPC) in terms of polystyrene.

[0019] In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, "(meth)acryloyl" is a concept that includes both acryloyl and methacryloyl groups, "(meth)acrylate" is a concept that includes both acrylate and methacrylate, and "(meth)acrylamide" is a concept that includes both an acrylamide group and a methacrylamide group.

[0020] In this specification, the bonding direction of a divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z," the compound may be "X-O-CO-Z" or "X-CO-O-Z." Unless otherwise specified, the compounds described in this specification may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, only one type of isomer or isotope may be contained, or multiple types may be contained.

[0021] In this specification, unless otherwise specified, the thickness (film thickness) of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0022] In this specification, unless otherwise specified, the boiling point means the boiling point under normal pressure (1 atmosphere, 760 mmHg). In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0023] [Photosensitive Composition] The photosensitive composition of the present invention (hereinafter also simply referred to as "photosensitive composition") will be described in detail below. The photosensitive composition of the present invention contains a polyimide precursor, a polymerizable compound that is a compound different from the polyimide precursor, and a compound represented by formula (1) described below (hereinafter also referred to as "specific compound"), wherein the polymerizable compound contains a compound having two or more polymerizable groups, and the acid value of the polyimide precursor is 75 mgKOH / g or less.

[0024] While the reason why the photosensitive composition having the above-described configuration can solve the problems of the present invention is not entirely clear, the present inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The photosensitive composition of the present invention contains a polyimide precursor having an acid value of 75 mg KOH / g or less, thereby suppressing unintended reactions, such as decomposition reactions, originating from acid groups of the polyimide in the formed film, and thereby providing the formed film with excellent migration resistance. Furthermore, the photosensitive composition of the present invention is speculated to include a polymerizable compound having two or more polymerizable groups, and to include a compound represented by formula (1) as an initiator, thereby improving the reactivity of the polymerizable groups with respect to the exposure dose, resulting in excellent resolution. Furthermore, the radicals generated from the compound represented by formula (1) have a large molecular size and multiple aromatic ring structures that easily interact with the polyimide precursor. Therefore, it is speculated that the radicals have low diffusibility when the photosensitive composition of the present invention is subjected to patternwise exposure, making it easy to maintain the optical pattern during patternwise exposure, i.e., providing excellent resolution. Hereinafter, excellent migration resistance of a film formed from the photosensitive composition of the present invention will be simply referred to as "excellent migration resistance," and excellent resolution and / or migration resistance will be referred to as "excellent effects of the present invention."

[0025] [Polyimide Precursor] The photosensitive composition contains a polyimide precursor having an acid value of 75 mgKOH / g or less. The acid value will be described in detail later. The polyimide precursor is a resin that can be converted into a polyimide, which is a resin having an imide structure, by heat treatment, light treatment, or chemical treatment. The polyimide is preferably a resin having a cyclic imide structure, and may have a substituent.

[0026] The polyimide precursor preferably has a polymerizable group. In this specification, even if the polyimide precursor has a polymerizable group, the polyimide precursor is not considered a polymerizable compound. Examples of the polymerizable group include known polymerizable groups such as radically polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radically polymerizable groups being preferred. Examples of the radically polymerizable group include a group having an ethylenically unsaturated double bond, such as a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a styryl group, an allyl group, and a vinyl ether group, with a (meth)acryloyl group being preferred. It is also preferred that the polymerizable group be a polymerizable group that can polymerize with a polymerizable group in a polymerizable compound, as described below.

[0027] The polyimide precursor may have an acid group, but is preferably free of acid groups, since this allows the acid value of the polyimide precursor and the dissolution rate (described later) to be adjusted and the effects of the present invention to be more excellent. Examples of acid groups include a carboxy group, a phenolic hydroxy group, a sulfonic acid group, a phosphoric acid group, and salts thereof.

[0028] The polyimide precursor preferably has a repeating unit represented by formula (1). In other words, the polyimide formed from the polyimide precursor contained in the photosensitive composition is preferably a resin synthesized from the polyimide precursor having a repeating unit represented by formula (1) (for example, a resin obtained by a ring-closing reaction).

[0029]

[0030] In formula (1), A １ and A ２ R each independently represents an oxygen atom or —NH—. １１１ represents a divalent organic group. １１３ and R １１４ R each independently represents a hydrogen atom or a monovalent organic group. １１５ represents a tetravalent organic group.

[0031] In formula (1), A １ and A ２each independently represents an oxygen atom or —NH—. １ and A ２ is preferably an oxygen atom.

[0032] In formula (1), R １１１ represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a group formed by combining these. The divalent organic group is preferably a divalent aliphatic group having 2 to 20 carbon atoms, a divalent aromatic ring group having 6 to 20 carbon atoms, or a group formed by combining these, and more preferably a divalent aromatic ring group having 6 to 20 carbon atoms. The aliphatic group may be linear, branched, or cyclic. The aromatic ring group may be monocyclic or polycyclic. The aliphatic group and the aromatic ring group may have a heteroatom. Examples of the heteroatom include -O-, -CO-, -S-, and -SO. ２ It may be contained in the divalent organic group as a group such as - and -NHCO-. １１１ As the diamine, a divalent organic group derived from a diamine is also preferred. The diamine is preferably a diamine used in the production of a polyimide precursor, with aliphatic diamines or aromatic diamines being more preferred. The diamine is preferably a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a group combining these, with diamines having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamines) being more preferred. Examples of the aromatic ring group include groups having the following structure:

[0033]

[0034] In AR-8 to AR-10, A represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, —O—, —CO—, —S—, or —SO ２ A represents an alkylene group having 1 to 3 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, or -SO ２ - is preferred, and -CH ２ -, -O-, -S-, -SO２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ - is more preferred, and -O- is even more preferred.

[0035] R １１１ As for *-Ar ０ -L ０ -Ar ０ -* is also preferred. ０ each independently represents a divalent aromatic hydrocarbon group. ０ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２ represents -, -NHCO-, a group formed by combining these, or a single bond. * represents the bonding position. ０ They may be the same or different from each other.

[0036] Ar ０ The number of carbon atoms in the divalent aromatic hydrocarbon group represented by the formula (I) is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenylene group. ０ has the same meaning as A described above, and the preferred embodiments are also the same.

[0037] Examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; meta- or para- Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethyl biphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4 -amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)anthracene ...3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraafluorobenzoate aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4- or 2,5-diaminocumene, 2,5- Dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane , 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl. Further, examples of diamines include compounds represented by any one of formulas (DA-1) to (DA-18).

[0038]

[0039]

[0040] Further, the diamine also includes a diamine having two or more alkylene glycol units in the main chain, and as the diamine having two or more alkylene glycol units in the main chain, a diamine containing two or more ethylene glycol chains and / or two or more propylene glycol chains in one molecule is preferred. Diamines not containing aromatic rings are also preferred. Examples of the diamine include the Jeffamine (registered trademark) series (KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0041] In formula (1), R １１３ and R １１４each independently represents a hydrogen atom or a monovalent organic group. R １１３ and R １１４ preferably represents a monovalent organic group.

[0042] R １１３ or R １１４ Examples of the monovalent organic group represented by R include an aliphatic group, an aromatic ring group, and an arylalkyl group. Examples include an aromatic ring group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 25 carbon atoms. More specifically, examples include a phenyl group and a benzyl group. １１３ or R １１４ The monovalent organic group represented by the formula (I) may have an acid group as a substituent, but it is also preferable that the monovalent organic group does not have an acid group, since this allows the acid value of the polyimide precursor and the dissolution rate described below to be adjusted, and the effects of the present invention are more excellent. The acid group is as described above. The monovalent organic group may be the monovalent organic group X described below. R １１３ or R １１４ The monovalent organic group represented by the formula (I) also includes a leaving group which is eliminated by the action of an acid.

[0043] R １１３ and R １１４ Preferably, at least one of R represents a group having a polymerizable group, １１３ and R １１４ It is more preferable that both R and R represent a group having a polymerizable group. Examples of the polymerizable group include the groups exemplified as the polymerizable group that the resin may have. １１３ and R １１４ As the alkyl group, a group having an ethylenically unsaturated double bond is preferred, and a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by formula (III) is more preferred.

[0044]

[0045] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２- or a (poly)oxyalkylene group having 4 to 30 carbon atoms. * indicates the bonding position.

[0046] In formula (III), R ２００ represents a hydrogen atom or a methyl group. ２００ As the alkyl group, a methyl group is preferred.

[0047] In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, or a (poly)oxyalkylene group having 4 to 30 carbon atoms. The number of carbon atoms in the alkylene group constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of repeating oxyalkylene units constituting the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The (poly)oxyalkylene group is a concept that encompasses both an oxyalkylene group and a polyoxyalkylene group. R ２０１ Examples of the alkyl group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and —CH ２ CH(OH)CH ２ -, and examples thereof include an ethylene group, a propylene group, a trimethylene group, or -CH ２ CH(OH)CH ２ - is preferred, and an ethylene group is more preferred.

[0048] In formula (1), R １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group having an aromatic ring is preferred, and a group represented by formula (5) or a group represented by formula (6) is more preferred.

[0049]

[0050] In formula (5), R １１２ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a fluorine atom, -O-, -CO-, -S-, -SO ２* represents a bonding position. In formula (6), * represents a bonding position.

[0051] In formula (5), R １１２ has the same meaning as A described above, and the preferred embodiments are also the same.

[0052] The tetravalent organic group may be, for example, a tetracarboxylic acid residue remaining after removing the acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic acid dianhydride is preferably a compound represented by formula (7).

[0053]

[0054] In formula (7), R １１５ represents a tetravalent organic group. １１５ is R in formula (1). １１５ The same definition and preferred embodiments are also the same.

[0055] Examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride. hydrate, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalene Examples thereof include tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

[0056] Examples of the tetracarboxylic dianhydride include compounds represented by any one of formulas (DAA-1) to (DAA-5).

[0057]

[0058] (Monovalent Organic Group X) The monovalent organic group X is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic. The cyclic group may be monocyclic or polycyclic. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30. The number of carbon atoms in the cyclic alkyl group (cycloalkyl group) is preferably 3 to 30. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, and 2-ethylhexyl; monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and polycyclic cycloalkyl groups such as adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, campholoyl, dicyclohexyl, and pinenyl. The substituent that the alkyl group may have is preferably an aromatic ring group, as described below.

[0059] The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be either a monocyclic or polycyclic ring. Examples of rings constituting the aromatic ring group include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring; a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring. Examples of aromatic heterocyclic groups include a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring. As the substituent that the aromatic ring group may have, the above-mentioned alkyl group is preferred.

[0060] The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or a repeating unit represented by formula (1-B).

[0061]

[0062] In formula (1-A) and formula (1-B), A １１ , A １２ , R １１１ , R １１３ , and R １１４ are A in formula (1), respectively. １ , A ２ , R １１１ , R １１３ , and R １１４ In formula (1-A), R １１２ is R in formula (5) １１２ The same definition and preferred embodiments are also the same.

[0063] In formula (1-A), the bonding positions of the carbonyl group to the benzene ring are preferably 4, 5, 3', and 4' in formula (1-A).In formula (1-B), the bonding positions of the carbonyl group to the benzene ring are preferably 1, 2, 4, and 5 in formula (1-B).

[0064] The content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, based on all repeating units of the polyimide precursor, in order to obtain a more excellent effect of the present invention. The upper limit is preferably 100 mol% or less. In order to obtain a more excellent effect of the present invention, the content of the repeating unit represented by formula (1) having an acid group is preferably 70 mol% or less, more preferably 40 mol% or less, even more preferably 15 mol% or less, and particularly preferably 5 mol% or less, based on all repeating units of the polyimide precursor. The lower limit is preferably 0 mol%.

[0065] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1).

[0066] The polyimide precursor preferably contains fluorine atoms. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the polyimide precursor. The upper limit is preferably 50% by mass or less.

[0067] The polyimide precursor may be obtained by copolymerizing the repeating unit represented by formula (1) with an aliphatic group having a siloxane structure, which can improve adhesion to a substrate. Examples of the aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane and bis(paraaminophenyl)octamethylpentasiloxane.

[0068] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyimide precursor has a polydispersity (Mw / Mn) of preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0069] <Acid Value> The acid value of the polyimide precursor is 75 mgKOH / g or less. From the viewpoint of more excellent effects of the present invention, it is preferably 60 mgKOH / g or less, more preferably 30 mgKOH / g or less, even more preferably 10 mgKOH / g or less, and particularly preferably 5 mgKOH / g or less. The lower limit of the acid value of the polyimide precursor is not particularly limited, but 0 mgKOH / g is preferable. The acid value (mgKOH / g) is the number of mg of potassium hydroxide (KOH) required to neutralize 1 g of sample. The acid value is determined by a method based on JIS K0070. Examples of methods for adjusting the acid value of the polyimide precursor include a method for adjusting the content of acid groups contained in the polyimide precursor. More specifically, for example, a method for synthesizing a polyimide precursor using a raw material having no acid group or a raw material having an acid group, and a method for reacting an acid group with a protecting group are exemplified. Examples of the protecting group include, for example, R １１３ or R １１４ Examples of the monovalent organic group include a monovalent organic group represented by the following formula:

[0070] <Dissolution Rate> In order to obtain superior effects of the present invention, the dissolution rate of the polyimide precursor in 200 mL of a 2.38 wt% aqueous trimethylammonium hydroxide solution (TMAH 2.38 wt% aq) at 23°C is preferably 100 mg / min or less, more preferably 50 mg / min or less, and even more preferably 10 mg / min or less. The lower limit of the dissolution rate is not particularly limited, but is preferably 1 μg / min or more, more preferably 3 μg / min or more, and even more preferably 5 μg / min or more. The dissolution rate in 200 mL of TMAH 2.38 wt% aq can be measured, for example, by the following method. The polyimide precursor is dissolved in N-methyl-2-pyrrolidone (NMP) to a concentration of 30% by mass, applied to a glass substrate so that the film thickness after drying is 100 μm, and heated on a hot plate at 100°C until the amount of NMP remaining is less than 1% to remove the NMP. The obtained polyimide precursor film is immersed in 200 mL of 2.38 wt % aqueous TMAH at 23°C for 1 minute. The immersed film is dried, and the weight of the polyimide precursor film before and after immersion is measured. The dissolution rate (mg / min) can be calculated by dividing the difference by the immersion time. The weight of the polyimide precursor film can be measured using an electronic balance (e.g., manufactured by Mettler). The dissolution rate can be adjusted, for example, by adjusting the structure, acid value, molecular weight, etc. of the polyimide precursor.

[0071] In terms of obtaining better effects of the present invention, the content of the polyimide precursor is preferably 5.0 to 95.0 mass %, more preferably 10.0 to 90.0 mass %, and still more preferably 15.0 to 73.0 mass %, based on the total solid content of the photosensitive composition.

[0072] [Polymerizable Compound] The photosensitive composition contains a polymerizable compound different from the polyimide precursor. The polymerizable compound is a compound having one or more polymerizable groups in the molecule. Examples of the polymerizable group include known polymerizable groups such as radically polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radically polymerizable groups being preferred. The radically polymerizable group is preferably a group having an ethylenically unsaturated double bond. Examples of the group having an ethylenically unsaturated double bond include a vinyl group, a styryl group, a (meth)acryloyl group, a (meth)acrylamide group, an allyl group, and a vinyl ether group, with a vinyl group, a styryl group, or a (meth)acryloyl group being preferred, and a (meth)acryloyl group being more preferred.

[0073] The polymerizable compound is preferably a low molecular weight compound. The weight average molecular weight (Mw) of the polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. There is no particular lower limit, but it is preferably 100 or more, more preferably 150 or more.

[0074] The number of polymerizable groups in the polymerizable compound is preferably 1 or 2 or more, more preferably 2 to 10, and even more preferably 2 to 6. Examples of the polymerizable compound include a polymerizable compound having one polymerizable group per molecule (hereinafter also referred to as a "monofunctional polymerizable compound"), a polymerizable compound having two polymerizable groups per molecule (hereinafter also referred to as a "bifunctional polymerizable compound"), and a polymerizable compound having three or more polymerizable groups per molecule (hereinafter also referred to as a "trifunctional or higher functional polymerizable compound"). The polymerizable compound is preferably a bifunctional polymerizable compound or a trifunctional or higher functional polymerizable compound. In the photosensitive composition, the polymerizable compound includes a compound having two or more polymerizable groups. That is, the polymerizable compound includes at least one selected from the group consisting of bifunctional polymerizable compounds and trifunctional or higher functional polymerizable compounds. The polymerizable compound may further include a monofunctional polymerizable compound.

[0075] Examples of bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include, for example, diethylene glycol dimethacrylate (2G, manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (3G, manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol #200 dimethacrylate (4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), SR205NS (manufactured by Sartomer Inc.), and SR209 (manufactured by Sartomer Inc.).

[0076] Examples of trifunctional or higher functional polymerizable compounds include dipentaerythritol (tri / tetra / penta / hexa)(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds with a glycerin tri(meth)acrylate skeleton. "(Tri / tetra / penta / hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0077] Examples of the polymerizable compound include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20, etc., manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide-modified (meth)acrylate compounds (KAYARAD RP-1040, etc., manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300, etc., manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL (registered trademark) 135, etc., manufactured by Daicel-Allnex Corporation), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0078] Examples of the polymerizable compound include urethane (meth)acrylates (preferably tri- or higher functional urethane (meth)acrylates). The number of polymerizable groups in the urethane (meth)acrylate is preferably 6 or more, and more preferably 8 or more. The upper limit is preferably 20 or less. Examples of tri- or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); AH-600 (manufactured by Kyoeisha Chemical Co., Ltd.); UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0079] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 3.0 to 50.0 mass%, more preferably 5.0 to 40.0 mass%, and even more preferably 15.0 to 35.0 mass%, based on the total solids content of the photosensitive composition. The mass ratio of the content of the polymerizable compound to the content of the polyimide precursor is preferably 0.10 or more, more preferably 0.20 or more, and even more preferably 0.22 or more, from the viewpoints of achieving the effects of the present invention and achieving superior step-conforming properties. The upper limit of this mass ratio is not particularly limited, but is preferably 1.00 or less, more preferably 0.75 or less, and even more preferably 0.60 or less, from the viewpoint of achieving superior migration resistance. The step-conforming properties refer to the step-conforming properties of the photosensitive composition layer when transferring a transfer film, described below, onto a pattern having steps.

[0080] [Specific Compound] The photosensitive composition contains a specific compound represented by formula (1).

[0081]

[0082] In formula (1), each R independently represents a substituent. The substituent represented by R is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an alkenyl group, an aryl group, an aryloxy group, a formyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, an amino group, a carboxy group, a nitro group, and a cyano group. From the viewpoint of achieving superior effects of the present invention, a halogen atom, an alkyl group, or an alkoxy group is preferred, and an alkoxy group is more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms in the alkynyl group, alkenyl group, acyl group, alkoxycarbonyl group, and acyloxy group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Each of the groups represented as the substituents above may further have a substituent if possible. Such a substituent is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a halogen atom or a hydroxy group. When a plurality of Rs are present, the plurality of Rs may be the same or different.

[0083] In formula (1), each n independently represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. The sum of all n's is an integer of 0 or greater, preferably an integer of 1 or greater, more preferably an integer of 0 to 10, and still more preferably an integer of 0 to 5. When n is 1 or greater, R is preferably located at at least one of the ortho-position and the para-position relative to the bonding position with the biimidazole skeleton.

[0084] Of the compounds represented by formula (1), compounds represented by formula (1-1) or (1-2) are preferred, and compounds represented by formula (1-1) are more preferred. In formulas (1-1) and (1-2), the definitions and preferred embodiments of R and n are the same as those in formula (1).

[0085]

[0086] Examples of the compound represented by formula (1) include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, and 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl) ) biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl) 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)- phenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2',4-tris(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, Examples of the biimidazole include 2,2'-bis(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, and 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole. Preferred are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, and 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole.

[0087] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 0.1 to 20.0 mass %, more preferably 1.0 to 10.0 mass %, based on the total solid content of the photosensitive composition.

[0088] [Chain Transfer Agent] The photosensitive composition preferably contains a chain transfer agent, in order to obtain more excellent resolution. Known compounds can be used as the chain transfer agent, such as N-phenylglycine compounds, phenoxyacetic acid compounds, thiol compounds, disulfide compounds, thiophenoxy compounds, halogenated hydrocarbons, and secondary alcohols, with N-phenylglycine compounds being preferred. Examples of the N-phenylglycine compound include N-phenylglycine and derivatives thereof, with a compound represented by the following formula (II) being preferred:

[0089]

[0090] In formula (II), X represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a hydrocarbon group or a carboxy group, which may have a substituent. The hydrocarbon group, which may have a substituent, preferably has 1 to 10 carbon atoms, more preferably 2 to 9 carbon atoms. Examples of the hydrocarbon group include an alkyl group, a phenyl group, and a benzyl group. Examples of the substituent that the hydrocarbon group may have include a carboxy group, an amino group, an alkylamino group, and an anilinocarbonyl group. Examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, a carboxyalkyl group having 2 to 9 carbon atoms, a carboxyphenyl group, a carboxybenzyl group, an anilinocarbonylalkyl group having 2 to 9 carbon atoms, an anilinocarbonylphenyl group, and an anilinocarbonylbenzyl group.

[0091] In formula (II), R ｃ represents a hydroxy group, an alkoxy group, and —O － M ＋ Represents M ＋ represents an alkali metal cation. The number of carbon atoms in the alkoxy group is preferably 1 to 3, and more preferably 1. Examples of the alkali metal cation include Li ＋ , Na ＋ , and K ＋ Examples include:

[0092] Examples of the compound represented by formula (II) include the following compounds:

[0093]

[0094] The chain transfer agent may be used alone or in combination of two or more. The content of the chain transfer agent is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, based on the total solid content of the photosensitive composition. The content of the chain transfer agent is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, based on the total solid content of the photosensitive composition.

[0095] [Polymerization Inhibitor] The photosensitive composition preferably contains a polymerization inhibitor in order to obtain more excellent resolution. Examples of the polymerization inhibitor include radical scavengers, and specific examples thereof include imino compounds such as phenothiazine, phenoxazine, and bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy- phenolic compounds such as 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, quinone compounds such as methaquinone and benzoquinone, nitro compounds, and nitroso compounds, with phenothiazine, phenoxazine, or quinone compounds being preferred.

[0096] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 0.01 to 5.0 mass% and more preferably 0.1 to 3.0 mass% based on the total solid content of the photosensitive composition. The mass ratio of the content of the polymerization inhibitor to the content of the specific compound is preferably 0.01 to 2.0 and more preferably 0.03 to 0.7, in terms of more excellent effects of the present invention.

[0097] [Sensitizer] The photosensitive composition preferably contains a sensitizer, in order to obtain more excellent resolution. The sensitizer is not particularly limited, and examples thereof include benzoin-based compounds, benzophenone-based compounds, xanthone-based compounds, thioxanthone-based compounds, acetophenone-based compounds, anthraquinone-based compounds, ketal-based compounds, fluorene-based compounds, naphthoquinone-based compounds, and coumarin-based compounds. Benzophenone-based or thioxanthone-based compounds are preferred, and benzophenone-based compounds are more preferred. Examples of benzophenone-based compounds include benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone (EAB-F), and 4,4'-bis(ethylmethylamino)benzophenone, with EAB-F being preferred.

[0098] Examples of the sensitizer include the compounds described in paragraphs

[0113] to

[0116] of JP-A-2021-120946, the contents of which are incorporated herein by reference.

[0099] The content of the sensitizer is preferably 5.0% by mass or less, more preferably 1.0% by mass or less, based on the total solid content of the photosensitive composition, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total solid content of the photosensitive composition.

[0100] [Filler] The photosensitive composition preferably contains a filler in terms of better migration resistance and a smaller linear expansion coefficient. From the standpoints of durability, reliability, and dimensional stability in design, it is preferable that the linear expansion coefficient of the film formed is small. In terms of better migration resistance, the average particle size of the filler is preferably 500 nm or less, more preferably 300 nm or less, even more preferably 150 nm or less, and particularly preferably 100 nm or less. The lower limit of the average particle size of the filler is more than 0 nm, preferably 5 nm or more, and more preferably 10 nm or more. The average particle size of the filler is also preferably 5 to 300 nm, more preferably 10 to 100 nm. The average particle size of the filler is a value calculated by the following particle size measurement method. Particle size measurement method: A rectangular region of 3 μm × 10 μm in a cross section along the normal direction of the surface of a photosensitive composition layer formed using the photosensitive composition is observed with a scanning electron microscope, and the long diameters of all fillers observed in the region are measured at five different locations on the film. The average value of the long diameters of all fillers measured in each measurement is defined as the average particle size of the filler.

[0101] The particle size measurement method is described in detail below. A photosensitive composition is applied to a substrate (preferably a glass substrate) to form a photosensitive composition layer. The thickness of the photosensitive composition layer is preferably 3 μm or more. Furthermore, to form the photosensitive composition layer, a drying treatment may be performed, if necessary, after the photosensitive composition is applied. A cross section of the obtained photosensitive composition layer along the normal direction to the surface (the surface opposite the substrate side) is cut out, and a rectangular region of 3 μm x 10 μm on the cross section is observed with a scanning electron microscope, and the major axes of all fillers observed within the region are measured. The scanning electron microscope used is an S-4800 manufactured by Hitachi High-Tech Corporation. The magnification used for observation is 50,000x. The above procedure is performed at five different locations on the photosensitive composition layer, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure is taken as the average particle size of the filler. The major axis refers to the length of the longest line segment connecting any two points on the outline of the filler's outer shape in the observed image. Furthermore, when fillers are aggregated to form aggregates in the observed image, the major axis of each filler constituting the aggregate is measured.

[0102] Examples of fillers include organic fillers and inorganic fillers, with inorganic fillers being preferred. Examples of fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as undoped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride. The filler preferably contains at least one selected from the group consisting of silicon dioxide (silica), boron nitride, barium sulfate, and silicates, and more preferably contains silicon dioxide (silica).

[0103] The shape of the filler may be either spherical or non-spherical (for example, crushed or fibrous), with spherical being preferred. The filler may be surface-treated. Examples of surface treatments include treatments to introduce functional groups and treatments using known surface treatment agents. Examples of the functional groups include polymerizable groups (for example, the polymerizable group possessed by compound Z) and hydrophobic groups. Examples of surface treatment agents include silane coupling agents, titanate coupling agents, and silazane compounds. Examples of methods for surface treatment of the filler include a dry method in which surface treatment is performed in a gas phase and a wet method in which surface treatment is performed in a liquid phase.

[0104] Examples of fillers include NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, silicon dioxide, solid content concentration 100% by mass), Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), YA050C-MJE (manufactured by Admatechs Co., Ltd., silicon dioxide, solid content concentration 50% by mass MEK slurry), SFP-20M (manufactured by Denka Co., Ltd., silicon dioxide), PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), and M Examples of such an emulsion include EK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), Y50SP-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass), and Y50SZ-AM1 (manufactured by Admatechs Co., Ltd., silicon dioxide, MEK slurry with a solids concentration of 50% by mass).

[0105] The refractive index of the filler is preferably 0.5 to 30.0, and more preferably 1.2 to 1.8. The refractive index can be measured by the method described above.

[0106] The filler may be used alone or in combination of two or more. The content of the filler is preferably 20.0 mass% or more, more preferably 30.0 mass% or more, and even more preferably 40.0 mass% or more, based on the total solid content of the photosensitive composition. The content of the filler is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, based on the total solid content of the photosensitive composition. The mass ratio of the filler content to the polyimide precursor content is preferably 0.5 to 30.0, and more preferably 1.0 to 20.0.

[0107] [Thermal Base Generator] The photosensitive composition may contain a thermal base generator. When the photosensitive composition contains a thermal base generator, the ring-closing reaction of the polyimide precursor is accelerated, the polyimide is easily produced, and the migration resistance is improved.

[0108] The thermal base generator is preferably an acidic compound or an onium salt compound (a compound consisting of a cation and an anion) that generates a base upon heating. The onium salt compound is preferably an ammonium salt compound (a compound consisting of an ammonium cation and an anion), an iminium salt compound (a compound consisting of an iminium cation and an anion), a sulfonium salt compound (a compound consisting of a sulfonium cation and an anion), an iodonium salt compound (a compound consisting of an iodonium cation and an anion), or a phosphonium salt compound (a compound consisting of a phosphonium cation and an anion), with an iminium salt compound being more preferred. The anion constituting the onium salt compound is preferably a carboxylate anion, a phenol anion, a phosphate anion, or a sulfate anion, with a carboxylate anion being more preferred. The anion constituting the ammonium salt compound preferably further has an aromatic ring. The aromatic ring may, for example, be A in the formula (A1) described below. ａ１Examples of the temperature at which the acidic compound and the onium salt compound generate a base include aromatic rings that constitute aromatic ring groups represented by the formula: The temperature at which the acidic compound and the onium salt compound generate a base is preferably the heating temperature in step 3 of the laminate manufacturing method described below. The temperature at which the thermal base generator generates a base can be determined, for example, by using differential scanning calorimetry to heat the compound to be measured in a pressure-resistant capsule to 250°C at 5°C / min, and reading the peak temperature of the lowest exothermic peak, and using this peak temperature as the base generation temperature.

[0109] The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. The base may be linear, branched, or cyclic, and is preferably cyclic.

[0110] The acidic compound is preferably a compound represented by formula (A1).

[0111]

[0112] In formula (A1), A ａ１ represents a p-valent organic group. ａ１ represents a monovalent organic group. ａ１ represents an (m+1)-valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

[0113] In formula (A1), A ａ１represents a p-valent organic group. Examples of the organic group include an aliphatic hydrocarbon group and an aromatic ring group, with an aromatic ring group being preferred. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group. The alkenyl group may be linear, branched, or cyclic. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20, and even more preferably 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group. Examples of p-valent aliphatic hydrocarbon groups (where p is an integer of 2 or greater) include groups formed by removing (p-1) hydrogen atoms from the above-mentioned monovalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may further have a substituent.

[0114] The aromatic ring group may be either a monocyclic or polycyclic ring. The aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the aromatic ring group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group, a phenanthrene ring group, an anthracene ring group, a naphthacene ring group, a chrysene ring group, a triphenylene ring group, a fluorene ring group, a biphenyl ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, a pyridinium ring group, a benzophenone ... Examples of aromatic ring groups include a benzene ring group, an indolizine ring group, an indole ring group, a benzofuran ring group, a benzothiophene ring group, an isobenzofuran ring group, a quinolizine ring group, a quinoline ring group, a phthalazine ring group, a naphthyridine ring group, a quinoxaline ring group, a quinoxazoline ring group, an isoquinoline ring group, a carbazole ring group, a phenanthridine ring group, an acridine ring group, a phenanthroline ring group, a thianthrene ring group, a chromene ring group, a xanthene ring group, a phenoxathiin ring group, a phenothiazine ring group, and a phenazine ring group, and a benzene ring group is preferred. The aromatic ring group may further have a substituent.

[0115] In formula (A1), R ａ１ represents a monovalent organic group. Examples of the monovalent organic group include A ａ１ Examples of the monovalent organic group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic ring group represented by the following formula: The monovalent organic group may further have a substituent. The substituent is preferably a carboxy group.

[0116] In formula (A1), L ａ１ represents an (m+1)-valent linking group. Examples of the (m+1)-valent linking group include an ether group (—O—), a carbonyl group (—CO—), an ester group (—COO—), a thioether group (—S—), and —SO ２ -, -NR Ｎ - (R Ｎrepresents a hydrogen atom or a substituent), divalent linking groups such as alkylene groups (preferably having 1 to 10 carbon atoms) and alkenylene groups (preferably having 2 to 10 carbon atoms); trivalent linking groups having a group represented by "-N<" and trivalent linking groups having a group represented by "-CR<" (R represents a hydrogen atom or a substituent); tetravalent linking groups having a group represented by ">C<"; k-valent linking groups having a cyclic group such as an aromatic ring group or an alicyclic group; and groups combining these.

[0117] In formula (A1), m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0118] In formula (A1), p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.

[0119] The ammonium cation constituting the ammonium salt compound is preferably a cation represented by formula (101). The iminium cation constituting the iminium salt compound is preferably a cation represented by formula (102).

[0120]

[0121] In formula (101), R １ ~R ４ R each independently represents a hydrogen atom or an aliphatic group. １ ~R ４ At least two of R may be bonded to each other to form a ring. ５ and R ６ R each independently represents a hydrogen atom or an aliphatic group. ７ represents an aliphatic group. ５ ~R ７ At least two of these may be bonded to each other to form a ring.

[0122] R １ ~R ４ , and R ５ ~R ７The aliphatic group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic group is preferably 1 to 10. The aliphatic group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. The aliphatic group may have a substituent. Examples of the substituent include an arylcarbonyl group. The aliphatic group may have a substituent such that the methylene group (-CH ２ -) may be replaced with a heteroatom (for example, an oxygen atom, a sulfur atom, or -NR-, where R represents a hydrogen atom or a substituent). ５ ~R ７ At least one of the R is preferably an aliphatic group having —NR—, and more preferably an alkyl group having —NR—. ５ ~R ７ At least two of R may be bonded to each other to form a ring; ５ and R ７ , and R ６ and R ７ are preferably bonded to each other to form a ring. In other words, the ring formed is preferably a polycyclic heterocycle, more preferably a bicyclic heterocycle.

[0123] The thermal base generator is also preferably a compound represented by formula (B1) or formula (B2).

[0124]

[0125] Formula (B1) and Formula (B1) １ ~Rb ３ each independently represents an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom. １ and Rb ２ At least one of Rb represents an organic group not having a tertiary amine structure or a halogen atom. The tertiary amine structure refers to a structure in which a nitrogen atom forms a covalent bond with three carbon atoms, and does not include an amide group. １ and Rb ２Preferred examples of the substituent include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). The alkyl group, alkenyl group, aryl group, and arylalkyl group may have a substituent other than a tertiary amino group. The substituent is not particularly limited, and examples include a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an alkenyl group, an aryl group, an aryloxy group, a formyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, a primary amino group, a secondary amino group, a carboxy group, a nitro group, and a cyano group. The groups exemplified above as substituents may further have the aforementioned substituents, if possible. Rb １ and Rb ２ may be bonded to each other to form a ring which may have a substituent. The ring may be either a monocyclic or polycyclic ring. The number of ring atoms in the ring is preferably 4 to 7, more preferably 5 or 6. Examples of the substituent which the ring may have include Rb １ and Rb ２ These are the same as the substituents that may be possessed by the groups exemplified as Rb. ３Examples of the alkyl group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and even more preferably having 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an arylalkenyl group, or an arylalkyloxy group is preferred. The alkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, alkoxy group, aryloxy group, and arylalkyloxy group may have a substituent other than a tertiary amino group. Examples of the substituent other than a tertiary amino group include Rb １ and Rb ２ These are the same as the substituents that may be possessed by the groups exemplified as:

[0126] The effect of the present invention is more excellent, and therefore Rb １ ~Rb ３ Preferably, at least one of the ring structures includes a ring structure, and more preferably, at least two of the ring structures include a ring structure. The ring structure may be either a monocyclic or polycyclic ring, and is preferably a monocyclic ring or a bicondensed ring formed by condensing two monocyclic rings. The ring structure may be either an aliphatic ring or an aromatic ring, and is preferably a cyclohexane ring or a benzene ring.

[0127] Examples of the thermal base generator include the thermal base generators described in WO 2018 / 038002 and the base generators described in JP 2024-149522 A.

[0128] The thermal base generator may be used alone or in combination of two or more. The content of the thermal base generator is preferably 0.1 to 10.0 mass %, more preferably 0.2 to 5.0 mass %, based on the total solid content of the photosensitive composition. The mass ratio of the content of the thermal base generator to the content of the polyimide precursor is preferably 0.01 to 0.1, more preferably 0.024 to 0.05.

[0129] [Adhesion improver] The photosensitive composition may contain an adhesion improver in terms of adhesion to the substrate.As the adhesion improver, for example, silane coupling agent, aluminum-based adhesion aid, titanium-based adhesion aid, the compound having sulfonamide structure, the compound having thiourea structure, phosphoric acid derivative polycompound, β-ketoester compound and amino compound can be listed, and silane coupling agent is preferred.

[0130] <Silane coupling agent> Examples of the silane coupling agent include compounds described in paragraph 0167 of WO 2015 / 199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011 / 080992, compounds described in paragraphs 0060 to 0061 of JP 2014-191252, compounds described in paragraphs 0045 to 0052 of JP 2014-041264, compounds described in paragraph 0055 of WO 2014 / 097594, and compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use a silane coupling agent having a nitrogen atom. Examples of silane coupling agents include the following compounds: In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0131]

[0132] Other adhesion improvers include, for example, compounds described in paragraphs 0289 to 0295 of Japanese Patent No. 7354479, the contents of which are incorporated herein by reference.

[0133] The adhesion improver may be used alone or in combination of two or more. The content of the adhesion improver is preferably 0.1 to 10.0 mass %, more preferably 0.5 to 5.0 mass %, based on the total solid content of the photosensitive composition.

[0134] [Surfactant] The photosensitive composition preferably contains a surfactant. Examples of the surfactant include a fluorine-based surfactant, a hydrocarbon-based surfactant, and a silicone-based surfactant. A silicone-based surfactant is preferred as the surfactant. From the viewpoint of improving environmental compatibility, it is also preferred that the surfactant does not contain a fluorine atom.

[0135] Examples of fluorosurfactants include acrylic compounds that have a molecular structure containing a functional group having a fluorine atom, and when heated, the functional group having the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016), and Megafac DS-21). Furthermore, the fluorosurfactant may be a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound. The fluorosurfactant may be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups). Further, examples of fluorine-based surfactants include fluorine-containing polymers having a group with an ethylenically unsaturated double bond in the side chain, such as Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0136] As the fluorine-based surfactant, from the viewpoint of improving environmental compatibility, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferred.

[0137] Commercially available fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, and F-780 (all manufactured by DIC Corporation); EXP. MFS-324, EXP. MFS-330, EXP. MFS-578, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (all manufactured by DIC Corporation); Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC); PolyFox Examples of such products include PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA); Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by NEOS Corporation); and U-120E (manufactured by Unichem).

[0138] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester. Commercially available hydrocarbon surfactants include, for example, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan Corporation); NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Yushi Co., Ltd.); Olfine E1010, Surfynol 104, 400, and 440 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0139] Examples of silicone surfactants include linear polymers consisting of siloxane bonds, modified siloxane polymers with organic groups introduced into the side chains and / or terminals, and polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.Preferred silicone surfactants are polymers having a repeating unit with a hydrophilic group in the side chain and a repeating unit with a group having a siloxane bond in the side chain.The polymers may be either random copolymers or block copolymers.

[0140] The repeating unit having a group having a siloxane bond in the side chain is preferably a repeating unit represented by formula (SX1) or a repeating unit represented by formula (SX2).

[0141]

[0142] In formula (SX1), each R independently represents an alkyl group having 1 to 3 carbon atoms. １ represents a hydrogen atom or a methyl group. １ represents a single bond or a divalent organic group. When a plurality of R's are present, the R's may be the same or different.

[0143]

[0144] In formula (SX2), R １ represents a hydrogen atom or a methyl group. ２ represents an alkylene group having 1 to 10 carbon atoms. ３ represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0145] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0146]

[0147] In formula (SX3), R ４ and R ５ each independently represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0148] Commercially available silicone surfactants include, for example, EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2, and S-506 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-626 6, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001 , KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP -301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, and KP-652 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, and BYK323 (all manufactured by BYK-Chemie).

[0149] Other examples of the surfactant include nonionic surfactants other than those mentioned above, such as those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0150] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably from 0.01 to 5.0% by mass, more preferably from 0.1 to 1.0% by mass, based on the total solid content of the photosensitive composition.

[0151] [Rust inhibitor] The photosensitive composition preferably contains a rust inhibitor. Examples of the rust inhibitor include heterocyclic compounds. Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, pyrimidine compounds, and pyridine compounds, and triazole compounds, benzotriazole compounds, or tetrazole compounds are preferred. Examples of heterocyclic compounds include compounds described in International Publication No. 2022 / 039027.

[0152] The content of the rust inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.1 to 1.0 mass %, based on the total solid content of the photosensitive composition.

[0153] [Other Additives] The photosensitive composition may contain other additives in addition to those described above. Examples of other additives include plasticizers, solvents, photoacid generators, curing agents, aliphatic thiol compounds, thermally crosslinkable compounds, hydrogen donor compounds, impurities, alkoxysilane compounds, maleimide compounds, and hydrosilylation agents.

[0154] <Plasticizer> The photosensitive composition may contain a plasticizer. When the photosensitive composition layer described below is formed using a transfer film, it is preferable to contain a plasticizer in order to ensure that the photosensitive composition layer has excellent conformability to unevenness when laminated to an object to be laminated, and to form a film with high precision. In particular, when the photosensitive composition contains a filler, it is preferable that the photosensitive composition contains a plasticizer. The plasticizer is a compound different from the various components described above, and preferably does not have a polymerizable group.

[0155] The molecular weight of the plasticizer is preferably from 200 to 1000, more preferably from 250 to 800, and even more preferably from 300 to 600. When the plasticizer has a molecular weight distribution, the above molecular weight refers to the weight average molecular weight.

[0156] The boiling point of the plasticizer is preferably 230 to 500°C, more preferably 280 to 480°C, even more preferably 300 to 450°C, and particularly preferably 350 to 450°C. In this specification, the boiling point of a compound is a value determined by the following measurement method. When a compound is distilled under normal pressure (760 mmHg), the boiling point is the gas temperature at which condensation of the evaporated gas begins (measured from 23°C to 300°C, with a temperature increase rate of 1°C / min). The compound is distilled using a Liebig condenser, and if distillation does not begin at 300°C under normal pressure, the distillation is carried out under reduced pressure. Similar distillation was carried out sequentially at pressures of 100 mmHg, 50 mmHg, and 5 mmHg (measurement from 23°C to 300°C, temperature increase rate 1°C / min, if distillation did not start at 300°C, distillation was carried out at the next pressure), and the boiling point at atmospheric pressure was calculated using the nomograph described in Science of Petroleum, Vol. II, p. 1281 (1938) from the temperature and pressure at which condensation of the evaporated gas began. The boiling point at atmospheric pressure was taken as the calculated boiling point. If distillation did not start at 300°C under 5 mmHg, the boiling point at atmospheric pressure was deemed to be greater than 500°C. The method of using a nomograph is well known. Specifically, a straight line was drawn between the boiling point at reduced pressure on line A and the degree of reduced pressure on line C (Procedure 1), and the value at the intersection of the line drawn in Procedure 1 and line B was read (Procedure 2), and this was deemed to be the boiling point at atmospheric pressure.

[0157] The viscosity of the plasticizer at 25° C. is preferably 0.01 to 500 mPa·s, more preferably 0.05 to 300 mPa·s, and even more preferably 0.1 to 100 mPa·s. The viscosity can be measured using a B-type viscometer.

[0158] Examples of the plasticizer include polycarboxylic acid esters, phosphoric acid esters, polyether esters, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and benzyl benzoate, with polycarboxylic acid esters being preferred.

[0159] Examples of polycarboxylic acid esters include aliphatic dicarboxylic acid esters (e.g., adipic acid esters, azelaic acid esters, and sebacate esters); aromatic dicarboxylic acid esters (e.g., phthalic acid esters); trimellitic acid esters; and citrate esters (e.g., tributyl acetyl citrate). Examples of polycarboxylic acid esters include ethyl phthalyl ethyl glycolate, dihexyl phthalate, tributyl o-acetyl citrate, benzyl 2-ethylhexyl phthalate, bis(2-ethylhexyl) isophthalate, tris(2-ethylhexyl) trimellitate, and bis(2-butoxyethyl) adipate.

[0160] Examples of phosphate esters include triamyl phosphate and tris(2-butoxyethyl) phosphate.

[0161] The polyether esters are preferably organic acid esters of polyalkylene glycol. Examples of organic acids include monocarboxylic acids (e.g., butanoic acid, isobutanoic acid, 2-ethylbutyric acid, 2-ethylhexyl acid, and decanoic acid). Specific examples of polyether esters include triethylene glycol bis-2-ethylhexanoate.

[0162] Examples of alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers include hexaethylene glycol monomethyl ether (mPEG6-OH), pentaethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether, nonaethylene glycol monomethyl ether, pentaethylene glycol dimethyl ether, hexaethylene glycol dimethyl ether, heptaethylene glycol dimethyl ether, octaethylene glycol dimethyl ether, and nonaethylene glycol dimethyl ether.

[0163] The plasticizer may be used alone or in combination of two or more. The content of the plasticizer is preferably 5.0 to 50.0 mass %, more preferably 10.0 to 30.0 mass %, based on the total solid content of the photosensitive composition.

[0164] <Solvent> The photosensitive composition may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse various components other than the solvent that may be contained in the photosensitive composition. Examples of the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these. The solvents may be used alone or in combination. The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solids content of the photosensitive composition.

[0165] The photoacid generator is a compound that generates an acid when exposed to light (for example, exposure light). When the polyimide precursor has an acid-decomposable group, the photosensitive composition preferably contains a photoacid generator.

[0166] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators. Examples of ionic photoacid generators include compounds having a sulfonium structure, onium salt compounds having a diaryliodonium or triarylsulfonium structure, and ammonium salt compounds having a quaternary ammonium structure. Examples of ionic photoacid generators include those described in paragraphs

[0114] to

[0133] of JP 2014-085643 A. Examples of nonionic photoacid generators include trichloromethyl-s-triazine and its derivatives (trichloromethyl-s-triazines which may have a substituent), compounds having a diazomethane structure, compounds having an imide sulfonate structure, and compounds having an oxime sulfonate structure. Examples of trichloromethyl-s-triazine and its derivatives, diazomethane compounds, and imide sulfonate compounds include those described in paragraphs

[0083] to

[0088] of JP 2011-221494 A. Furthermore, examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of WO 2018 / 179640.

[0167] The photosensitive composition may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Because halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, the following contents are preferred.

[0168] The content of impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive composition. The lower limit is often 0 ppb by mass or more, and may be 1 ppb by mass or more, or 0.1 ppm by mass or more, relative to the total mass of the photosensitive composition. The content of impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0169] Examples of methods for adjusting the impurity content include a method of using raw materials with low impurity contents as raw materials for the photosensitive composition, a method of purifying the raw materials for the photosensitive composition before use, and a method of preventing impurities from being mixed in when preparing the photosensitive composition.

[0170] In the photosensitive composition, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane is preferably low. Specifically, the content of each of these compounds is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive composition. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, relative to the total mass of the photosensitive composition. The content of these compounds can be adjusted using the same method as for the impurities described above. Furthermore, these compounds can be quantified using known measurement methods.

[0171] Examples of the aliphatic thiol compound, the thermally crosslinkable compound, and the hydrogen donor compound include various components described in WO 2022 / 039027.

[0172] [Transfer Film] The transfer film of the present invention has a temporary support and a photosensitive composition layer formed using the above-described photosensitive composition.

[0173] FIG. 1 is a cross-sectional schematic diagram showing an example of an embodiment of a transfer film. The transfer film 100 shown in FIG. 1 has a configuration in which a temporary support 12, a photosensitive composition layer 14, and a cover film 16 are laminated in this order. Although the transfer film 100 shown in FIG. 1 has the cover film 16, the transfer film may have no cover film 16. Furthermore, as described below, the transfer film may further have an intermediate layer and / or a thermoplastic resin layer. Each component of the transfer film will be described in detail below.

[0174] [Temporary Support] The transfer film has a temporary support, which is a member that supports the photosensitive composition layer and is ultimately removed by a peeling treatment.

[0175] The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is also preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate (PET) films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. Furthermore, the temporary support is preferably free of deformations such as wrinkles and scratches.

[0176] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support. Specifically, the transmittance at each of the wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more. The upper limit is preferably less than 100%. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. The number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / 10 mm. ２ Preferably, 10 pieces / 10 mm or less ２ More preferably, 3 pieces / 10 mm or less ２ More preferably, 0 pieces / 10 mm or less ２is particularly preferred.

[0177] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using an SEM (scanning electron microscope).

[0178] In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that comes into contact with the photosensitive composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２ Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp output and illuminance can be adjusted as appropriate.

[0179] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0180] Examples of the temporary support include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0181] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support for the purpose of imparting handleability. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The film thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0182] [Photosensitive Composition Layer] The photosensitive composition layer is a layer formed using the photosensitive composition. The various components that can be contained in the photosensitive composition layer are synonymous with the various components that can be contained in the photosensitive composition, and the preferred embodiments are also the same. However, the preferred ranges of the contents of the various components in the photosensitive composition layer are the same as the preferred ranges obtained by replacing the above-mentioned "contents (% by mass) of the various components relative to the total solid content of the photosensitive composition" with "contents (% by mass) of the various components relative to the total mass of the photosensitive composition layer." Specifically, the phrase "The content of the polyimide precursor is preferably 5.0% by mass or more relative to the total solid content of the photosensitive composition" should be replaced with "The content of the polyimide precursor is preferably 5.0% by mass or more relative to the total mass of the photosensitive composition layer."

[0183] From the viewpoints of improving reliability, improving the handling properties of the transfer film, and improving lamination properties, the water content of the photosensitive composition layer is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less, relative to the total mass of the photosensitive composition layer. The lower limit of the water content of the photosensitive composition layer is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the photosensitive composition layer. Specific examples of the water content in the photosensitive composition layer include 2.5% by mass, 1.5% by mass, and 0.3% by mass, relative to the total mass of the photosensitive composition layer.

[0184] From the viewpoints of improving reliability, improving the handling properties of the transfer film, and improving lamination properties, the amount of residual solvent in the photosensitive composition layer is preferably 6.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less, relative to the total mass of the photosensitive composition layer. The lower limit of the amount of residual solvent in the photosensitive composition layer is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the photosensitive composition layer. Specific examples of the amount of residual solvent in the photosensitive composition layer include 3.5% by mass, 2.5% by mass, 1.5% by mass, and 0.3% by mass, relative to the total mass of the photosensitive composition layer.

[0185] The average thickness of the photosensitive composition layer is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 3 μm or more, and particularly preferably 5 μm or more, from the viewpoint of superior migration resistance, and is preferably 40 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less, from the viewpoint of superior resolution.

[0186] The transfer film may have layers other than those described above.

[0187] [Intermediate layer and thermoplastic resin layer] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of the intermediate layer and the thermoplastic resin layer include those described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0188] [Cover Film] The transfer film may have a cover film. The number of fisheyes having a diameter of 80 μm or more contained in the cover film is 5 / m. ２ The following are preferred: Fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is introduced into the film when the material is thermally melted and then kneaded, extruded, and / or biaxially stretched, cast, or other methods are used to produce the film.

[0189] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less２ More preferably, 5 or less pieces / mm ２ The following is more preferable: This can suppress defects caused by the transfer of irregularities due to particles contained in the cover film to the photosensitive composition layer.

[0190] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.If Ra is within this range, for example, when the transfer film is long, the winding property of the transfer film is excellent.In addition, from the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0191] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film, and examples of the cover film include the cover films described in paragraphs 0083 to 0087 and 0093 of JP-A No. 2006-259138.

[0192] Examples of cover films include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.). The cover film may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0193] The transfer film may include other layers in addition to the above-described layers. Examples of the other layers include a high refractive index layer. Examples of the high refractive index layer include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0194] [Method for manufacturing transfer film] A known manufacturing method can be applied to the manufacturing method of the transfer film. In the manufacturing method of the transfer film, a photosensitive composition is preferably applied to a temporary support to form a photosensitive composition layer, and more preferably, a coating of the photosensitive composition is dried to form the photosensitive composition layer. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

[0195] For example, a method for manufacturing the transfer film 100 shown in Figure 1 includes a step of applying a photosensitive composition to the surface of a temporary support 12 to form a coating film, and then drying this coating film to form a photosensitive composition layer 14. Furthermore, the transfer film 100 shown in Figure 1 is manufactured by pressing a cover film 16 onto the photosensitive composition layer of the transfer film manufactured by the above manufacturing method. The transfer film 100 shown in Figure 1 may also be wound up after manufacturing and stored as a roll-form transfer film 100. The roll-form transfer film 100 can be provided in its original form for the lamination step with a substrate in a roll-to-roll system described below.

[0196] As described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the photosensitive composition layer. Examples of the intermediate layer-forming composition, the method for forming the intermediate layer, the thermoplastic resin layer-forming composition, and the method for forming the thermoplastic resin layer are described in paragraphs 0133 to 0136 and 0143 to 0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0197] [Uses] The photosensitive composition can be used to form a film (hereinafter also referred to as a "specific film"), and the specific film can be applied to various uses. The specific film can be applied, for example, as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plating member. More specifically, examples of the specific film include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, an interlayer insulating film in a build-up substrate for a semiconductor package, an organic interposer, a color filter, an overcoat film for a color filter, and an etching resist for wiring formation. In particular, the photosensitive composition and transfer film can be suitably used to form an insulating film, and the insulating film is preferably used as an insulating film for a semiconductor package. That is, the photosensitive composition and transfer film are preferably used to form an insulating film for a semiconductor package. The photosensitive composition and transfer film are also preferably used to manufacture a laminate having a photosensitive composition layer having a pattern on a substrate.

[0198] [Method for producing laminate] The method for producing the laminate of the present invention is not particularly limited as long as it is a method for forming a photosensitive composition layer on a substrate using the photosensitive composition to obtain a laminate. Specifically, the method for producing a laminate preferably includes the following steps 1 to 3. Step 1: Step of forming a photosensitive composition layer on a substrate using the photosensitive composition. Step 2: Step of forming a pattern including vias in the photosensitive composition layer. Step 3: Step of subjecting the pattern to at least one of heating and exposure. Each step in the method for producing a laminate will be described in detail below.

[0199] [Step 1] Step 1 is a step of forming a photosensitive composition layer on a substrate using a photosensitive composition. Examples of methods for forming the photosensitive composition layer include a method of applying a photosensitive composition. Examples of methods for applying the photosensitive composition include the photosensitive composition application method in the transfer film manufacturing method described above. The photosensitive composition layer may be formed by drying a coating of the photosensitive composition. The photosensitive composition layer may also be formed using the transfer film described above. Examples of methods for forming a photosensitive composition layer using a transfer film include a method in which the surface of the photosensitive composition layer in the transfer film opposite the temporary support side is brought into contact with the substrate and the transfer film and substrate are laminated together. Examples of lamination methods include known transfer methods and lamination methods. Preferred are methods in which the substrate is laminated on the surface of the photosensitive composition layer and pressure and heat are applied using a roll or the like. Examples of the lamination method include known laminators such as a vacuum laminator and an auto-cut laminator. The lamination temperature is not particularly limited, but is preferably 70 to 130°C. When a transfer film is used, step 1 is preferably carried out by a roll-to-roll method. The substrate to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer. The roll-to-roll method refers to a method in which a substrate that can be wound up and unwound is used as the substrate, and includes a step of unwinding the substrate before any of the steps included in the method for producing a laminate of the present invention, and a step of winding the substrate after any of the steps, and at least any of the steps (preferably all steps or all steps other than the heating step) is carried out while the substrate is being transported. As the unwinding method in the unwinding step and the winding method in the winding step, known methods may be used in production methods that apply the roll-to-roll method.

[0200] <Substrate> Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer. The refractive index of the substrate is preferably 1.50 to 1.52. The substrate may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass, such as Corning Gorilla Glass, can also be used. Materials contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. When the substrate includes a resin substrate, a resin film with low optical distortion and / or high transparency is more preferred. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0201] The substrate having a conductive layer is preferably a resin substrate having a conductive layer, and more preferably a resin film having a conductive layer, because it can be produced by a roll-to-roll process. The substrate having a conductive layer may be a laminate obtained by the above-mentioned method for producing a laminate.

[0202] Examples of the conductive layer include any conductive layer used in general circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer in the substrate having a conductive layer may be one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, it is preferable that each conductive layer is made of a different material. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４ It is preferably less than Ωcm.

[0203] The conductive layer may be patterned. Methods for producing a patterned conductive layer include, for example, subtractive methods such as etching and additive methods. Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching. The etching method may also be a method using an etching resist.

[0204] [Step 2] Step 2 is a step of forming a pattern including vias in the photosensitive composition layer. The pattern including vias may be formed only in the photosensitive composition layer, or may be formed in both the photosensitive composition layer and the substrate. The pattern including vias may be either a through hole or a via hole. Examples of the shape of the via include a square, trapezoid, and inverted trapezoid cross-sectional shape; and a circle and a square front shape (the shape when the via is observed from the direction in which the via bottom is visible). In order to improve the adhesion of plated copper to the via wall surface, an inverted trapezoid cross-sectional shape is preferred. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or more, and preferably 2 or more.

[0205] The method for forming a pattern containing vias preferably includes an exposure step of patternwise exposing a photosensitive composition layer, and a development step of developing the pattern-exposed photosensitive composition layer with a developer to form a pattern. Note that "patternwise exposure" refers to a form of patternwise exposure, i.e., exposure in which exposed areas and unexposed areas exist.

[0206] <Exposure Step> The exposure step is a step of patternwise exposing the photosensitive composition layer. The positional relationship between the exposed and unexposed areas in the patternwise exposure is not particularly limited and may be adjusted as appropriate. The patternwise exposure may be performed from the side opposite the substrate of the photosensitive composition layer, or from the substrate side of the photosensitive composition layer.

[0207] The light source used for exposure may be any light source that irradiates light in a wavelength range to which the photosensitive component in the photosensitive composition layer (e.g., the compound represented by formula (1)) is sensitive (e.g., light in wavelength ranges of 254 nm, 313 nm, 365 nm, and 405 nm). Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 10 to 1000 mJ / cm ２ is more preferred.

[0208] When a photosensitive composition layer is formed using a transfer film in step 1, in the exposure step, pattern exposure may be performed after peeling the temporary support from the photosensitive composition layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. In order to prevent mask contamination due to contact between the photosensitive composition layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support. The pattern exposure may be performed through a mask or by direct exposure using a laser or the like. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified. It is preferable to peel the temporary support from the photosensitive composition layer before the development step.

[0209] <Developing Step> The developing step is a step of forming a pattern by developing the exposed photosensitive composition layer using a developer after the exposure step. Examples of the developer include organic solvent developers.

[0210] Examples of organic solvent developers include developers containing organic solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Cyclopentanone or propylene glycol monomethyl ether acetate is preferred as the organic solvent developer, and cyclopentanone is more preferred. In the organic solvent developer, a mixture of multiple organic solvents may be used, or the organic solvent may be mixed with an organic solvent other than those mentioned above or with water. The water content of the organic solvent developer is preferably less than 10% by mass, based on the total mass of the organic solvent developer, and more preferably substantially free of water. The organic solvent content of the organic solvent developer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total mass of the organic solvent developer. The upper limit is preferably 100% by mass or less, based on the total mass of the organic solvent developer.

[0211] Examples of development methods include puddle development, shower development, spin development, and dip development. In shower development, unnecessary portions can be removed by spraying a developer onto the photosensitive composition layer after exposure. It is also preferable to spray a detergent or the like onto the layer after development and remove development residues by rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0212] [Step 3] Step 3 is a step of at least one of heating and exposure to light, preferably at least heating, of the pattern obtained in step 2. Step 3 promotes a reaction (e.g., a ring-closing reaction) of the polyimide precursor in the photosensitive composition, and a polyimide can be formed.

[0213] The temperature and time of the heat treatment can be appropriately selected depending on the structure of the polyimide precursor. The heat treatment temperature is preferably 120 to 400°C, more preferably 150 to 400°C, and even more preferably 180 to 350°C. The heat treatment time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and even more preferably 1 to 9 hours. The heat treatment may be carried out in either an air environment or a nitrogen-substituted environment. The atmospheric pressure in the heat treatment environment is preferably 8.1 kPa or more, more preferably 50.66 kPa or more. The upper limit is preferably 121.6 kPa or less, more preferably 111.46 kPa or less, and even more preferably 101.3 kPa or less.

[0214] The light source and exposure dose for the exposure treatment can be appropriately selected depending on the type of photosensitive component in the photosensitive composition. Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 2000 mJ / cm. ２ is preferred, and 10 to 2000 mJ / cm ２ is more preferred.

[0215] [Other Steps] The method for producing a laminate may include other steps in addition to those described above. Examples of other steps include the following steps.

[0216] <Cover Film Peeling Step> When the transfer film has a cover film in the laminate manufacturing method, it is preferable to include a step of peeling off the cover film of the transfer film. As the method for peeling off the cover film, a known method can be applied.

[0217] <Contacting Process with Treatment Liquid> Between Step 2 and Step 3, a step of contacting the pattern obtained in Step 2 with a treatment liquid containing a basic compound and a solvent may be included. In particular, when the photosensitive composition does not contain a thermal base generator, the method for producing a laminate preferably includes the contacting process with a treatment liquid. Examples of the basic compound include nitrogen-containing compounds. Furthermore, basic compounds among the compounds exemplified above as thermal base generators can also be used as the basic compound. The content of the basic compound is preferably 0.1 to 10 mass %, more preferably 1 to 8 mass %, based on the total mass of the treatment liquid. Examples of the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents, ketone solvents, aromatic hydrocarbon solvents, aprotic polar solvents, cyclic ether solvents, ester solvents, amide solvents, lactone solvents, and solvents containing two or more of these.

[0218] The method for contacting the pattern with the treatment liquid is not particularly limited, and examples thereof include a method of immersing the pattern in the treatment liquid, a method of spraying the treatment liquid onto the pattern, a method of pouring the treatment liquid onto the pattern, etc. The contact time with the treatment liquid is preferably, for example, 1 to 30 minutes.

[0219] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing the laminate may further include a step of performing a treatment to reduce the visible light reflectance of the conductive layer. When the substrate is a substrate having a plurality of conductive layers, the treatment to reduce the visible light reflectance may be performed on some or all of the conductive layers. Examples of treatments to reduce the visible light reflectance include oxidation treatments. For example, copper can be oxidized to copper oxide, thereby blackening the conductive layer, thereby reducing the visible light reflectance of the conductive layer. Suitable embodiments of treatments to reduce the visible light reflectance include those described in paragraphs 0017 to 0025 of JP 2014-150118 A and paragraphs 0041, 0042, 0048, and 0058 of JP 2013-206315 A, the contents of which are incorporated herein by reference.

[0220] <Etching Step> When the base material is a substrate having a conductive layer, the method for producing a laminate may include a step (etching step) of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern (film) formed in step 2 or step 3 as an etching resist film. Examples of the etching method include the wet etching method described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching.

[0221] The method for producing the laminate also preferably uses a substrate having a plurality of conductive layers on both surfaces thereof, and sequentially or simultaneously forms patterns on the conductive layers formed on both surfaces. With this configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation from both surfaces of the substrate by roll-to-roll is also preferred.

[0222] [Laminate] The laminate is a laminate obtained by the above-described laminate manufacturing method. The laminate has a substrate and a photosensitive composition layer having a pattern including vias. The laminate is used, for example, in semiconductor devices. Examples of semiconductor devices include various semiconductor devices such as semiconductor packages used in electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0223] [Method for manufacturing a semiconductor package] The method for manufacturing a laminate described above can be suitably applied as a method for manufacturing a semiconductor package. Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as a method for manufacturing a build-up substrate. Specifically, examples include a manufacturing method including steps Z1 to Z4 in this order. Step Z1: A step of forming a photosensitive composition layer on a substrate having a conductive layer. Step Z2: A step of forming a pattern having vias in the photosensitive composition layer. Step Z3: A step of heat-treating the pattern. Step Z4: A step of forming a circuit pattern on the pattern.

[0224] Steps Z1 to Z3 in the method for manufacturing a semiconductor package include the above-mentioned steps 1 to 3, respectively.

[0225] [Step Z4] Step Z4 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. Examples of semi-additive processes include the following: First, after step Z3, the via bottoms, via walls, and the entire surface of the pattern are subjected to electroless copper plating using a palladium catalyst or the like to form a seed layer. The seed layer serves to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection insulation reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby suppressing damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of a pattern having vias through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst used in the electroless plating process is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Commercially available electroless copper plating solutions include, for example, "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0226] After electroless copper plating, it is preferable to thermocompress the surface of the photosensitive composition layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the photosensitive composition layer is preferably 5 to 30 μm, since it can be made thicker than the wiring height after electrolytic copper plating. After thermocompression bonding of the transfer film, the photosensitive composition layer is exposed, for example, through a mask on which the desired wiring pattern is drawn. Examples of the exposure method include the exposure method in step 2-1. After exposure, the temporary support of the transfer film is peeled off, and the exposed photosensitive composition layer is developed using a developer to form a pattern. After forming the pattern, development residues of the photosensitive composition may be removed using plasma or the like. After development, electrolytic copper plating is performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern is peeled off using an alkaline aqueous solution or an amine-based stripper. After peeling the pattern, the seed layer between the wiring is removed (flash etching). Flash etching is performed, for example, using an oxidizing solution containing sulfuric acid and an acidic solution such as hydrogen peroxide. Examples of oxidizing solutions include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Co., Ltd. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium can be removed using an acidic solution such as nitric acid and hydrochloric acid.

[0227] After the pattern is removed or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The preferred thermosetting conditions are a curing temperature of 150 to 240°C and a curing time of 15 to 500 minutes.

[0228] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z3 and before step Z4. By performing the roughening step, the surface of the pattern can be roughened to improve adhesion to the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of roughening liquids include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0229] The above-described steps are repeated depending on the number of layers required to manufacture a semiconductor package. It is preferable to form a solder resist on the outermost layer.

[0230] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes a specific film. The semiconductor package preferably includes the laminate described above, and more preferably is manufactured using the semiconductor package manufacturing method described above. In the semiconductor package, the specific film may be used as an insulating film, or may be used as an organic interposer or insulating film in a so-called build-up substrate.

[0231] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0232] [Preparation of Photosensitive Composition] Various components were mixed to prepare mixtures in the amounts (solid content ratios) shown in the following table. Next, the mixtures were diluted with a mixed solvent containing 25% by mass of MEK (methyl ethyl ketone) and 75% by mass of NMP to a solid content of 30% by mass, thereby preparing the photosensitive compositions of Examples 1 to 109 and Comparative Examples 1 to 4.

[0233] The various components contained in the photosensitive composition are listed below.

[0234] 〔resin〕

[0235]

[0236] <Method for Synthesizing Resin A-1> 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours, 20.0 g, 64.5 mmol), 2-hydroxyethyl methacrylate (16.8 g, 129 mmol), hydroquinone (0.05 g), pyridine (20.4 g, 258 mmol), and diethylene glycol dimethyl ether (100 g) were mixed and stirred at 60°C for 18 hours to obtain a reaction mixture (a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate). The resulting diester was then subjected to a chlorination reaction using thionyl chloride (SOCl2) to obtain a reaction mixture. Next, a solution of 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) in N-methylpyrrolidone (100 mL) was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. The reaction mixture was reacted at 0°C for 1 hour, after which ethanol (70 g) was added and stirred at room temperature for 1 day. The resulting reaction solution was added to water (5 L) and stirred at 5,000 rpm for 15 minutes to obtain a precipitate, which was a crude polymer. The precipitate collected by filtration from the mixture was stirred in water (3 L) for 30 minutes and collected by filtration again. The resulting precipitate was dried under reduced pressure at 45°C for 3 days to obtain Resin A-1, a polyimide precursor. Resin A-1 had a weight average molecular weight (Mw) of 18,000 and an acid value of 0 mgKOH / g.

[0237] <Method for Synthesizing Resin A-2> 4,4'-oxydiphthalic dianhydride (77.6 g) and diphenyl-3,3',4,4'-tetracarboxylic dianhydride (73.6 g) were placed in a 2 L separable flask, 2-hydroxyethyl methacrylate (134.0 g) and γ-butyrolactone (400 mL) were added, and pyridine (79.1 g) was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, a solution of dicyclohexylcarbodiimide (DCC, 206.3 g) dissolved in γ-butyrolactone (180 mL) was added to the reaction mixture over 40 minutes while stirring under ice cooling. Next, a suspension of 4,4'-oxydianiline (ODA, Mw = 200.24, 93.0 g) in γ-butyrolactone (350 mL) was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, ethanol (30 mL) was added and stirred for 1 hour, after which γ-butyrolactone (400 mL) was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to ethyl alcohol (3 L) to obtain a crude polymer precipitate. The resulting crude polymer was collected by filtration and dissolved in tetrahydrofuran (1.5 L) to obtain a crude polymer solution. The resulting crude polymer solution was purified using an anion exchange resin (Amberlyst TM15, manufactured by Organo Corporation) to obtain a polymer solution. The resulting polymer solution was added dropwise to water (28 L) to precipitate the polymer, and the resulting precipitate was collected by filtration and dried under vacuum to obtain Resin A-2, a powdered polyimide precursor. Resin A-2 had a weight average molecular weight (Mw) of 22,000 and an acid value of 0 mgKOH / g. The imide group content of the polyimide obtained from Resin A-2 was 27.4 mass% per repeating unit.

[0238] <Synthesis method of resin A-3> Resin A-3 was synthesized in the same manner as for resin A-1, except that 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) was replaced with 3,5-diaminobenzoic acid (8.94 g, 58.7 mmol). Resin A-3 had a weight average molecular weight (Mw) of 20,000 and an acid value of 90 mgKOH / g.

[0239] <Method for synthesizing resin A-4> Resin A-4 was synthesized in accordance with the method for synthesizing resin A-1, except that 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) was replaced with 4,4'-diaminodiphenyl ether (7.39 g, 39.1 mmol) and 3,5-diaminobenzoic acid (2.98 g, 19.6 mmol). Resin A-4 had a weight average molecular weight (Mw) of 18,000 and an acid value of 30 mgKOH / g.

[0240] <Method for synthesizing resin A-5> Resin A-5 was synthesized in accordance with the method for synthesizing resin A-1, except that 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) was replaced with 4,4'-diaminodiphenyl ether (3.69 g, 19.6 mmol) and 3,5-diaminobenzoic acid (5.96 g, 39.1 mmol). Resin A-5 had a weight average molecular weight (Mw) of 23,000 and an acid value of 60 mgKOH / g.

[0241] <Method for synthesizing resin A-6> Resin A-6 was synthesized in accordance with the method for synthesizing resin A-1, except that 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) was replaced with 4,4'-diaminodiphenyl ether (9.85 g, 52.2 mmol) and 3,5-diaminobenzoic acid (0.99 g, 6.5 mmol). Resin A-6 had a weight average molecular weight (Mw) of 17,000 and an acid value of 10 mgKOH / g.

[0242] <Method for synthesizing resin A-7> Resin A-7 was synthesized in accordance with the method for synthesizing resin A-1, except that 4,4'-diaminodiphenyl ether (11.08 g, 58.7 mmol) was replaced with 4,4'-diaminodiphenyl ether (10.5 g, 55.4 mmol) and 3,5-diaminobenzoic acid (0.50 g, 3.3 mmol). Resin A-7 had a weight average molecular weight (Mw) of 21,000 and an acid value of 5 mgKOH / g.

[0243] The acid value of each of the resins was determined according to JIS K0070 by dissolving 0.1 g of the synthesized resin in 20 ml of NMP and titrating with KOH using thymolphthalein as an indicator.

[0244] The dissolution rate of each resin in 200 mL of 2.38% by mass TMAHaq at 23° C. was determined by the method described above, and all were 1 mg / min or less.

[0245] [Polymerizable compounds] SR205NS: a bifunctional polymerizable compound, manufactured by Sartomer Co., Ltd., triethylene glycol dimethacrylate SR209: a bifunctional polymerizable compound, manufactured by Sartomer Co., Ltd., tetraethylene glycol dimethacrylate BPE-100: a bifunctional polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate Viscoat #295: a trifunctional polymerizable compound, manufactured by Osaka Organic Chemical Industry Co., Ltd., trimethylolpropane triacrylate TMPTMA: a trifunctional polymerizable compound, manufactured by TCI, trimethylolpropane trimethacrylate M-130G: a monofunctional polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., methoxypolyethylene glycol methacrylate AM-130G: a monofunctional polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., methoxypolyethylene glycol #600 acrylate SR355NS: tetrafunctional polymerizable compound, manufactured by Sartomer, ditrimethylolpropane tetraacrylate A-9550: penta- to hexafunctional polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol polyacrylate DPHA: hexafunctional polymerizable compound, manufactured by TCI, dipentaerythritol hexaacrylate

[0246] [Specific Compounds and Comparative Compounds] Compounds C-1 to C-5 are specific compounds, and compound C-9 is a compound different from the specific compounds. Compound C-1: TR-HABI 101, manufactured by Tronly Corporation Compound C-2: TR-HABI 102, manufactured by Tronly Corporation Compound C-3: TR-HABI 107, manufactured by Tronly Corporation Compound C-4: TR-HABI 103, manufactured by Tronly Corporation Compound C-5: TR-HABI 104, manufactured by Tronly Corporation Compound C-9: Irgacure OXE-02, manufactured by BASF Corporation

[0247] [Other additives] Compound D-1: chain transfer agent, the following compound

[0248]

[0249] MEHQ: polymerization inhibitor, 4-methoxyphenol Phenothiazine: polymerization inhibitor EAB-F: sensitizer, 4,4'-bis(diethylamino)benzophenone Compound G-1: thermal base generator, the following compound

[0250]

[0251] F-551A: Fluorine-based surfactant, Megafac (registered trademark) F551A, manufactured by DIC Corporation S-506: Silicone-based surfactant, manufactured by DIC Corporation HAT: Rust inhibitor, 5-amino-1H-tetrazole Compound J-1: The following compound

[0252]

[0253] YA050C-MJE: Filler, silicon dioxide (spherical silica slurry), average particle size 50 nm, manufactured by Admatechs Co., Ltd.

[0254] [Preparation of Transfer Film] The prepared photosensitive composition was applied to a temporary support (QS62, manufactured by Toray Industries, Inc., 16 μm thick PET film) and dried at 100° C. to form a photosensitive composition layer. The film thickness of the photosensitive composition layer was adjusted to 12 μm after drying. Next, a protective film (FG-201, polypropylene film, manufactured by Oji F-Tex Co., Ltd., 30 μm thick) was laminated to the side of the photosensitive composition layer opposite the temporary support to obtain a transfer film.

[0255] [Evaluation] Using the photosensitive compositions or transfer films obtained in each of the Examples and Comparative Examples, the resolution of the photosensitive compositions, the step-following ability of the transfer films, and the migration resistance and linear expansion coefficient of the films formed were evaluated.

[0256] [Resolution] A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the above-mentioned transfer film was laminated onto the substrate to obtain a laminate having a substrate / photosensitive composition layer / temporary support. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. The obtained laminate was exposed from the temporary support side through a mask having a pattern of L / S (line / space) = 100 / 100 (μm / μm) (high-pressure mercury lamp, cumulative illuminance of 0 to 1000 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ 5 mJ / cm ２ The temporary support was peeled off 30 minutes after the exposure, and the obtained sample was immersed in cyclopentanone at 23°C for 120 seconds, and then immersed in PGMEA (propylene glycol monomethyl ether acetate) at 23°C for 30 seconds to remove the unexposed areas and form a pattern. The obtained pattern, L / S = 100 / 100 (µm / µm), was observed using an optical microscope, and the exposure amount at which the line width of the pattern was closest to the line width of the mask (100 µm) was determined to be the optimal exposure amount.

[0257] Next, the laminate having the above-mentioned substrate / photosensitive composition layer / temporary support was exposed (high-pressure mercury lamp, the above-mentioned optimal exposure amount) through a mask having a pattern of L / S = 7 / 7 (μm / μm) from the temporary support side. 30 minutes after exposure, the temporary support was peeled off, and the obtained sample was immersed in cyclopentanone at 23 ° C. for 120 seconds, and then immersed in PGMEA at 23 ° C. for 30 seconds to obtain a patterned sample. The patterned sample was observed using an SEM (scanning electron microscope), and the resolution was evaluated according to the following criteria. 20 patterns were observed, and if defects such as pattern collapse, pattern lifting, and inter-pattern connection were observed in two or less patterns, it was considered that the pattern had been formed. In practical use, the resolution is preferably rated A or higher.

[0258] A: A pattern with L / S = 7 / 7 (μm / μm) was formed. B: A pattern with L / S = 7 / 7 (μm / μm) was not formed.

[0259] [Step-conforming ability] A test substrate was prepared by forming a 2 μm-thick copper pattern (L / S=25 / 25 (μm / μm)) with comb-shaped wiring on a silicon wafer. The transfer film, from which the protective film had been peeled off, was laminated so that the photosensitive composition layer faced the wiring-formed surface of the test substrate. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50° C., a rubber roller temperature of 100° C., a linear pressure of 3 N / cm, and a transport speed of 1 m / min. The copper patterns after lamination were observed with an optical microscope, and step-conforming ability was evaluated according to the following criteria.

[0260] A: No air had entered between the wires, or only a small amount of air had entered between the wires (air bubble area was less than 10% of the area between the wires). B: Some air had entered between the wires (air bubble area was 10% or more but less than 40% of the area between the wires). C: Air had entered between the wires (air bubble area was 40% or more of the area between the wires).

[0261] [Migration Resistance] A test substrate was prepared by forming a 2.0 μm-thick copper pattern (L / S=25 / 25 (μm / μm)) in a comb-like pattern on a silicon wafer. Each photosensitive composition was applied to the test substrate and dried so that the thickness of the photosensitive composition layer on the copper pattern became 12 μm. The resulting photosensitive composition layer was then exposed to light using an ultra-high pressure mercury lamp. The cumulative exposure dose measured with an illuminometer at a wavelength of 365 nm was 300 mJ / cm. ２ After the exposure, a heat treatment was carried out in a nitrogen atmosphere at 200°C for 100 minutes to prepare an evaluation sample. Ten evaluation samples were prepared and placed in a chamber at 130°C and 85% RH (relative humidity) using a HAST tester. A voltage of 3.3 V was applied to check the time and number of samples until migration occurred, and the migration resistance was evaluated according to the following criteria. Note that the initial resistance value measured at room temperature (23°C) was 1 × 10 １４ Ω or more, the resistance value is 1 × 10 ３ When the resistance drops to Ω or less, it is counted as the occurrence of migration. In practical terms, it is preferable that the migration resistance be rated C or higher.

[0262] A: After 100 hours, no migration was observed in any of the samples, and after 200 hours, migration was observed in 4 or fewer samples. B: After 100 hours, migration was observed in 1 to 4 samples, and after 200 hours, migration was observed in 1 to 4 samples. C: After 100 hours, migration was observed in 1 to 4 samples, and after 200 hours, migration was observed in 5 to 10 samples. D: After 100 hours, migration was observed in 5 to 10 samples, and after 200 hours, migration was observed in 5 to 10 samples.

[0263] [Linear expansion coefficient] A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the prepared photosensitive composition was applied to the substrate and dried to obtain a laminate having a photosensitive composition layer of 30.0 μm in thickness on the substrate. The obtained laminate was exposed to light (high-pressure mercury lamp, integrated illuminance of 300 mJ / cm measured with an illuminometer at a wavelength of 365 nm) from the side opposite to the substrate side of the photosensitive composition layer. ２ ), and then heated in an oven (200°C, 100 minutes). After immersion in 2M hydrochloric acid for 8 hours for a peeling treatment, the film was rinsed (in pure water at room temperature for 1 hour) and then peeled off from the substrate to obtain a free-standing film derived from the photosensitive composition layer. If the free-standing film could not be peeled off by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about a week for peeling. The obtained free-standing film was cut into strips to prepare measurement samples. The produced free-standing film was cut into strips (19 mm x 5 mm) and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a heating rate of 10°C / min, a chuck distance of 20 mm, and a load of 45 mN. The linear expansion coefficient was measured as a value (ppm / K) in the temperature range of 50°C to 150°C during heating, and was calculated as the average of three measurements. The linear expansion coefficient was evaluated according to the following evaluation criteria.

[0264] A: Linear expansion coefficient is 35 ppm / K or less B: Linear expansion coefficient is more than 35 ppm / K

[0265] [Results] The following tables show the formulations and evaluation results of the photosensitive compositions. Table 2 is a continuation of Table 1, and Table 3 is a continuation of Table 2. Table 5 is a continuation of Table 4, and Table 6 is a continuation of Table 5. For example, the photosensitive composition of Example 1 contains Resin A-1 and SR205NS listed in Table 1, Compounds C-1, D-1, MEHQ, EAB-F, and G-1 listed in Table 2, and HAT and J-1 listed in Table 3. In the tables, "Amount" indicates the content (mass %) relative to the total solid content of the photosensitive composition. In the tables, the "B / A" column indicates the mass ratio of the content of the polymerizable compound (B) to the content of the polyimide precursor (A) (content of polymerizable compound (B) / content of polyimide precursor (A)). In the tables, (n) (n is an integer) listed after the component of the polymerizable compound indicates the number of polymerizable groups in the polymerizable compound.

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272] Comparison of Examples 1 to 5, 15 to 20, 31 to 36, and 45 to 49 confirmed that when the mass ratio of the polymerizable compound content to the polyimide precursor content was 0.22 or more, better step-conforming ability was achieved. Comparison of Examples 99 to 105 with other Examples confirmed that when the photosensitive composition contained a filler, the linear expansion coefficient was smaller. Comparison of Examples 15 to 28, 31 to 58, and 87 to 98 confirmed that when R in the specific compound was an alkoxy group, better migration resistance was achieved. Comparison of Examples 1, 63, and 106 to 109 confirmed that when the acid value of the polyimide precursor was 10 mgKOH / g or less, better migration resistance was achieved.

[0273] The photosensitive compositions of Examples 110 to 127 were prepared in the same manner as the photosensitive compositions of Examples 1 to 109 and Comparative Examples 1 to 4, except that the compositions were changed to the blending amounts (blending amounts relative to the solid content) shown in the table below. Next, [Preparation of Transfer Films] and [Evaluation] were carried out using the photosensitive compositions of Examples 110 to 127 in the same manner as the photosensitive compositions of Examples 1 to 109 and Comparative Examples 1 to 4. However, in Example 127, when preparing the sample for evaluating [Migration Resistance] and the sample for measuring [Linear Expansion Coefficient], after exposure, the sample was immersed for 120 seconds in a treatment solution prepared by mixing the following components, and then heat-treated.

[0274] <Treatment Solution> PGMEA: 90.3 parts by mass Gamma-butyrolactone: 4.7 parts by mass N-(3-dimethylaminopropyl) methacrylamide: 5 parts by mass

[0275] The various components contained in the photosensitive composition are as follows: Compound G-2: thermal base generator, the following compound. Compound G-3: thermal base generator, the following compound. Compound D-2: chain transfer agent, N-phenylglycine, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Compound D-3: chain transfer agent, methoxybutyl-β-mercaptopropionate, manufactured by Sakai Chemical Industry Co., Ltd. Compound F-2: sensitizer, 4,4'-bis(dimethylamino)benzophenone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Compound F-3: sensitizer, 2-isopropylthioxanthone, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Compound I-2: rust inhibitor, 3-amino-1H-1,2,4-triazole, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Compound I-3: rust inhibitor, 1H-triazole, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

[0276]

[0277] The formulations of the photosensitive compositions and the evaluation results are shown in the following tables. Table 8 is a continuation of Table 7, and Table 9 is a continuation of Table 8. The meanings of each column in Tables 7 to 9 are the same as those in Tables 1 to 6.

[0278]

[0279]

[0280]

[0281] [Fabrication of Semiconductor Packages] The transfer film of each example was laminated on both sides of a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which a circuit pattern had been formed, and photosensitive composition layers were formed on both sides of the glass epoxy substrate. A vacuum laminator was used for this. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. The resulting laminate was exposed (high-pressure mercury lamp, optimal exposure dose as described above) from the temporary support side through a mask with a 100 μm diameter light-shielding portion. After exposure, the substrate was immersed in cyclopentanone for 120 seconds and then in PGMEA for 30 seconds, and the unexposed portions were removed to form a pattern. After heat treatment (200°C for 100 minutes), residues were removed using a sodium permanganate aqueous solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at a predetermined position using a known dry film resist, and electrolytic plating was performed. The resist pattern was then stripped using a stripping solution. In Example 127, the unexposed portions were removed to form a pattern, and the substrate was then immersed in the above-described treatment solution for 120 seconds before being subjected to a heat treatment. Finally, a seed layer etching process was performed to form copper wiring on the cured film. The above steps from lamination to heat treatment were performed three times in total. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the resulting semiconductor package substrate operated normally.

[0282] 12: Temporary support 14: Photosensitive composition layer 16: Cover film 100: Transfer film

Claims

1. A photosensitive composition comprising: a polyimide precursor; a polymerizable compound that is a compound different from the polyimide precursor; and a compound represented by formula (1), wherein the polymerizable compound comprises a compound having two or more polymerizable groups, and the acid value of the polyimide precursor is 75 mg KOH / g or less. In formula (1), each R independently represents a substituent, and each n independently represents an integer of 0 to 5.

2. The photosensitive composition according to claim 1, wherein the acid value of the polyimide precursor is 10 mgKOH / g or less.

3. The photosensitive composition according to claim 1, wherein the dissolution rate of the polyimide precursor in 200 mL of a 2.38 mass % aqueous trimethylammonium hydroxide solution at 23° C. is 100 mg / min or less.

4. The photosensitive composition according to claim 1, wherein the polyimide precursor has a polymerizable group.

5. The photosensitive composition according to claim 1, wherein the weight average molecular weight of the polyimide precursor is 10,000 to 50,000.

6. The photosensitive composition according to claim 1, wherein the content of the polyimide precursor is 10.0 to 90.0 mass % based on the total solid content of the photosensitive composition.

7. The photosensitive composition according to claim 1, wherein the polymerizable compound has a weight average molecular weight of 150 to 1,000.

8. The photosensitive composition according to claim 1, wherein the content of the polymerizable compound is 3.0 to 50.0% by mass based on the total solid content of the photosensitive composition.

9. The photosensitive composition according to claim 1, wherein the mass ratio of the content of the polymerizable compound to the content of the polyimide precursor is 0.20 or more.

10. The photosensitive composition of claim 1 further comprising a chain transfer agent.

11. The photosensitive composition according to claim 10, wherein the content of the chain transfer agent is 0.01 to 5.0% by mass based on the total solid content of the photosensitive composition.

12. The photosensitive composition of claim 1, further comprising a polymerization inhibitor.

13. The photosensitive composition according to claim 12, wherein the content of the polymerization inhibitor is 0.01 to 5.0% by mass based on the total solid content of the photosensitive composition.

14. The photosensitive composition of claim 1 further comprising a sensitizer.

15. The photosensitive composition according to claim 14, wherein the content of the sensitizer is 0.01 to 5.0% by mass based on the total solid content of the photosensitive composition.

16. The photosensitive composition of claim 1 further comprising a filler.

17. The photosensitive composition of claim 16, wherein the filler comprises at least one selected from the group consisting of silicon dioxide, boron nitride, barium sulfate, and silicates.

18. The photosensitive composition according to claim 16, wherein the average particle size of the filler is 100 nm or less.

19. The photosensitive composition according to claim 16, wherein the content of the filler is 30.0 mass % or more based on the total solid content of the photosensitive composition.

20. The photosensitive composition according to claim 16, wherein the content of the filler is 90.0 mass % or less based on the total solid content of the photosensitive composition.

21. A transfer film having a temporary support and a photosensitive composition layer formed by using the photosensitive composition according to any one of claims 1 to 20.

22. A method for producing a laminate, comprising: step 1 forming a photosensitive composition layer on a substrate using the photosensitive composition according to any one of claims 1 to 20; step 2 forming a pattern including vias in the photosensitive composition layer; and step 3 subjecting the pattern to at least one of heating and exposure.

23. A laminate produced by the method for producing a laminate according to claim 22.

24. A semiconductor package comprising the laminate of claim 23.

Images