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

Abstract

The present invention addresses a first problem of providing a photosensitive composition from which it is possible to form a pattern having a low relative permittivity and excellent resolution. The present invention addresses a second problem of providing a transfer film, a laminate production method, a laminate, and a semiconductor package, in which the photosensitive composition is involved.　A photosensitive composition according to the present invention contains a siloxane polymer having a carboxy group, and a compound β having a structure that reduces the amount of the carboxy group in the siloxane polymer through light exposure.

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] Photosensitive materials are used in interlayer insulating films within semiconductor chips, connection layers with printed wiring boards (e.g., build-up layers and interposers), etc. In particular, with the recent trend toward miniaturization of semiconductor wiring, there is a demand for materials that can form insulating films with high resolution.

[0003] For example, Patent Document 1 discloses a photosensitive siloxane resin composition as a photosensitive composition capable of providing a cured film that can be used as an insulating film.

[0004] International Publication No. 2018 / 168435

[0005] The present inventors have conducted an investigation into forming a pattern using the photosensitive composition described in Patent Document 1 and have found that there is room for further improvement in resolution and further reduction in relative dielectric constant.

[0006] Therefore, an object of the present invention is to provide a photosensitive composition capable of forming a pattern having excellent resolution and a low dielectric constant, and also to provide a transfer film, a method for producing 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 above problems can be solved by the following configuration, and have completed the present invention.

[0008] [1] A photosensitive composition comprising: a siloxane polymer having a carboxy group; and a compound β having a structure that reduces the amount of the carboxy group in the siloxane polymer upon exposure. [2] The photosensitive composition according to [1], wherein the siloxane polymer has a repeating unit represented by formula (a1) described below. [3] The photosensitive composition according to [1] or [2], wherein the siloxane polymer further has a polymerizable group. [4] The photosensitive composition according to any one of [1] to [3], wherein the compound β is a compound B having a structure that can accept electrons from the carboxy group in the siloxane polymer in a photoexcited state. [5] The photosensitive composition according to any one of [1] to [4], wherein the compound β is a nitrogen-containing aromatic compound. [6] The photosensitive composition according to any one of [1] to [5], further comprising a filler. [7] The photosensitive composition according to [6], wherein the content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition. [8] The photosensitive composition according to [6] or [7], wherein the average particle size of the filler is 300 nm or less. [9] A photosensitive composition comprising: a siloxane polymer having a carboxy group and a polymerizable group; a compound β having a structure that reduces the amount of the carboxy group in the siloxane polymer upon exposure; and a filler, wherein the siloxane polymer has a repeating unit represented by formula (a1) described below; the compound β is a nitrogen-containing aromatic compound; and the average particle size of the filler is 300 nm or less.

[10] The photosensitive composition according to any one of [1] to [9], further comprising a polymerizable compound.

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

[10] , further comprising a photopolymerization initiator.

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

[11] .

[13] A method for producing a laminate, comprising: a step X1 of forming a photosensitive layer on a substrate using the photosensitive composition according to any one of [1] to

[11] ; a step X2 of patternwise exposing the photosensitive layer; and a step X3 of developing the exposed photosensitive layer with a developer to form a pattern.

[14] The method for producing a laminate according to

[13] , wherein the step X2 is a step of reducing the carboxy groups of the siloxane polymer to change its solubility in a developer.

[15] The method for producing a laminate according to

[13] or

[14] , wherein the substrate is an organic substrate having a copper pattern.

[16] The method for producing a laminate according to any one of

[13] to

[15] , wherein the developer is an alkaline developer.

[17] A laminate produced by the production method according to any one of

[13] to

[16] .

[18] A semiconductor package comprising the laminate according to

[17] .

[0009] According to the present invention, a photosensitive composition capable of forming a pattern having excellent resolution and a low dielectric constant can be provided. Furthermore, according to the present invention, a transfer film, a method for producing a laminate, a laminate, and a semiconductor package related to the photosensitive composition can be provided.

[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. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

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

[0014] 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.

[0015] In this specification, the terms "actinic rays" and "radiation" refer to bright line spectra of mercury lamps 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). In addition, in the present invention, light refers to actinic rays or radiation.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light typified by mercury lamps, excimer lasers, extreme ultraviolet light, X-rays, EUV light, and the like, but also exposure using particle beams such as electron beams and ion beams.

[0017] In this specification, unless otherwise specified, the content ratio of each repeating unit in a resin is a molar ratio.

[0018] In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0019] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] In this specification, the term "(meth)acryloyl group" encompasses both acryloyl and methacryloyl groups, and the term "(meth)acrylate" encompasses both acrylate and methacrylate.

[0021] In this specification, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22°C and a pH of 7.0 is 0.1 g or more.

[0022] The "solid content" of a composition refers to the components that form a composition layer formed using this composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0023] 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.

[0024] [Photosensitive Composition] The photosensitive composition of the present invention contains a siloxane polymer having a carboxy group (hereinafter also referred to as a "specific siloxane polymer") and a compound β (hereinafter also simply referred to as a "compound β") having a structure that reduces the amount of the carboxy group in the siloxane polymer upon exposure to light.

[0025] Although the detailed mechanism of action of the photosensitive composition of the present invention is unclear, the inventors speculate as follows. In the photosensitive layer formed using the photosensitive composition, the polarity changes due to a decrease in the content of carboxy groups in the specific siloxane polymer in the exposed areas, resulting in a change in solubility in the developer. That is, in the exposed areas, the solubility in alkaline developers decreases, while the solubility in organic solvent developers increases. On the other hand, in the unexposed areas, the solubility in the developer remains largely unchanged. As a result, the photosensitive layer has lithographic properties, and a pattern with excellent resolution can be formed. Furthermore, the content of carboxy groups in the specific siloxane polymer decreases in the formed pattern, resulting in a low dielectric constant.

[0026] The mechanism by which the content of carboxy groups in the specific siloxane polymer is reduced by exposure to light includes, for example, a mechanism by decarboxylation. The mechanism by which the content of carboxy groups in the specific siloxane polymer is reduced by decarboxylation is, for example, a mechanism by which the carboxy groups are converted to CO２ This refers to elimination as carbon dioxide, and does not include the conversion of a carboxy group into a group other than a carboxy group by esterification, etc. It is presumed that when a photosensitive layer formed using a photosensitive composition is exposed to light, a decarboxylation reaction of the carboxy group possessed by the specific siloxane polymer may occur due to the action of compound β.

[0027] Examples of embodiments of the photosensitive composition are shown below. - Embodiment X-1: A photosensitive composition containing a specific siloxane polymer, compound β, and a filler, and substantially free of a polymerizable compound and a photopolymerization initiator. - Embodiment X-2: A photosensitive composition containing a specific siloxane polymer, compound β, a filler, and a polymerizable compound, and substantially free of a photopolymerization initiator. - Embodiment X-3: A photosensitive composition containing a specific siloxane polymer, compound β, and a filler, and also containing a polymerizable compound and a photopolymerization initiator.

[0028] In Embodiment X-1, "substantially free of polymerizable compounds" means that the content of polymerizable compounds is less than 1% by mass, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, based on the total solid content of the photosensitive composition. In Embodiments X-1 and X-2, "substantially free of photopolymerization initiators" means that the content of photopolymerization initiators is less than 0.1% by mass, preferably 0 to 0.05% by mass, and more preferably 0 to 0.01% by mass, based on the total solid content of the photosensitive composition. As an embodiment of the photosensitive composition, Embodiment X-1 or Embodiment X-3 is preferred, and Embodiment X-3 is more preferred.

[0029] In the following description, the term "better effects of the present invention" may refer to better resolution of a pattern formed by a photosensitive composition and / or a smaller relative dielectric constant.

[0030] Various components that may be contained in the photosensitive composition of the present invention will be described in detail below.

[0031] [Specific Siloxane Polymer] The photosensitive composition contains a siloxane polymer having a carboxy group (specific siloxane polymer). The specific siloxane polymer is a polymer having a carboxy group and a siloxane bond. The specific siloxane polymer preferably contains a repeating unit having a carboxy group, in terms of providing better effects of the present invention. As the repeating unit having a carboxy group, a repeating unit having a carboxy group and containing a siloxane bond is preferred, a repeating unit represented by the following formula (a0) is more preferred, a repeating unit of an M-form having a carboxy group or a repeating unit of a T-form having a carboxy group is even more preferred, a repeating unit of a T-form having a carboxy group is particularly preferred, and a repeating unit represented by formula (a1) is most preferred. As the repeating unit represented by formula (a1), a repeating unit represented by formula (a1a) or formula (a1b) is particularly preferred, in terms of providing better effects of the present invention.

[0032] The M repeating unit refers to a repeating unit in which two of the four bonds on a silicon atom are bonded to oxygen atoms and the remaining two are bonded to hydrogen atoms or monovalent organic groups, and the T repeating unit refers to a repeating unit in which three of the four bonds on a silicon atom are bonded to oxygen atoms and the remaining one is bonded to a hydrogen atom or monovalent organic group.

[0033] The repeating units represented by formula (a0), formula (a1), formula (a1a), and formula (a1b) will be described below.

[0034]

[0035] In the formula, m represents an integer of 1 to 3. m is preferably 2 or 3, and more preferably 3. R represents a hydrogen atom or a monovalent organic group. The monovalent organic group represented by R is not particularly limited, and examples thereof include R that can be contained in formula (b2) and formula (b3) described below. Ｔ１Examples include the same as the monovalent organic group represented by the formula (a1). When m is 1, the multiple Rs present may be the same or different. When m is 3, R does not exist. X represents an (n+1)-valent linking group. X has the same meaning as X in formula (a1) described later, and preferred embodiments are also the same.

[0036]

[0037] In formula (a1), X represents an (n+1)-valent linking group. Examples of the (n+1)-valent linking group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, —O—, —S—, and —SO ２ -, >N-, -NR Ｓ１ -, and -CO-. Ｓ１ represents a hydrogen atom or a monovalent organic group (e.g., an alkyl group). The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the divalent linear or branched aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. The number of carbon atoms in the divalent cyclic aliphatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. The divalent cyclic aliphatic hydrocarbon group may be either a cycloalkyl group or a cycloalkenyl group. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Examples of the divalent aromatic hydrocarbon group include a phenylene group. The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent. In addition, the divalent aliphatic hydrocarbon group may have a methylene group (—CH ２ -) may be substituted with a group represented by the following formula (A) (* represents a bonding position). When the divalent aliphatic hydrocarbon group contains a group represented by the following formula (A), the group represented by the following formula (A) can also function as a polymerizable group.

[0038]

[0039] The number of atoms excluding hydrogen atoms constituting the (n+1)-valent linking group is, for example, preferably 5 to 300, more preferably 5 to 200, still more preferably 5 to 100, and particularly preferably 5 to 60. Ｓ１ The monovalent organic group represented by the formula (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0040] The n+1-valent linking group represented by X is preferably an n+1-valent linking group containing an amide bond or an n+1-valent linking group containing a sulfide bond, and more preferably an n+1-valent linking group containing an amide bond. Ｓ２ A sulfide bond is a bond represented by -S-. R Ｓ２ represents a hydrogen atom or a monovalent organic group. In an (n+1)-valent linking group containing an amide bond, the number of amide bonds may be one or more, for example, one to three. In an (n+1)-valent linking group containing a sulfide bond, the number of sulfide bonds may be one or more, for example, one to three.

[0041] Examples of the n+1-valent linking group containing an amide bond include a linking group containing one or more amide bonds and a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, —O—, —S—, —SO ２ -, >N-, -NR Ｓ１ -, and -CO-. Ｓ１ represents a hydrogen atom or a monovalent organic group (e.g., an alkyl group). The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group, as well as R Ｓ１ Examples of the monovalent organic group represented by the formula (I) include the divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups exemplified in the description of the (n+1)-valent linking group in the upper part, and R Ｓ１The number of atoms excluding hydrogen atoms constituting the (n+1)-valent linking group containing an amide bond is, for example, preferably 5 to 300, more preferably 5 to 200, still more preferably 5 to 100, and particularly preferably 5 to 60.

[0042] Examples of the (n+1)-valent linking group containing an amide bond include -L Ｓ１ -A Ｓ１ -L Ｓ２ -, and a group represented by the following formula (LS1).

[0043]

[0044] L Ｓ１ ~L Ｓ６ each independently represents an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, or an arylene group, and among these, an alkylene group, a cycloalkylene group, an alkenylene group, or a cycloalkenylene group is preferred. Ｓ１ ~L Ｓ６ The alkylene group and alkenylene group represented by the formula (I) may be either linear or branched, but is preferably linear. Ｓ１ ~L Ｓ６ The number of carbon atoms in the alkylene group and alkenylene group represented by the formula (I) is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 6. Ｓ１ ~L Ｓ６ The number of carbon atoms in the cycloalkylene group and cycloalkenylene group represented by the formula (I) is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Ｓ１ ~L Ｓ６ The number of carbon atoms in the arylene group represented by the formula (I) is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Ｓ１ ~L Ｓ６ The alkylene group, cycloalkylene group, alkenylene group, cycloalkenylene group, or arylene group represented by the following formula (I) may further have a substituent.

[0045] A Ｓ１ and A Ｓ２ each independently represents an amide bond (—NR Ｓ２ -CO-).Ｓ２ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. Ｓ２ The monovalent organic group represented by the formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0046] * in formula (LS1) １ , * ２ , and * ３ represents a bonding position. １ , * ２ , and * ３ One of these is the bonding position to the silicon atom as shown in formula (a1), and the other two are the bonding positions to the carboxy group as shown in formula (a1).

[0047] Examples of the n+1-valent linking group containing a sulfide bond include a linking group containing one or more sulfide bonds and a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, —O—, —SO 4 ２ -, >N-, -NR Ｓ１ -, and -CO-. Ｓ１ represents a hydrogen atom or a monovalent organic group (e.g., an alkyl group). The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group, as well as R Ｓ１ Examples of the monovalent organic group represented by the formula (I) include the divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups exemplified in the description of the (n+1)-valent linking group in the upper part, and R Ｓ１ The number of atoms excluding hydrogen atoms constituting the (n+1)-valent linking group containing a sulfide bond is, for example, preferably 5 to 300, more preferably 5 to 200, still more preferably 5 to 100, and particularly preferably 5 to 60.

[0048] Examples of the (n+1)-valent linking group containing a sulfide bond include -L Ｓ７ -S-L Ｓ８ - is mentioned. Ｓ７ and L Ｓ８ is the L mentioned above. Ｓ１ ~L Ｓ６The same definition and preferred embodiments are also the same. Ｓ７ and L Ｓ８ Among these, a straight-chain alkylene group or a straight-chain alkenylene group is preferred.

[0049] In formula (a1), n ​​represents an integer of 1 or more. n is preferably 1 to 5, and more preferably 1 or 2.

[0050]

[0051]

[0052] In formula (a1a) and formula (a1b), X １ and X ２ is the L mentioned above. Ｓ１ ~L Ｓ６ The same definition and preferred embodiments are also the same.

[0053] The content of the repeating unit having a carboxy group (preferably a repeating unit represented by formula (a1)) is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, even more preferably 30 to 90 mol %, and particularly preferably 40 to 80 mol %, relative to all repeating units of the siloxane polymer. The specific siloxane polymer may contain one type of repeating unit having a carboxy group (preferably a repeating unit represented by formula (a1)), or two or more types. When two or more types are contained, the total content thereof preferably falls within the above-mentioned numerical range.

[0054] Specific examples of repeating units having a carboxy group (preferably repeating units represented by formula (a1)) are listed below, but the examples are not limited thereto.

[0055]

[0056]

[0057]

[0058] The specific siloxane polymer preferably has a polymerizable group. Examples of the polymerizable group include a radically polymerizable group or a cationically polymerizable group. The radically polymerizable group is preferably a (meth)acryloyl group or a vinyl group, more preferably a vinyl group, and even more preferably a vinyl group directly bonded to a silicon atom. The cationically polymerizable group is preferably an epoxy group or an oxetane group. The epoxy group as a cationically polymerizable group may be present as part of a ring structure. That is, the epoxy group may have a polycyclic structure consisting of an epoxy ring and another ring (e.g., a cycloalkane ring). Examples of cationically polymerizable groups having an epoxy group as part of their ring structure include a 1,2-epoxycyclohexyl group. The oxetane group as a cationically polymerizable group may be present as part of a ring structure. That is, the oxetane group may have a polycyclic structure consisting of an oxetane ring and another ring (e.g., a cycloalkane ring).

[0059] The position at which the polymerizable group is introduced is not particularly limited, and the polymerizable group may be introduced into the repeating unit having the carboxy group described above, or may be introduced into a position other than the repeating unit having the carboxy group described above. In terms of achieving better effects of the present invention, it is preferable that the specific siloxane polymer further contains a repeating unit having a polymerizable group different from the repeating unit having the carboxy group described above.

[0060] The repeating unit having a polymerizable group is preferably a repeating unit having a polymerizable group and containing a siloxane bond. The repeating unit having a polymerizable group and containing a siloxane bond is preferably a repeating unit in which a group represented by -Y-(Z)p is bonded to the silicon atom of the siloxane bond. Note that Y, Z, and p in the above formula have the same meanings as Y, Z, and p in formulas (b1) to (b3) described below, and preferred embodiments are also the same.

[0061] Examples of repeating units having a polymerizable group and containing a siloxane bond include D-form repeating units having a polymerizable group (for example, a repeating unit represented by the following formula (b3)), M-form repeating units having a polymerizable group (for example, a repeating unit represented by the following formula (b2)), and T-form repeating units having a polymerizable group (for example, a repeating unit represented by the following formula (b1)). The number of polymerizable groups in the repeating unit having a polymerizable group may be one or more, and is preferably 1 to 3, for example, and more preferably 1. The D-form repeating unit refers to a repeating unit in which one of the four bonds of a silicon atom is bonded to an oxygen atom and the other three are bonded to hydrogen atoms or monovalent organic groups.

[0062]

[0063] In formula (b1), formula (b2), and formula (b3), Y represents a single bond or a p+1 valent linking group. When Y represents a single bond, p represents 1. Examples of the p+1 valent linking group represented by Y include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, -O-, and -SO ２ -, >N-, -NR Ｔ２ -, and -CO-. Ｔ２ represents a hydrogen atom or a monovalent organic group (e.g., an alkyl group). Examples of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group include the same divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group that the n+1-valent linking group may have, and the preferred embodiments are also the same. The number of atoms excluding hydrogen atoms constituting the p+1-valent linking group is, for example, preferably 5 to 300, more preferably 5 to 200, and even more preferably 5 to 100. R Ｔ２ The monovalent organic group represented by the formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0064] Specific examples of the p+1-valent linking group represented by Y include, for example, -L Ｔ３ -L Ｔ４ - is mentioned. Ｔ３is a methylene group (-CH ２ -) represents an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) which may be substituted with one or a combination of two or more linking groups selected from the group consisting of -O-, -NH-, and -CO-. Ｔ３ L in the middle Ｔ４ The atom at the bonding position with L is preferably a carbon atom. Ｔ４ is —O— or —NR Ｔ２ -. Note that R Ｔ２ is as mentioned above.

[0065] Y is preferably a single bond in that the effects of the present invention are more excellent.

[0066] In formula (b1), formula (b2), and formula (b3), Z represents a polymerizable group. Examples of the polymerizable group include the same polymerizable groups as those described above.

[0067] In formula (b1), formula (b2), and formula (b3), p represents an integer of 1 or more, preferably 1 to 5, more preferably 1 or 2, and even more preferably 1.

[0068] In formula (b2) and formula (b3), R Ｔ１ represents a hydrogen atom or a monovalent organic group. Ｔ１ The monovalent organic group represented by the formula (I) is not particularly limited, but is preferably, for example, an alkyl group or phenyl group having 1 to 6 carbon atoms. The number of carbon atoms in the alkyl group is preferably 1 to 3, and more preferably 1 or 2. The alkyl group and phenyl group may have a substituent.

[0069] The content of the repeating unit having a polymerizable group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol%, based on the total repeating units of the specific siloxane polymer. The specific siloxane polymer may contain one type of repeating unit having a polymerizable group, or two or more types. When two or more types are contained, the total content thereof preferably falls within the above-mentioned numerical range.

[0070] Specific examples of repeating units having a polymerizable group are listed below, but the present invention is not limited thereto.

[0071]

[0072]

[0073] The specific siloxane polymer may further contain other repeating units (hereinafter also referred to as "other repeating units") different from the repeating units having a carboxy group and the repeating units having a polymerizable group described above. The other repeating units are preferably repeating units containing a siloxane bond. The repeating units containing a siloxane bond may be any of D-form repeating units, M-form repeating units, T-form repeating units, and Q-form repeating units.

[0074] Examples of the D-form repeating unit, the M-form repeating unit, and the T-form repeating unit include a repeating unit represented by formula (c3), a repeating unit represented by formula (c2), and a repeating unit represented by formula (c1), respectively. Note that a Q-form repeating unit is a repeating unit in which all four bonds of a silicon atom are bonded to oxygen atoms, and corresponds to a repeating unit represented by formula (c4).

[0075]

[0076] R in formula (c1), formula (c2), and formula (c3) Ｕ１ represents a hydrogen atom or a monovalent organic group. Ｕ１ represents R in formula (b1), formula (b2), and formula (b3). Ｔ１ The same definition and preferred embodiments are also the same.

[0077] Specific examples of other repeating units are listed below, but the present invention is not limited thereto.

[0078]

[0079] The weight-average molecular weight of the specific siloxane polymer is preferably 500 to 5,0000, more preferably 700 to 30,000, and even more preferably 1,000 to 20,000. The dispersity of the specific siloxane polymer is preferably 1.0 to 4.0, and more preferably 1.5 to 3.0. The acid value of the specific siloxane polymer is preferably 50 to 300 mgKOH / g, more preferably 60 to 250 mgKOH / g, even more preferably 70 to 200 mgKOH / g, and particularly preferably 90 to 180 mgKOH / g. The double bond equivalent (also referred to as C=C value) of the specific siloxane polymer is preferably 2.0 to 10.0 mmol / g, more preferably 3.0 to 7.0 mmol / g, and even more preferably 3.5 to 6.0 mmol / g. The C=C value of the specific siloxane polymer can be measured by iodometric titration.

[0080] <Method for synthesizing specific siloxane polymer> The specific siloxane polymer can be synthesized by a known method. Hereinafter, a method for synthesizing the specific siloxane polymer will be described using the siloxane polymer having repeating units represented by the above-mentioned formula (a1), formula (a1a), and formula (a1b) as an example. The siloxane polymer having repeating units represented by the above-mentioned formula (a1), formula (a1a), and formula (a1b) can be synthesized by, for example, hydrolysis and polycondensation reaction of compounds represented by formula (a1z), formula (a1az), and formula (a1bz), respectively. Note that X, n, X in the following formula (a1z), formula (a1az), and formula (a1bz) １ , and X ２ represents X, n, and X in formula (a1), formula (a1a), and formula (a1b). １ , and X ２ The same definition and preferred embodiments are also the same.

[0081]

[0082] In formula (a1z), formula (a1az), and formula (a1bz), Z represents a hydrolyzable group. The hydrolyzable group represented by Z is preferably an alkoxy group, a halogen atom, or an acetoxy group, and more preferably an alkoxy group. The alkoxy group is preferably an alkoxy group having 2 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group.

[0083] The compounds represented by formula (a1az) and formula (a1bz) can be synthesized, for example, by reacting 3-aminopropyltrialkoxysilane, 3-(2-aminoethyl)aminopropyltrialkoxysilane, or the like with a dibasic acid anhydride (for example, succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, or the like).

[0084] Siloxane polymers having repeating units represented by the above-mentioned formula (a1a) and formula (a1b) can also be synthesized by synthesis methods other than those described above. Examples of other synthesis methods include a method in which a compound represented by formula (a1aa) or formula (a1bb) is subjected to hydrolysis and polycondensation reaction to synthesize a polysiloxane having an amino group, and then the resulting polysiloxane is reacted with a dibasic acid anhydride.

[0085]

[0086] In addition, Z in the above formula (a1aa) and formula (a1bb) has the same meaning as Z in formula (a1az) and formula (a1bz), and the preferred embodiments are also the same.

[0087] The specific siloxane polymer may be used alone or in combination of two or more. The lower limit of the content of the specific siloxane polymer is preferably 5.0 mass% or more, more preferably 10.0 mass% or more, based on the total solid content of the photosensitive composition. The upper limit of the content of the specific siloxane polymer is preferably 99.0 mass% or less, more preferably 98.0 mass% or less, based on the total solid content of the photosensitive composition. When two or more specific siloxane polymers are contained in the photosensitive composition, the total content thereof is preferably within the above numerical range.

[0088] When the photosensitive composition contains a filler, the content of the specific siloxane polymer is preferably 5.0 to 70.0 mass%, more preferably 5.0 to 50.0 mass%, more preferably 5.0 to 40.0 mass%, even more preferably 5.0 to 35.0 mass%, and particularly preferably 15.0 to 35.0 mass%, based on the total solid content of the photosensitive composition. When the photosensitive composition does not contain a filler, the content of the specific siloxane polymer is preferably 75.0 mass% or more, more preferably 80.0 mass% or more, based on the total solid content of the photosensitive composition.

[0089] [Compound β] The photosensitive composition contains compound β. Compound β is a compound different from the various components described above. Compound β is a compound having a structure (hereinafter also referred to as "specific structure S0") that reduces the amount of carboxy groups in the specific siloxane polymer upon exposure to light.

[0090] The specific structure S0 is a structure that exhibits the effect of reducing the amount of carboxy groups in the specific siloxane polymer when exposed to light. The specific structure S0 is preferably a structure that transitions from a ground state to an excited state when exposed to light and exhibits the effect of reducing the number of carboxy groups in the specific siloxane polymer in the excited state. An example of the specific structure S0 is a structure that can accept electrons from carboxy groups in the specific siloxane polymer in a photoexcited state (hereinafter also referred to as "specific structure S1").

[0091] The specific structure S0 of compound β may be the overall structure constituting the entire compound β, or may be a partial structure constituting a part of compound β. Compound β may be either a low molecular weight compound or a high molecular weight compound, and is preferably a low molecular weight compound. Furthermore, when compound β is a low molecular weight compound, it is preferable that the low molecular weight compound does not have a repeating unit. When compound β is a low molecular weight compound, the molecular weight of compound β is preferably less than 5,000, more preferably less than 1,000, even more preferably 65 to 300, and particularly preferably 75 to 250.

[0092] The specific structure S0 is preferably a structure (specific structure S1) that can accept electrons from a carboxy group of the specific siloxane polymer in a photoexcited state. That is, the compound β is preferably a compound B having a structure (specific structure S1) that can accept electrons from a carboxy group of the specific siloxane polymer in a photoexcited state. According to the compound B, the carboxy group of the specific siloxane polymer is converted to CO ２ As will be described later, specific examples of the specific structure SO include aromatic rings, and among these, heteroaromatic rings are preferred, and nitrogen-containing aromatic rings are more preferred.

[0093] In terms of superior pattern forming ability, the compound β is preferably an aromatic compound having an aromatic ring as the specific structure S0, more preferably a heteroaromatic compound having a heteroaromatic ring as the specific structure S0, and even more preferably a nitrogen-containing aromatic compound having a heteroaromatic ring as the specific structure S0. That is, the specific structure S0 is preferably an aromatic ring, more preferably a heteroaromatic ring, and even more preferably a nitrogen-containing aromatic ring. The aromatic compound is a compound having one or more aromatic rings. The nitrogen-containing aromatic compound is a compound having a heteroaromatic ring having one or more nitrogen atoms (e.g., 1 to 4) as ring member atoms. Only one aromatic ring may be present in the compound β, or multiple aromatic rings may be present. When multiple aromatic rings are present, for example, the aromatic rings may be present in a side chain of a resin, etc. In the compound β, the aromatic ring can be used as a structure (specific structure S0) that reduces the amount of carboxy groups in the specific siloxane polymer upon exposure. The aromatic ring may be either a monocyclic or polycyclic ring, with polycyclic rings being preferred. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (e.g., 2 to 5, etc.) aromatic ring structures, and it is preferable that at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. The aromatic ring may be a heteroaromatic ring, and it is preferable that it has one or more (e.g., 1 to 4, etc.) heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms, etc.) as ring member atoms, and it is more preferable that it has one or more (e.g., 1 to 4, etc.) nitrogen atoms as ring member atoms. The number of ring member atoms of the aromatic ring is preferably 5 to 15.

[0094] The aromatic ring of compound β is preferably a polycyclic ring (a polycyclic aromatic ring) in that it has a higher molar absorption coefficient at a wavelength of 365 nm. The number of monocyclic aromatic rings (the number of fused rings) in the polycyclic aromatic ring is preferably 2 or more, and more preferably 3 or more in that it has a higher molar absorption coefficient at a wavelength of 365 nm. The upper limit is preferably 6 or less. In addition, it is also preferable that the polycyclic aromatic ring has a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, etc.) as a ring member atom (in other words, it is a polycyclic heteroaromatic ring).

[0095] Examples of the aromatic ring contained in compound β include monocyclic aromatic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring; aromatic rings formed by condensing two rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, and a quinazoline ring; and aromatic rings formed by condensing three rings such as an acridine ring, a benzo[f]quinoline ring, a benzo[h]quinoline ring, a phenanthridine ring (benzo[c]quinoline ring), a benzo[h]isoquinoline ring, a phenanthroline ring, and a phenazine ring.

[0096] The aromatic ring may have one or more (e.g., 1 to 5) substituents. Examples of the substituents include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. When the aromatic ring has two or more substituents, the multiple substituents may be bonded to each other to form a non-aromatic ring. It is also preferable that the aromatic ring is directly bonded to a carbonyl group to form an aromatic carbonyl group in compound β. It is also preferable that multiple aromatic rings are bonded via carbonyl groups. It is also preferable that the aromatic ring is bonded to an imide group to form an aromatic imide group in compound β. The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring. In addition, when a series of aromatic ring structures is formed by a plurality of aromatic rings (e.g., 2 to 5 rings) bonded by a structure selected from the group consisting of a single bond, a carbonyl group, and a multiple bond (e.g., an optionally substituted vinylene group, -C≡C-, and -N=N-), the series of aromatic ring structures as a whole is regarded as one specific structure. In addition, it is preferable that one or more of the aromatic rings constituting the series of aromatic ring structures is the heteroaromatic ring.

[0097] In terms of achieving superior pattern forming ability, compound β is preferably a compound that satisfies one or more of requirements (1) to (4), more preferably satisfies at least one of requirements (1) and (2), and even more preferably satisfies at least requirements (1) and (2) (is a polycyclic heteroaromatic ring). The heteroatom contained in the heteroaromatic ring preferably contains at least a nitrogen atom. Requirement (1): Contains a polycyclic aromatic ring. Requirement (2): Contains a heteroaromatic ring. Requirement (3): Contains an aromatic carbonyl group. Requirement (4): Contains an aromatic imide group.

[0098] Other suitable embodiments of compound β include, for example, acridinium salts, (iso)quinolinium salts, and iridium complexes. (Iso)quinolinium salts refer to quinolinium salts and isoquinolinium salts. Compound β may also exhibit the function of compound β through the action of two compounds. Examples of such two compounds include a combination of an aromatic compound (b1) that is unsubstituted or substituted with an electron-donating group (preferably an alkyl group or an alkoxy group) and an aromatic compound (b2) that is substituted with an electron-withdrawing group (preferably a cyano group or an alkoxycarbonyl group). In this combination, electrons are transferred from the photoexcited aromatic compound (b1) to the aromatic compound (b2), generating a cation radical of the aromatic compound (b1). This cation radical accepts electrons from the carboxy group, thereby exhibiting the function of compound β.

[0099] Compound β is preferably one or more selected from the group consisting of acridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine, because they have a higher molar absorption coefficient at 365 nm and excellent photosensitivity to 365 nm light. These compounds may further have a substituent. The substituent is preferably an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group.

[0100] When the compound β is a resin, the specific structure S0 may be bonded to the main chain of the resin via a single bond or a linking group. The compound β as a resin can be obtained, for example, by polymerizing a monomer having a polycyclic heteroaromatic ring (e.g., a vinyl polycyclic heteroaromatic ring and / or a (meth)acrylate monomer having the specific structure S0 (preferably a polycyclic heteroaromatic ring)). If necessary, it may be copolymerized with other monomers.

[0101] In terms of superior pattern-forming ability, the molar absorption coefficient of compound β at light with a wavelength of 365 nm is preferably 100 L / (mol cm) or more, more preferably 500 L / (mol cm) or more, even more preferably more than 1,000 L / (mol cm), and particularly preferably 4,000 L / (mol cm) or more. The upper limit is preferably 20,000 L / (mol cm) or less. The molar absorption coefficient at light with a wavelength of 365 nm is the molar absorption coefficient measured by dissolving compound β in acetonitrile. If compound β is not soluble in acetonitrile, the solvent used to dissolve compound β may be changed as appropriate. Having the molar absorption coefficient of compound β within the above range is particularly advantageous when exposing a photosensitive layer through a temporary support (preferably a PET film). In other words, because the absorption coefficient is appropriately low, the generation of bubbles due to decarbonation can be controlled even when exposed through a temporary support, preventing deterioration of the pattern shape. Examples of compounds having a high molar absorption coefficient for light with a wavelength of 365 nm include compounds in which three or more aromatic rings are condensed to form an aromatic ring. Examples of compounds in which three or more aromatic rings are condensed to form an aromatic ring include the compounds described above.

[0102] Examples of compound β include monocyclic aromatic compounds such as pyridine, 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, pyrazine, pyrimidine, and triazine; compounds in which two rings are fused to form an aromatic ring, such as quinoline, 2,4-dimethylquinoline, quinoline, isoquinoline, 1-methylisoquinoline, 1-phenylisoquinoline, quinoxaline, and quinazoline; and compounds in which three or more rings are fused to form an aromatic ring, such as acridine, 9-methylacridine, benzo[f]quinoline, benzo[h]quinoline, phenanthridine, benzo[h]isoquinoline, phenanthroline, and phenazine. These compounds may further have a substituent. Preferred examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, and a nitro group. Compound β preferably includes at least one selected from the group consisting of acridine, 9-alkylacridine (preferably 9-methylacridine), 9-phenylacridine, quinoline, 2,4-dialkylquinoline (preferably 2,4-dimethylquinoline), isoquinoline, and 1-alkylisoquinoline (preferably 2-methylquinoline).

[0103] Compound β may be used alone or in combination of two or more. From the viewpoint of achieving better pattern forming ability, the content of compound β is preferably 0.1% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the photosensitive composition. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, even more preferably 30.0% by mass or less, particularly preferably 20.0% by mass or less, and most preferably 15.0% by mass or less, relative to the total solid content of the photosensitive composition. When two or more types of compound β are contained in the photosensitive composition, the total content thereof preferably falls within the above-mentioned numerical range.

[0104] In terms of more excellent pattern forming ability, the total number of specific structures S0 contained in the compound β is preferably 1 mol % or more, more preferably 3 mol % or more, even more preferably 5 mol % or more, and particularly preferably 10 mol % or more, relative to the total number of carboxy groups contained in the specific siloxane polymer. In terms of the film quality of the obtained film, the upper limit is preferably 200 mol % or less, more preferably 100 mol % or less, and even more preferably 80 mol % or less, relative to the total number of carboxy groups contained in the specific siloxane polymer.

[0105] [Filler] The photosensitive composition preferably contains a filler. When the photosensitive composition contains a filler, the resulting cured film has a better linear expansion coefficient and average dielectric loss tangent.

[0106] 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 chion-doped glass; alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride. The 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).

[0107] The shape of the filler may be either spherical or non-spherical (e.g., 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 modifiers. Examples of the functional groups include polymerizable groups (e.g., polymerizable groups contained in polymerizable compounds described below) and hydrophobic groups. Examples of surface modifiers include known surface modifiers such as silane coupling agents, titanate coupling agents, and silazane compounds.

[0108] Examples of fillers include Seahoster KE-S30 (manufactured by Nippon Shokubai Co., Ltd., silicon dioxide, solid content concentration 100% by mass), NHM-3N (manufactured by Tokuyama Corporation, 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), SO-C series (e.g., SO-C2, etc., manufactured by Admatechs Co., Ltd., silicon dioxide), SO-E series (e.g., SO-E2, etc., manufactured by Admatechs Co., Ltd., silicon dioxide), and PMA-ST (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide). Examples of suitable MEK slurry include MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd., silicon dioxide), MEK-EC-2430Z (manufactured by Nissan Chemical Industries, Ltd., solids concentration 30% by mass), barium sulfate (manufactured by Nippon Solvay K.K., solids concentration 100% by mass), NHM-5N (manufactured by Tokuyama Corporation, silicon dioxide, 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).

[0109] The average particle diameter of the filler is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The lower limit is preferably more than 0 nm, more preferably 5 nm or more. The average particle diameter of the filler is also preferably 5 to 100 nm. The average particle diameter of the filler is calculated by the following particle diameter measurement method. Particle diameter measurement method: A coating liquid containing a filler is applied to a substrate to form a coating film, and a rectangular region of 3 μm × 10 μm in a cross section of the coating film taken along the normal direction to the surface is observed with a scanning electron microscope. The major axes of all fillers observed within the region are measured at five different locations on the coating film, and the average value of the major axes of all fillers measured in each measurement is defined as the average particle diameter of the filler. The coating liquid may be the photosensitive composition of the present invention.

[0110] The procedure for the particle size measurement method is described in detail below. First, a coating liquid containing a filler is applied to a substrate to form a coating film. The thickness of the coating film is preferably 3 μm or more. A glass substrate is used as the substrate. When forming the coating film, a drying treatment may be performed as necessary. A cross section along the normal direction of the surface of the obtained coating film (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 diameters of all fillers observed within the region are measured. As the scanning electron microscope, for example, an S-4800 manufactured by Hitachi High-Tech Corporation is used. The magnification for observation is 50,000 times. The above operation is performed at five different locations on the coating film, and the average (arithmetic mean) of the major diameters of all fillers measured in each operation is taken as the average particle size of the filler. Note that the major diameter refers to the length of the longest line segment connecting any two points on the outline of the filler 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.

[0111] The refractive index of the filler is preferably 0.5 to 3.0, more preferably 1.2 to 1.8.

[0112] The filler may be used alone or in combination of two or more. The content of the filler is often 10.0 mass% or more, preferably 30.0 mass% or more, more preferably 50.0 mass% or more, even more preferably 60.0 mass% or more, particularly preferably 65.0 mass% or more, and most preferably 70.0 mass% or more, based on the total solid content of the photosensitive composition. The upper limit is preferably 90.0 mass% or less, more preferably 80.0 mass% or less, and even more preferably 75.0 mass% or less, based on the total solid content of the photosensitive composition. When two or more types of fillers are contained in the photosensitive composition, the total content thereof is preferably within the above numerical range.

[0113] [Polymerizable Compound] The photosensitive composition preferably contains a polymerizable compound, which is a compound different from the above-mentioned various components.

[0114] The polymerizable compound is a compound having one or more polymerizable groups in one molecule. Examples of the polymerizable group that the polymerizable compound has include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred and a methacryloyl group being more preferred.

[0115] 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"). Bifunctional polymerizable compounds are preferred as the polymerizable compound. The upper limit of the number of functionalities of the polymerizable compound is not particularly limited, and is preferably 10 or less functionalities, more preferably 8 or less functionalities, and even more preferably 5 or less functionalities. From the viewpoint of better effects of the present invention, tetrafunctionalities or less are particularly preferred, and bifunctionalities are most preferred.

[0116] Examples of bifunctional polymerizable compounds include polyethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Commercially available bifunctional polymerizable compounds include 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 dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0117] 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.

[0118] Commercially available polymerizable compounds 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.).

[0119] 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.); and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).

[0120] The polymerizable compound may be used alone or in combination of two or more. The content of the polymerizable compound is preferably 30.0 mass% or less, more preferably 25.0 mass% or less, even more preferably 20.0 mass% or less, particularly preferably 15.0 mass% or less, and most preferably 10.0 mass% or less, based on the total solid content of the photosensitive composition. The lower limit is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, based on the total solid content of the photosensitive composition. When two or more polymerizable compounds are contained in the photosensitive composition, the total content thereof is preferably within the above numerical range.

[0121] [Photopolymerization initiator] The photosensitive composition may contain a photopolymerization initiator. The photopolymerization initiator is a compound different from the above-mentioned various components. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator, and a photoradical polymerization initiator is preferred.

[0122] Examples of the photopolymerization initiator include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure). As the photopolymerization initiator, oxime ester compounds or aminoacetophenone compounds are preferred.

[0123] Examples of the oxime ester compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazol-3-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF and trade name: Lunar 6, manufactured by DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Power Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O- acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.).

[0124] Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, Omnirad series, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0125] Examples of the photopolymerization initiator include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO), and H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

[0126] Examples of the photopolymerization initiator include those described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0127] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 10.0 mass% or less, more preferably 5.0 mass% or less, and even more preferably 2.0 mass% or less, based on the total solid content of the photosensitive composition. The lower limit is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, based on the total solid content of the photosensitive composition. When two or more photopolymerization initiators are contained in the photosensitive composition, the total content thereof is preferably within the above numerical range.

[0128] [Surfactant] The photosensitive composition may contain a surfactant, which is a compound different from the above-mentioned various components.

[0129] Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of nonionic surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. From the viewpoint of improving environmental compatibility, it is preferred that the surfactant does not contain a fluorine atom. The surfactant is preferably a hydrocarbon-based surfactant or a silicone-based surfactant.

[0130] 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 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).

[0131] Examples of fluorosurfactants include acrylic compounds that have a functional group containing a fluorine atom, and when heated, the functional group containing the fluorine atom is cleaved, causing the fluorine atom to volatilize. Examples of such fluorosurfactants include the Megafac DS series (manufactured by DIC Corporation, Megafac DS-21, etc., as described in The Chemical Daily (February 22, 2016) and The Nikkei Business Daily (February 23, 2016)). 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 also be a block polymer. The fluorosurfactant may also be a fluorine-containing polymer compound having 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 having an ethylenically unsaturated group in the side chain. Specific examples include Megafac RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation). From the viewpoint of improving environmental compatibility, preferred fluorine-based surfactants are 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).

[0132] Examples of hydrocarbon surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of hydrocarbon surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1, and HYDROPALAT WE 3323 (all manufactured by BASF); Solsperse 20000 (manufactured by Lubrizol Japan); NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Paionin D-1105, D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.); and Olfine E1010, Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0133] 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.

[0134] 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).

[0135]

[0136] 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. A plurality of R's may be the same or different.

[0137]

[0138] 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.

[0139] The repeating unit having a hydrophilic group in the side chain is preferably a repeating unit represented by formula (SX3).

[0140]

[0141] 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.

[0142] Examples of silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (all manufactured by DIC Corporation); DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.); X-22-4952, X-22-4272, and X-22-6266 , KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KF-6001, K F-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-12 No. 5, 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 Perform 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).

[0143] Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

[0144] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.0001 to 10.0 mass%, more preferably 0.001 to 5.0 mass%, and even more preferably 0.005 to 3.0 mass%, based on the total solid content of the photosensitive composition. When two or more surfactants are contained in the photosensitive composition, the total content thereof preferably falls within the above-mentioned numerical range.

[0145] [Other Additives] The photosensitive composition may contain other additives in addition to the various components described above. Examples of other additives include resins other than the specific siloxane polymer, triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, hydrogen donor compounds, solvents, impurities, plasticizers, sensitizers, and alkoxysilane compounds. Examples of triazole, benzotriazole, tetrazole, and derivatives thereof, aliphatic thiol compounds, thermal crosslinking compounds, polymerization inhibitors, and hydrogen donor compounds are described, for example, in WO 2022 / 039027. Examples of plasticizers, sensitizers, and alkoxysilane compounds are described, for example, in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0146] 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., dimethyl sulfoxide and sulfolane), amide solvents, cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), lactone solvents, and mixed solvents containing two or more of these. The solvents may be used alone or in combination of two or more. The content of the solvent is preferably from 50 to 1,900 parts by mass, more preferably from 100 to 1,200 parts by mass, and even more preferably from 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive composition.

[0147] 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.

[0148] 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, based on the total solid content of the photosensitive composition. The lower limit is often 0 ppb by mass or more, but may be 1 ppb by mass or more, or may be 0.1 ppm by mass or more, based on the total solid content of the photosensitive composition.

[0149] Examples of methods for adjusting the impurity content include a method of using raw materials with low impurity contents as raw materials for the various components that may be contained in the photosensitive composition, a method of purifying the various components that may be contained in the photosensitive composition, and a method of preventing impurities from being mixed in when preparing the photosensitive composition.

[0150] The content of impurities can be measured by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

[0151] In the photosensitive composition, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, 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, based on the total solid content of the photosensitive composition. The lower limit may be 10 ppb by mass or more, or 100 ppb by mass or more, based on the total solid content of the photosensitive composition. The content of these compounds can be adjusted in the same manner as for the above-mentioned impurities. The content of these compounds can be measured using known measurement methods.

[0152] [Transfer film] The transfer film has a temporary support and a photosensitive layer formed using the photosensitive composition described above. The composition layer may further have other layers such as an intermediate layer and a thermoplastic resin layer in addition to the photosensitive layer. Hereinafter, the photosensitive layer and other layers optionally included may be collectively referred to as the "composition layer." The transfer film may also have a configuration further including a cover film that protects the surface of the composition layer.

[0153] 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 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 100 may have a configuration without the cover film 16. Furthermore, the transfer film may further have an intermediate layer and / or a thermoplastic resin layer as a composition layer other than the photosensitive layer. Each component of the transfer film will be described in detail below.

[0154] [Temporary Support] The transfer film has a temporary support, which is a member that supports a composition layer such as a photosensitive layer, and is ultimately removed by a peeling treatment.

[0155] 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 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. It is also preferable that the temporary support does not have any deformations such as wrinkles or scratches.

[0156] The temporary support preferably has high transparency in order to allow 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 particularly 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. Specifically, the number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 3 or less per mm ２ More preferably, 0 pieces / mm ２ As a specific example of the number of fine particles, foreign matter and defects having a diameter of 1 μm or more on the temporary support, 2 particles / mm ２ , and 0 pieces / mm ２ Examples include:

[0157] 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 is the average value of any five points measured by cross-sectional observation using a SEM.

[0158] In order to improve the adhesion between the temporary support and the photosensitive layer, the surface of the temporary support that comes into contact with the 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 ２Examples 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.

[0159] 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.).

[0160] Examples of temporary supports 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.

[0161] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide 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, for example, 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.).

[0162] [Photosensitive Layer] The photosensitive layer is a layer formed using the photosensitive composition described above. The various components that can be contained in the photosensitive 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 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 layer." Specifically, the phrase "The content of the specific siloxane polymer 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 specific siloxane polymer is preferably 5.0% by mass or more relative to the total mass of the photosensitive layer."

[0163] <Thickness of Photosensitive Layer> The average thickness of the photosensitive layer is preferably 0.5 to 40 μm, more preferably 0.5 to 25 μm, and even more preferably 3 to 20 μm. When the average thickness of the photosensitive layer is 40 μm or less, it is preferred in terms of excellent pattern resolution, and when the average thickness of the photosensitive layer is 0.5 μm or more, it is preferred in terms of excellent reliability.

[0164] [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.

[0165] [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 Preferably, 0 pieces / m ２ The fisheyes are foreign matter, undissolved matter, and / or oxidized and deteriorated matter of the material that is trapped in the cover film when the cover film is produced by thermally melting the material and then kneading, extrusion and / or biaxial stretching and casting.

[0166] 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 less ２More preferably, 5 or less pieces / mm ２ More preferably, 0 pieces / mm ２ This makes it possible to suppress defects caused by the transfer of irregularities caused by particles contained in the cover film to the photosensitive layer.

[0167] 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 the above 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, the upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0168] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of the cover film include those described in paragraphs 0083 to 0087 and 0093 of JP 2006-259138 A, the contents of which are incorporated herein by reference.

[0169] 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.).

[0170] [Other Layers] The transfer film may include other layers in addition to the above layers. Examples of other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0171] [Method for producing transfer film] The method for producing the transfer film is not particularly limited as long as it is a production method using a photosensitive composition. In the method for producing the transfer film, it is preferable to form a photosensitive layer by applying the photosensitive composition on a temporary support.

[0172] For example, a method for manufacturing the transfer film 100 shown in FIG. 1 includes a manufacturing method including a step of applying a photosensitive composition to the surface of a temporary support 12 to form a coating film, and then drying the coating film to form a photosensitive layer 14. The transfer film 100 shown in FIG. 1 is manufactured by pressing a cover film onto the photosensitive layer of the transfer film manufactured by the above manufacturing method. The transfer film 100 shown in FIG. 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 used as is in the lamination step with a substrate in a roll-to-roll system, which will be described later.

[0173] The transfer film may have an intermediate layer and / or a thermoplastic resin layer. Examples of the composition for forming an intermediate layer, the method for forming an intermediate layer, the composition for forming a thermoplastic resin layer, and the method for forming a 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.

[0174] [Method of Forming Photosensitive Layer] The photosensitive layer can be formed by, for example, a known method, such as a method of applying and drying the above-described photosensitive composition.

[0175] Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating. The photosensitive composition used in the method for forming the photosensitive layer preferably contains a solvent. The solvent has the same meaning as the solvent that may be contained in the photosensitive composition described above, and preferred embodiments are also the same.

[0176] [Uses] The pattern (cured film) obtained from the photosensitive layer formed using the above-described photosensitive composition or the above-described transfer film can be used in various applications. For example, it can be used in electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partition walls, spacers, microlenses, optical filters, anti-reflection films, etching resists, and plating members. Specific examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for printed wiring boards, protective films or insulating films for TFT substrates, interlayer insulating films in build-up substrates for semiconductor packages, organic interposers, color filters, overcoat films for color filters, and etching resists for wiring formation.

[0177] [Method for producing laminate] The method for producing the laminate is not particularly limited as long as it is a method using the photosensitive composition or the transfer film described above. The method for producing the laminate preferably includes steps X1 to X3. The method for producing the laminate preferably further includes step X4 and / or step X5 in addition to steps X1 to X3, as necessary. Step X1: A step of forming a photosensitive layer on a substrate using a photosensitive composition or a transfer film. Step X2: A step of patternwise exposing the photosensitive layer. Step X3: A step of developing the exposed photosensitive layer using a developer to form a pattern. Step X4: A step of exposing (preferably, full-surface exposure) the pattern obtained by development in step 3. Step X5: A step of heating the pattern obtained through steps X1 to X3 or the pattern obtained through steps X1 to X4.

[0178] The developer used in step 3 may be either an alkaline developer or an organic solvent-based developer. When the specific siloxane polymer contained in the photosensitive layer contains a polymerizable group and / or when the photosensitive layer contains a polymerizable compound, the developer used in step 3 is preferably an alkaline developer. As described below, step 2 is preferably a step of reducing the carboxyl groups of the specific siloxane polymer to change its solubility in the developer. In particular, when compound β is compound B having a structure capable of accepting electrons from the carboxyl groups of the specific siloxane polymer in a photoexcited state, radicals are generated in the system by the decarboxylation reaction of the specific siloxane polymer in step 2, and these radicals may also promote polymerization reactions of various compounds, such as specific siloxane polymers and polymerizable compounds having polymerizable groups. As a result, a negative pattern can be formed by using an alkaline developer as the developer in step 3. The formed pattern has a reduced carboxyl group content and a low dielectric constant.

[0179] When the specific siloxane polymer contained in the photosensitive layer does not contain a polymerizable group and the photosensitive layer does not contain a polymerizable compound, the developer used in step 3 may be either an alkaline developer or an organic solvent-based developer, but when the developer used in step 3 is an organic solvent-based developer, it is preferable to further include step X4 after step X3. In such a case, when the developer used in step 3 is an alkaline developer, a negative pattern can be formed, and when the developer used in step 3 is an organic solvent-based developer, a positive pattern can be formed via step 4. The formed pattern has a reduced carboxy group content and a low dielectric constant.

[0180] Furthermore, by carrying out step 5, the impurity concentration in the pattern can be reduced, and the crosslinking reaction of unreacted residues of the silyl-containing component can be promoted, thereby further improving the film strength.

[0181] Each step of the method for producing the laminate will be described in detail below.

[0182] [Step X1] Step X1 is a step of forming a photosensitive layer on a substrate. In other words, step X1 may be a step of forming a photosensitive layer using a photosensitive composition, or a step of forming a photosensitive layer using a transfer film. In particular, step X1 is preferably a step of forming a photosensitive layer using a photosensitive composition. The photosensitive composition or transfer film used in step X1 is as described above. When a photosensitive composition is used, step X1 is preferably a step of applying the photosensitive composition to a substrate to form a photosensitive layer. Examples of a method for applying the photosensitive composition include the method of forming a photosensitive layer in the above-mentioned method for producing a transfer film.

[0183] When a transfer film is used, step X1 is preferably a step of contacting the surface of the photosensitive layer in the transfer film opposite the temporary support side with the substrate, and laminating the transfer film and the substrate. For lamination, known laminators such as laminators, vacuum laminators, and auto-cut laminators may be used. Examples of lamination methods include known transfer methods and lamination methods, and a method in which a substrate is placed on the surface of the photosensitive layer and then pressurized and heated using a roll or the like is preferred. Examples of lamination methods include known laminators such as vacuum laminators and auto-cut laminators. The lamination temperature is preferably 70 to 130°C.

[0184] Process X1 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 process of unwinding the substrate before any of the processes included in the method for producing a laminate, and a process of winding the substrate after any of the processes, and at least one of the processes (preferably all of the processes or all of the processes other than the heating process) is carried out while the substrate is being transported. Examples of the unwinding method and the winding method include known methods.

[0185] <Substrate> Examples of the substrate include glass substrates, glass epoxy substrates, silicon substrates, and resin substrates, as well as substrates 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. Examples of the substrate include tempered glass such as Gorilla Glass (manufactured by Corning Incorporated). Materials that can be contained in the substrate include, for example, materials used in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. Resin substrates are preferably resin films with low optical distortion and / or high transparency. Examples of resin substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0186] As the substrate having a conductive layer, a resin substrate having a conductive layer is preferred, and a resin film having a conductive layer is more preferred, because it can be produced by a roll-to-roll method.As the substrate having a conductive layer, an organic substrate having a copper pattern is also preferred.As the organic substrate, for example, a resin substrate can be mentioned.

[0187] Examples of the conductive layer include a conductive layer used for circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably at least one 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. Furthermore, the conductive layer in the substrate having a conductive layer may be either one layer or two or more layers. When the substrate having a conductive layer includes two or more conductive layers, the conductive layers may be the same or different, and are preferably different. 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 SiO２ Conductivity is defined as a material having a volume resistivity of 1×10 ６ It means that the volume resistivity is less than 1×10 ４ Preferably, the resistivity is less than Ωcm. When the substrate having a conductive layer has two or more conductive layers, it is preferable that at least one of the conductive layers contains a conductive metal oxide.

[0188] [Step X2] Step X2 is a step of patternwise exposing the photosensitive layer after the above-mentioned step X1. Step X2 is preferably a step of reducing the content of carboxy groups in the specific siloxane polymer in the photosensitive layer to change its solubility in a developer. "Patternwise exposure" refers to a form of patternwise exposure, i.e., exposure in a form in which exposed and unexposed areas exist. The positional relationship between the exposed and unexposed areas in the patternwise exposure is not particularly limited. The exposure direction may be from the side opposite the substrate of the photosensitive layer, or from the substrate side of the photosensitive layer.

[0189] The reduction rate of the carboxyl group content of the specific siloxane polymer in the photosensitive layer was determined by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure, and measuring the reduction rate of the carboxyl group content in the range of 1680 to 1720 cm －１ The maximum absorption peak due to the C═O stretching of the carboxyl group can be calculated from the reduction rate of the peak top height of the maximum absorption peak present in the wavelength range of 1680 to 1720 cm －１ appears in the wavelength range.

[0190] The exposure light source is not particularly limited as long as it emits light in a wavelength range that can reduce the content of carboxy groups in the specific siloxane polymer (light with a wavelength that excites the specific structure in compound β, for example, 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 10 to 10,000 mJ / cm. ２ is preferred, and 50 to 3000 mJ / cm ２ is more preferred.

[0191] When the photosensitive layer is formed using a transfer film having a temporary support, step X2 may be a step of performing pattern exposure after peeling the temporary support from the photosensitive layer, or a step of performing pattern exposure through the temporary support before peeling the temporary support. Step 2 is preferably a step of performing pattern exposure through the temporary support before peeling the temporary support, in order to prevent contamination of the photomask due to contact between the photosensitive layer and the photomask and to prevent adverse effects on exposure due to foreign matter attached to the photomask. Furthermore, it is preferable to peel the temporary support from the photosensitive layer before step X3. The pattern exposure may be either exposure through a photomask or direct exposure using a laser or the like. Examples of photomasks 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 larger. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. Specifically, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is an example.

[0192] [Step X3] Step X3 is a step of forming a pattern by developing the exposed photosensitive layer using a developer after Step X2. The photosensitive layer exposed in Step X2 has a difference in solubility in the developer between the exposed and unexposed areas (dissolution contrast) due to a decrease in the carboxy group content in the exposed areas of the photosensitive layer. The dissolution contrast in the photosensitive layer allows a pattern to be formed in Step X3. For example, when the developer used in Step X3 is an alkaline developer, Step X3 removes the unexposed areas to form a negative pattern. On the other hand, when the developer used in Step X3 is an organic solvent developer, Step X3 removes the exposed areas to form a positive pattern. It is preferable to reduce the carboxy group content of the specific siloxane polymer in the resulting positive pattern in Step X4, which will be described later.

[0193] Examples of the developer include an alkaline developer and an organic solvent developer, with an alkaline developer being preferred. The alkaline developer is not particularly limited, as long as it can remove the unexposed portions of the photosensitive layer. An alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred. The alkaline developer may also contain a water-soluble organic solvent and / or a surfactant. The water content in the alkaline 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 alkaline developer. The upper limit is preferably less than 100% by mass. Examples of the alkaline developer include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous tetramethylammonium hydroxide solution. The concentration of the alkaline component constituting the alkaline developer may be, for example, a 0.1% by mass aqueous solution, a 1.0% by mass aqueous solution, or a 2.38% by mass aqueous solution. Examples of alkaline developers include those described in JP-A-5-072724 and paragraph 0194 of WO 2015 / 093271.

[0194] 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. Examples of organic solvent developers include cyclopentanone and propylene glycol monomethyl ether acetate. The organic solvent developer may contain two or more organic solvents, or may contain water. The content of water in the organic solvent developer is preferably less than 10% by mass, based on the total mass of the organic solvent developer. It is more preferable that the organic solvent developer is substantially free of water. The content of the organic solvent in 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.

[0195] Examples of the development method include puddle development, shower development, spin development, and dip development. A development method in which a developer is sprayed onto the exposed photosensitive layer by showering is preferred. After development, a cleaning agent or the like may be sprayed by showering and development residues may be removed by scrubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0196] [Step X4] Step X4 is a step of exposing the pattern obtained in Step X3. When the developer in Step X3 is an organic solvent developer, Step X4 is preferably carried out. Step X4 is a step of exposing the positive pattern obtained in Step 3 to light to reduce the content of carboxy groups in the specific siloxane polymer. Specifically, it is preferable to pattern-expose the photosensitive layer using light of a wavelength that excites the specific structure in compound β in the photosensitive layer. The exposure may be either full-surface exposure or pattern-exposure. Examples of the exposure method and exposure conditions include the exposure method and exposure conditions in Step X2.

[0197] [Step X5] Step X5 is a step of heating the pattern obtained in Step X3 or Step 4. By performing Step X5, the impurity concentration in the pattern can be reduced, and the crosslinking reaction of unreacted residues of the silyl-containing component can be promoted, thereby further improving film strength. The purity of the pattern means that the various components contained in the pattern are substantially composed of only the specific siloxane polymer. Specifically, the total content of the specific siloxane polymer is preferably 90% by mass or more, more preferably 95% by mass or more, relative to the total mass of the pattern. The upper limit is preferably 100% by mass or less, relative to the total mass of the pattern. For example, when the photosensitive composition and the photosensitive layer contain a polymerizable compound, the pattern obtained through Step 3 or Step 4 may contain polymeric impurities, such as polymers formed by polymerization of polymerizable compounds. It is presumed that performing Step X5 depolymerizes the polymeric impurities and removes the depolymerized impurities, thereby improving the purity of the pattern.

[0198] The temperature of the heat treatment is preferably 150 to 400°C, more preferably 200 to 350°C, even more preferably 200 to 300°C, and particularly preferably 200 to 250°C. The time of the heat treatment 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.

[0199] [Other Steps] The method for producing a laminate may include other steps in addition to the steps described above. Examples of other steps include the following steps.

[0200] <Step of Peeling Off Cover Film> When the photosensitive layer is formed using a transfer film having a cover film, the method for producing a laminate preferably includes a step of peeling off the cover film. Examples of the method for peeling off the cover film include known methods.

[0201] <Step of Reducing Visible Light Reflectance> When the substrate is a substrate having a conductive layer, the method for producing a laminate may 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. Specifically, treatments include a treatment in which copper is oxidized to blacken it as copper oxide, 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.

[0202] <Etching Step> When the substrate is a substrate having a conductive layer, the method for producing a laminate may include a step of etching the conductive layer in an area where the etching resist film is not disposed, using the pattern formed in step X3 or step X4 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.

[0203] A preferred method for manufacturing a laminate is to use a substrate having a plurality of conductive layers on both surfaces thereof, and to sequentially or simultaneously form patterns on the conductive layers formed on both surfaces. With the above 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.

[0204] [Laminate] The laminate is not particularly limited as long as it is a laminate produced by a laminate production method.

[0205] [Method for manufacturing circuit wiring] The method for manufacturing circuit wiring is not particularly limited as long as it is the manufacture of circuit wiring using a photosensitive composition or a transfer film. The method for manufacturing circuit wiring preferably includes the steps of: bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with the conductive layer in the substrate having a conductive layer, and laminating the transfer film and the substrate having a conductive layer; or applying a photosensitive composition to the substrate to form a photosensitive layer; pattern-exposing the photosensitive layer; developing the exposed photosensitive layer with a developer to form a pattern; heating the pattern; and etching the conductive layer in the region where the pattern is not arranged.

[0206] Examples of the steps in the method for producing a circuit wiring include the steps in the method for producing a laminate. The method for producing a circuit wiring is preferably carried out in multiple sets, with each set consisting of the laminating step or the step of forming a photosensitive layer using a photosensitive composition to the etching step. The film used as the etching resist film can also be used as a protective film (insulating film) for the formed circuit wiring.

[0207] [Method for Manufacturing Semiconductor Package] Examples of methods for manufacturing semiconductor packages include known manufacturing methods such as methods for manufacturing build-up substrates. Specifically, examples include methods for manufacturing semiconductor packages that include steps Z1, Z2, Z3, and Z4 (preferably steps Z1, Z2, Z3, Z3-1, and Z4 in this order). Step Z1: forming a photosensitive layer on a substrate having a conductive layer using a photosensitive composition or a transfer film; Step Z2: pattern-exposing the photosensitive layer; Step Z3: developing the exposed photosensitive layer using a developer to form a pattern having vias; Step Z4: forming a circuit pattern on the pattern; Step Z3-1: heating the pattern

[0208] Steps Z1, Z2, and Z3-1 in the method for manufacturing a semiconductor package include step X1, step X2, and step X5, respectively.

[0209] [Step Z3] Step Z3 is a step of developing the exposed photosensitive layer with a developer to form a pattern having vias. Examples of the method of developing with a developer include the method of developing with the developer in Step X3.

[0210] The shape of the vias in the pattern may be, for example, a square, trapezoid, inverted trapezoid, or other cross-sectional shape, as well as a circular or square front shape (the shape of the via when observed from the direction in which the via bottom is visible). The cross-sectional shape of the vias in the pattern is preferably an inverted trapezoid, as this improves the adhesion of plated copper to the via wall surface. The via size (diameter) is often 300 μm or less, preferably 200 μm or less, more preferably less than 40 μm, even more preferably 30 μm or less, even more preferably 20 μm or less, particularly preferably 15 μm or less, and most preferably 10 μm or less. The lower limit is preferably 1 μm or more, more preferably 5 μm or more. The number of vias may be 1 or 2 or more, with 2 or more being preferred.

[0211] [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 the circuit pattern, as it allows for the formation of fine wiring. In the semi-additive process, a seed layer is formed by electroless copper plating using a palladium catalyst or the like on the via bottom, via wall, and the entire surface of the pattern after step Z3. The seed layer is used to form a power supply layer for electrolytic copper plating. The seed layer preferably has a thickness of 0.1 to 2.0 μm. When the seed layer has a thickness of 0.1 μm or more, a decrease in connection reliability during electrolytic copper plating can be suppressed. When the seed layer has a thickness of 2.0 μm or less, there is no need to increase the amount of etching when flash etching the seed layer between wirings, and damage to the wiring during etching can also be suppressed.

[0212] 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. A palladium-tin mixed catalyst is preferred as the catalyst used in the electroless plating process. The average particle size of the mixed catalyst is preferably 10 nm or less. Furthermore, the plating composition used in the electroless plating process preferably contains hypophosphorous acid as a reducing agent. Examples of commercially available electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0213] After electroless copper plating, it is preferable to thermocompress the surface of the photosensitive layer of the transfer film opposite the temporary support onto the electroless copper plating using a roll laminator. The thickness of the photosensitive 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, it is preferable to expose the photosensitive layer through a photomask on which the desired wiring pattern is drawn. Examples of exposure methods include the exposure method in step X2. Furthermore, after exposure, the temporary support of the transfer film is peeled off, and the exposed photosensitive layer is developed using an alkaline developer to form a pattern. Furthermore, after forming the pattern, development residues of the photosensitive composition may be removed using plasma or the like. After development, electrolytic copper plating may be performed to form a copper circuit layer and via filling. After electrolytic copper plating, the pattern may be peeled off using an alkaline aqueous solution or an amine-based stripper, and the seed layer between the wiring may also be removed (flash etching). Flash etching may be performed using an oxidizing solution containing, for example, 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 Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium may be removed using an acidic solution such as nitric acid or hydrochloric acid.

[0214] After pattern peeling or flash etching, a post-baking treatment is preferably carried out. The post-baking treatment sufficiently heat-cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The curing temperature is preferably 150 to 240°C. The curing time is preferably 15 to 500 minutes.

[0215] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed between the step Z3-1 and the step Z4. By performing the roughening step, the surface of the pattern is roughened, thereby improving adhesion to the circuit wiring and also removing smears. Examples of the roughening step include known desmearing treatments, and a treatment involving contact with a roughening liquid is preferred. Examples of the roughening liquid 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.

[0216] Steps Z1, Z2, Z3, and Z4 (preferably steps Z1, Z2, Z3, Z3-1, and Z4) may be repeated depending on the number of layers required. In addition, it is preferable to form a solder resist on the outermost layer of the resulting semiconductor package.

[0217] [Method for Manufacturing Semiconductor Device] The method for manufacturing a semiconductor device is not particularly limited as long as it includes a method for manufacturing a semiconductor package. Examples of the semiconductor device include 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.).

[0218] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes the laminate described above. The pattern (cured film) may be used as an insulating film or an organic interposer in a build-up base material.

[0219] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, processing procedures, etc. 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 interpreted as being limited by the examples shown below. In the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0220] [Preparation of Photosensitive Composition] Various components were mixed to obtain the solid content ratios shown in the table below, and then diluted to a solid concentration of 30% by mass, a MEK (methyl ethyl ketone) concentration of 20% by mass, and a NMP (N-methylpyrrolidone) concentration of 50% by mass to prepare photosensitive compositions. Note that when the silica was not in a slurry form (when it was in a powder form), the silica was dispersed in a 50% by mass MEK solution to form a slurry, and then the components were mixed together to prepare the photosensitive composition.

[0221] [Siloxane Polymer] The siloxane polymers (Aa-1) to (Aa-6) in Table 2 are shown below. Synthetic products were used as the siloxane polymers (Aa-1) to (Aa-6).

[0222] <<Synthesis of Siloxane Polymer (Aa-1)>> <Synthesis of Monomer M> 50 g of succinic anhydride was dissolved in 500 g of ethyl acetate, and 90 g of aminopropyltrimethoxysilane was slowly added thereto. The mixture was stirred at room temperature for 2 hours, and after confirming that the raw materials had disappeared, the mixture was concentrated to obtain Monomer M.

[0223] (Monomer M)

[0224] <Synthesis of Siloxane Polymer (Aa-1)> 14.0 g of monomer M, 9.9 g of phenyltrimethoxysilane, 50 g of ethyl acetate, and 25 g of isopropanol were mixed. 0.2 g of concentrated hydrochloric acid and 5.6 g of water were added to the mixture, and the mixture was allowed to react at 50°C for 5 hours. 100 g of 1-methoxy-2-propanol was added to the resulting reaction solution, and the mixture was concentrated to 30 g. This operation was repeated twice to remove the hydrochloric acid, water, ethyl acetate, and isopropanol, thereby obtaining a 1-methoxy-2-propanol solution of siloxane polymer (Aa-1). The weight average molecular weight of the resulting polymer, measured using GPC in terms of standard polystyrene, was 3,000, and the acid value was 120 mgKOH / g.

[0225] <<Synthesis of Siloxane Polymers (Aa-2) to (Aa-6)>> Siloxane polymers (Aa-2) to (Aa-6) were synthesized in the same manner as for the above-described siloxane polymer (Aa-1), except that the types and amounts of monomers used were changed.

[0226] <<Siloxane Polymers (Aa-1) to (Aa-6)>> Siloxane polymers (Aa-1) to (Aa-6) are shown below. The composition ratio of the repeating units of each polymer is expressed in mole percent. Table 1 also shows the weight-average molecular weight, acid value (mg KOH / g), and double bond valence (C=C valence (mmol / g)) of siloxane polymers (Aa-1) to (Aa-6). The double bond valence is a value measured by titration using iodine.

[0227]

[0228]

[0229] [Compound β] 2,4-DMQ: 2,4-dimethylquinoline 1-MIQ: 1-methylisoquinoline 9MeAC: 9-methylacridine

[0230] [Filler] YA050C-MJE: Spherical silica slurry, methacrylic surface treated, MEK slurry with a solid content of 50% by mass, manufactured by Admatechs Co., Ltd. SFP-20M: Silica, manufactured by Denka Co., Ltd. SO-C2: Silica, manufactured by Admatechs Co., Ltd.

[0231] [Polymerizable compounds] NK4G: NK ester 4G (bifunctional polyethylene glycol methacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. A-NOD-N: NK ester A-NOD-N (bifunctional alkyl acrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. DPHA: dipentaerythritol hexaacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0232] [Photopolymerization initiator] Oxe01: IRGACURE OXE-01, manufactured by BASF Omn-379EG: Omnirad 379EG, manufactured by IGM Resins B.V.

[0233] [Measurement of Average Particle Diameter] The photosensitive compositions of each Example and Comparative Example were coated on a glass substrate and dried to form a coating film with a thickness of 4.0 μm. A cross section of the resulting coating film was cut out along the normal direction to the surface, and the cross section was observed under a scanning electron microscope. The major axes of all fillers observed within a region measuring 3 μm in the longitudinal direction parallel to the thickness direction of the coating film and 10 μm in the transverse direction perpendicular to the longitudinal direction were measured. The above procedure was performed at five different locations on the coating film, and the average (arithmetic mean) of the major axes of all fillers measured in each procedure was taken as the average particle diameter of the filler. After measuring the average particle diameter as described above for the photosensitive compositions of each Example and Comparative Example, the coating film was heated at 230° C. for 8 hours, and then the average particle diameter was measured again using the same procedure as described above. The average particle diameter was the same as the average particle diameter before heat treatment.

[0234] [Evaluation 1: Photolithography (resolution)] [Coating method] The photosensitive composition shown in Table 2 was coated and dried on glass (Corning glass, 5 cm length x 5 cm width x 1.1 mm thickness) to a dry thickness of 10 μm to form a photosensitive layer. A temporary support (PET film, Lumirror 16FB40, 16 μm thickness, manufactured by Toray Industries, Inc.) and a photomask were laminated in this order on the obtained photosensitive layer to obtain a laminate. The photomask used had multiple circular light-shielding sections with diameters of 20 μm, 15 μm, and 10 μm, and the distance between the light-shielding sections (distance from center to center of circle) was 300 μm. The obtained laminate was subjected to pattern exposure using an ultra-high pressure mercury lamp from the side opposite the temporary support side of the photomask. At this time, the integrated illuminance measured with an illuminometer at a wavelength of 365 nm was 500 mJ / cm. ２ The photomask was then removed from the laminate. After exposure, the laminate was left to stand for 30 minutes, and the temporary support was peeled off from the laminate. The laminate was then developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) as a developer. After development, the laminate was rinsed for 20 seconds at room temperature using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. The resulting laminate was then heat-treated in an oven (250°C, 8 hours), and the photolithography properties were evaluated based on the smallest diameter (minimum resolution pattern size) of vias that could be formed without film loss and without residue at the via bottom.

[0235] <Evaluation criteria for photolithography (resolution)> A: A via with a diameter of 10 μm could be formed. B: A via with a diameter of 15 μm could be formed. C: A via with a diameter of 20 μm could be formed. D: The entire surface was dissolved by development, and a via could not be formed.

[0236] [Transfer Film Method] The obtained photosensitive composition was applied to a temporary support (PET film, Lumirror 16FB40, thickness 16 μm, manufactured by Toray Industries, Inc.) and dried to form a photosensitive layer with a film thickness of 10 μm. Next, a cover film (polypropylene film, FG-201, thickness 30 μm, manufactured by Oji F-Tex Co., Ltd.) was provided on the photosensitive layer to obtain each transfer film. The cover film was peeled from the prepared transfer film and laminated onto a polyimide substrate on which a copper pattern with a line width of 3 μm was formed, thereby obtaining a laminate having a laminate structure in the order of "temporary support / photosensitive layer / copper pattern / substrate (polyimide)". The lamination conditions were a substrate temperature of 40°C, a rubber roller temperature (lamination temperature) of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. Lamination properties were good. When the same procedure as in the evaluation of the coating method was carried out using each transfer film, the photolithographic properties of each transfer film were the same as those in the evaluation of the coating method.

[0237] [Evaluation 2: Evaluation of CTE, relative dielectric constant, and dielectric loss tangent] [Preparation of measurement samples] For each photosensitive composition listed in Table 2 below, a measurement sample was prepared according to the following method X. A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate, and the photosensitive composition shown in Table 2 was applied to the substrate and dried to obtain a laminate having a photosensitive layer with a thickness of 10.0 μm on the substrate. The obtained laminate was exposed to light (high-pressure mercury lamp, integrated illuminance of 100 mJ / cm2 measured with an illuminometer at a wavelength of 365 nm) from the side opposite the substrate side of the photosensitive layer. ２ ), and then dip-developed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) for 90 seconds. Then, the substrate was rinsed for 20 seconds at room temperature using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. This was then heated in an oven (250°C, 8 hours), immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, rinsed (pure water at room temperature for 1 hour), and then peeled from the substrate to obtain a free-standing film derived from the photosensitive layer. If the free-standing film could not be peeled by the above peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week for peeling. The obtained free-standing film was cut into strips to prepare measurement samples.

[0238] [Coefficient of Linear Expansion (CTE)] The measurement sample obtained by Method X was processed to a size of 19 mm x 5 mm, and the CTE 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 16 mm, and a load of 49 mN. The measurement was carried out in a temperature range of -60 to 350°C. The CTE was taken as the average value (ppm / K) in the temperature range of 50 to 100°C during heating. Three samples were measured, and the average value was taken as average value X (ppm / K).

[0239] <CTE evaluation criteria> A: Average value X is less than 15 ppm / K B: Average value X is 15 ppm / K or more and less than 20 ppm / K C: Average value X is 20 ppm / K or more and less than 30 ppm / K D: Average value X is 30 ppm / K or more and less than 50 ppm / K E: Average value X is 50 ppm / K or more and less than 60 ppm / K F: Average value X is 60 ppm / K or more

[0240] [Dielectric Constant and Dielectric Loss Tangent] The dielectric constant and dielectric loss tangent of the measurement sample obtained by Method X were measured using a 28 GHz split cylinder resonator (manufactured by Kanto Electronics Application Development Co., Ltd.) The measurement was performed on three samples, and the dielectric constant and dielectric loss tangent were evaluated based on the average values.

[0241] <Evaluation criteria for dielectric constant> A: Dielectric constant is less than 2.9 B: Dielectric constant is 2.9 or more and less than 3.1 C: Dielectric constant is 3.1 or more and less than 3.3 D: Dielectric constant is 3.3 or more

[0242] <Evaluation criteria for dielectric dissipation factor> A: Dielectric dissipation factor is less than 0.005 B: Dielectric dissipation factor is 0.005 or more and less than 0.007 C: Dielectric dissipation factor is 0.007 or more and less than 0.010 D: Dielectric dissipation factor is 0.010 or more and less than 0.015 E: Dielectric dissipation factor is 0.015 or more

[0243] Table 2 is shown below. The "Content" column indicates the solid content concentration (% by mass) of each component relative to the total solid content in the photosensitive composition. Note that "Not measurable" in the evaluation result column for Comparative Example 1-1 means that a pattern could not be formed using the photosensitive composition of Comparative Example 1-1 (the composition was completely dissolved during development), and therefore none of the CTE, average relative dielectric constant, and average dielectric loss tangent could be measured.

[0244]

[0245]

[0246] The evaluation results shown in Table 2 clearly demonstrate that the photosensitive composition of the present invention can achieve the desired effects. A comparison of Examples 1-1 and 1-2 confirmed that when the specific siloxane polymer contains a polymerizable group, the CTE of the formed pattern is smaller. Furthermore, a comparison of Examples 1-1 to 1-5 confirmed that when the specific siloxane polymer contains a repeating unit in which a group represented by -Y-(Z)p is bonded to a silicon atom of a siloxane bond, and Y represents a single bond, Z represents a vinyl group, and p represents 1, the CTE, dielectric constant, and dielectric loss tangent of the formed pattern are all smaller. Furthermore, a comparison of Examples 1-11 to 1-13 and a comparison of Examples 2-14 to 1-16 confirmed that when the photosensitive composition contains a polymerizable compound, when the content of the polymerizable compound is 10.0 mass% or less with respect to the total mass of the photosensitive composition, at least one of the CTE, the relative dielectric constant, and the dielectric loss tangent of the formed pattern becomes smaller.

[0247] Comparison of the Examples confirmed that when the photosensitive composition contains a filler, at least one of the CTE, dielectric constant, and dielectric dissipation factor of the formed pattern is smaller. Comparison of Examples 2-5, 2-7, and 2-8 confirmed that when the average particle size of the filler is 300 nm or less, the resolution is superior. Comparison of Examples 2-5 and 2-9 to 2-13 confirmed that when the filler content is 50.0 mass% or more (preferably 60.0 mass% or more, more preferably 70.0 mass% or more) relative to the total mass of the photosensitive composition, at least one of the CTE and dielectric dissipation factor of the formed pattern is smaller. Comparison of Examples 2-17 to 2-19 confirmed that when the photosensitive composition contains a polymerizable compound, the CTE of the formed pattern is smaller when the polymerizable group of the polymerizable compound is a methacryloyl group. The reason for this is presumably that when the polymerizable group of the polymerizable compound is a methacryloyl group, the depolymerization reaction is more likely to proceed during the heat treatment of the pattern (step Z5), and as a result, the amount of impurities in the pattern is more likely to be reduced. It has also been confirmed that when the polymerizable compound is tetrafunctional or less (preferably bifunctional), at least one of the CTE and dielectric tangent of the formed pattern is smaller. The reason for this is presumably that, because the number of polymerizable groups in the polymerizable compound is small and the polymerizable group is an acryloyl group, the depolymerization reaction is more likely to proceed during the heat treatment of the pattern (step Z5), and as a result, the amount of impurities is more likely to be reduced.

[0248] In each example, instead of forming a photosensitive layer using a photosensitive composition, measurement samples were prepared using a transfer film prepared according to the following procedure. Each photosensitive composition was applied to a temporary support (PET film, Lumirror 16FB40, 16 μm thick, manufactured by Toray Industries, Inc.) and dried to form a photosensitive layer with a thickness of 10 μm. A cover film (polypropylene film, FG-201, 30 μm thick, manufactured by Oji F-Tex Co., Ltd.) was then placed on the photosensitive layer to obtain each transfer film. The cover film was peeled from the resulting transfer film, and the exposed photosensitive layer was laminated onto the copper surface of a copper-clad polyimide film (Metaloyal, manufactured by Toray Industries, Inc.). The lamination conditions were a substrate temperature of 40°C, a rubber roller temperature (lamination temperature) of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 1 m / min. Lamination properties were good. Furthermore, the temporary support was peeled off from the obtained sample to obtain a laminate having a laminate structure of "photosensitive layer / copper / substrate (polyimide)" in this order. The obtained laminate was exposed to light from the side opposite to the substrate side of the photosensitive layer (high-pressure mercury lamp, integrated illuminance of 100 mJ / cm measured with an illuminometer at a wavelength of 365 nm). ２ ), and then dip-developed in a 1% by mass aqueous solution of sodium carbonate (liquid temperature: 25°C) for 90 seconds. The resulting sample was then rinsed at room temperature for 20 seconds using pure water as a rinse solution, and air was blown to remove any remaining rinse solution. The resulting sample was then heated in an oven (250°C, 8 hours), immersed in 2M hydrochloric acid for 8 hours for a peeling treatment, 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 layer. If the free-standing film could not be peeled off by the peeling treatment, it was further immersed in 2M hydrochloric acid for about 1 week to peel it off. The resulting free-standing film was cut into strips to prepare measurement samples. The obtained measurement sample was evaluated for linear expansion coefficient (CTE), average relative dielectric constant, and average dielectric loss tangent in the same manner as the photosensitive composition. The evaluation results were the same as those for the measurement sample prepared by Method X.

[0249] 12: Temporary support 14: Photosensitive layer 16: Cover film 100: Transfer film

Claims

1. a siloxane polymer having a carboxy group; and a compound β having a structure that reduces the amount of the carboxy groups in the siloxane polymer upon exposure to light.

2. The photosensitive composition according to claim 1 , wherein the siloxane polymer has a repeating unit represented by the following formula (a1): 【Chemistry 1】 In the formula, X represents a linking group having a valence of (n+1), and n represents an integer of 1 or more.

3. The photosensitive composition according to claim 1 or 2, wherein the siloxane polymer further comprises a polymerizable group.

4. 3. The photosensitive composition according to claim 1, wherein the compound β is a compound B having a structure capable of accepting electrons from the carboxy group of the siloxane polymer in a photoexcited state.

5. The photosensitive composition according to claim 1 or 2, wherein the compound β is a nitrogen-containing aromatic compound.

6. The photosensitive composition according to claim 1 or 2, further comprising a filler.

7. The photosensitive composition according to claim 6 , wherein the content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition.

8. 7. The photosensitive composition according to claim 6, wherein the filler has an average particle size of 300 nm or less.

9. a siloxane polymer having a carboxy group and a polymerizable group; a compound β having a structure that reduces the amount of the carboxy group contained in the siloxane polymer upon exposure to light; A photosensitive composition comprising: The siloxane polymer has a repeating unit represented by the following formula (a1): the compound β is a nitrogen-containing aromatic compound, The photosensitive composition, wherein the filler has an average particle size of 300 nm or less. 【Chemistry 2】 In the formula, X represents a linking group having a valence of (n+1), and n represents an integer of 1 or more.

10. The photosensitive composition according to claim 1 or 2, further comprising a polymerizable compound.

11. The photosensitive composition according to claim 1 or 2, further comprising a photopolymerization initiator.

12. A transfer film comprising a temporary support and a photosensitive layer formed using the photosensitive composition according to claim 1 or 2.

13. A step X1 of forming a photosensitive layer on a substrate using the photosensitive composition according to claim 1 or 2; A process X2 of pattern-exposing the photosensitive layer; and a step X3 of developing the exposed photosensitive layer with a developer to form a pattern.

14. The method for producing a laminate according to claim 13, wherein the step X2 is a step of reducing the carboxyl groups of the siloxane polymer to change its solubility in a developer.

15. The method for producing a laminate according to claim 13, wherein the substrate is an organic substrate having a copper pattern.

16. The method for producing a laminate according to claim 13 , wherein the developer is an alkaline developer.

17. A laminate produced by the method according to claim 13.

18. A semiconductor package comprising the laminate of claim 17.

19. A siloxane polymer having a carboxy group and a polymerizable group, a compound β having a structure that reduces the amount of the carboxy group contained in the siloxane polymer upon exposure to light; A photosensitive composition comprising: The siloxane polymer has a repeating unit represented by the following formula (a1): the compound β is a nitrogen-containing aromatic compound, The average particle size of the filler is 300 nm or less, The photosensitive composition according to claim 9 , wherein the content of the filler is 50% by mass or more based on the total solid content of the photosensitive composition. 【Chemistry 3】 In the formula, X represents a linking group having a valence of (n+1), and n represents an integer of 1 or more.

20. A siloxane polymer having a carboxy group, a compound β having a structure that, upon exposure to light, causes a decarboxylation reaction of the carboxy group contained in the siloxane polymer, thereby reducing the amount of the carboxy group contained in the siloxane polymer; The siloxane polymer has a repeating unit represented by the following formula (a1):

2. The photosensitive composition according to claim 1, wherein the compound β comprises an acridine, a 9-alkylacridine, a quinoline which may have a substituent, or an isoquinoline which may have a substituent. 【Chemistry 4】 In the formula, X represents an (n+1)-valent linking group consisting of one or a combination of two or more selected from the group consisting of a divalent linear or branched aliphatic hydrocarbon group which may have a substituent, -O-, -S-, -SO 2 -, >N-, -NR S1 -, and -CO-. R S1 represents a hydrogen atom or a monovalent organic group. n represents an integer of 1 or greater.

21. A siloxane polymer having a carboxy group, a compound β having a structure that reduces the amount of the carboxy group in the siloxane polymer upon exposure to light, The siloxane polymer having a carboxy group does not have a structure in which a hydrogen atom of a carboxy group is substituted with an acid labile group, The photosensitive composition of claim 1 , which is substantially free of a polymerizable compound.

22. A siloxane polymer having a carboxy group, a compound β having a structure that reduces the amount of the carboxy group in the siloxane polymer upon exposure to light, Does not contain an acid generator The photosensitive composition of claim 1 , which is substantially free of a polymerizable compound.

23. A cured film obtained by curing the photosensitive composition described in claim 1.

24. A cured film obtained by curing the photosensitive composition described in claim 9.

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