Organopolysiloxane, composition, cured product, and method for producing semiconductor package

Abstract

The present invention addresses the problem of providing an organopolysiloxane which is capable of forming a film that has a low linear expansion coefficient and is not susceptible to occurrence of cracks. An organopolysiloxane according to the present invention comprises a unit represented by formula (1) and a unit represented by formula (2).　Formula (1): Ra-M-L-SiO3 / 2, Formula (2): Rb 2-SiO2 / 2

Description

Organopolysiloxane, composition, cured product, and method for manufacturing semiconductor package

[0001] The present invention relates to an organopolysiloxane, a composition, a cured product, and a method for producing a semiconductor package.

[0002] Organopolysiloxanes are used in a variety of fields, including as materials for interlayer insulating films in semiconductor chips and connection layers (e.g., build-up layers and interposers) with printed wiring boards.

[0003] For example, Patent Document 1 discloses a composition containing an organopolysiloxane.

[0004] International Publication No. 2018 / 168435

[0005] The present inventors have investigated films formed using organopolysiloxanes such as those described in Patent Document 1 and have found that it is difficult to achieve both a low linear expansion coefficient and resistance to cracking.

[0006] Therefore, an object of the present invention is to provide an organopolysiloxane that can form a film that has a low linear expansion coefficient and is less susceptible to cracking, as well as a composition, a cured product, and a method for producing a semiconductor package related to the organopolysiloxane.

[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] An organopolysiloxane comprising a unit represented by formula (1) and a unit represented by formula (2) described below. [2] The organopolysiloxane according to [1], in which the total number of monocyclic ring structures is 4 or more. [3] The organopolysiloxane according to [1], in which M has 3 or more aromatic rings as the one or more rings. [4] The organopolysiloxane according to [1] or [2], in which M has 4 or more aromatic rings as the one or more rings. [5] The organopolysiloxane according to any one of [1] to [4], in which M has 2 or more nitrogen atoms. [6] The organopolysiloxane according to [1], in which M is a group represented by formula (X) described below or a group represented by formula (Y) described below. [7] The organopolysiloxane according to any one of [1] to [6], wherein M has at least one aromatic heterocycle having a nitrogen atom as a ring member atom as the one or more rings. ａ [9] The organopolysiloxane according to any one of [1] to [7], wherein R is a monovalent group having a polymerizable group. ｂ are each independently a hydrogen atom, a methyl group, a vinyl group, or a phenyl group.

[10] The organopolysiloxane according to any one of [1] to [9], wherein the organopolysiloxane has a weight average molecular weight of 5,000 or more.

[11] A composition comprising the organopolysiloxane according to any one of [1] to

[10] .

[12] A cured product obtained by curing the organopolysiloxane according to any one of [1] to

[10] .

[13] A method for producing a semiconductor package, comprising: Step Z1 of forming a composition layer comprising the organopolysiloxane according to any one of [1] to

[10] on a substrate; and Step Z2 of forming a pattern having vias in the composition layer.

[14] A method for producing a semiconductor package, comprising: Step Z1 of forming a composition layer containing the organopolysiloxane according to any one of [1] to

[10] on a substrate; Step Z12 of heating or exposing the composition layer; and Step Z13 of forming a pattern having vias in the heated or exposed composition layer using a laser.

[0009] The present invention provides an organopolysiloxane that can form a film that has a low linear expansion coefficient and is resistant to cracking. It also provides a composition, a cured product, and a method for producing a semiconductor package related to the organopolysiloxane.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] In this specification, the bonding direction of the divalent group (for example, —O—CO—) is not particularly limited. １ｚ -L ２ｚ -L ３ｚ In the bond ２ｚ When is —O—CO—, L １ｚ The position where it is bonded to the side is *1, L ３ｚ If the position bonded to the side is *2, then L ２ｚ may be *1-O-CO-*2 or *1-CO-O-*2.

[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, "actinic rays" and "radiation" refer to the bright line spectrum of a mercury lamp, such as g-rays, h-rays, and i-rays, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using a mercury lamp, far ultraviolet light represented by an excimer laser, X-rays, EUV light, etc., but also exposure using particle beams such as electron beams and ion beams.

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

[0018] 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.

[0019] In this specification, unless otherwise specified, the layer thickness (film thickness) 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.

[0020] [Organopolysiloxane] The organopolysiloxane of the present invention (hereinafter also referred to as the "specific compound") contains a unit represented by formula (1) and a unit represented by formula (2). The unit represented by formula (1) corresponds to a type of so-called T unit, and the unit represented by formula (2) corresponds to a type of so-called D unit.

[0021] Although the detailed mechanism of action of the specific compound is not clear, the present inventors speculate as follows. It is speculated that the units represented by formula (1) in the specific compound cause, for example, the groups represented by M in formula (1) to interact with each other, resulting in a smaller linear expansion coefficient of the resulting film, and that the inclusion of units represented by formula (2) can further reduce the linear expansion coefficient of the resulting film and make it less susceptible to cracking. Note that, when the substrate to which the film formed using the specific compound is transferred is a copper plate (copper wiring), a low linear expansion coefficient means a linear expansion coefficient as low as that of a copper plate. Hereinafter, superiority in at least one of the effects of reducing the linear expansion coefficient and the effect of making it less susceptible to cracking is also referred to as "superior effect of the present invention."

[0022] Examples of the structure of the specific compound include an irregular form such as a random structure, a ladder structure, a cage (fully condensed cage) structure, and an incomplete cage structure (a partially cleaved cage structure in which some silicon atoms are missing from the cage structure and some silicon-oxygen bonds are cleaved in the cage structure), and a ladder structure is preferred.

[0023] The specific compound may have a polymerizable group. The type of the polymerizable group is not particularly limited, and examples thereof include radically polymerizable groups and cationically polymerizable groups. Examples of the radically polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a styryl group, and an allyl group. Examples of the cationically polymerizable group include an oxiranyl group and an oxetanyl group. The number of polymerizable groups contained in the specific compound is not particularly limited, and may be one or more.

[0024] Formula (1) R ａ -ML-SiO ３／２

[0025] In formula (1), R ａ represents a hydrogen atom or a monovalent group. M represents a divalent linking group containing one or more rings, wherein the total number of monocyclic ring structures in the one or more rings is 3 or more. L represents a single bond or a divalent linking group.

[0026] R ａ Examples of the monovalent group represented by the formula (R) include a group having a polymerizable group (a monovalent group having a polymerizable group), an alkyl group, an alkoxy group, an alkyl ester group, and an acyl group (for example, an acetyl group). The group having a polymerizable group is not particularly limited as long as it is a group having a polymerizable group that the specific compound described above can have. Furthermore, the group having a polymerizable group may be the polymerizable group itself. As the group having a polymerizable group, a polymerizable group, -(an alkylene group which may have -O-)-polymerizable group, or -COO-alkylene group-polymerizable group is preferred. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 5. R ａ is preferably a group having a hydrogen atom or a polymerizable group. ａ It is also preferable that the group is a monovalent group having no ring.

[0027] The one or more rings contained in the divalent linking group represented by M are preferably at least one ring selected from the group consisting of aromatic rings (aromatic hydrocarbon rings and aromatic heterocyclic rings) and alicyclic rings (aliphatic heterocyclic rings and aliphatic hydrocarbon rings), and more preferably at least one ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. The ring may have a substituent to improve the alignment degree of the cured liquid crystal layer. The substituent is preferably an alkyl group, an alkoxy group, an alkyl ester group, or an acyl group (e.g., an acetyl group). The one or more rings contained in the divalent linking group represented by M may be either a monocyclic or polycyclic ring. That is, the aromatic ring and the alicyclic ring may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The aromatic ring and the alicyclic ring may also be a fused ring. The number of ring members in the monocyclic ring constituting the aromatic ring and the alicyclic ring is preferably 5 to 12, more preferably 5 or 6. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 12, more preferably 6. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, with a benzene ring being preferred. The number of carbon atoms in the aromatic heterocycle is preferably 3 to 12, and more preferably 3 to 6. Examples of aromatic heterocycles include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a triazine ring, a phenanthroline ring, a thiazole ring, and a benzothiazole ring, with a thiophene ring, a triazine ring, or a thiazole ring being preferred. The number of carbon atoms in the alicyclic ring is preferably 6 to 12, and more preferably 6. Examples of alicyclic rings include cycloalkane rings such as a cyclopentane ring and a cyclohexane ring.

[0028] The ring preferably has a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. When the ring has a heteroatom, the ring preferably has a heteroatom as a ring member atom constituting the ring, and more preferably has a nitrogen atom as a ring member atom.

[0029] The divalent linking group represented by M contains one or more rings, and the total number of monocyclic ring structures in the one or more rings is 3 or more, preferably 4 or more. The upper limit of the total number of the monocyclic ring structures is preferably 10 or less, more preferably 6 or less. In other words, it is preferable that the total number of monocyclic ring structures possessed by the divalent linking group represented by M is 1 or more, and also satisfies the above-mentioned preferred embodiment. The monocyclic ring structure refers to a ring structure such as a monocyclic aromatic hydrocarbon ring, a monocyclic aromatic heterocycle, or a monocyclic alicyclic ring. For example, in a ring obtained by condensing two monocyclic rings, the number of monocyclic ring structures is counted as two. Specifically, a thienothiazole ring is a ring obtained by condensing a thiophene ring and a thiazole ring, and the number of monocyclic ring structures is two. Furthermore, for example, when M contains two benzene rings and one thienothiazole ring, the total number of monocyclic ring structures is four.

[0030] It is preferable that M has two or more (preferably 2 to 10) nitrogen atoms. The number of nitrogen atoms is not limited to the number of nitrogen atoms in the rings in M, but indicates the number of nitrogen atoms in M ​​as a whole. Specifically, when M is "-benzene ring-N=N-triazine ring-", the number of nitrogen atoms is five, and therefore this corresponds to the above-mentioned preferred embodiment of M. It is also preferable that M has at least an aromatic heterocycle having a nitrogen atom as a ring member atom.

[0031] M preferably has 3 or more aromatic rings as the 1 or more rings, and more preferably has 4 or more aromatic rings. The upper limit of the number of aromatic rings that M has is preferably 10 or less, and more preferably 6 or less.

[0032] M is preferably a group represented by formula (X) or a group represented by formula (Y).

[0033]

[0034] In formula (X), * represents a bonding position. ｘ１ represents a ring. ｘ２ represents a single bond, —COO—, —O—, or —CH ２represents O-, -N=N-, -CH=CH-, -C≡C- or -CH=N-. nx represents an integer of 3 or more. In formula (Y), * represents a bonding position. Ar ｙ１ ~Ar ｙ４ each independently represents a monocycle. ｙ１ ~L ｙ３ each independently represents a single bond, —COO—, —O—, or —CH ２ represents O-, -NH-, -N=N-, -CH=CH-, -C≡C- or -CH=N-. ｙ１ represents a hydrogen atom or a monovalent group; my1 represents an integer of 0 or more; my2 and my3 each independently represent an integer of 1 or more; provided that multiple L ｘ１ The L may be the same or different. ｘ２ Ar may be the same or different. ｙ１ When there are multiple Ar ｙ１ Ar may be the same or different. ｙ２ When there are multiple Ar ｙ２ Ar may be the same or different. ｙ３ When there are multiple Ar ｙ３ They may be the same or different. ｙ１ If there are multiple L ｙ１ They may be the same or different. ｙ２ If there are multiple L ｙ２ They may be the same or different. ｙ３ If there are multiple L ｙ３ They may be the same or different.

[0035] L ｘ１ Examples of the ring represented by the formula (I) include the rings exemplified by one or more rings contained in the divalent linking group represented by the formula (I), and a benzene ring, a triazine ring, or a thienothiazole ring is preferred. Ｘ１ The ring represented by the formula (I) constitutes a divalent group. ｘ２ is preferably a single bond, —COO— or —N═N—. ｘ２ As for R ａ L directly bonded to ｘ２ is a single bond, and other Lｘ２ is also preferably -COO- or -N=N-. nx is an integer of 3 or more, preferably an integer of 4 or more. The upper limit is preferably an integer of 10 or less, more preferably an integer of 6 or less.

[0036] Ar ｙ１ ~Ar ｙ４ The monocyclic ring represented by the formula (I) may be a monocyclic ring selected from the rings exemplified as one or more rings contained in the divalent linking group represented by the formula (I). ｙ１ ~Ar ｙ３ The ring represented by the formula (I) constitutes a divalent group. ｙ４ The ring represented by the formula L constitutes a trivalent group. ｙ１ ~L ｙ３ is preferably a single bond, —COO—, —NH— or —N═N—. ｙ１ As the monovalent group represented by R ａ and preferred embodiments are also the same. my1 is an integer of 0 or more, and preferably an integer of 1 or more. The upper limit is preferably an integer of 10 or less, more preferably an integer of 6 or less, and even more preferably an integer of 3 or less. my2 and my3 are integers of 1 or more. The upper limit is preferably an integer of 10 or less, more preferably an integer of 6 or less, and even more preferably an integer of 3 or less. Furthermore, my1 + my2 + my3 is preferably an integer of 2 or more, more preferably an integer of 2 to 10, even more preferably an integer of 2 to 7, and particularly preferably an integer of 3 to 5.

[0037] In formula (X), * represents a bonding position, one of the *'s is bonded to L in formula (1), and the other *'s is bonded to R ａ There are no particular limitations on the bonding position as long as it is bonded to L ｘ１ * is directly bonded to L, and L ｘ２ * is directly bonded to R ａ As above, * in formula (Y) represents a bonding position, one of the *'s is bonded to L in formula (1), and the other *'s is bonded to R ａ The bonding position is not particularly limited as long as it is bonded to A. ｙ１ * is directly bonded to L, and A ｙ３ * is directly bonded to R ａ It is preferred to bind to

[0038] Examples of the divalent linking group represented by L include alkylene groups, -O-, -CO-, -COO-, -S-, and combinations thereof, with -alkylene group-O-, -alkylene group-CO-, -alkylene group-COO-, -alkylene group-S-alkylene group-, or -alkylene group-S-alkylene group-O- being preferred. The alkylene group may be linear, branched, or cyclic, with linear being preferred. The alkylene group preferably has 1 to 10 carbon atoms. Furthermore, L is also preferably a divalent linking group that does not have a ring.

[0039] In addition, the above L ｘ１ and Ar ｙ１ ~Ar ｙ４ As described above, the monocyclic ring represented by may have a substituent. The substituent is preferably an alkyl group, an alkoxy group, an alkyl ester group (an alkyloxycarbonyl group or an alkylcarbonyloxy group), an acyl group (e.g., an acetyl group), or a group having a polymerizable group. Details of the group having a polymerizable group are given in R ａ The monovalent group represented by the formula (I) is as described above.

[0040] The unit represented by formula (1) may be used alone or in combination of two or more types. The content of the unit represented by formula (1) is preferably 20 to 80 mol% relative to the total amount (100 mol%) of the units of the specific compound, and from the viewpoint of achieving better effects of the present invention, is more preferably 25 to 70 mol%, even more preferably 30 to 65 mol%, and particularly preferably 40 to 55 mol%. The content of the unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 95 mol% or more relative to the total amount (100 mol%) of the units represented by formula (T) (so-called T units) in the specific compound. The upper limit is preferably 100 mol% or less.

[0041] The specific compound may have a T unit different from the unit represented by formula (1). When the specific compound has a polymerizable group, it is also preferable that the T unit different from the unit represented by formula (1) has a polymerizable group.

[0042] The content of the unit represented by formula (1) and other units (for example, T units described later) is, for example, ２９ It can be measured using Si-NMR (nuclear magnetic resonance analysis).

[0043] Formula (T) R ｔ -SiO ３／２ In formula (T), R ｔ represents a substituent.

[0044] Formula (2) R ｂ ２ -SiO ２／２

[0045] In formula (2), R ｂ each independently represents a hydrogen atom, a linear or branched monovalent hydrocarbon group, or a monovalent group having at least one ring.

[0046] R ｂ The monovalent hydrocarbon group represented by the formula (I) is preferably a linear or branched monovalent aliphatic hydrocarbon group. The number of carbon atoms in the monovalent aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the monovalent aliphatic hydrocarbon group include alkyl groups (e.g., methyl and ethyl groups), alkenyl groups (e.g., vinyl groups), alkynyl groups, and groups formed by combining these groups, with alkyl groups or alkenyl groups being preferred. R ｂ Examples of the ring contained in the monovalent group represented by the formula (I) include the rings exemplified by the one or more rings contained in the divalent linking group represented by the formula (I), and a phenyl group is preferred as the monovalent group. ａ A group represented by -ML- is also preferred. ａ Details of the group represented by -ML- are as described above in formula (1). ｂ is a hydrogen atom, an alkyl group, an alkenyl group, a monovalent aromatic hydrocarbon ring group, or R ａ A group represented by -ML- is preferred, and a hydrogen atom, a methyl group, a vinyl group or a phenyl group is more preferred. ｂ Preferably, at least one of R represents a linear or branched monovalent aliphatic hydrocarbon group, andｂ It is more preferable that at least one of R represents an alkyl group, and ｂ More preferably, all of represent an alkyl group.

[0047] The units represented by formula (2) may be used alone or in combination of two or more. The content of the units represented by formula (2) is preferably 20 to 80 mol% relative to the total units (100 mol%) of the specific compound, and from the viewpoint of achieving better effects of the present invention, 30 to 75 mol% is more preferable, 35 to 70 mol% is even more preferable, and 45 to 60 mol% is particularly preferable. The content of the units represented by formula (2) is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 95 mol% or more relative to the total amount of units represented by formula (D) (so-called D units) in the specific compound. The upper limit is preferably 100 mol% or less.

[0048] The content of the unit represented by formula (2) and other units (for example, the D unit described later) is, for example, ２９ It can be measured using Si-NMR (nuclear magnetic resonance analysis).

[0049] Formula (D) R ｄ ２ -SiO ２／２ In formula (D), R ｄ each independently represents a substituent.

[0050] The total content of the units represented by formula (1) and the units represented by formula (2) is preferably 90 mol % or more, more preferably 95 mol % or more, based on the total units of the specific compound. The upper limit is preferably 100 mol % or less.

[0051] The weight average molecular weight of the specific compound is preferably 3,000 or more, and more preferably 5,000 or more in terms of better effects of the present invention. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 50,000 or less.

[0052] The method for producing the specific compound is not particularly limited, and the specific compound can be produced, for example, by hydrolytic condensation of raw materials including a monomer that becomes a unit represented by formula (1) through hydrolytic condensation and a monomer that becomes a unit represented by formula (2) through hydrolytic condensation. As described above, the specific compound preferably has a ladder structure. A method for producing a specific compound with a ladder structure includes, for example, a method in which, when a monomer that becomes a unit represented by formula (1) and a monomer that becomes a unit represented by formula (2) are hydrolytically condensed, the reaction is carried out while discharging by-products such as alcohols (e.g., methanol) generated in the system to the outside of the system.

[0053] [Composition] The composition contains a specific compound. The composition is preferably used to form a composition layer described below. The composition may contain other components as long as it contains the specific compound. Examples of other components include a solvent, a polymerization initiator described below, and an additive described below.

[0054] The water content of the composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the composition is improved. The lower limit of the water content of the composition is preferably 0.001% by mass or more, and can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoints of reducing the effort required for managing storage conditions, adhesion, developability, etc. Specific examples of the water content of the composition include 0.05% by mass, 0.2% by mass, and 1.4% by mass. The water content of the composition may fluctuate during storage. Methods for maintaining the water content of the composition during storage include adjusting the humidity under storage conditions and reducing the porosity of the container during storage.

[0055] The metal content of the composition is set to 5 ppm by mass (parts per million (10 ppm)) based on the total mass of the composition from the viewpoints of insulation properties and reliability. －６) is preferably less than 1 ppm by mass, more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoints of reducing the effort required for reducing the metal content and improving mechanical properties and adhesion, the lower limit of the metal content in the composition is preferably 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more, relative to the total mass of the composition. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, and tin, but do not include metals contained as complexes of organic compounds and metals. When the composition contains multiple metals, the total amount of these metals is preferably within the above range. Specific examples of the metal content include 0.002 ppm by mass, 0.05 ppm by mass, and 0.3 ppm by mass, relative to the total mass of the composition.

[0056] Examples of methods for reducing metals (metal impurities) unintentionally contained in a composition include selecting raw materials with a low metal content as raw materials constituting the composition, filtering the raw materials constituting the composition, and lining the inside of an apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination.

[0057] The content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, relative to the total mass of the composition. In particular, the content of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass, relative to the total mass of the composition. From the viewpoint of reducing the effort required for reducing halogen ions, the lower limit of halogen ions in the composition can be 0.01 ppm by mass or more, or even 0.1 ppm by mass or more, relative to the total mass of the composition. Specific examples of the amount of halogen ions include 0.02 ppm by mass, 0.5 ppm by mass, and 2.5 ppm by mass, relative to the total mass of the composition. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0058] The composition may contain a monomer component. The monomer component is typically a raw material for organopolysiloxane. The monomer component is preferably one that becomes a unit represented by formula (1) or a unit represented by formula (2) upon hydrolysis and condensation. Examples of the monomer component include a compound having a trialkoxysilyl group, a compound having a structure in which the trialkoxysilyl group is partially hydrolyzed, and a compound having a trihydroxysilyl group. From the viewpoint of reducing the linear expansion coefficient, the content of the monomer component is preferably less than 10% by mass, more preferably less than 5% by mass, and even more preferably less than 3% by mass, relative to the total mass of the composition. Furthermore, from the viewpoint of suppressing cracking, the content of the monomer component is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the composition.

[0059] [Cured Product] The cured product is a cured product obtained by curing a specific compound, and also includes a cured product obtained by curing the above-mentioned composition. Examples of a method for producing a cured product include a method of subjecting the specific compound or the above-mentioned composition to a curing treatment. Examples of the curing treatment include the treatment of step Z3 described below.

[0060] [Transfer Film] The transfer film preferably has a temporary support and a composition layer containing a specific compound.

[0061] The temporary support is a member that supports the composition layer and is ultimately removed by a peeling treatment. 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. A film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heat is also preferred. Examples of the film include polyethylene terephthalate film (e.g., biaxially oriented polyethylene terephthalate film), polymethyl methacrylate film, cellulose triacetate film, polystyrene film, polyimide film, and polycarbonate film, with polyethylene terephthalate film being preferred. It is also preferred that the temporary support be free of deformations such as wrinkles and scratches. The thickness of the temporary support is preferably 5 to 200 μm. From the viewpoints of ease of handling and versatility, it is more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm.

[0062] When pattern exposure is performed through the temporary support, the temporary support preferably has high transparency. Specifically, the transmittance at 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%. When a pattern is formed using a UV laser through the temporary support, the temporary support preferably has low transparency at the UV laser wavelength. Specifically, when a laser with a wavelength of 355 nm is used, the transmittance at a wavelength of 355 nm is preferably 80% or less, more preferably 60% or less, even more preferably 40% or less, and particularly preferably 20% or less. The lower limit is preferably 0% or more. In terms of pattern formability during pattern exposure through the temporary support, via formability during laser processing, 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 pattern formability during pattern exposure through the temporary support, via formability during laser processing, and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support is small. Specifically, the number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in 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:

[0063] 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.

[0064] Examples of the temporary support include a 25 μm thick biaxially oriented polyethylene terephthalate film, a 16 μm thick biaxially oriented polyethylene terephthalate film, a 12 μm thick biaxially oriented polyethylene terephthalate film, and a 9 μm thick biaxially oriented polyethylene terephthalate film.

[0065] Examples of the temporary support include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference. Commercially available temporary supports include, for example, Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, Lumirror #25T60, and Therapeel 25WZ (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0066] The composition layer is preferably a layer formed using the above-described composition. The composition layer may contain other components as long as it contains a specific compound. Examples of other components include polymerization initiators, additives, and fillers. Examples of polymerization initiators include thermal polymerization initiators such as peroxides, photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Examples of additives include heterocyclic compounds (e.g., triazole, benzotriazole, tetrazole, and derivatives thereof, rust inhibitors), surfactants, fillers, aliphatic thiol compounds, polymerization inhibitors, hydrogen donor compounds, impurities, plasticizers, sensitizers, polymerizable compounds, and thermally crosslinkable compounds. Examples of heterocyclic compounds, aliphatic thiol compounds, polymerization inhibitors, and hydrogen donor compounds include, for example, the various components described in WO 2022 / 039027. Examples of plasticizers and sensitizers include, for example, the various components described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0067] Examples of fillers include organic fillers and inorganic fillers. 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 composition layer preferably does not contain a filler. Even if the composition layer does not contain a filler, the linear expansion coefficient can be reduced by containing a specific compound. Furthermore, if the composition layer does not contain a filler, the surface roughness of the composition layer is easily reduced.

[0068] <Intermediate layer and thermoplastic resin layer> The transfer film may have an intermediate layer or a thermoplastic resin layer. Examples of the intermediate layer and the thermoplastic resin layer include the intermediate layer and the thermoplastic resin layer described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0069] <Cover Film> The transfer film may include a cover film. When the transfer film includes a cover film, the cover film is preferably provided as the outermost layer on the side opposite to the temporary support.

[0070] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of the cover film include the cover films described in paragraphs 0083 to 0087 and 0093 of JP 2006-259138 A, the contents of which are incorporated herein by reference.

[0071] 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.).

[0072] The transfer film may have a high refractive index layer. Examples of the high refractive index layer include those described in paragraphs 0168 to 0188 of WO 2021 / 187549, the contents of which are incorporated herein by reference.

[0073] The method for producing the transfer film may be a known method, and preferably includes a step of applying a composition containing a specific compound onto a temporary support to form a composition layer.

[0074] [Uses] Films obtained from a composition layer containing a specific compound can be used in a variety of applications. For example, they can be used as electrode protective films, insulating films, planarizing films, overcoat films, hard coat films, passivation films, partitions, 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.

[0075] [Method for Manufacturing a Semiconductor Package] The method for manufacturing a semiconductor package is not particularly limited as long as it uses the above-described composition or transfer film. Examples of methods for manufacturing a semiconductor package include known manufacturing methods such as manufacturing methods for build-up substrates. A first preferred embodiment of the method for manufacturing a semiconductor package is preferably a manufacturing method including the following steps Z1 and Z2, and more preferably a manufacturing method including steps Z1 to Z4. Step Z1: forming a composition layer on a substrate using a composition or a transfer film; Step Z2: forming a pattern having vias in the composition layer; Step Z3: heating or exposing the pattern; and Step Z4: forming a circuit pattern on the obtained pattern. Furthermore, a first preferred embodiment of the method for manufacturing a semiconductor package is a manufacturing method including the following steps Z1 to Z4, which preferably further includes step Z5 of forming a composition layer on the semiconductor package manufactured by step Z4 using a composition or a transfer film, and steps Z2 to Z5 are repeatedly performed.

[0076] <Step Z1> Step Z1 is a step of forming a composition layer on a substrate using a composition or a transfer film. The composition layer contains a specific compound. Step Z1 is preferably a step of contacting the surface of the composition layer in the transfer film opposite the temporary support side with the substrate to bond the transfer film to the substrate. It is also preferably a step of applying a composition to the substrate. Examples of methods for bonding the transfer film include known transfer methods and methods using known laminators such as laminators, vacuum laminators, and auto-cut laminators, and methods that involve pressure and heat application using a roll or the like are preferred. Furthermore, if the transfer film has a cover film, step Z1 is preferably performed after peeling the cover film from the transfer film.

[0077] Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer, with a substrate having a conductive layer being preferred. The substrate may be a light-transmitting substrate such as a glass substrate, or may be tempered glass such as Corning Gorilla Glass. Examples of materials contained in the substrate include those described 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. Specific examples include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0078] <Step Z2> Step Z2 is a step of forming a pattern having vias in the composition layer. The pattern having vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate. Methods for forming a pattern having vias include, for example, methods using a drill, a laser, and plasma. As a method for forming a pattern using a laser, the method of step Z13 described below can be used.

[0079] Furthermore, when the composition layer is photosensitive, the method for forming a pattern having vias preferably includes a step of pattern-exposing the composition layer, a step of developing the exposed composition layer with a developer to form a pattern, and a step of etching the conductive layer in areas where the pattern is not arranged. It is more preferable to include a step of curing the pattern between the step of forming the pattern and the step of etching. The exposure may be performed from the side opposite the substrate of the composition layer, or from the substrate side of the composition layer.

[0080] Examples of the developer include an alkaline developer and an organic solvent developer. Examples of the development method include puddle development, shower development, spin development, and dip development, and a development method in which the developer is sprayed onto the composition layer after exposure by showering is preferred.

[0081] The light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.) to which various photosensitive components in the composition layer (e.g., a specific compound, a polymerizable compound, a polymerization initiator, etc.) are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0082] The exposure dose is 5 to 200 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0083] In step Z2, exposure may be carried out after peeling off the temporary support, or exposure may be carried out through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. Examples of masks include quartz masks, soda lime glass masks, and film masks. A polyester film is preferred as the material for the film mask, and a polyethylene terephthalate film is more preferred. Examples of film mask materials include XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).

[0084] The pattern having vias may be either through holes or via holes. The shape of the vias in the pattern may be, for example, a square, trapezoid, or inverted trapezoid in cross section; or a circle or square in front view (the shape of the via when observed from the direction in which the via bottom is visible). An inverted trapezoid is preferred as the cross section because it improves the adhesion of plated copper to the via wall. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more.

[0085] <Step Z3> Step Z3 is a step of heating or exposing the composition layer. Step Z3 is preferably a step of curing the composition layer. The heating temperature is preferably 100 to 300°C, and the heating time is preferably 10 minutes to 10 hours. Examples of the exposure method include the exposure method in step Z2.

[0086] <Step Z4> Step Z4 is a step of forming a circuit pattern on the pattern. The material of the circuit pattern is not particularly limited, and is preferably a metal or alloy containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Among these, metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel-chromium alloys, are preferred, with copper being more preferred. A semi-additive process is preferred as a method for forming the circuit pattern because it allows for the formation of fine wiring. For example, in the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of a via-containing pattern. The electroless copper plating process is carried out by depositing metallic copper on the surface of the via-containing pattern through a reaction between copper ions and a reducing agent. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst for the electroless plating treatment is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating solution for the electroless plating treatment preferably contains hypophosphorous acid (reducing agent). Examples of 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.

[0087] A second preferred embodiment of the method for manufacturing a semiconductor package includes a method including the above-mentioned step Z1 and the following steps Z12 to Z13, with a method including the following steps Z11 to Z13 being preferred, and a manufacturing method including the following steps Z11 to Z13 and further including the following step Z14 either before step Z12, between steps Z12 and Z13 (after step Z12 or before step Z13), or after step Z13 being more preferred. That is, second preferred embodiments of the method for manufacturing a semiconductor package include a method including step Z11, step Z14, step Z12, and step Z13 in this order (hereinafter referred to as "Aspect 2-1"), a method including step Z11, step Z12, step Z13, and step Z14 in this order (hereinafter referred to as "Aspect 2-2"), and a method including step Z11, step Z12, step Z14, and step Z13 in this order (hereinafter referred to as "Aspect 2-3"), with Aspect 2-2 being preferred in that it provides a more excellent via shape. It is also preferable that a second preferred embodiment of the method for producing a semiconductor package further includes the following step Z15. In the case of embodiment 2-1 or embodiment 2-3, step Z15 is preferably performed after step Z13, and in the case of embodiment 2-2, step Z15 is preferably performed after step Z14. Step Z11: forming a composition layer on a substrate using a transfer film Step Z12: heating or exposing the composition layer Step Z13: forming a pattern having vias in the heated or exposed composition layer using a laser Step Z14: removing the temporary support Step Z15: forming a circuit pattern on the obtained pattern Furthermore, a second preferred embodiment of the method for producing a semiconductor package is a production method including steps Z11 to Z15, and further includes step Z16 of forming a composition layer on the obtained semiconductor package using a transfer film, and it is preferable that steps Z12 to Z16 are repeatedly performed.

[0088] <Step Z11> Step Z11 is a step of forming a composition layer on a substrate using a transfer film. As a method for Step Z11, the method of forming a composition layer using a transfer film in Step Z1 described above can be used.

[0089] <Step Z12> Step Z12 is a step of heating or exposing the composition layer obtained in Step Z11. Step Z12 is preferably a step of curing the composition layer. The heating and exposing methods can be the same as those used in Step Z3.

[0090] <Step Z13> Step Z13 is a step of forming a pattern having vias using a laser in the heated or exposed composition layer obtained in step Z12. Step Z13 may be performed before or after step Z14, which will be described later. That is, the pattern formation using a laser may be performed via a temporary support, or may be performed after removing the temporary support.

[0091] The shape of the via is not particularly limited, and examples thereof include a square, trapezoid, and inverted trapezoid cross-sectional shape; and a circle and a square front shape (the shape of the via when observed from the direction in which the via bottom is visible). An inverted trapezoid cross-sectional shape is preferred because it improves the adhesion of plated copper to the via wall surface.

[0092] The vias may be either through holes or via holes. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or 2 or more, and preferably 2 or more.

[0093] The vias are preferably formed by irradiating the composition layer with a laser beam after heating or exposure. ２Examples of lasers include a carbon dioxide laser, a UV-YAG laser, a UV laser, a YAG laser, and an excimer laser. The number of shots in the laser light irradiation is preferably 5 or less, and more preferably 3 or less. In order to keep the number of shots within the above range, it is preferable to set the laser energy and pulse width to a certain value or more. The laser output is preferably 0.1 W or more, more preferably 0.3 W or more, and even more preferably 0.5 W or more. The upper limit is preferably 30 W or less, more preferably 10 W or less, and even more preferably 5 W or less. The laser pulse width is preferably 1 μsec or more, more preferably 5 μsec or more, and even more preferably 10 μsec or more. The upper limit is preferably 40 μsec or less, more preferably 35 μsec or less, and even more preferably 30 μsec or less.

[0094] Via formation using a laser can be carried out using a commercially available laser device. Examples of commercially available carbon dioxide laser devices include "LC-2E21B / 1C" manufactured by Hitachi Via Mechanics, Ltd., "ML605GTWII" manufactured by Mitsubishi Electric Corporation, "605GTWIII(-P)" manufactured by Mitsubishi Electric Corporation, and a substrate drilling laser processing machine manufactured by Matsushita Welding Systems Co., Ltd. Furthermore, examples of UV-YAG laser devices include "LU-2L212 / M50L" manufactured by Via Mechanics, Ltd.

[0095] <Step Z14> Step Z14 is a step of removing the temporary support. The method for removing the temporary support is not particularly limited, but a method of peeling off the temporary support is preferred. Peeling off the temporary support can be performed by a known method.

[0096] <Step Z15> Step Z15 is a step of forming a circuit pattern on the obtained pattern. The method of step Z15 can be the same as that of step Z4 described above.

[0097] The method for manufacturing a semiconductor package may include a roughening step of roughening a pattern having vias. In a first preferred embodiment, the roughening step is preferably carried out after the step Z3 and before the step Z4. In the method of aspect 2-1 or aspect 2-3 of the second preferred embodiment, the roughening step is preferably carried out after the step Z13 and before the step Z15. Furthermore, in the method of aspect 2-2 of the second preferred embodiment, the roughening step is preferably carried out after the step Z13 and before the step Z14. In the method of aspect 2-2 of the second preferred embodiment, the roughening step may be carried out after the step Z14 and before the step Z15. By carrying out the roughening step, the pattern surface can be roughened to improve adhesion with the circuit wiring. Furthermore, smears can be removed at the same time. Examples of the roughening step include a known desmearing treatment, and a treatment involving contact with a roughening solution is preferred. Examples of the roughening solution include a roughening solution containing chromium and sulfuric acid, a roughening solution containing an alkaline permanganate (e.g., a sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.

[0098] Furthermore, a dry desmear treatment is also preferred as the roughening step. An example of the dry desmear treatment is a desmear treatment using plasma. By treating the pattern using plasma generated by introducing a gas into a plasma generator, smears generated in via holes can be removed. The method for generating plasma is not particularly limited, and examples thereof include microwave plasma, high-frequency plasma, atmospheric pressure plasma, and vacuum plasma, with vacuum plasma being preferred. The type of gas used in the plasma treatment is not particularly limited, and F ２ , C.F. ３ , C ２ F ５ and SF ６ fluorine atom-containing gases such as N ２ and O ２ The treatment time in the dry desmear treatment is preferably 30 seconds or more, more preferably 60 seconds or more, further preferably 90 seconds or more, and particularly preferably 120 seconds or more. The upper limit is preferably 10 minutes or less, more preferably 5 minutes or less.

[0099] From the viewpoint of improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper, it is preferable to carry out a heat treatment after forming the circuit pattern. The heating temperature is preferably 150 to 240°C, and the heating time is preferably 15 to 500 minutes.

[0100] In the method for manufacturing a semiconductor package, steps Z1 to Z5 may be repeated depending on the number of layers required. Also, in the method for manufacturing a semiconductor package, steps Z11 to Z16 may be repeated depending on the number of layers required. It is preferable to form a solder resist on the outermost layer of the resulting semiconductor package.

[0101] <Other Steps> The method for manufacturing a semiconductor package may include other steps in addition to the steps described above. Examples of such other steps include a step of peeling off the cover film, a step of reducing visible light reflectance, and a step of etching. Examples of methods for peeling off the cover film include known methods. Suitable examples of the treatment for reducing 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. Examples of etching methods 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.

[0102] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment 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 construed as being limited by the examples shown below.

[0103] [Preparation of Compositions] Methyl isobutyl ketone solutions (compositions) containing 40% by mass of the evaluation compounds shown in the table below were prepared using solutions containing each evaluation compound (specific compound or comparative compound) obtained by the synthesis method shown below. When specific compounds having a polymerizable group (SQ-3, SQ-4, SQ-5, SQ-11, SQ-12, SQ-16, SQ-17, and SQ-18) were used, dicumyl peroxide was further added in an amount of 1% by mass relative to the total mass of the specific compounds having a polymerizable group.

[0104] <Synthesis of Specific Compounds SQ-1 to SQ-19> In a 300 mL three-neck flask, predetermined amounts of various monomers corresponding to the structure of the specific compound of interest and methyl isobutyl ketone (75.0 g) were mixed and stirred while heating at an external temperature of 80 ° C. To this was added a 0.1 mass % aqueous potassium hydroxide solution (18.0 g) at a constant rate over 5 minutes, and the mixture was stirred and heated for 5 hours. During heating, the reaction was carried out while removing refluxed methanol from the system using a Dean-Stark apparatus. After stopping the stirring and cooling to room temperature (25 ° C.) in a water bath, methyl isobutyl ketone (150 g) and 5 mass % saline (150 g) were added, and the organic phase was extracted. The organic phase was washed once with 5% by mass saline (150 g) and twice with pure water (150 g), dried over magnesium sulfate (45 g), and then concentrated under a reduced pressure of 35 mmHg at 50°C to obtain a methyl isobutyl ketone solution containing any one of specific compounds SQ-1 to SQ-19. As described above, each composition was prepared using the obtained methyl isobutyl ketone solution containing each specific compound.

[0105] <Synthesis of Specific Compounds SQ-20 to SQ-22> In a 300 mL three-necked flask, (3-mercaptopropyl)trimethoxysilane (46.5 g), dimethoxydimethylsilane (28.5 g), and methyl isobutyl ketone (75.0 g) were mixed and stirred while heating at an external temperature of 80°C. A 0.1% by mass aqueous potassium hydroxide solution (18.0 g) was added dropwise at a constant rate over 5 minutes, and the mixture was stirred and heated for 5 hours. During heating, the reaction was carried out while removing refluxed methanol from the system using a Dean-Stark apparatus. After stopping the stirring and cooling to room temperature (25°C) in a water bath, methyl isobutyl ketone (150 g) and 5% by mass saline (150 g) were added, and the organic phase was extracted. The organic phase was washed once with 5% by mass saline (150 g) and twice with pure water (150 g), successively. After drying over magnesium sulfate (45 g), the mixture was concentrated at 50°C under a reduced pressure of 35 mmHg, yielding a thiol-containing organopolysiloxane as a solution with a solids content of 20%. In a 300 mL three-neck flask, raw material compounds that react with thiol groups to give the target specific compound in accordance with its structure and the thiol-containing organopolysiloxane prepared by the above method were mixed so that the thiol groups and the raw material compounds were equimolar. The mixture was stirred under a nitrogen atmosphere at an external temperature of 80°C, and V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was added at 0.25 mol% relative to the raw material compounds. After 2 hours, 0.25 mol% of V-601 relative to the raw material compounds was added, and the mixture was heated and stirred at 90°C for 2 hours. After stopping stirring and cooling to room temperature (25°C) in a water bath, the mixture was concentrated under reduced pressure of 35 mmHg at 50°C to obtain a methyl isobutyl ketone solution containing any one of specific compounds SQ-20 to SQ-22. As described above, each composition was prepared using the obtained methyl isobutyl ketone solution containing each specific compound.

[0106] <Synthesis of Comparative Compounds P-1 to P-2> Comparative compounds P-1 to P-2 were synthesized with reference to the synthesis method of the specific compound described above. As described above, each composition was prepared using the resulting methyl isobutyl ketone solution containing each comparative compound.

[0107] The structures of the compounds evaluated are shown below, where Me represents a methyl group.

[0108]

[0109]

[0110]

[0111] The structures and synthesis routes of the monomers used for each evaluation compound are shown below.

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] For the synthesis of SQ-20, SQ-M1D was used as a raw material compound to be reacted with organopolysiloxane having a thiol group. Similarly, for the synthesis of SQ-21, the following SQ-M21 was used as a raw material compound.

[0126]

[0127] Similarly, SQ-M6D was used as a raw material compound for the synthesis of SQ-22.

[0128]

[0129] [Evaluation] <Coefficient of Linear Expansion (CTE)> A copper-clad polyimide film (Metalloyal, manufactured by Toray Industries, Inc.) was used as a substrate. The prepared composition was applied to the substrate and dried to obtain a laminate having a composition layer with a thickness of 30.0 μm on the substrate. After heating in an oven (200°C, 1.5 hours), the film was 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 from the substrate to obtain a free-standing film derived from the composition 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 and peeled. In Comparative Example 2, even after the additional hydrochloric acid treatment, a free-standing film could not be obtained and could not be evaluated. The produced free-standing film was cut into strips (50 mm x 3 mm) to prepare measurement samples, and the linear expansion coefficient was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 20 mm, and a load of 45 mN. The linear expansion coefficient was measured in the temperature range of 30 to 50°C during heating, and was calculated as the average value of three measurements. The lower the linear expansion coefficient, the better. For example, it may be 110 ppm / K or less, and preferably 100 ppm / K or less.

[0130] <Cracks> The surface of the free-standing film prepared above was observed using an optical microscope. Using the optical microscope, 10 random points (1 mm x 1 mm) were observed, and the presence or absence of cracks was evaluated based on the following criteria. A grade of B or higher is preferred.

[0131] (Evaluation criteria) "A": Cracks were observed in 0 out of 10 points. "B": Cracks were observed in 1 or 2 out of 10 points. "C": Cracks were observed in 3 or more out of 10 points. "D": A free-standing film was not obtained, and evaluation was not possible.

[0132] In the table, the column "Number of monocyclic ring structures of M" indicates the total number of monocyclic ring structures in the ring contained in the group represented by M. The column "Number of nitrogen atoms of M" indicates the number of nitrogen atoms possessed by the group represented by M. The column "Content (mol %) of units of formula (1)" indicates the content (mol %) of units represented by formula (1) relative to the total units (100 mol %) of the specific compound. The column "Content (mol %) of units of formula (2)" indicates the content (mol %) of units represented by formula (2) relative to the total units (100 mol %) of the specific compound. The column "Polymerizable group" indicates "A" when the specific compound has a polymerizable group, and "B" when the specific compound does not have a polymerizable group. The column "Mw" indicates the weight average molecular weight of the specific compound, and the measurement method is as described above.

[0133]

[0134] From the evaluation results in the table, it was confirmed that if a specific compound is used, a film having a low linear expansion coefficient and being less susceptible to cracking can be obtained. From a comparison between Example 2 and Examples 1 and 13, it was confirmed that the effects of the present invention are more excellent when the content of the unit represented by formula (2) is 30 to 75 mol% relative to the total units (100 mol%) of the specific compound. From a comparison between Example 2 and Example 15, it was confirmed that the effects of the present invention are more excellent when the weight-average molecular weight of the specific compound is 5,000 or more. From a comparison between Examples 4 and 5 and Example 9, a comparison between Example 12 and Example 8, and a comparison between Example 11 and Example 6, it was confirmed that the effects of the present invention are more excellent when the specific compound has a polymerizable group (R ａ It was confirmed that the effects of the present invention are more excellent when M is a monovalent group having a polymerizable group. Comparisons of Examples 6 and 14 with Examples 3 and 10, and comparisons of Examples 7 and 8 with Example 9, etc., confirmed that the effects of the present invention are more excellent when M has two or more nitrogen atoms. Comparisons of Examples 2, 3, and 10 with Example 9, etc., confirmed that the effects of the present invention are more excellent when M is a divalent linking group having four or more monocyclic ring structures.

[0135] [Semiconductor Package Production] The composition of each example was applied and dried to obtain a laminate having a 30.0 μm thick composition layer on a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, manufactured by Mitsubishi Gas Chemical Co., Inc.) on which a circuit pattern had been formed. Subsequently, a pattern having vias with a diameter of 80 μm was formed at predetermined positions on the composition layer by laser processing, followed by heat treatment (200°C, 1.5 hours). Residue was then removed using an aqueous sodium permanganate solution as a roughening solution, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, followed by electrolytic plating, and then the resist pattern was stripped with a stripping solution. Finally, a seed layer etching process was performed, followed by heat treatment (180°C, 1 hour) to form copper wiring on the insulating film formed by the composition layer. The process from application of the composition to heat treatment was performed a total of three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was then sealed and mounted to produce a semiconductor package. The semiconductor package thus obtained was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the obtained semiconductor package substrate operated normally.

Claims

1. An organopolysiloxane comprising a unit represented by formula (1) and a unit represented by formula (2): Formula (1) R ａ -ML-SiO ３／２ Formula (2) R ｂ ２ -SiO ２／２ In formula (1), R ａ represents a hydrogen atom or a monovalent group. M represents a divalent linking group containing one or more rings, and the total number of monocyclic ring structures in the one or more rings is 3 or more. L represents a single bond or a divalent linking group. In formula (2), R ｂ each independently represents a hydrogen atom, a linear or branched monovalent hydrocarbon group, or a monovalent group having at least one ring.

2. The organopolysiloxane according to claim 1, wherein the total number of monocyclic ring structures is 4 or more.

3. The organopolysiloxane according to claim 1, wherein M has three or more aromatic rings as said one or more rings.

4. The organopolysiloxane according to claim 1, wherein M has four or more aromatic rings as said one or more rings.

5. The organopolysiloxane of claim 1, wherein M has two or more nitrogen atoms.

6. The organopolysiloxane according to claim 1, wherein M is a group represented by formula (X) or a group represented by formula (Y). In formula (X), * represents a bonding position. ｘ１ represents a ring. ｘ２ represents a single bond, —COO—, —O—, or —CH ２ represents O-, -N=N-, -CH=CH-, -C≡C- or -CH=N-. nx represents an integer of 3 or more. In formula (Y), * represents a bonding position. Ar ｙ１ ~Ar ｙ４ each independently represents a monocycle. ｙ１ ~L ｙ３ each independently represents a single bond, —COO—, —O—, or —CH ２ represents O-, -NH-, -N=N-, -CH=CH-, -C≡C- or -CH=N-. ｙ１ represents a hydrogen atom or a monovalent group. my1 represents an integer of 0 or greater. my2 and my3 each independently represent an integer of 1 or greater.

7. The organopolysiloxane according to claim 1, wherein M has at least one aromatic heterocycle having a nitrogen atom as a ring member as one or more of the rings.

8. R ａ The organopolysiloxane according to any one of claims 1 to 7, wherein is a monovalent group having a polymerizable group.

9. R ｂ The organopolysiloxane according to any one of claims 1 to 7, wherein each independently represents a hydrogen atom, a methyl group, a vinyl group, or a phenyl group.

10. The organopolysiloxane according to any one of claims 1 to 7, wherein the organopolysiloxane has a weight average molecular weight of 5,000 or more.

11. A composition comprising the organopolysiloxane according to any one of claims 1 to 7.

12. A cured product obtained by curing the organopolysiloxane according to any one of claims 1 to 7.

13. A method for manufacturing a semiconductor package, comprising: Step Z1: forming a composition layer containing the organopolysiloxane according to any one of claims 1 to 7 on a substrate; and Step Z2: forming a pattern having vias in the composition layer.

14. A method for manufacturing a semiconductor package, comprising: step Z1 of forming a composition layer containing the organopolysiloxane according to any one of claims 1 to 7 on a substrate; step Z12 of heating or exposing the composition layer; and step Z13 of forming a pattern having vias in the heated or exposed composition layer using a laser.

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