Resin composition, cured film, pattern production method, transfer film, and printed wiring board

Abstract

The present invention addresses the problem of providing: a resin composition capable of forming a film having a low dielectric loss tangent and a small linear expansion coefficient; and a cured film, a pattern production method, a transfer film, and a printed wiring board relating to the resin composition.　A resin composition according to the present invention contains an organic pigment and a resin, the water content of the organic pigment is 1.50% by mass or less; the content of the organic pigment is more than 10% by mass relative to the total solid content in the resin composition; and the acid value of the resin is less than 50 mg KOH / g.

Description

Resin composition, cured film, pattern manufacturing method, transfer film, printed circuit board

[0001] The present invention relates to a resin composition, a cured film, a pattern manufacturing method, a transfer film, and a printed circuit board.

[0002] In semiconductor packages and build-up substrates for multilayer printed circuit boards, insulating films are provided between wirings and between each layer for purposes such as forming and protecting circuit wiring. Similarly, in display devices equipped with touch panels such as capacitive input devices (e.g., organic electroluminescent (EL) display devices and liquid crystal display devices), insulating films are provided for purposes such as forming and protecting conductive patterns such as electrode patterns corresponding to sensors in the viewing area, peripheral wiring sections, and wiring sections of the output wiring sections.

[0003] As a composition capable of forming the insulating film described above, for example, Patent Document 1 discloses a resin composition containing an epoxy resin, an active ester compound, and a smear (resin residue) suppressing component, wherein the smear suppressing component is one or more selected from the group consisting of pigments, dyes, rubber particles, antioxidants, and infrared absorbers.

[0004] Japanese Patent Publication No. 2014-005464

[0005] In recent years, with the increasing diversification and performance of devices, there has been a growing demand for the development of new material systems capable of forming films that exhibit desired effects. Examples of properties required for films applied to semiconductor packages and printed circuit boards include low dielectric properties and a small coefficient of thermal expansion.

[0006] In view of the above circumstances, the present invention aims to provide a resin composition that can form a film with a low dielectric loss tangent and a small coefficient of thermal expansion. Furthermore, the present invention aims to provide a cured film, a pattern manufacturing method, a transfer film, and a printed circuit board related to the above resin composition.

[0007] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0008] [1] A resin composition comprising an organic pigment and a resin, wherein the water content of the organic pigment is 1.50% by mass or less, the content of the organic pigment is more than 10% by mass relative to the total solids in the resin composition, and the acid value of the resin is less than 50 mg KOH / g. [2] The resin composition according to [1], wherein the content of the organic pigment is 20% by mass or more relative to the total solids in the resin composition. [3] The resin composition according to [1] or [2], wherein the water content of the organic pigment is 0.80% by mass or less. [4] The resin composition according to any one of [1] to [3], wherein the organic pigment comprises at least one selected from the group consisting of azo pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, and isoindoline pigment. [5] The resin composition according to any one of [1] to [4], wherein Xp calculated from formula (X) described later is 0.32 or more. [6] The resin composition according to any one of [1] to [5], wherein the resin comprises at least one selected from the group consisting of epoxy resin, maleimide resin, polyimide resin, polyphenylene ether resin, organopolysiloxane resin, polyester resin, polyetherketone resin, and polyolefin resin. [7] The resin composition according to any one of [1] to [6], wherein the resin comprises at least one selected from the group consisting of epoxy resin, maleimide resin, polyimide resin, branched polyphenylene ether resin, and organopolysiloxane resin, and if the resin comprises epoxy resin, further comprises an active ester compound. [8] The resin composition according to any one of [1] to [7], used for forming an insulating film of a circuit board. [9] A cured film obtained by curing the resin composition according to any one of [1] to [8].

[10] A method for manufacturing a pattern, comprising the steps of: forming a composition layer on a substrate using a resin composition described in any of [1] to [8]; forming a pattern on the formed composition layer; and curing the composition layer on which the pattern has been formed.

[11] A transfer film comprising a composition layer formed using a resin composition described in any of [1] to [8] and a temporary support.

[12] The transfer film according to

[11] , used for forming an insulating film of a printed wiring board.

[13] A printed circuit board having an insulating film formed using any of the resin compositions described in [1] to [8].

[0009] The present invention provides a resin composition that can form a film with a low linear dielectric loss tangent and a small coefficient of linear expansion. Furthermore, the present invention also provides a cured film, a pattern manufacturing method, a transfer film, and a printed circuit board related to the above resin composition.

[0010] This is a schematic diagram showing an example of the layer structure of a transfer film.

[0011] The present invention will be described in detail below. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits. Also in this specification, if there are two or more types of a component, the "content" of that component means the total content of those two or more types of components. In this specification, in numerical ranges described in steps, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the value shown in the example. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] The term "process" as used herein includes not only independent processes but also processes that cannot be clearly distinguished from other processes, provided that the intended purpose of the process is achieved.

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

[0015] In this specification, "transparent" means that the average transmittance of visible light with a wavelength 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 Hitachi U-3310 spectrophotometer.

[0016] In this specification, "active light" or "radiation" means, for example, the emission line spectra of mercury lamps such as g-rays, h-rays, and i-rays, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). Also, in this invention, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure with mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams.

[0017] In this specification, "solids" in a resin composition means the components that form a film using the resin composition. Typically, if the resin composition contains a solvent (e.g., an organic solvent and water), it means all components excluding the solvent. Furthermore, any liquid components that form a film are also considered to be solids.

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

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

[0020] In this specification, the bonding direction of the divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -CO-O-, the compound may be "X-O-CO-Z" or "X-CO-O-Z".

[0021] In this specification, unless otherwise specified, the thickness (film thickness) of a film (or 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 less than 0.5 μm. The above average thickness is the average thickness obtained by preparing sections of the object to be measured using an ultramicrotome, measuring the thickness at any five points, and arithmetically averaging them. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the above-mentioned other layers, and the reference layer and the above-mentioned other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." It should be noted that these vertical directions are for convenience within this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward.

[0022] [Resin Composition] The resin composition of the present invention will be described in detail below. The resin composition of the present invention (hereinafter also simply referred to as "resin composition") is a resin composition comprising an organic pigment and a resin, wherein the water content of the organic pigment is 1.50% by mass or less, the content of the organic pigment is more than 10% by mass relative to the total solids in the resin composition, and the acid value of the resin is less than 50 mgKOH / g.

[0023] The reason why the resin composition having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. It should be noted that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is included within the scope of the present invention. The dielectric loss tangent is a numerical value that indicates the degree to which electrical energy is lost as thermal energy due to the vibration of the dipole moment of molecules within an object (dielectric) under the influence of an external electric field. Effective methods for lowering the dielectric loss tangent include, for example, the use of low-polarity or non-polar components, and the immobilization (rigidification) of dipoles within the object. However, despite the fact that organic pigments generally tend to be highly polar, the inventors have found that when using the organic pigment of the present invention with a water content of 1.50% by mass or less, a film with a lower dielectric loss tangent can be formed. Organic pigments with a water content within the above range are considered to have high crystallinity, with fewer highly polar areas or voids on the surface and inside that would easily retain moisture. It is presumed that, within the film, vibrations due to the influence of an external electric field are less likely to occur in each component, including the organic pigment and resin, and even if vibrations do occur, the range in which each component can move is narrow, thus reducing the dielectric loss tangent of the film. In addition, it is presumed that the acid value of the resin contained in the film is less than 50 mg KOH / g, and its low polarity also contributed to the reduction of the dielectric loss tangent of the film. Furthermore, since organic pigments tend to be highly polar, it is presumed that the interaction between organic pigments themselves, and between organic pigments and the resin, improved, resulting in a smaller coefficient of thermal expansion. Thus, the resin composition of the present invention can form a film exhibiting desired properties.

[0024] Hereinafter, as a characteristic of the resin composition of the present invention, a lower dielectric loss tangent of the film formed by the resin composition will be simply referred to as "lower dielectric loss tangent," a smaller coefficient of linear expansion of the film formed by the resin composition will be simply referred to as "smaller coefficient of linear expansion," and achieving at least one of a superior dielectric loss tangent and a superior coefficient of linear expansion will be referred to as "superior effect of the present invention."

[0025] [Organic Pigment] The resin composition of the present invention is characterized by containing an organic pigment (hereinafter also referred to as "specified organic pigment") having a water content of 1.50% by mass or less in an amount of more than 10% by mass relative to the total solid content of the resin composition.

[0026] The water content of an organic pigment is determined by measuring the amount of water contained in a sample obtained by heating and drying the organic pigment extracted from a resin composition under a nitrogen atmosphere, followed by humidity control treatment, using a Karl Fischer automatic moisture analyzer based on the vaporization method. The water content of an organic pigment is the ratio of the amount of water to the total mass of the organic pigment sample, and its unit is mass percent. Details of the method for measuring the water content of an organic pigment are described in the examples below.

[0027] The water content of the specified organic pigment is preferably 1.20% by mass or less, and more preferably 0.80% by mass or less, in that it allows for the formation of a film with a lower dielectric loss tangent. There is no particular lower limit to the water content of the specified organic pigment, but it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, in that it provides a superior coefficient of linear expansion.

[0028] The water content of organic pigments can be adjusted by their chemical structure and degree of crystallinity. For example, organic pigments with a high degree of crystallinity tend to have a lower water content. Furthermore, organic pigments whose parameter Xp (described later) falls within a predetermined range tend to have an even lower water content.

[0029] Examples of organic pigments that can be used as specific organic pigments include diketopyrrolopyrrole pigments, azo pigments (monoazo pigments, bisazo pigments, and condensed azo pigments), phthalocyanine pigments, isoindoline pigments, quinacridone pigments, isoindolinone pigments, imidazolon pigments, benzimidazolone pigments, pyranthrone pigments, indanthron pigments, anthraquinone pigments, dioxazine pigments, benzofuranone pigments, perylene pigments, and azomethine pigments. Among these, at least one selected from the group consisting of azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, and isoindoline pigments is preferred in that it can form a film with a lower dielectric loss tangent, and at least one selected from the group consisting of azo pigments, diketopyrrolopyrrole pigments, and isoindoline pigments is more preferred in that it can form a film with a lower coefficient of thermal expansion. Furthermore, there are no particular restrictions on the color exhibited by the specified organic pigments, and red, yellow, blue, orange, purple, green, and black pigments can be used as appropriate.

[0030] As a specific organic pigment, in order to form a film with a smaller coefficient of linear expansion, it is preferable that Xp (hereinafter also referred to as "parameter Xp"), calculated from the following formula (X) based on the chemical structure of the organic pigment, be 0.25 or higher, more preferably 0.32 or higher, and even more preferably 0.40 or higher. Xp = (Nn + No + Ns + Ncl + Nh) / Nc (X) In formula (X), Nc, Nn, No, Ns, Ncl, and Nh represent the number of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, chlorine atoms, and hydrogen atoms bonded to heteroatoms, respectively, contained in the organic pigment. There is no particular upper limit to the parameter Xp. The parameter Xp may be, for example, 1.00 or less, and is preferably 0.80 or less in terms of superior dielectric loss tangent.

[0031] For example, in the organic pigment PR254 shown below, Nc = 18, Nn = 2, No = 2, Ns = 0, Ncl = 2, and Nh = 2. Substituting these into equation (X), Xp = 0.44 is calculated.

[0032]

[0033] The average particle size of the specific organic pigment is preferably 500 nm or less, more preferably 300 nm or less, even more preferably 150 nm or less, and preferably 5 nm or more, and more preferably 10 nm or more. The average particle size of the specific organic pigment is the value calculated by the following particle size measurement method. The resin composition is applied to a substrate (preferably a glass substrate) to form a composition layer. The thickness of the composition layer is preferably 3 μm or more. In addition, when forming the composition layer, a drying treatment may be performed as necessary after applying the resin composition. A cross section is cut along the normal direction of the surface of the obtained composition layer (the surface opposite to the substrate side), and a rectangular area of ​​3 μm × 10 μm of the cross section is observed with a scanning electron microscope, and the major axis of all particles (specific organic pigment) observed within the above area is measured. As a scanning electron microscope, for example, Hitachi High-Tech S-4800 is used. The magnification when observing is 50,000x. The above procedure is performed at five different locations in the composition layer, and the average value (arithmetic mean) of the major axes of all particles measured in each procedure is taken as the average particle diameter. The major axis refers to the length of the longest line segment connecting any two points on the outline of the particle's outer shape in the observation image. If particles aggregate to form an aggregate in the observation image, the major axis of each particle constituting the aggregate is measured.

[0034] The shape of the specific organic pigment may be either spherical or non-spherical (e.g., crushed or fibrous).

[0035] The specific organic pigment may be used alone or in combination of two or more types. The content of the specific organic pigment is more than 10% by mass relative to the total solid content of the resin composition, and is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, in terms of superior effects of the present invention. There is no particular upper limit to the content of the specific organic pigment, but is preferably 70% by mass or less, and more preferably 60% by mass or less, in terms of superior film-forming properties.

[0036] [Resin] The resin composition of the present invention contains a resin having an acid value of less than 50 mgKOH / g (hereinafter also referred to as "specified resin").

[0037] The acid value of the specific resin is preferably 20 mg KOH / g or less, and more preferably 10 mg KOH / g or less, in terms of superior dielectric loss tangent. There is no particular lower limit to the acid value of the specific resin, and the acid value of the specific resin may be 0 mg KOH / g. In this specification, the acid value of the resin is the value measured according to the method described in JIS K0070:1992. Details of the method for measuring the acid value of the resin are described in the examples below.

[0038] The type of specific resin is not particularly limited as long as the acid value is less than 50 mg KOH / g. Examples of specific resins include epoxy resins, maleimide resins, polyimide resins, polyphenylene ether resins, organopolysiloxane resins, polyamide resins, polyester resins, polyetherketone resins, polyolefin resins, epoxy acrylate resins, cyanate resins, bismaleimidotriazine resins, and benzoxazine resins. Among these, at least one selected from the group consisting of epoxy resins, maleimide resins, polyimide resins, polyphenylene ether resins, organopolysiloxane resins, polyester resins, polyetherketone resins, polyolefin resins, and bismaleimidotriazine resins is preferred in that it can form a film with a smaller coefficient of linear expansion, and at least one selected from the group consisting of epoxy resins, maleimide resins, polyimide resins, branched polyphenylene ether resins, and organopolysiloxane resins is more preferred in that it has a superior dielectric loss tangent. Furthermore, if the specific resin includes an epoxy resin, the resin composition preferably further contains a curing agent, and more preferably further contains an active ester compound, which will be described later.

[0039] The specific resin contained in the resin composition may be a precursor of the resin described above. A resin precursor is a resin that is converted into a resin by heat treatment, light treatment, or chemical treatment.

[0040] The specific resin may have reactive groups. Examples of reactive groups include polymerizable groups and functional groups other than polymerizable groups. Examples of polymerizable groups include known polymerizable groups such as radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. As for the radical polymerizable groups, groups having an ethylenically unsaturated double bond are preferred. Examples of groups having an ethylenically unsaturated double bond include (meth)acryloyl groups, (meth)acrylamide groups, vinyl groups, styryl groups, allyl groups, and vinyl ether groups, with (meth)acryloyl groups being preferred. Examples of functional groups other than polymerizable groups include amino groups, hydroxyl groups, and thiol groups, with amino groups being preferred, and secondary amino groups (e.g., phenylamino groups, methylamino groups, and ethylamino groups) or primary amino groups (-NH ２ ) is more preferable. Functional groups other than silanol groups (Si-OH) are also preferred.

[0041] (Epoxy Resins) Epoxy resins are resins that have epoxy groups. Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, and trimethylol type epoxy resin.

[0042] The epoxy resin may also preferably contain both a liquid epoxy resin at 20°C (hereinafter also referred to as "liquid epoxy resin") and a solid epoxy resin at 20°C (hereinafter also referred to as "solid epoxy resin"), as this provides excellent flexibility and improves the tensile strength of the resulting cured layer.

[0043] Preferably, the liquid epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a naphthalene type epoxy resin, with bisphenol A type epoxy resin, bisphenol F type epoxy resin, or a naphthalene type epoxy resin being more preferred. Examples of liquid epoxy resins include HP4032, HP4032D, EXA4032SS and HP4032SS (naphthalene type epoxy resins) (all manufactured by DIC Corporation); 828US (bisphenol A type epoxy resin), jER828EL (bisphenol A type epoxy resin), jER807 (bisphenol F type epoxy resin) and jER152 (phenol novolac type epoxy resin) (all manufactured by Mitsubishi Chemical Corporation); and ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) (manufactured by Nippon Steel Chemical Co., Ltd.). As the liquid epoxy resin, 828US, HP4032SS, or ZX1059 are preferred.

[0044] As solid epoxy resins, tetrafunctional naphthalene-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl-type epoxy resins, or naphthylene ether-type epoxy resins are preferred, tetrafunctional naphthalene-type epoxy resins, biphenyl-type epoxy resins, or naphthylene ether-type epoxy resins are more preferred, and biphenyl-type epoxy resins are even more preferred. Examples of solid epoxy resins include HP-4700, HP-4710 (tetrafunctional naphthalene-type epoxy resin), N-690 (cresol novolac-type epoxy resin), N-695 (cresol novolac-type epoxy resin), HP7200, HP7200H, HP7200K-65I (dicyclopentadiene-type epoxy resin), EXA7311, EXA7311-G3, and HP6000 (naphthylene ether-type epoxy resin) (all manufactured by DIC Corporation); EPPN-502H (trisphenol epoxy resin) Examples include lipids, NC7000L (naphthol novolac epoxy resin), NC3000H, NC3000, NC3000L and NC3100 (biphenyl type epoxy resin) (all manufactured by Nippon Kayaku Co., Ltd.); ESN475 (naphthol novolac type epoxy resin) and ESN485 (naphthol novolac type epoxy resin) (both manufactured by Nippon Steel Chemical Co., Ltd.); and YX4000H, YL6121 (biphenyl type epoxy resin) and YX4000HK (bixylenol type epoxy resin) (all manufactured by Mitsubishi Chemical Corporation). As solid epoxy resins, YX4000HK, NC3000H, NC3000L or HP7200H are preferred.

[0045] (Maleimide resin) Maleimide resin is a resin having maleimide groups. Bismaleimide resin is preferred as the maleimide resin. As the bismaleimide resin, at least one selected from bismaleimide resin represented by the following formula (III) and novolac-type maleimide resin represented by the following formula (IV) is preferred.

[0046] In formula (III), R represents a divalent organic group comprising an aromatic ring or a linear, branched, or cyclic aliphatic hydrocarbon group. R is preferably a divalent group composed of a benzene group, a toluene group, a xylene group, a naphthalene group, a linear, branched, or cyclic saturated hydrocarbon group, or a combination thereof. R is preferably a divalent group represented by the following formulas (v), (vi), or (vii).

[0047]

[0048]

[0049] In equation (IV), s represents an integer between 0 and 20.

[0050] The maleimide resin may be a compound described in paragraphs 0020 to 0023 of Japanese Patent Publication No. 2003-321608, and this is incorporated herein by reference. Examples of commercially available maleimide resins include BMI-1000, 2000, 3000, 4000, 5000, 5100 and 7000 (all manufactured by Yamato Chemical Industries, Ltd., bismaleimide resin), BANI-X (manufactured by Shin-Nakamura Chemical Co., Ltd., bismaleimide resin), BANI-M (manufactured by Shin-Nakamura Chemical Co., Ltd., bismaleimide resin), and MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type maleimide resin).

[0051] (Polyimide Resins) In this specification, the term "polyimide resin" is used as a general term for both resins having repeating units containing an imide structure (hereinafter also referred to as "ring-closed products") and polyamic acid esters which are precursors thereof. When the polyimide resin is a ring-closed product, a resin having a cyclic imide structure is preferred. The polyimide resin may also have substituents. As the polyimide resin, a polyimide precursor having repeating units represented by formula (1), or a resin synthesized from such a polyimide precursor (for example, a ring-closed product obtained by a ring-closing reaction) is preferred. The polyimide precursor preferably has repeating units represented by formula (1).

[0052]

[0053] In formula (1), A１ and A ２ each independently represents an oxygen atom or —NH—. R １１１ represents a divalent organic group. R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group. R １１５ represents a tetravalent organic group.

[0054] In formula (1), A １ and A ２ each independently represents an oxygen atom or —NH—. A １ and A ２ is preferably an oxygen atom.

[0055] In formula (1), R １１１ represents a divalent organic group. Examples of the divalent organic group include a divalent aliphatic group, a divalent aromatic ring group, and a group combining these. As the divalent organic group, a divalent aliphatic group having 2 to 20 carbon atoms, a divalent aromatic ring group having 6 to 20 carbon atoms, or a group combining these is preferable, and a divalent aromatic ring group having 6 to 20 carbon atoms is more preferable. The aliphatic group may be linear, branched, or cyclic. The aromatic ring group may be monocyclic or polycyclic. The aliphatic group and the aromatic ring group may have a hetero atom. The hetero atom may be included in the divalent organic group as a group such as —O—, —CO—, —S—, —SO ２ —, and —NHCO—, etc. R １１１ is also preferably a divalent organic group derived from diamine. As the diamine, a diamine used in the production of a polyimide precursor is preferable, and an aliphatic diamine or an aromatic diamine is more preferable. As the diamine, a diamine having a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a group combining these is preferable, and a diamine having an aromatic ring group having 6 to 20 carbon atoms (aromatic diamine) is more preferable.

[0056] In formula (1), R １１３ and R １１４Each of these independently represents a hydrogen atom or a monovalent organic group. １１３ and R １１４ Preferably, at least one of them represents a group having a reactive group, R １１３ and R １１４ It is more preferable that both represent a group having a reactive group. Examples of reactive groups include reactive groups that may be present in the resin described above, including in preferred embodiments. The monovalent organic group is preferably an alkyl group which may have substituents, or an aromatic ring group which may have substituents, and more preferably an alkyl group which may have an aromatic ring group. The alkyl group may be linear, branched, or cyclic. The cyclic may be monocyclic or polycyclic. The number of carbon atoms in a linear or branched alkyl group is preferably 1 to 30. The number of carbon atoms in a cyclic alkyl group (cycloalkyl group) is preferably 3 to 30.

[0057] In formula (1), R １１５ represents a tetravalent organic group. Preferably, the tetravalent organic group is one having an aromatic ring, and more preferably, the group represented by formula (5) or the group represented by formula (6).

[0058]

[0059] In formula (5), R １１２ These are divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may contain a fluorine atom, -O-, -CO-, -S-, -SO ２ - represents a group consisting of -NHCO- or a combination thereof, or a single bond. * represents a bond position. In formula (6), * represents a bond position.

[0060] The polyimide precursor may contain other repeating units in addition to the repeating unit represented by formula (1). The content of the repeating unit represented by formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more, relative to the total repeating units of the polyimide precursor. The upper limit is preferably 100 mol% or less.

[0061] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polydispersity (Mw / Mn) of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2.0 to 3.0.

[0062] (Polyphenylene ether resin) Polyphenylene ether resin is a resin having a phenylene ether group. Polyphenylene ether resin may have either a linear structure or a branched structure, with a branched structure being preferred. In a polyphenylene ether resin having a branched structure, it is preferable that ether bonds are directly bonded to at least three positions of the benzene ring constituting the polyphenylene ether resin, namely the ipso, ortho, and para positions of the benzene ring.

[0063] A branched polyphenylene ether resin can be obtained, for example, by polymerization using two or more phenol compounds. Preferred phenol compounds are those having hydrogen atoms at the ortho and para positions and possessing a reactive group, or a mixture of a phenol compound having hydrogen atoms at the ortho and para positions but lacking a reactive group, and a phenol compound that does not have a hydrogen atom at the ortho position but has a hydrogen atom at the para position and possessing a reactive group.

[0064] Examples of phenol compounds used in the synthesis of polyphenylene ether resins include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinyl-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6-ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, and 2-dodecylphenol. Examples include 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2,6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethylphenol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, and 2,6-ditolylphenol. Among these, 2,6-dimethylphenol or 2-allylphenol are preferred as the phenol compound.

[0065] Furthermore, the polyphenylene ether resin may also preferably have a reactive group. The reactive group is preferably a group having an ethylenically unsaturated double bond, and is preferably a vinylphenyl group or a (meth)acryloyl group. When the polyphenylene ether resin has a reactive group, the resin composition preferably contains a maleimide compound. The maleimide compound reacts with the polyphenylene ether resin to obtain a modified polyphenylene ether. The maleimide compound is a compound having a maleimide group. The maleimide compound included in the resin composition together with the polyphenylene ether resin having a reactive group may be the maleimide resin described above. An example of a modified polyphenylene ether is the resin obtained by curing the resin composition described in International Publication No. 2022 / 102756.

[0066] Examples of polyphenylene ether resins include poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether. Examples of polyphenylene ether resins include the resin described in Japanese Patent Application Publication No. 2022-157695, the details of which are incorporated herein by reference.

[0067] (Organopolysiloxane resin) Organopolysiloxane resin is a resin whose main structure is a siloxane bond, and specifically, in M ​​units (R ３ SiO １／２ ), D unit (R ２ SiO ２／２ ), T unit (RSIO ３／２ ), and Q unit (SiO ４／２) is a compound having one or more structural units. Here, R represents a monovalent organic group. The organopolysiloxane resin preferably has at least one selected from the group consisting of T units and D units, and more preferably has T units, in that it can form a film with a smaller coefficient of linear expansion.

[0068] In the formulas representing each of the above units, R independently represents a monovalent organic group. Examples of monovalent organic groups include hydrocarbon groups and heteroatom-containing groups. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or cyclic, with linear being preferred. The linear aliphatic hydrocarbon group may be linear or branched, with linear being preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 12. The number of carbon atoms in the aromatic hydrocarbon group is preferably 4 to 20, more preferably 5 to 12, and even more preferably 5 to 6. Examples of heteroatom-containing groups include groups in which one or more carbon atoms of the hydrocarbon group are substituted with heteroatoms. Preferred heteroatoms are oxygen atoms, nitrogen atoms, or sulfur atoms. The hydrocarbon group and heteroatom-containing group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, and polymerizable groups described later.

[0069] Organopolysiloxane resins may have polymerizable groups, and it is preferable that they have polymerizable groups in that they can form films with a lower coefficient of thermal expansion. Known polymerizable groups include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. Among the radical polymerizable groups, groups having an ethylenically unsaturated double bond are preferred. Examples of groups having an ethylenically unsaturated double bond include vinyl groups, styryl groups, (meth)acryloyl groups, (meth)acrylamide groups, allyl groups, and vinyl ether groups.

[0070] Organopolysiloxane resins are preferably made up of at least one unit selected from the group consisting of units represented by formula (T1) and units represented by formula (D1), in order to form films with a lower coefficient of thermal expansion. The unit represented by formula (T1) is included in the above T units, and the unit represented by formula (D1) is included in the above D units. Formula (T1) R １ SiO ３／２ Formula (D1) R １ R ２ SiO ２／２ In equations (T1) and (D1), R １ Each of these independently represents a group represented as R-L-*. * represents the bond position. R is SiO ３／２ and SiO ２／２ R represents a monovalent ring group which may have substituents that do not contain any of the above. L represents a single bond or a divalent linking group. However, the number of carbon atoms in the shortest linking chain connecting R and Si is 6 or less. ２ R represents an alkyl group or aromatic ring group with 10 or fewer carbon atoms. １ When the number of carbon atoms in the group represented by NRc is denoted by NRh, and the number of heteroatoms by NRh, then NRh / NRc ≥ 0.43. If L is a single bond, then NRh is 4 or greater.

[0071] R １ The ring group represented by may be either an aromatic ring group or an aliphatic ring group. The ring group may be either a monocyclic or polycyclic ring. The number of ring member atoms of the ring group is preferably 3 to 18, more preferably 5 to 12, and even more preferably 5 to 10. Among these, the ring constituting the ring group is preferably a 5-membered ring, a 6-membered ring, or a fused ring of a 5-membered ring and a 6-membered ring. The ring group may be either a hydrocarbon ring group or a heterocyclic ring, with a heterocyclic ring being preferred. Examples of heteroatoms contained in the heterocyclic ring include nitrogen, oxygen, sulfur, boron, and phosphorus. Among these, it is preferable that the heterocyclic ring contains at least one selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus. The number of heteroatoms contained in the heterocyclic ring is not particularly limited, but is preferably 1 to 6, and more preferably 2 to 4.

[0072] The number of carbon atoms in the divalent linking group represented by L is preferably 0 to 18, more preferably 0 to 10, and even more preferably 1 to 8. The divalent linking group preferably contains a heteroatom. Examples of heteroatoms include nitrogen, oxygen, sulfur, boron, and phosphorus atoms, with nitrogen, oxygen, sulfur, or phosphorus atoms being preferred. The number of heteroatoms contained in the divalent linking group is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 6. In particular, it is preferable that the total number of oxygen, nitrogen, and sulfur atoms satisfies the above preferred embodiment. L preferably contains at least one selected from the group consisting of -NH-, -CO-, -CS-, -O-, and a divalent heterocyclic group.

[0073] As for L, it is a single bond, -Al Ａ１ -, -Al Ａ１ -L Ａ１ -, -Al Ａ１ -L Ａ１ - Al Ａ１ -, or -Al Ａ１ -L Ａ１ - Al Ａ１ -L Ａ１ - is preferred, and a single bond or -Al Ａ１ -L Ａ１ - is more preferable, -Al Ａ１ -L Ａ１ - is even more preferable. Al Ａ１ Each of them independently, SiO ３／２ and SiO ２／２ An alkylene group which may have substituents that do not contain any of the above, or SiO ３／２ and SiO ２／２ Represents an arylene group which may have substituents that do not contain any of the following: SiO ３／２ and SiO ２／２ A C1-C5 alkylene group which may have substituents that do not contain any of the above is preferred. Ａ１ Each of these is independently -NR ＮＬ -, -CO-, -CS-, -O-, -S-, a divalent heterocyclic group, or a group formed by a combination of these.

[0074] In L, the number of carbon atoms in the shortest linking chain between R and Si is 6 or less, preferably 3 to 6, and more preferably 4 or 5. The shortest linking chain between R and Si is an atomic chain that links the atom bonded to the ring group represented by R with the atom bonded to Si, and is selected so as to minimize the number of atoms. For example, if the unit represented by formula (T1) has the structure represented by Ex1 below, the shortest linking chain between R and Si is a chain made up of the numbered atoms, with 6 atoms, and the number of carbon atoms in the shortest linking chain between R and Si is 4. Also, for example, if the unit represented by formula (T1) has the structure represented by Ex2 below, the shortest linking chain between R and Si is a chain made up of the numbered atoms, with 6 atoms, and the number of carbon atoms in the shortest linking chain between R and Si is 5. If L is a single bond, the number of atoms in the shortest linking chain between R and Si is 0.

[0075]

[0076] In formula (D1), R ２ represents an alkyl group or aromatic ring group having 10 or fewer carbon atoms. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The number of carbon atoms in the aromatic ring group is preferably 3 to 6, and more preferably 6. An example of the aromatic ring group is a phenyl group.

[0077] R １When the number of carbon atoms in the group represented by NRc is denoted by NRh, and the number of heteroatoms is denoted by NRh / NRc ≥ 0.43, Rc ≥ 0.45 is more preferred, NRh / NRc ≥ 0.47 is even more preferred, and NRh / NRc ≥ 0.50 is particularly preferred. It is also preferable that 2.50 ≥ NRh / NRc is preferred, 1.50 ≥ NRh / NRc is more preferred, and 1.30 ≥ NRh / NRc is even more preferred. NRh is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. However, when L is a single bond, NRh is 4 or more. There is no particular upper limit to NRh, but it is often 10 or less, and preferably 8 or less. NRc is preferably 1 or more, and more preferably 4 or more. There is no particular upper limit to NRc, but it is often 15 or less, and preferably 12 or less.

[0078] Furthermore, organopolysiloxanes are preferably those having a unit represented by formula (T2) in that they can form films with a lower dielectric loss tangent. The unit represented by formula (T2) is included in the above T unit. Formula (T2) R ａ -M-L ａ -SiO ３／２ In formula (T2), R ａ represents a hydrogen atom or a monovalent group. M represents a divalent linking group containing one or more rings, where the total number of monocyclic ring structures in the one or more rings is three or more. L ａ This represents a single bond or a divalent linking group.

[0079] R ａ Examples of monovalent groups represented by include polymerizable groups, alkyl groups, alkoxy groups, alkyl ester groups, and acetyl groups. Examples of polymerizable groups include those mentioned above. Furthermore, the polymerizable group may be the polymerizable group itself. Preferred polymerizable groups are polymerizable groups or -(-O- ａ Preferably, it is a hydrogen atom or a group having a polymerizable group. Also, R ａ It is also preferable that the group be a monovalent group without a ring.

[0080] The one or more rings of 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 heterocycles) and alicyclic rings (aliphatic heterocycles and aliphatic hydrocarbon rings), and more preferably at least one ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. The above rings may have substituents. Preferred substituents are alkyl groups, alkoxy groups, alkyl ester groups, or acetyl groups. The one or more rings of the divalent linking group represented by M may be monocyclic or polycyclic. In other words, the aromatic ring and alicyclic ring may be monocyclic or polycyclic, with monocyclic being preferred. The aromatic ring and alicyclic ring may also be fused rings. The number of ring members of the monocyclic ring constituting the aromatic hydrocarbon ring and alicyclic ring is preferably 5 to 12, more preferably 5 or 6. The number of carbon atoms of the aromatic hydrocarbon ring is preferably 6 to 12, more preferably 5 or 6. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, and phenanthroline rings, with benzene rings 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 furan rings, pyrrole rings, thiophene rings, pyridine rings, triazine rings, thiazole rings, and benzothiazole rings. The number of carbon atoms in the alicyclic ring is preferably 6 to 12, and more preferably 5 or 6. Examples of alicyclic rings include cyclopentane rings and cycloalkane rings such as cyclohexane rings.

[0081] 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 three or more. The upper limit of the total number of monocyclic ring structures is preferably 10 or less, and more preferably 6 or less. The monocyclic ring structures refer to ring structures such as monocyclic aromatic hydrocarbon rings, monocyclic heterocyclic rings, and monocyclic alicyclic rings. For example, in a ring obtained by the fusion of two monocyclic rings, the number of monocyclic ring structures is counted as two. Specifically, a thienothiazole ring is a ring obtained by the fusion of a thiophene ring and a thiazole ring, and the number of monocyclic ring structures is two. Also, for example, if M contains two benzene rings and one thienothiazole ring, the total number of monocyclic ring structures is four. M is preferably a group represented by formula (X1) or a group represented by formula (Y1).

[0082]

[0083] In equation (X1), * indicates the bonding position. ｘ１ L represents a ring. ｘ２ These are single bonds, -COO-, -O-, and -CH ２ O-, -N=N-, -CH=CH-, -C≡C-, or -CH=N- represent. nx represents an integer greater than or equal to 3. In equation (Y1), * represents the joining position. Ar ｙ１ ~Ar ｙ４ Each of these independently represents a single ring. ｙ１ ~L ｙ３ These are, independently, single bonds, -COO-, -O-, and -CH ２ R 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. However, multiple L ｘ１ They may be the same or different. Multiple L ｘ２ They may be the same or different. ｙ１ If there are multiple instances of Ar ｙ１ They may be the same or different. ｙ２ If there are multiple instances of Ar ｙ２ They may be the same or different. ｙ３When there are a plurality of Ar ｙ３ they may be the same or different from each other. When there are a plurality of L ｙ１ they may be the same or different from each other. When there are a plurality of L ｙ１ they may be the same or different from each other. When there are a plurality of L ｙ２ they may be the same or different from each other. When there are a plurality of L ｙ２ they may be the same or different from each other. When there are a plurality of L ｙ３ they may be the same or different from each other. When there are a plurality of L ｙ３ they may be the same or different from each other.

[0084] L ｘ１ Examples of the ring represented by L include, for example, rings exemplified by one or more rings included in the divalent linking group represented by M described above, and a benzene ring, a triazine ring or a thienothiazole ring is preferable. Note that the ring represented by the above L Ｘ１ constitutes a divalent group. L ｘ２ is preferably a single bond, -COO- or -N=N-. Further, L ｘ２ is preferably R ａ where the L directly bonded to R ｘ２ is a single bond, and the other L ｘ２ is -COO- or -N=N-. nx is an integer of 3 or more. The upper limit is preferably an integer of 10 or less, and more preferably an integer of 6 or less.

[0085] Ar ｙ１ ~Ar ｙ４ The monocyclic ring represented by is a monocyclic ring among the rings exemplified by one or more rings included in the divalent linking group represented by M described above. Note that the ring represented by the above Ar ｙ１ ~Ar ｙ３ constitutes a divalent group. Further, the ring represented by the above Ar ｙ４ constitutes a trivalent group. L ｙ１ ~L ｙ３ is preferably a single bond, -COO-, -NH-, or -N=N-. The monovalent group represented by R ｙ１ is preferably R ａThis is synonymous with a monovalent base represented by , and the preferred embodiment is also the same. my1 is an integer greater than or equal to 0, preferably an integer greater than or equal to 1. The upper limit is preferably an integer less than or equal to 10, more preferably an integer less than or equal to 6, and even more preferably an integer less than or equal to 3. my2 and my3 are integers greater than or equal to 1. The upper limit is preferably an integer less than or equal to 10, more preferably an integer less than or equal to 6, and even more preferably an integer less than or equal to 3. Furthermore, my1 + my2 + my3 is preferably an integer greater than or equal to 2, more preferably an integer between 2 and 10, even more preferably an integer between 2 and 7, and particularly preferably an integer between 3 and 5.

[0086] In equation (X1), * represents the bonding position, and one of the *s is L in equation (T2). ａ Combined, the other side of * is R ａ If it binds to L, the binding position is not particularly restricted. ｘ１ * is directly linked to L ａ Combined with L ｘ２ * is directly bonded to R ａ It is preferable to bond to L in formula (T2). Similarly to the above, * in formula (Y1) represents the bonding position, and one of the *s is L in formula (T2). ａ Combined, the other side of * is R ａ If it binds to A, the binding position is not particularly restricted. In particular, A ｙ１ * is directly linked to L ａ Combined with A ｙ３ * is directly bonded to R ａ It is preferable that it be bonded to

[0087] L ａ Examples of divalent linking groups represented by include alkylene groups, -O-, -CO-, -COO-, and combinations thereof, with -alkylene group-O-, -alkylene group-CO-, or -alkylene group-COO- being preferred. The alkylene group may be linear, branched, or cyclic, with linear being preferred. The number of carbon atoms in the alkylene group is preferably 1 to 10. Also, L ａ As such, divalent linking groups that do not have a ring are also preferred.

[0088] The units represented by formula (T2) may be used individually or in combination of two or more. The content of the units represented by formula (T2) 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 T units in the organopolysiloxane (100 mol%). The upper limit is preferably 100 mol% or less.

[0089] T units, D units, and M units may each be used individually or in combination of two or more. The content of T units may be, for example, 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% or more, relative to the total units (100 mol%) of the organopolysiloxane resin. There is no particular upper limit, and it may be 100 mol% of the total units of the organopolysiloxane resin. The content of D units may be, for example, 0 to 70 mol%, preferably 0 to 30 mol%, relative to the total units of the organopolysiloxane resin. The combined content of T units and D units may be, for example, 50 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more, relative to the total units of the organopolysiloxane resin. The content of T units and D units may be 100 mol% or less, relative to the total units of the organopolysiloxane resin. The content of M units may be, for example, 0 to 30 mol%, and preferably 0 to 10 mol%, relative to the total units of the organopolysiloxane resin. The content of Q units may be, for example, 0 to 30 mol%, and preferably 0 to 10 mol%, relative to the total units of the organopolysiloxane resin.

[0090] The content of each unit in organopolysiloxane resin is, for example, ２９ It can be measured using Si-NMR (nuclear magnetic resonance analysis). Furthermore, the content of each of the above units is measured relative to the composition layer or cured film containing the organopolysiloxane resin. ２９ Measurement may also be performed using Si-NMR. In that case, the results will ２９ By calculating the peak area of ​​the peak corresponding to each unit in the Si-NMR spectrum and then calculating the area ratio of each peak area to the calculated total area, the content ratio of each unit in the organopolysiloxane resin can be determined. ２９In the Si-NMR spectrum, peaks corresponding to M, D, T, and Q units appear, for example, in the ranges where the chemical shift values ​​are approximately 0 ppm or greater, approximately -30 to approximately 0 ppm, approximately -70 to approximately -30 ppm, and approximately -120 to approximately -70 ppm, respectively.

[0091] The method for producing organopolysiloxane resins is not particularly limited; for example, they can be produced by hydrolyzing and condensing raw materials containing monomers that become each unit through hydrolysis condensation.

[0092] Examples of organopolysiloxane resin structures include irregular forms such as random structures, ladder structures, cage structures (fully condensed cage structures), and incomplete cage structures (partially cleaved cage structures in which some silicon atoms are missing from the cage structure and some silicon-oxygen bonds in the cage structure are broken), with ladder structures being preferred.

[0093] (Polyamide resins) Polyamide resins are resins that have amide bonds. Examples of polyamide resins include acrylamide resins, vinylamide resins, and allylamide resins.

[0094] (Polyester resin) Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

[0095] (Polyetherketone Resin) The polyetherketone resin is not particularly limited, and known aromatic polyetherketones can be used. The aromatic polyetherketone is preferably a polyetheretherketone. The polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which the bonds are arranged in the order of ether bond, ether bond, carbonyl bond (ketone). It is preferable that each bond is linked by a divalent aromatic group. The aromatic polyetherketone may be used alone or in combination of two or more types.

[0096] Examples of aromatic polyetherketones include polyether ether ketone (PEEK) having the chemical structure represented by the following formula (P1), polyether ketone (PEK) having the chemical structure represented by the following formula (P2), polyether ketone ketone (PEKK) having the chemical structure represented by the following formula (P3), polyether ether ketone ketone (PEEKK) having the chemical structure represented by the following formula (P4), and polyether ketone ether ketone ketone (PEKEKK) having the chemical structure represented by the following formula (P5).

[0097]

[0098] In formulas (P1) to (P5), n is preferably 10 or more, and more preferably 20 or more, from the viewpoint of mechanical properties. On the other hand, in terms of easily producing aromatic polyether ketones, n is preferably 5,000 or less, and more preferably 1,000 or less. That is, n is preferably 10 to 5,000, and more preferably 20 to 1,000.

[0099] (Polyolefin resins) Examples of polyolefin resins include polymers of compounds having cyclic aliphatic hydrocarbon groups and groups having ethylenically unsaturated bonds, and elastomers containing styrene-derived repeating units (polystyrene-based elastomers).

[0100] Polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include, for example, thermoplastic resins having structural units formed from monomers made of cyclic olefins such as norbornene or polycyclic norbornene monomers, and are also called thermoplastic cyclic olefin resins. Polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be ring-opened polymers of the above-mentioned cyclic olefins or hydrogenated ring-opened copolymers using two or more cyclic olefins, or they may be addition polymers of cyclic olefins with chain olefins or aromatic compounds having an ethylenically unsaturated bond such as vinyl groups. Furthermore, polar groups may be introduced into polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. Polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more.

[0101] The ring structure of the cyclic aliphatic hydrocarbon group may be a monoring, a fused ring formed by the fusion of two or more rings, or a bridged ring. Examples of ring structures of cyclic aliphatic hydrocarbon groups include cyclopentane rings, cyclohexane rings, cyclooctane rings, isoborone rings, norbornane rings, and dicyclopentane rings. Compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be monofunctional ethylenically unsaturated compounds or polyfunctional ethylenically unsaturated compounds. The number of cyclic aliphatic hydrocarbon groups in a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, or it may be two or more. A polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a polymer obtained by polymerizing a compound having at least one cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, or it may be a polymer of a compound having two or more cyclic aliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or it may be a copolymer with another ethylenically unsaturated compound that does not have a cyclic aliphatic hydrocarbon group. Furthermore, the polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.

[0102] Examples of polystyrene-based elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymer (SEPS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and polystyrene-poly(ethylene / ethylene-propylene)-polystyrene triblock copolymer (SEEPS), as well as their hydrogenated derivatives.

[0103] (Epoxy acrylate resin) The epoxy acrylate resin can be any reaction product obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid, or any reaction product obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid and then adding a polybasic acid anhydride. It is not particularly limited and can be widely used. Examples of epoxy resins used here include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, and polyfunctional epoxy resin. Examples of unsaturated carboxylic acids used here include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid. Examples of polybasic acid anhydrides used here include maleic acid anhydride. The epoxy acrylate resin can be used alone or in a mixture of two or more types.

[0104] (Cyanate resin) Examples of cyanate resins include the resins described in paragraphs 0028 to 0033 of Japanese Patent Application Publication No. 2024-091769, the details of which are incorporated herein by reference.

[0105] (Bismaleimidotriazine resin) Examples of bismaleimidotriazine resins include the resins described in paragraphs 0044 to 0048 of Japanese Patent Application Publication No. 2018-204037, the contents of which are incorporated herein by reference.

[0106] (Benzoxazine resin) Examples of benzoxazine resins include the resin described in paragraph 0038 of Japanese Patent Application Publication No. 2024-091769, the details of which are incorporated herein by reference.

[0107] The weight-average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 5,000 to 50,000. The number-average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polydispersity (Mw / Mn) of the specific resin is preferably 1.0 to 3.5, and more preferably 2.0 to 3.0.

[0108] The specific resin may be used alone or in combination of two or more types. The content of the specific resin is preferably less than 90% by mass, more preferably 75 to 99% by mass, and even more preferably 85 to 99% by mass, relative to the total solid content of the resin composition.

[0109] [Polymerization Initiator] The resin composition may contain a polymerization initiator. If the resin composition contains polymerizable compounds as described later, it is preferable that the resin composition contains a polymerization initiator. The polymerization initiator is a compound different from the various components described above. The polymerization initiator may be a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator, with a radical polymerization initiator being preferred. The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator.

[0110] Examples of photopolymerization initiators 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). Oxime ester compounds or aminoacetophenone compounds are preferred as photopolymerization initiators, and oxime ester compounds are more preferred.

[0111] Examples of photopolymerization initiators include those described in paragraphs 0031 to 0042 of Japanese Patent Publication No. 2011-095716 and paragraphs 0064 to 0081 of Japanese Patent Publication No. 2015-014783, the contents of which are incorporated herein by reference.

[0112] While thermal polymerization initiators can be selected according to the type of polymerizable compound, thermal radical polymerization initiators are preferred. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of polymerizable compounds. In addition, the aforementioned photopolymerization initiators may also have the function of initiating polymerization with heat and may be added as thermal polymerization initiators.

[0113] Examples of thermal polymerization initiators include known azo compounds and known peroxide compounds. Examples of azo compounds include azobis compounds. Azo compounds may be compounds having a cyano group or compounds without a cyano group. Examples of peroxide compounds include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. Examples of thermal polymerization initiators include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0114] Polymerization initiators may be used alone or in combination of two or more. When the resin composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.005 to 20.0% by mass, and more preferably 0.01 to 10% by mass, relative to the total solid content of the resin composition.

[0115] [Curing Agent] When the resin composition contains epoxy resin as a specific resin, it is preferable to further contain a curing agent that has the function of reacting with epoxy resin. Examples of curing agents include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents.

[0116] As the active ester curing agent, an active ester compound having one or more active ester groups in one molecule can be used. Examples of active ester compounds include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. From the viewpoint of improving heat resistance, active ester compounds obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester compounds obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred.

[0117] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolacs. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by the condensation of one molecule of dicyclopentadiene with two molecules of phenol.

[0118] Preferred examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, and active ester compounds containing a benzoylated phenol novolac. Among these, active ester compounds containing a naphthalene structure or active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0119] Commercially available active ester compounds include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (all manufactured by DIC Corporation); as an active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Corporation); and acetyl phenol novolac. Examples of active ester compounds containing benzoyl compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds containing benzoyl compounds of phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds that are acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); and examples of active ester compounds that are benzoyl compounds of phenol novolacs include "YLH1026", "YLH1030", and "YLH1048" (all manufactured by Mitsubishi Chemical Corporation).

[0120] The curing agent may be used alone or in combination of two or more types. When the resin composition contains a curing agent, the curing agent content is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and even more preferably 1 to 20% by mass, relative to the total solid content of the resin composition. Furthermore, when the number of epoxy groups in the epoxy resin is set to 1, the number of active groups in the curing agent is preferably 0.1 to 2, and more preferably 0.2 to 1.5. Here, "number of epoxy groups in the epoxy resin" is the sum of all values ​​obtained by dividing the mass of epoxy resin present in the resin composition by the epoxy equivalent. Similarly, "number of active groups in the curing agent" is the sum of all values ​​obtained by dividing the mass of curing agent present in the resin composition by the active group equivalent.

[0121] [Polymerizable Compounds] The resin composition may contain polymerizable compounds. Polymerizable compounds are compounds different from the various components described above. Polymerizable compounds are compounds having one or more polymerizable groups in their molecule. Examples of polymerizable groups include polymerizable groups that may be present in the specific resins described above, with groups having an ethylenically unsaturated double bond being preferred, (meth)acryloyl groups, vinyl groups, or styryl groups being more preferred, and (meth)acryloyl groups being even more preferred.

[0122] The number of polymerizable groups in a polymerizable compound is preferably 2 to 10, and more preferably 2 to 6. Examples of polymerizable compounds include polymerizable compounds having one polymerizable group per molecule (hereinafter also referred to as "monofunctional polymerizable compounds"), polymerizable compounds having two polymerizable groups per molecule (hereinafter also referred to as "bifunctional polymerizable compounds"), and polymerizable compounds having three or more polymerizable groups per molecule (hereinafter also referred to as "trifunctional or more polymerizable compounds"). Bifunctional polymerizable compounds or trifunctional or more polymerizable compounds are preferred as polymerizable compounds.

[0123] Examples of bifunctional polymerizable compounds include polyethylene glycol (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tricyclodecane dimenanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Examples of trifunctional or higher 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, while "(tri / tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.

[0124] Examples of polymerizable compounds include urethane (meth)acrylate (preferably trifunctional or more functional urethane (meth)acrylate). 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.

[0125] Polymerizable compounds may be used individually or in combination of two or more. When the resin composition contains polymerizable compounds, the content of polymerizable compounds is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 10.0% by mass, relative to the total solid content of the resin composition.

[0126] [Surfactants] The resin composition may contain surfactants. Examples of surfactants include fluorine-based surfactants, hydrocarbon-based surfactants, and silicone-based surfactants. Silicone-based surfactants are preferred as surfactants. In terms of improving environmental suitability, it is also preferable that the surfactant does not contain fluorine atoms. Nonionic surfactants other than those mentioned above are also examples of surfactants. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 04502784 and paragraphs 0060 to 0071 of Japanese Patent Application Publication No. 2009-237362, the contents of which are incorporated herein by reference.

[0127] Surfactants may be used alone or in combination of two or more. When the resin composition contains a surfactant, the surfactant content is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.0% by mass, and even more preferably 0.1 to 0.8% by mass, relative to the total solid content of the resin composition.

[0128] [Additives] The resin composition may contain additives other than the components listed above. Examples of additives include solvents, fillers other than specific organic pigments, heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, hydrogen-donating compounds, impurities, plasticizers, sensitizers, and maleimide compounds.

[0129] The resin composition may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the resin composition other than the solvent. Examples of solvents include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone, methyl isobutyl ketone, and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents (e.g., n-propyl acetate), amide solvents, lactone solvents, and solvents containing two or more of these. The solvent may be used alone or in combination of two or more. The solvent content is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and even more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids content of the resin composition.

[0130] The resin composition may contain fillers other than specific organic pigments. Examples of fillers other than specific organic pigments include inorganic fillers. Examples of inorganic fillers include silicon dioxide (silica); silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as thia-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 dioxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitrides.

[0131] Examples of heterocyclic compounds, aliphatic thiol compounds, thermally crosslinkable compounds, polymerization inhibitors, and hydrogen-donating compounds include the various components described in International Publication No. 2022 / 039027. Examples of plasticizers and sensitizers include paragraphs 0097-0119 of International Publication No. 2018 / 179640. Examples of maleimide compounds (compounds having a maleimide ring) include known maleimide compounds and maleimide compounds described in International Publication No. 2022 / 102756.

[0132] [Membrane] The resin composition of the present invention can form a film. The method for forming the film is not particularly limited, and examples include applying the resin composition to a substrate, drying it, and then performing a curing treatment. That is, the film is preferably a cured film formed by curing the resin composition. In the cured film, some or all of the components contained in the resin composition may have reacted by the curing treatment, and some of the components contained in the resin composition (for example, the solvent) may have been removed.

[0133] The above curing treatment can be heat treatment. The heating temperature is preferably 100°C or higher, and more preferably 150°C or higher. The upper limit is preferably 400°C or lower. The heating time is preferably 0.5 hours or more, and more preferably 1.5 hours or more. The upper limit is preferably 5.0 hours or lower. The above curing treatment preferably includes a heat treatment at a temperature of 150°C or higher and a heating time of 1.5 hours or more. The heat treatment may be carried out in either an air environment or a nitrogen-purged environment. A drying treatment may be carried out before the heat treatment. Alternatively, the drying treatment and the heat treatment may be carried out simultaneously.

[0134] The thickness of the above film is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more, in terms of superior insulating properties. The thickness of the film is preferably 40 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less, in terms of superior pattern resolution.

[0135] [Transfer Film] The transfer film of the present invention comprises a temporary support and a composition layer formed using the above resin composition.

[0136] Figure 1 is a schematic diagram showing an example of an embodiment of a transfer film. The transfer film 100 shown in Figure 1 has a configuration in which a temporary support 12, a composition layer 14, and a cover film 16 are arranged in this order. Although Figure 1 shows a form in which the transfer film 100 has a cover film 16, the transfer film may also have a form without a cover film. Furthermore, as will be described later, the transfer film may further have an intermediate layer and / or a thermoplastic resin layer. The individual components of the transfer film will be described in detail below.

[0137] [Temporary Support] The transfer film has a temporary support. The temporary support is a component that supports the composition layer and is ultimately removed by a peeling process.

[0138] The temporary support may have either a single-layer or multi-layer structure. A film is preferred for the temporary support, and a resin film is more preferred. A film that is flexible and does not undergo significant deformation, shrinkage, or elongation under pressure, or under pressure and heat, is also preferred as the temporary support. Examples of the above films include polyethylene terephthalate (PET) 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. Furthermore, it is preferable that the temporary support does not have deformations such as wrinkles or scratches.

[0139] The temporary support is preferably highly transparent so that pattern exposure can be performed through it. Specifically, the transmittance at wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or higher, more preferably 70% or higher, even more preferably 80% or higher, and most preferably 90% or higher. The upper limit is preferably less than 100%. Examples of preferred transmittance values ​​at each of the above wavelengths include 87%, 92%, and 98%. In terms of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the haze of the temporary support be 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 higher. In terms of pattern formation during pattern exposure through the temporary support and the transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, and defects contained in the temporary support be small. The number of fine particles, foreign matter, and defects with a diameter of 1 μm or more in the temporary support was 50 per 10 mm. ２ The following is preferable: 10 pieces / 10 mm ２ The following is more preferable: 3 pieces / 10 mm ２ The following is even more preferable: 0 pieces / 10 mm ２ That is particularly preferable.

[0140] The thickness of the temporary support is preferably 5 to 200 μm, more preferably 5 to 150 μm, even more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm, in terms of ease of handling and versatility. The thickness of the temporary support can be calculated as the average value of any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

[0141] To improve adhesion between the temporary support and the composition layer, the surface of the temporary support in contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When surface modification is performed by UV irradiation, the exposure dose of UV irradiation should be 10 to 2000 mJ / cm². ２ Preferably, 50 to 1000 mJ / cm² ２This is more preferable. Examples of UV irradiation light sources 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.

[0142] Examples of temporary supports include biaxially oriented polyethylene terephthalate film with a thickness of 25 μm, biaxially oriented polyethylene terephthalate film with a thickness of 16 μm, biaxially oriented polyethylene terephthalate film with a thickness of 12 μm, and biaxially oriented polyethylene terephthalate film with a thickness of 9 μm. The temporary support may also be made from recycled materials. Examples of recycled materials include used films that have been washed and chipped, and the resulting material has been made into a film. Examples of commercially available recycled materials include the Ecouse series (manufactured by Toray Industries, Inc.).

[0143] Examples of provisional supports include paragraphs 0017-0018 of Japanese Patent Publication No. 2014-085643, paragraphs 0019-0026 of Japanese Patent Publication No. 2016-027363, paragraphs 0041-0057 of International Publication No. 2012 / 081680, and paragraphs 0029-0040 of International Publication No. 2018 / 179370, the contents of which are incorporated herein by reference.

[0144] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support for the purpose of providing handling properties. 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. Examples of commercially available temporary supports include Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, Lumirror #25T60 and Therapiel 25WZ (all manufactured by Toray Industries, Inc.); Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360 and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0145] [Composition Layer] The composition layer is a layer formed using the above resin composition. The various components that may be included in the composition layer are the same as the various components that may be included in the above resin composition, and the preferred embodiments are also the same. However, the preferred numerical range for the content of various components in the composition layer is the same as the preferred range obtained by replacing "content of various components relative to the total solid content of the resin composition (mass%)" with "content of various components relative to the total mass of the composition layer (mass%)". Specifically, the statement "the content of specific organic pigments is more than 10% by mass relative to the total solid content of the resin composition" should be read as "the content of specific organic pigments is more than 10% by mass relative to the total mass of the composition layer".

[0146] The average thickness of the composition layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 3.0 μm or more, and particularly preferably 5.0 μm or more. The average thickness of the composition layer is preferably 40 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less, in terms of excellent pattern resolution.

[0147] The transfer film may have other layers besides those mentioned above.

[0148] [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 thermoplastic resin layer include the intermediate layer and thermoplastic resin layer described in paragraphs 0164 to 0204 of International Publication No. 2021 / 166719, the contents of which are incorporated herein by reference.

[0149] [Cover Film] The transfer film may have a cover film. If the transfer film has a cover film, it is preferable that the cover film be provided as the outermost layer opposite to the temporary support. The number of fish eyes with a diameter of 80 μm or more contained in the cover film is 5 per meter. ２ The following is preferable. Fish eyes refer to foreign matter, undissolved material, and / or oxidized degradation products that are incorporated into the film when the material is heated and melted, kneaded, extruded and / or biaxially stretched and cast.

[0150] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 particles / mm². ２ The following is preferable: 10 pieces / mm ２ The following is more preferable: 5 pieces / mm ２ The following is even more preferable: This makes it possible to suppress defects caused by the transfer of irregularities resulting from particles contained in the cover film to the composition layer.

[0151] The arithmetic mean roughness Ra of the cover film surface 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 in a long form, the winding performance when winding the transfer film is excellent. Furthermore, in terms of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0152] Examples of cover films include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of cover films include the cover films described in paragraphs 0083 to 0087 and 0093 of Japanese Patent Application Publication No. 2006-259138, the contents of which are incorporated herein by reference.

[0153] Examples of cover films include Alphan® FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan® E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapiel® 25WZ (manufactured by Toray Film Processing Co., Ltd.), and Lumirror® 16QS62 (16KS40) (manufactured by Toray Industries, Inc.). The cover film may also be a recycled product. Examples of recycled products include those obtained by washing and chipping used film, and then forming the resulting material into a film. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0154] The transfer film may include other layers in addition to the layers described above. Examples of other layers include high refractive index layers. Examples of high refractive index layers include those described in paragraphs 0168-0188 of International Publication No. 2021 / 187549, the contents of which are incorporated herein by reference.

[0155] [Method for Manufacturing Transfer Film] A known manufacturing method can be applied to manufacture the transfer film. Preferably, the method for manufacturing the transfer film involves applying a resin composition to a temporary support to form a composition layer, and more preferably, the resin composition coating is dried to form the composition layer. Examples of application methods include slit coating, spin coating, curtain coating, and inkjet coating.

[0156] For example, a method for manufacturing the transfer film 100 shown in Figure 1 includes the steps of applying a resin composition to the surface of a temporary support 12 to form a coating film, and then drying this coating film to form a composition layer 14. Furthermore, the transfer film 100 shown in Figure 1 is manufactured by pressing a cover film 16 onto the composition layer of the transfer film manufactured by the above manufacturing method. Alternatively, the transfer film 100 shown in Figure 1 may be wound up after manufacturing and stored as a roll of transfer film 100. The roll of transfer film 100 can be provided in its original form for the lamination process with a substrate using a roll-to-roll method, which will be described later.

[0157] Furthermore, as described above, the transfer film may have an intermediate layer and / or a thermoplastic resin layer between the temporary support and the composition layer. Examples of resin compositions for forming the intermediate layer, methods for forming the intermediate layer, resin compositions for forming the thermoplastic resin layer, and methods for forming the thermoplastic resin layer include the methods described in paragraphs 0133-0136 and 0143-0144 of International Publication No. 2021 / 033451, the contents of which are incorporated herein by reference.

[0158] [Applications] The above resin composition or transfer film is preferably used for forming patterns and / or films. The above patterns and films can be applied to various applications, such as insulating films, electrode protective films, planarization films, overcoat films, hardcoat films, passivation films, partitions, spacers, microlenses, optical filters, anti-reflective films, etching resists, and plated members. More specifically, examples include protective films or insulating films for touch panel electrodes, protective films or insulating films for circuit boards such as printed wiring boards and printed circuit 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. Among these, the above resin composition and transfer film can be suitably used for forming insulating films, and the insulating film is preferably used as an insulating film for circuit boards. Examples of circuit boards include printed wiring boards such as FPCs (Flexible Printed Circuits) and multilayer wiring boards, as well as semiconductor packages, antennas, etc. In other words, circuit boards (more preferably printed wiring boards, semiconductor packages, or antennas) having an insulating film formed using the above-mentioned resin composition and transfer film are suitable applications for the resin composition of the present invention. Furthermore, the above-mentioned resin composition or transfer film is also preferably used in the manufacture of laminates having a composition layer with a pattern on a substrate.

[0159] [Method for Manufacturing Patterns] The method for manufacturing patterns using the above resin composition is not particularly limited, but a method of forming patterns on a substrate is preferred. Among these, a method having the following steps 1 and 2 is more preferred as a method for manufacturing patterns, and a method having steps 1 to 3 is even more preferred. Step 1: A step of forming a composition layer on a substrate using the resin composition. Step 2: A step of forming a pattern on the composition layer. Step 3: A step of curing the composition layer on which the pattern has been formed.

[0160] [Step 1] Step 1 is a step of forming a composition layer on a substrate using a resin composition. Methods for forming the composition layer include a method of coating the resin composition and a method of using a transfer film. A method of coating the resin composition is the method of coating the resin composition in the above-mentioned method of manufacturing a transfer film. The composition layer may also be formed by drying a coating film of the resin composition.

[0161] A specific method for forming a composition layer using a transfer film is to bring the surface of the composition layer in the transfer film opposite to the temporary support side into contact with the substrate, thereby bonding the transfer film and the substrate. Examples of bonding methods include known transfer methods and lamination methods, and a method in which the substrate is placed on top of the surface of the composition layer and pressure and heat are applied using a roll or the like is preferred. Examples of the lamination method include using a known laminator such as a laminator, vacuum laminator, and auto-cut laminator. Among these, a method using a vacuum laminator or a roll-to-roll bonding method is preferred. The lamination temperature is preferably 60 to 160°C, more preferably 70 to 150°C, and even more preferably 80 to 140°C. The pressing pressure is preferably 0.098 to 1.77 MPa, more preferably 0.29 to 1.47 MPa. The heating and pressing time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds.

[0162] After bonding the transfer film and the substrate, the composition layer may be smoothed by pressing a heat-sealing member from the temporary support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heat-sealing conditions for the lamination described above. The smoothing treatment can be performed using a commercially available laminator. The bonding and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.

[0163] In step 1, when forming a composition layer using a transfer film having a cover film, it is preferable to perform step 1 after peeling the cover film from the transfer film. Also, when forming a composition layer using a transfer film in step 1, the temporary support may be removed between step 1 and step 2, or after step 2. The method for removing the temporary support is not particularly limited, and known methods can be applied. For example, a method for peeling off the temporary support may be used, and peeling may be performed by a roll-to-roll method. Details of the roll-to-roll method are as described above.

[0164] <Substrate> Examples of substrates include glass substrates, glass epoxy substrates, silicon substrates, and resin substrates, as well as substrates having a conductive layer, with substrates having a conductive layer being preferred. The substrate may be composed of a translucent substrate such as a glass substrate, or it may be tempered glass such as Corning's Gorilla Glass. Materials included in the above substrate include, for example, the materials described in Japanese Patent Publication No. 2010-086684, Japanese Patent Publication No. 2010-152809, and Japanese Patent Publication No. 2010-257492. As for the resin substrate, a resin film with low optical distortion and / or high transparency is preferred. Specifically, examples include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, cycloolefin polymer, liquid crystal polymer, and polyimide.

[0165] 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, as it can be manufactured by a roll-to-roll method. Furthermore, when employing a vacuum lamination method or the like, glass epoxy substrates, metal substrates, polyester substrates having a conductive layer, polyimide substrates having a conductive layer, BT resin substrates having a conductive layer, and thermosetting polyphenylene ether substrates having a conductive layer are also preferred. In addition, the substrate having a conductive layer may be a laminate obtained by a method for manufacturing a laminate including steps 1 and 2 described above. When the base material is a substrate having the conductive layer described above, it is preferable in step 1 to bond the transfer film and the substrate having a conductive layer so that the conductive layer and the composition layer are in contact. This produces a laminate in which the conductive layer and the cured film described later are in contact.

[0166] Examples of conductive layers include known conductive layers used in circuit wiring or touch panel wiring. From the viewpoint of conductivity and fine wire formation, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, with a metal layer being more preferred, a copper layer or silver layer being even more preferred, and a copper layer being particularly preferred. Furthermore, the conductive layer may consist of one or more layers. The conductive layer may be used alone or in combination of two or more types. Examples of materials for the conductive layer include elemental metals, alloys, and conductive metal oxides. Examples of elemental metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, Au, Pd, Co, Ti, W, Sn, and In, with Cu, Cr, Ni, Ti, Al, Zn, Au, Pd, or Ag being preferred, and Cu being more preferred. Examples of alloys include alloys containing two or more of the metals listed above as elemental metals, with Ni-Cr alloys, Cu-Ni alloys, or Cu-Ti alloys being preferred. Examples of conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ２ Examples include: Conductivity is such that the volume resistivity is 1 × 10⁻⁶. ６ This means that the volume resistivity is less than Ωcm, and the volume resistivity is 1 × 10⁻⁶. ４It is preferable that the density is less than Ωcm.

[0167] The conductive layer may be patterned. Methods for manufacturing a patterned conductive layer include, for example, subtractive and additive methods such as etching. Etching methods include, for example, the wet etching method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, and known dry etching methods such as plasma etching. The etching method may also involve the use of an etching resist.

[0168] The base material may be a component-embedded substrate that has components built into it.

[0169] [Step 2] Step 2 is the step of forming a pattern on the composition layer. The pattern may be formed only on the composition layer, or on both the composition layer and the substrate. Examples of methods for forming the pattern include drilling, laser processing, and plasma. When the composition layer is formed using a transfer film, the laser processing may be performed after peeling off the temporary support, or it may be performed through the temporary support before peeling off the temporary support.

[0170] Furthermore, if the composition layer is photosensitive, the method for forming the pattern preferably includes the steps of pattern exposure of the composition layer, developing the exposed composition layer with a developer to form the pattern, and etching the conductive layer in areas where the pattern is not present. More preferably, a step of curing the pattern is included between the pattern formation step and the etching step. The composition layer may be exposed from the side opposite to the substrate, or from the substrate side.

[0171] Examples of developers include alkaline developers and organic solvent developers. Examples of development methods include paddle development, shower development, spin development, and dip development, with a preferred development method being spraying the developer onto the exposed composition layer with a shower. Alternatively, after development, a cleaning agent may be sprayed with a shower and the development residue removed by scrubbing with a brush or the like. The developer temperature is preferably 20 to 40°C.

[0172] The light source used for exposure can be any light source that emits light in the wavelength range in which the various photosensitive components in the composition layer (e.g., specific compounds, polymerizable compounds, polymerization initiators, etc.) are photosensitive (e.g., light in the wavelength range of 254 nm, 313 nm, 365 nm, and 405 nm, etc.). Specifically, examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes). The exposure dose is 5 to 1000 mJ / cm². ２ Preferably, 10 to 200 mJ / cm² ２ This is preferable.

[0173] When a composition layer is formed using a transfer film, exposure may be performed after peeling off the temporary support, or exposure may be performed through the temporary support before peeling off the temporary support and then peeling off the temporary support. It is preferable to perform pattern exposure without peeling off the temporary support in order to prevent mask contamination due to contact between the composition layer and the mask and to avoid the influence of foreign matter adhering to the mask on exposure. Pattern exposure may be performed through the mask or direct exposure using a laser or the like. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they are easy to enlarge. As the material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. An example of a film mask material is XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).

[0174] The pattern formed in the composition layer may be a pattern having vias. 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 as a cross-sectional shape; and a circular or square as a front shape (the shape when the via is observed from the direction in which the via is visible). An inverted trapezoid is preferred as a cross-sectional shape because it improves the adhesion of the plated copper to the via wall surface. 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 2 or more is preferred.

[0175] [Step 3] Step 3 is a step of curing the patterned composition layer. Examples of curing treatments for curing the composition include heat treatment and exposure treatment. The curing treatment preferably includes at least heat treatment. Examples of heat treatments include the heat treatment described as a curing treatment in the above-mentioned method for manufacturing the film. Examples of exposure methods include the exposure method in Step 2.

[0176] [Other Processes] The method for manufacturing the pattern may include other processes in addition to the above processes. Other processes include, for example, a process of peeling off the cover film, a process of reducing the visible light reflectance, and an etching process. A known method is a known method for peeling off the cover film. A known method for reducing the visible light reflectance is, for example, the descriptions in paragraphs 0017 to 0025 of Japanese Patent Application Publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Publication No. 2013-206315, the contents of which are incorporated herein by reference. An example of an etching process is the wet etching method described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155, and a known dry etching method such as plasma etching.

[0177] [Method for Manufacturing Semiconductor Packages] The pattern manufacturing method described above can be suitably applied as a method for manufacturing semiconductor packages. Examples of known manufacturing methods for semiconductor packages include methods for manufacturing build-up substrates. A preferred method for manufacturing semiconductor packages is one having the following steps Z1 to Z4. Step Z1: A step of forming a composition layer on a substrate using a resin composition. Step Z2: A step of forming a pattern having vias on the composition layer. Step Z3: A step of curing the composition layer on which the pattern has been formed. Step Z4: A step of forming a circuit pattern on the obtained pattern.

[0178] Furthermore, the pattern manufacturing method described above can be suitably applied as a method for manufacturing a laminate. A preferred method for manufacturing a laminate further includes, in addition to steps Z1 to Z4, step Z5, in which a composition layer is formed on the semiconductor package manufactured in step Z4 using a resin composition, and steps Z2 to Z5 are repeatedly performed.

[0179] The above steps Z1 to Z3 include steps 1 to 3 in the pattern manufacturing method, including preferred embodiments.

[0180] [Process Z4] Process Z4 is a process for forming a circuit pattern on the above pattern. As a method for forming the circuit pattern, a semi-additive process is preferred in that it can form fine wiring. The following methods are examples of semi-additive processes. In the semi-additive process, first, a seed layer is formed by electroless copper plating using a palladium catalyst or the like on the via bottom, via wall surface, and the entire surface of the pattern having vias. The above seed layer is for forming a power supply layer for electrolytic copper plating, and the thickness of the seed layer is preferably 0.1 to 2.0 μm. If the thickness of the above seed layer is 0.1 μm or more, it tends to suppress a decrease in connection reliability during electrolytic copper plating, and if the thickness of the above seed layer is 2.0 μm or less, it does not need to increase the amount of etching when flash etching the seed layer between wirings, and it tends to suppress damage to the wiring during etching. Electroless copper plating is performed by depositing metallic copper on the surface of the pattern having vias through the reaction of 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 for electroless plating. The average primary particle size of the mixed catalyst is preferably 10 nm or less. Furthermore, the plating solution for electroless plating preferably contains hypophosphorous acid (reducing agent). Examples of electroless copper plating solutions include "MSK-DK" manufactured by Attec Japan Co., Ltd. and the "Surupap® PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0181] The method for manufacturing the laminate may include a roughening step in which a pattern having vias is roughened. The roughening step is preferably performed after step Z3 and before step Z4. By performing the roughening step, the surface of the pattern can be roughened to improve adhesion with circuit wiring. At the same time, smear can also be removed. Examples of roughening steps include known desmear treatments, and it is preferable to bring the pattern into contact with a roughening solution. Examples of roughening solutions include a roughening solution containing chromium and sulfuric acid, a roughening solution containing alkaline permanganate (e.g., sodium permanganate roughening solution), and a roughening solution containing sodium fluoride, chromium, and sulfuric acid.

[0182] The circuit pattern may be formed using metal foil. When forming the circuit pattern using metal foil, step Z4 may be performed between steps Z1 and Z2. For example, metal foil is laminated onto the surface of the composition layer, and then step Z2 is performed. Subsequently, the metal foil on the composition layer can be used to form the desired circuit pattern by conventional known techniques such as the subtractive method and the modified semi-additive method. As a method for laminating the composition layer and the metal foil, for example, a vacuum lamination method can be used. The lamination conditions can be those of the method using a transfer film in step 1 of the pattern manufacturing method.

[0183] It is preferable to perform heat treatment after circuit pattern formation in order to improve electrical insulation reliability, curing characteristics, and adhesion strength with plated copper. The heating temperature is preferably 150 to 240°C, and the heating time is preferably 15 to 500 minutes.

[0184] [Step Z5] Step Z5 is a step in which a composition layer is formed on the semiconductor package manufactured in Step Z4 using a transfer film. The method for forming the composition layer is the method in Step Z1 of the pattern manufacturing method, and the preferred embodiment is the same.

[0185] Steps Z2 to Z5 may be repeated according to the required number of layers. Furthermore, it is preferable to form a solder resist on the outermost layer of the resulting semiconductor package.

[0186] [Semiconductor Package] A semiconductor package having a film formed from a resin composition can be obtained by the semiconductor package manufacturing method described above. In the semiconductor package, the film formed from the resin composition may be used as an insulating film, or as an organic interposer or insulating film in a so-called build-up substrate.

[0187] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified 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 following examples. In the following examples, unless otherwise specified, "%" means "mass percent" and "parts" means "parts by mass".

[0188] The abbreviations used in the following explanation are as follows: DMAc: Dimethylacetamide MEK: Methyl ethyl ketone TAIC: Triallyl isocyanurate PGMEA: Propylene glycol methyl ether acetate

[0189] [Preparation of Resin Solution] <Resin Solution R1: Organopolysiloxane Resin 1> Monomer SQ-M1 was synthesized according to the following procedure.

[0190]

[0191] In a 300 mL three-necked flask, the synthesized monomer SQ-M1 (45 g), dimethoxydimethylsilane (8.6 g), and toluene (75.0 g) were mixed and stirred while heating at an ambient temperature of 80°C. A 0.1% potassium hydroxide aqueous solution (18.0 g) was added dropwise at a constant rate over 5 minutes, and the mixture was continued to heat and stir 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, tetrahydrofuran (150 g) and 5% saline solution (150 g) were added to extract the organic phase. The organic phase was sequentially washed once with 5% saline solution (150 g) and twice with pure water (150 g), dried with magnesium sulfate (45 g), and then concentrated under reduced pressure at 50°C and 35 mmHg to obtain resin solution R1 containing organopolysiloxane resin 1. The above-mentioned units of organopolysiloxane resin 1 correspond to the units represented by the above-mentioned formula (T2).

[0192] <Resin Solution R2: Organopolysiloxane Resin 2> Organopolysiloxane resin 2 was synthesized according to the following procedure. 2-amino-1,3,4-thiadiazole (11.4 g) was dissolved in DMI (40 g), and 3-isocyanate triisopropylmethoxysilane (23 g) was added to the solution under ice cooling, then stirred at 60°C for 6 hours. Subsequently, 0.5% KOH aqueous solution (6.3 mL) was added, and stirred at 80°C for 5 hours. After stirring, the resulting reaction solution was reprecipitated and purified with methanol to obtain organopolysiloxane resin 2 (yield 80%). Organopolysiloxane resin 2 was dissolved in DMAc to obtain resin solution R2 containing organopolysiloxane resin 2. The following units of organopolysiloxane resin 2 are represented by the above formula (T1) and correspond to the unit where NRh / NRc is 1.00.

[0193]

[0194] <Resin Solution R3: Organopolysiloxane Resin 3> Except for changing the raw material component 2-amino-1,3,4-thiadiazole to 4-aminophthalimide, organopolysiloxane resin 3 was synthesized using the same procedure as the synthesis method for organopolysiloxane resin 2 described above, and resin solution R3 containing organopolysiloxane resin 3 was obtained. The following units of organopolysiloxane resin 3 are represented by the above formula (T1) and correspond to units where NRh / NRc is 0.50.

[0195]

[0196] <Resin Solution R4: Epoxy Resin 1> Resin solution R4 containing epoxy resin and an active ester compound was prepared by mixing the following components: • Liquid bisphenol A type epoxy resin (epoxy equivalent 180, "828US" manufactured by Mitsubishi Chemical Corporation): 10 parts • Biphenyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.): 20 parts • Active ester compound ("HPC8000-65T" manufactured by DIC Corporation, active ester equivalent 223, toluene solution with 65% solids): 28 parts • Triazine-containing cresol novolac resin (DIC LA3018-50P (manufactured by Koei Chemical Industry Co., Ltd.), phenol equivalent 151, 2-methoxypropanol solution with 50% solids): 7 parts; curing accelerator (4-dimethylaminopyridine, manufactured by Koei Chemical Industry Co., Ltd.): 0.1 parts; phenoxy resin (YL7553BH30, 1:1 solution of MEK and cyclohexanone with 30% solids, weight-average molecular weight 40,000): 7 parts; methyl ethyl ketone: 15 parts; cyclohexanone: 15 parts

[0197] <Resin Solution R5: Epoxy Resin 2> 30 parts of a bisphenol A dicyanate prepolymer (BA230S75, manufactured by Lonza Japan Co., Ltd., cyanate equivalent approximately 232, MEK solution with 75% non-volatile content) and 10 parts of a phenol novolac type polyfunctional cyanate ester resin (PT30, manufactured by Lonza Japan Co., Ltd., cyanate equivalent approximately 124) were stirred and mixed together with 10 parts of MEK. To the obtained mixture, 40 parts of naphthol-type epoxy resin represented by the following general formula (1) (ESN-475V manufactured by Toto Chemical Co., Ltd., epoxy equivalent approximately 340, MEK solution with 65% non-volatile content), 8 parts of liquid bisphenol A-type epoxy resin (jER828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent approximately 185), 20 parts of phenoxy resin solution (YX-6954 manufactured by Japan Epoxy Resin Co., Ltd., a mixed solution of MEK and cyclohexanone with 30% non-volatile content), and an adduct of an imidazole compound and epoxy resin as a curing accelerator (jERcure manufactured by Japan Epoxy Resin Co., Ltd.) A resin solution R5 containing epoxy resin was prepared by mixing 0.3 parts of "P200H50" (a propylene glycol monomethyl ether solution with 50% non-volatile content) and 4 parts of a 1% N,N-dimethylformamide (DMF) solution of cobalt(II) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0198]

[0199] In general formula (1), n ​​represents a number between 1 and 6 as an average value, X represents a glycidyl group or a hydrocarbon group having 1 to 8 carbon atoms, and the ratio of hydrocarbon group to glycidyl group is between 0.05 and 2.0.

[0200] <Resin Solution R6: Maleimide Resin> Resin solution R6 containing maleimide resin was prepared by mixing the following components: ・Biphenyl aralkyl type maleimide resin (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content): 180 parts ・Polycarbonate resin (FPC2136, manufactured by Mitsubishi Gas Chemical Company, Inc., weight-average molecular weight 30,000): 10 parts ・Amine-based non-solid curing agent (jER Cure W, manufactured by Mitsubishi Chemical Corporation): 18 parts ・Toluene: 30 parts ・MEK: 30 parts

[0201] <Resin Solution R7: Polyimide Resin> A resin solution R7 containing a polyimide precursor was prepared according to the method described in Example 15 of Japanese Patent Application Publication No. 2021-123652.

[0202] <Resin Solution R8: Polyphenylene Ether Resin> Polyphenylene ether resin 1 was synthesized according to the method described in paragraph 0193 of Japanese Patent Publication No. 2022-157695. Resin solution R8 was prepared by mixing the following components containing polyphenylene ether resin 1: ・Polyphenylene ether resin 1: 100 parts ・Styrene elastomer (H1051, manufactured by Asahi Kasei Corporation): 49 parts ・TAIC (manufactured by Mitsubishi Chemical Corporation): 60 parts ・Maleimide resin (BMI-3000J, manufactured by Designer Molecules, weight-average molecular weight 3,000): 16 parts ・Perbutyl (registered trademark) P-40 (curing agent, manufactured by Nippon Oil & Fats Co., Ltd.): 3 parts ・Cyclohexanone: 540 parts

[0203] <Resin Solution R9: Acrylic Resin> Acrylic resin 1 was obtained according to the method described in paragraph 0079 of Japanese Patent Publication No. 4821206. Resin solution R9 was prepared by mixing the following components containing the obtained acrylic resin 1: ・Acrylic resin 1: 10 parts ・TO-1382 (manufactured by Toagosei Co., Ltd., reactive monomer): 12 parts ・CGI242 (manufactured by Ciba Specialty Chemicals Co., Ltd., photopolymerization initiator): 2 parts ・CGI113 (manufactured by Ciba Specialty Chemicals Co., Ltd., photopolymerization initiator): 6 parts ・Megafac® R-08 (manufactured by Dainippon Chemical Industries, Ltd., fluorine-based surfactant): 0.1 parts ・2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts ・PGMEA: 100 parts

[0204] <Resin Solution R10: Epoxy Acrylate Resin> Resin solution R10 containing epoxy acrylate resin was prepared by mixing the following components: • PR-3000 (Showa Denko Corporation, cresol novolac type epoxy acrylate resin, 1:1 (volume ratio) solution of solvent naphtha with a solid content of 68% by mass and diethylene glycol monoethyl ether acetate, acid value 50 mg KOH / g): 100 parts by mass • Irgacure 907 (BASF Japan Ltd., 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone): 2.5 parts by mass • HP-7200H (DIC Corporation) Dicyclopentadiene-type epoxy resin (epoxy equivalent 280), manufactured by Mitsubishi Chemical Corporation: 23 parts by mass; DICY7 (dicyandiamide), manufactured by Mitsubishi Chemical Corporation: 0.5 parts by mass; AC3816N (rubber particles), manufactured by Gantz Chemicals Ltd.: 3 parts by mass; DCPA (tricyclodecanedimethanol diacrylate), manufactured by Kyoeisha Chemical Industry Co., Ltd.: 12 parts by mass; EDGAc (ethyl diglycol acetate): 10 parts by mass; MEK (methyl ethyl ketone): 40 parts by mass

[0205] <Resin Solution R11: Organopolysiloxane Resin 4> Organopolysiloxane resin 4 was synthesized according to the following procedure. A mixture of cyanuric chloride (0.475 mol) and 2-butanone (620 mL) was cooled on ice, and 3-aminophenol (0.95 mol) was added in small amounts. Then, an aqueous solution of sodium acetate trihydrate (0.998 mol) dissolved in water (193 mL) was added to the above mixture. The above mixture was stirred at 45°C for 2 hours, then cooled to room temperature, and an aqueous solution of sodium carbonate (0.76 mol) dissolved in water (700 mL) was added dropwise to the above mixture and stirred for 30 minutes. After the above mixture was allowed to stand and the aqueous layer was removed, the organic layer was filtered through Celite, and 210 mL of ethanol was added. Water (1.75 L) was added dropwise to the obtained organic layer while stirring, the precipitated crystals were filtered off, and dried to obtain compound S-4A.

[0206]

[0207] 3-aminopropyltrimethoxysilane (10 mmol) and compound S-4A (10 mmol) were dissolved in DMI to a solid content concentration of 30% by mass, triethylamine (10 mmol) was added, and the mixture was stirred at 90°C for 3 hours to obtain S-4M. The obtained S-4M solution was cooled to 80°C, 0.05 mmol of 0.5 wt% KOH aqueous solution was added, and the mixture was stirred at 80°C for 5 hours. During the reaction, MeOH generated in the system was removed using a Dean-Stark tube. After stirring, the obtained reaction solution was reprecipitated and purified with water to obtain organopolysiloxane resin 4. Organopolysiloxane resin 4 was dissolved in DMAc to obtain resin solution R11 containing organopolysiloxane resin 4. The following units of organopolysiloxane resin 4 are represented by the above formula (T1) and correspond to the unit where NRh / NRc is 0.44.

[0208]

[0209] [Organic Pigments] The following organic pigments were prepared for use in the preparation of the resin composition. The chemical formulas for each organic pigment are shown below. • PR254: Pigment Red 254, diketopyrrolopyrrole red pigment • PR185: Pigment Red 185, azo red pigment • PY151: Pigment Yellow 151, azo yellow pigment • PY185: Pigment Yellow 185, isoindoline yellow pigment • PO13: Pigment Orange 13, bisazo orange pigment • PB16: Pigment Blue 16, phthalocyanine blue pigment • PV19: Pigment Violet 19, quinacridone purple pigment • PO71: Pigment Orange 71, diketopyrrolopyrrole orange pigment • PY139: Pigment Yellow 139, isoindoline yellow pigment • PR179: Pigment Red 179, perylene red pigment

[0210]

[0211] [Preparation of Resin Compositions] The resin compositions of Examples 1 to 21 and Comparative Examples 1 to 4 were prepared by mixing the resin solutions and organic pigments shown in the table below. In preparing each resin composition, a resin solution was mixed in an amount such that the total solid content of the resin solution was as shown in the "Solid Content (g)" column of the "Resin Solution" in the table, and an amount of organic pigment was mixed in the amount shown in the "Solid Content (g)" column of the "Organic Pigment" in the table.

[0212] [Preparation of Cured Film] A copper foil with a thickness of 18 μm (manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) was used as the substrate. Each resin composition was applied to the substrate, and the coating film was dried to obtain a laminate having the substrate and a composition layer with a thickness of 30.0 μm. The laminate was heat-treated in an oven (200°C, 1.5 hours), and then the copper foil was removed by etching treatment, which involved immersion in an iron chloride aqueous solution (concentration 40% by mass) for 1 hour, to obtain a cured film derived from the composition layer.

[0213] [Measurements] The following measurements were performed on the resin composition and cured film of each example.

[0214] <Acid Value of Resins> From each example of resin composition, only the organic pigment was filtered off, and resin samples were taken. The obtained samples were accurately weighed into a 100 mL beaker, and 40 mL of a THF / water = 3 / 1 (volume ratio) mixture was added and stirred to dissolve. The obtained solution was measured using an automatic titrator under the following titration conditions (N=2). A blank test was performed in the same manner, and the acid value of each resin was calculated from the following formula: Acid value (KOH mg / g) = (F × f × (titration volume (mL) - blank (mL)) × 56.11) / (sample weighing value (g) × solid content concentration (%) / 100) In the formula, f represents the titrator factor of the NaOH solution used for titration, and F represents the concentration (mol / L) of the NaOH solution used for titration. <Titration Conditions> Apparatus: Automatic titrator Solvent: THF / H ２ Mixture of 0 = 3 / 1 (volume ratio), 40 mL; Number of measurements: N = 2; Data acquisition potential: 4 mV; Data acquisition titration volume: 50 μL; Titrate: 0.1 mol / L NaOH solution; Sample volume: 0.30 g

[0215] <Moisture Content of Organic Pigments> Organic pigments were filtered from the resin compositions of each example, and the obtained organic pigments were heated at 80°C for 1 hour under a nitrogen atmosphere and dried, and then dried again at 200°C for 1.5 hours under a nitrogen atmosphere. The obtained organic pigments were humidified for more than 10 hours under an environment of 25°C and 50% RH, and the moisture content of the organic pigments was measured using a Karl Fischer automatic moisture analyzer under the following measurement conditions based on the vaporization method.

[0216] (Moisture content measurement conditions) • Measuring device: "AQ-2250" (manufactured by Hiranuma Sangyo Co., Ltd.) • Vaporizer: "AQS-225320" (manufactured by Hiranuma Sangyo Co., Ltd.) • Generated liquid: Aqualight RS-A • Heating temperature: 150°C • Nitrogen flow rate: 150 mL / min • Sample volume: Approximately 100 mg

[0217] <Parameter Xp> Following the method described above, the parameter Xp was determined by substituting the number of atoms in the organic pigment, based on the chemical structure of the organic pigment used in each example, into the above formula (X). The parameter Xp for each organic pigment is shown in the table below.

[0218] [Evaluation] The coefficient of linear expansion and dielectric loss tangent of the cured films prepared using the resin compositions of each example were evaluated by the following method.

[0219] <Dielectric Loss Tangent (Df)> The dielectric loss tangent of the fabricated cured film was measured using the resonance perturbation method at a frequency of 28 GHz. A 28 GHz cavity resonator (CP531, manufactured by Kanto Electronics Applied Development Co., Ltd.) was connected to a network analyzer (E8363B, manufactured by Agilent Technology). The measurement sample (the above-mentioned cured film) was inserted into the cavity resonator under conditions of 25°C and 50% RH humidity, and the dielectric loss tangent of the measurement sample was measured from the change in resonance frequency before and after insertion. Measurements were performed on three measurement samples, and the average value was taken as the dielectric loss tangent (Df) of the cured film for each example. The dielectric loss tangent was evaluated from the obtained values ​​according to the following evaluation criteria.

[0220] (Dielectric Loss Tangent Evaluation Criteria) A: Dielectric loss tangent is less than 0.0063. B: Dielectric loss tangent is 0.0063 or more and less than 0.0096. C: Dielectric loss tangent is 0.0096 or more and less than 0.0150. D: Dielectric loss tangent is 0.0150 or more.

[0221] <Coefficient of Linear Expansion (CTE)> The prepared cured film was cut into strips (50 mm x 3 mm) to be used as measurement samples, and the coefficient of linear expansion was measured using a TMA (thermomechanical analyzer, TA Instruments "TMA450EM"). The measurement conditions were a heating rate of 10°C / min, a chuck distance of 20 mm, and a load of 45 mN. The coefficient of linear expansion was measured in the range of 30 to 50°C during heating (ppm / K), and the average value of three measurements was obtained. The obtained coefficient of linear expansion was evaluated according to the following evaluation criteria.

[0222] (Linear expansion coefficient evaluation criteria) A: Linear expansion coefficient is less than 45 ppm / K. B: Linear expansion coefficient is 45 ppm / K or more and less than 58 ppm / K. C: Linear expansion coefficient is 58 ppm / K or more and less than 68 ppm / K. D: Linear expansion coefficient is 68 ppm / K or more.

[0223] [Results] The following shows the content of various components in the composition and the evaluation results. In the table, the "Content (mass%)" column for "Resin" shows the content (mass%) of resin relative to the total solid matter of the resin composition obtained by mixing the resin solution and the organic pigment in each example (if the resin composition contains two or more types of resin, it shows the total content of the two or more types of resin). In the table, the "Content (mass%)" column for "Organic Pigment" shows the content (mass%) of organic pigment relative to the total solid matter of the resin composition in each example. In the table, the "Df" column shows the evaluation result of the dielectric loss tangent by the above method, and the "CTE" column shows the evaluation result of the organic pigment by the above method.

[0224]

[0225] The results shown in the table above confirm that the resin composition of the present invention can form a film with a low dielectric loss tangent and a small coefficient of thermal expansion.

[0226] It was confirmed that when the content of the specific organic pigment is 20% by mass or more relative to the total solid content of the resin composition, a film with a lower dielectric loss tangent and lower linear expansion can be formed (comparison of Examples 1 and 2, etc.). Furthermore, it was confirmed that when the content of the specific organic pigment is 50% by mass or more relative to the total solid content of the resin composition, a film with even lower linear expansion can be formed (comparison of Examples 4 and 5, etc.).

[0227] It was confirmed that a film with a lower dielectric loss tangent can be formed when the water content of the specific organic pigment is 1.20% by mass or less (comparison of Examples 11-12, etc.). Furthermore, it was confirmed that a film with an even lower dielectric loss tangent can be formed when the water content of the specific organic pigment is 0.80% by mass or less (comparison of Examples 3 and 6-11, etc.).

[0228] It was confirmed that when the parameter Xp calculated from formula (X) based on the chemical structure of a specific organic pigment is 0.32 or higher, a film with lower linear expansion can be formed (comparison of Examples 3 and 6-11, etc.).

[0229] It was confirmed that when the resin composition contains an organopolysiloxane resin having the unit represented by formula (T2) described above, it can form a film with a lower dielectric loss tangent compared to an organopolysiloxane resin that does not have the unit represented by formula (T2) described above (comparison of Examples 3, 13, 14, and 21). Furthermore, it was confirmed that when the resin composition contains an organopolysiloxane resin having the unit represented by formula (T1) described above with an NRh / NRc of 0.43 or more, it can form a film with a lower coefficient of linear expansion compared to an organopolysiloxane resin that does not have the unit represented by formula (T1) described above with an NRh / NRc of 0.43 or more (comparison of Examples 3, 13, 14, and 21).

[0230] [Semiconductor Package] A polyethylene terephthalate film with a thickness of 16 μm (Toray Industries, Inc., "16KS40") was prepared as a temporary support. The resin composition of each example was applied to the temporary support, and the coating was dried to produce a transfer film having the temporary support and a composition layer with a thickness of 30.0 μm. The transfer film of each example was laminated to both sides of a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, Mitsubishi Gas Chemical Company) on which a circuit pattern was formed, and the composition layer was formed on both sides of the glass epoxy substrate. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under the following conditions: substrate temperature: 50°C, rubber roller temperature: 100°C, linear pressure: 3 N / cm, and transport speed: 2 m / min. After peeling off the temporary support, a pattern with vias of 80 μm in diameter was formed on the composition layer at predetermined positions by laser processing. After heat treatment (200°C, 1.5 hours), the residue was removed using an aqueous sodium permanganate solution as a roughening agent, and electroless plating was performed. Next, a resist pattern was formed at predetermined positions using a known dry film resist, electroplating was performed, and the resist pattern was peeled off with a stripping solution. Finally, after seed layer etching, copper wiring was formed on the insulating film formed by the composition layer by heat treatment (180°C, 1 hour). The above process from lamination to heat treatment was performed a total of three times, and finally, a solder resist was formed as the outermost layer. A semiconductor package was then fabricated by encapsulating and mounting semiconductor elements. A semiconductor package substrate was obtained by mounting the obtained semiconductor package at predetermined positions on a printed circuit board. It was confirmed that the obtained semiconductor package substrate was functioning correctly.

[0231] 12: Temporary support 14: Composition layer 16: Cover film 100: Transfer film

Claims

1. A resin composition comprising an organic pigment and a resin, wherein the water content of the organic pigment is 1.50% by mass or less, the content of the organic pigment is more than 10% by mass relative to the total solids in the resin composition, and the acid value of the resin is less than 50 mg KOH / g.

2. The resin composition according to claim 1, wherein the content of the organic pigment is 20% by mass or more with respect to the total solid content in the resin composition.

3. The resin composition according to claim 1 or 2, wherein the water content of the organic pigment is 0.80% by mass or less.

4. The resin composition according to claim 1 or 2, wherein the organic pigment comprises at least one selected from the group consisting of azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, and isoindoline pigments.

5. The resin composition according to claim 1 or 2, wherein Xp calculated from formula (X) is 0.32 or greater. Xp = (Nn + No + Ns + Ncl + Nh) / Nc (X) In formula (X), Nc, Nn, No, Ns, Ncl, and Nh represent the number of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, chlorine atoms, and hydrogen atoms bonded to heteroatoms contained in the organic pigment, respectively.

6. The resin composition according to claim 1 or 2, wherein the resin comprises at least one selected from the group consisting of epoxy resin, maleimide resin, polyimide resin, polyphenylene ether resin, organopolysiloxane resin, polyester resin, polyetherketone resin, and polyolefin resin.

7. The resin composition according to claim 1 or 2, wherein the resin comprises at least one selected from the group consisting of epoxy resin, maleimide resin, polyimide resin, branched polyphenylene ether resin, and organopolysiloxane resin, and if the resin comprises an epoxy resin, it further comprises an active ester compound.

8. The resin composition according to claim 1 or 2, used for forming an insulating film of a circuit board.

9. A cured film obtained by curing the resin composition according to claim 1 or 2.

10. A method for manufacturing a pattern, comprising the steps of: forming a composition layer on a substrate using the resin composition described in claim 1 or 2; forming a pattern on the formed composition layer; and curing the composition layer on which the pattern has been formed.

11. A transfer film having a composition layer formed using the resin composition described in claim 1 or 2, and a temporary support.

12. The transfer film according to claim 11, used for forming an insulating film of a printed circuit board.

13. A printed circuit board having an insulating film formed using the resin composition described in claim 1 or 2.

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