Compound having triazine structure, composition containing compound, and semiconductor element

Abstract

To provide a compound that has a triazine structure and allows a photocuring reaction, the cured product of which exhibits superior dielectric characteristics and thermal properties.SOLUTION: The invention has been completed by discovering that a compound having, as a repeating unit, a structural unit represented by general formula (1) can solve the present problem. (In formula (1), R1 represents a divalent linking group, and when a plurality of R1 are present in the compound, the plurality of R1 may be the same or different from each other. R2 represents a monovalent linking group, and when a plurality of R2 are present in the compound, the plurality of R2 may be the same or different from each other, at least one of which includes an acrylate group or a methacrylate group. X1, X2, and Y1 represent a direct bond or a divalent linking group, and when a plurality of them are present in the compound, they may be the same or different from each other. At least one of X1, X2, and Y1 includes an oxygen atom. Z1 and Z2 represent a monovalent linking group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound having a triazine structure and exhibiting photocurability when used in combination with a photoradical initiator, a composition containing the compound, and a semiconductor device. More specifically, the present invention relates to a compound having a triazine structure, capable of photocuring, and having excellent dielectric properties and heat resistance when cured. The compound of the present invention can be used for protective films, interlayer insulating films, and insulating films for rewiring layers of semiconductor devices. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance and mechanical properties, have been widely used for surface protection films, interlayer insulating films, and the like of semiconductor elements (Patent Document 1). When using polyimide resins or polybenzoxazole resins as surface protection films or interlayer insulating films, a known method is to form through-holes and the like by etching using a positive photoresist containing these resins. However, this method has the problem of requiring complicated processes such as applying and peeling off the photoresist. Therefore, heat-resistant materials that have been given photosensitivity have been investigated with the aim of streamlining the work process (Patent Document 2).

[0003] Thin films of polyimide resins and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, are generally obtained by thermally dehydrating and cyclizing a coating film of their precursors. However, dehydration shrinkage during cyclization can cause film defects. This is a factor that significantly affects the surface smoothness and dimensional stability of substrates in the manufacturing process of semiconductor packages and electronic devices (Patent Document 3).

[0004] Furthermore, the amount of data traffic from communication devices such as smartphones is steadily increasing, and communication frequencies are becoming higher in order to transmit data in a short time. In order to increase communication frequencies, it is necessary to suppress transmission loss, and materials with low dielectric constants and low dielectric loss tangents are needed.

[0005] Compounds with a triazine structure (Patent Document 4) are expected to have high heat resistance and, unlike polyimide resins and polybenzoxazole resins, do not require ring closure, so there is no risk of film burrs due to dehydration shrinkage. However, because they do not contain reactive groups in the skeleton, they cannot be photocured. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-199557 [Patent Document 2] Japanese Patent Application Publication No. 11-24271 [Patent Document 3] Japanese Patent Publication No. 2023-1636 [Patent Document 4] Patent No. 5759302 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a compound having a triazine structure, which is photocurable and exhibits excellent dielectric properties and heat resistance when cured. Another object of the present invention is to provide a composition and a semiconductor device containing the novel compound. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by using a compound having the following structure, and have thus completed the present invention. That is, various aspects and some preferred embodiments of the present invention are as follows: [1] A compound having a structural unit represented by the following general formula (1) as a repeating unit:

[0009] [ka]

[0010] In formula (1), R1 represents a divalent linking group, and when multiple R1s are present in the compound, the multiple R1s may be the same or different from each other. R2 represents a monovalent linking group, and when multiple R2s are present in the compound, the multiple R2s may be the same or different from each other, and at least one R2 contains an acrylate group or a methacrylate group. X1, X2, and Y1 represent direct bonds or divalent linking groups, and when multiple X1, X2, and Y1 are present in the compound, they may be the same or different from each other. At least one of X1, X2, and Y1 contains an oxygen atom. Z1 and Z2 represent monovalent linking groups. [2] The compound according to [1], wherein X1, X2 and Y1 are -O- or -NH-. [3] The compound according to [1], wherein at least one of R2 is a structure selected from (a), (b), (c), and (d).

[0011] [ka]

[0012] [4] The composition according to any one of [1] to [3]. [5] A dry film comprising a composition containing the compound according to any one of [1] to [3]. [6] A cured product of the composition described in [4]. [7] A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film for a rewiring layer, which comprises the composition according to [4] or the cured product according to [6]. [Effects of the Invention]

[0013] The compound according to the present invention and a resin composition containing the compound can be patterned and cured by exposure to light, and the resin composition can provide a cured product having excellent heat resistance and dielectric properties. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0015] The present invention relates to a compound represented by the above formula (1). In the above formula (1), R1 represents a divalent linking group, and when multiple R1s are present in the compound, the multiple R1s may be the same or different from each other. R2 represents a monovalent linking group, and when multiple R2s are present in the compound, the multiple R2s may be the same or different from each other, and at least one R2 contains an acrylate group or a methacrylate group. X1, X2, and Y1 represent direct bonds or divalent linking groups, and when multiple R2s are present in the compound, they may be the same or different from each other. At least one of X1, X2, and Y1 contains an oxygen atom. Z1 and Z2 represent monovalent linking groups.

[0016] In the above formula (1), R1 is a divalent linking group, and when a plurality of R1 are present in the compound, the plurality of R1 may be the same or different. In the above formula (1), R1 may be a residue obtained by removing a hydroxyl group or an amino group from a compound represented by the following formula (2):

[0017] In the above formula (1), R2 represents a monovalent linking group, and when there are multiple R2 in the compound, the multiple R2 may be the same or different, and at least one R2 contains an acrylate group or a methacrylate group. In the above formula (1), R1 can be a residue obtained by removing a hydroxyl group or an amino group from a compound represented by the following formula (3). It is preferable that at least one of R2 has a structure selected from the above formulas (a), (b), (c), and (d).

[0018] In the above formula (1), X1, X2, and Y1 represent a direct bond or a divalent linking group, and when a plurality of X1, X2, and Y1 are present in the compound, they may be the same or different. At least one of X1, X2, and Y1 contains an oxygen atom.

[0019] In the above formula (1), Z1 and Z2 represent monovalent linking groups.

[0020] The compound of the present invention represented by the above formula (1) can be obtained by dehydrochlorinating cyanuric chloride with compounds represented by the following formulae (2) and (3) in the presence of a dehydrochlorinating agent. X1, X2, and Y1 represent -O- or -NH-, with -O- being preferred from the viewpoint of dielectric properties. R1 represents a divalent linking group, and R2 represents a monovalent linking group.

[0021] [ka] Specific examples of the compound represented by formula (2) include bisphenol compounds, aromatic diamine compounds, aliphatic diamines, and diols and diamines having a siloxane skeleton. Examples of bisphenol compounds include 4,4'-dihydroxydiphenyl ether, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)propane, 9,9-bis(4-hydroxyphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, and 1,1-bis(4-hydroxyphenyl)-3 ,3,5-trimethylcyclohexane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2''-diallylbisphenol A, 5,5'-diallyl-2,2'-dihydroxybiphenyl, 4,4'-sulfonylbis(2-allylphenol), 4,4'-dihydroxybiphenyl, 4,4'-dihydroxytetraphenylmethane, 2,7-dihydroxynaphthalene, hydroquinone, SA-90 (SABIC), and UNIFINER V-575 (Unitika). Preferred bisphenol compounds are 4,4'-dihydroxydiphenyl ether, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2'-diallylbisphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxynaphthalene, and 4,4'-dihydroxytetraphenylmethane.

[0022] Examples of aromatic diamine compounds include phenylenediamine, diaminotoluene, diaminoxylene, diaminomesitylene, diaminodurene, diaminoazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenedianiline, methylenebis(methylaniline), methylenebis(dimethylaniline), methylenebis(methoxyaniline), methylenebis(dimethoxyaniline), methylenebis(ethylaniline), methylenebis(diethylaniline), methylenebis(ethoxyaniline), methylenebis(diethoxyaniline), isopropylidenedianiline, hexafluoroisopropylidenedianiline, diaminobenzophenone, diaminodimethylbenzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodimethyldiphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, and diaminofluorene.

[0023] Specific examples of aliphatic diamines include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3′-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, and 9,10-diaminophenanthrene.

[0024] Specific examples of diols and diamines having a siloxane skeleton include KF-6000 (Shin-Etsu Silicones Co., Ltd.), KF-8010 (Shin-Etsu Silicones Co., Ltd.), and PAM-E (Shin-Etsu Silicones Co., Ltd.) As the diols and diamines having a siloxane skeleton, KF-8010 is preferred.

[0025] Specific examples of the compound represented by formula (3) include 2-hydroxymethyl methacrylate, 4-hydroxyphenyl methacrylate, 2-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-allylphenol, 4-ethylphenol, 4-(1,1,3,3-tetramethylbutyl)phenol, 3-hydroxybenzotrifluoride, etc. Preferred examples of the compound represented by formula (3) include 2-hydroxymethyl methacrylate, 4-hydroxyphenyl methacrylate, 4-ethylphenol, 3-hydroxybenzotrifluoride, and 2-allylphenol.

[0026] When a compound has a plurality of formulas (3), it is preferable that at least one of them contains an acrylate group or a methacrylate group, and it is preferable to use a compound in which, in formula (3), R2 is a structure selected from (a), (b), (c), and (d).

[0027] [ka]

[0028] The dehydrochlorinating agent used in the above reaction can be a common basic compound. Specific examples include alkaline (earth) metal carbonates such as sodium carbonate, potassium carbonate, and calcium carbonate; alkaline (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkaline earth metal oxides such as calcium oxide; aliphatic tertiary amines such as trimethylamine, triethylamine, and tributylamine; aromatic amines such as aniline, dimethylaniline, and dimethylbenzylamine; and heterocyclic amines such as pyridine, picoline, and quinoline. The amount of these compounds used is preferably 1.00 to 10.00 mol per 1.0 mol of hydrogen chloride produced. If the amount is less than 1.00 mol, unreacted monomers may remain, while if the amount is more than 10.0 mol, much of the base may not participate in the reaction, which is uneconomical and may require a complicated removal process.

[0029] The ratio of the amounts of formula (2) and formula (3) charged to 1.0 mol of cyanuric chloride in the reaction is not particularly limited, but the amount of formula (2) is preferably 0.5 mol to 1.5 mol, more preferably 0.7 to 1.3 mol, and even more preferably 0.9 to 1.1 mol. The amount of formula (3) is preferably 0.5 mol to 1.5 mol, more preferably 0.7 to 1.3 mol, and even more preferably 0.9 to 1.1 mol. Various types of molecular structures can be synthesized by changing the order and molar ratio of cyanuric chloride, formula (2), and formula (3). For example, to synthesize a linear polymer, first react cyanuric chloride with formula (3) in a 1.00:1.00 molar ratio, and then react with 1.00 mol of formula (2). To convert the polymer terminals to formula (3), more than 1.00 mol of formula (3) can be added to 1.00 mol of cyanuric chloride to obtain the desired product. For example, if 1.00 mol of cyanuric chloride and 1.10 mol of formula (3) are added, it is preferable to add 0.95 mol of formula (2). Less than 0.95 mol of formula (2) results in insufficient molecular weight growth or unreacted cyanuric chloride residues. However, this is not a problem if you are intentionally trying to lower the molecular weight or satisfy the desired physical properties. Furthermore, if formula (2) is added in excess of 0.95 mol, the resin terminals will be formula (2), leaving unreacted hydroxyl and amino groups. While the unreacted sites can be left as long as they do not affect the desired physical properties, they can also be used as reactive groups. For example, if the unreacted sites are hydroxyl groups, they can be converted to methacrylate terminals by reaction with methacrylic acid chloride, or polymerized with other diol resins using terephthalic acid chloride.

[0030] In the above formula (1), Z1 and Z2 are not particularly limited as long as they are monovalent linking groups, but Z1 is preferably substituted with the structure of the above formula (2) or (3), and Z2 is preferably a hydrogen atom, an aliphatic group, an aromatic group, an acetyl group, a glycidyl group, a (meth)acrylic group, a carboxy group, an ester group, an amide group, a trifluoromethyl group, an imide group, or a urea group.

[0031] The solvent is not particularly limited as long as it does not interfere with the polymerization, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, tetrahydrofuran, 4-methyltetrahydropyran, N-methylpyrrolidone, N,N-dimethylformamide, and γ-butyrolactone.

[0032] Furthermore, a thermal polymerization inhibitor can be used, and specific examples include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, diphenylpicrylhydrazine, diphenylamine, etc., and when used, the amount used is preferably 0.1 to 10% by weight based on the reactants.

[0033] The reaction temperature cannot be generally defined because the preferred polymerization temperature range varies depending on the type of condensing agent and monomer used, but heating within the range of -50°C to 150°C is preferred.

[0034] The weight-average molecular weight of the compound represented by formula (1) is preferably 1,000 to 200,000, more preferably 1,500 to 100,000. A weight-average molecular weight of 1,500 or more can improve the strength and film properties of a cured film containing the compound of the present invention, and can also facilitate the formation of a desired film thickness when a composition containing the compound of the present invention is spin-coated. Furthermore, a weight-average molecular weight of 200,000 or less can maintain the solubility of the composition in a developer and the resolution of the composition upon irradiation with light. Here, the weight-average molecular weight is a value measured by gel permeation chromatography and converted from a standard polystyrene calibration curve.

[0035] The number of repetitions of the compound represented by the above formula (1) is preferably 3 to 700, and more preferably 5 to 400.

[0036] Next, the composition will be described. The composition preferably contains at least one compound of the present invention represented by formula (1), and at least one photopolymerization initiator or at least one curing catalyst.

[0037] The photopolymerization initiator used in the composition is not particularly limited as long as it is a conventionally known photopolymerization initiator used for photocuring a compound having an unsaturated double bond group.Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler's ketone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2- Examples of such oxime include hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and 2,4-diethylthioxanthone. These photopolymerization initiators may be used alone or in combination of two or more.

[0038] Among these, it is preferable to use a compound that efficiently generates radicals at an exposure wavelength of 310 to 436 nm (more preferably 365 nm) from the viewpoint that fine patterns can be formed using a reduced projection exposure machine (stepper, light source wavelength: 365 nm, 436 nm) that is standardly used in the manufacturing process of semiconductor protective films, etc. Preferred examples of the photopolymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione=2-(O-benzoyloxime) (manufactured by BASF Japan, "IRGACURE OXE-01"), ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02"), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins BV, "Omnirad 907"). The amount of the photopolymerization initiator used (if used) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 8 parts by mass, per 100 parts by mass of the compound represented by formula (1).

[0039] A sensitizer may be used in combination with a composition containing a photopolymerization initiator. The sensitizer that can be used in combination is not particularly limited as long as it is a conventionally known sensitizer, and examples thereof include 4,4'-bis(diethylamino)benzophenone. The amount of sensitizer used (if used) is preferably 2 parts by mass or less, more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the compound represented by formula (1). The use of a sensitizer in combination can increase the sensitivity to light during self-polymerization.

[0040] The curing catalyst used in the composition of the present invention is not particularly limited as long as it can promote the self-polymerization of the acrylic or methacrylic groups (hereinafter referred to as acrylic groups) possessed by the compound represented by formula (1) of the present invention by heating, and conventionally used catalysts can be appropriately adopted. Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; triphenylphosphine; tributylphosphine; organic metal salts such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Lewis acids such as boron trifluoride; and salts such as sodium carbonate and lithium chloride. The amount of the curing catalyst used (if used) is preferably 10 parts by weight or less, more preferably 1 to 5 parts by weight, per 100 parts by weight of the compound represented by formula (1).

[0041] The composition of the present invention may contain other components in addition to the essential component, the compound represented by formula (1), and an optional photopolymerization initiator and / or curing catalyst, or a compound capable of reacting with acrylic groups, and preferably contains a photopolymerization initiator. Other components that can be used in combination with the composition of the present invention include various additives such as organic solvents, adhesion enhancers such as coupling agents, thermoplastic resins, colorants, thickeners, thermal polymerization inhibitors, antifoaming agents, and leveling agents.

[0042] The organic solvent is not particularly limited, but examples thereof include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 4-formylmorpholine, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methyl amyl ketone. These organic solvents can be used alone or in combination. The use of organic solvents in combination is preferred because it improves the handleability of the composition. There is no particular restriction on the content of organic solvent in the composition of the present invention, but typically (if used) the content of the solvent in the composition is 95% by mass or less, preferably 20 to 90% by mass.

[0043] It is known that the addition of a compound containing a tertiary amine structure as an organic solvent promotes the reaction of acrylic groups. Therefore, among the above-mentioned organic solvents, it is desirable to use compounds containing a tertiary amine structure, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 4-formylmorpholine, and 1,3-dimethyl-2-imidazolidinone, either alone or in combination with a compound that does not contain a tertiary amine structure. When used in combination with a compound not containing a tertiary amine structure, the proportions of each added are not particularly limited. However, since compounds containing a tertiary amine structure generally have high boiling points and therefore require a long drying time after spin coating, the amount of the compound containing a tertiary amine structure in the solvent is preferably 50% or less.

[0044] The coupling agent used as the adhesion promoter is not particularly limited, but may typically be a silane coupling agent. Examples of silane coupling agents include, but are not limited to, 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. These may be used alone or in combination of two or more. Because silane coupling agents are unreactive with the compounds of the present invention (compounds, self-polymerized products, polybenzoxazole), components other than those acting at the substrate interface may remain as residual components after curing. Therefore, using large amounts of silane coupling agents as adhesion promoters may have undesirable effects, such as reduced physical properties. Depending on the type of substrate, even small amounts can be effective, so it is appropriate to use them within a range that does not cause undesirable effects. The proportion of silane coupling agent (if used) is typically 15% by mass or less, preferably greater than 0% by mass and less than 5% by mass, based on the total mass of the composition; however, the upper limit of the proportion may vary depending on the type of substrate.

[0045] Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of thickeners include Orben, Bentone, and montmorillonite. Examples of the thermal polymerization inhibitor include hydroquinone and 2,6-di-tert-butyl-p-methylphenol. Examples of the antifoaming agent include silicone-based, fluorine-based and polymer-based antifoaming agents. The amount of these additives used (when used) in the composition of the present invention is preferably 30% by mass or less, for example, as a rough guide, but this amount can be increased or decreased as appropriate depending on the purpose of use.

[0046] The composition of the present invention may contain inorganic fillers such as barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc. The blending ratio of the inorganic filler (if used) in the composition of the present invention is preferably 60 mass % or less.

[0047] The compound of the present invention and compositions containing the compound can also be used in the form of a dry film resist. Specifically, the compound and composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, or the like, followed by drying in a drying oven set at 45 to 140°C. A predetermined amount of solvent is removed, and a cover film or the like is optionally laminated to form a dry film resist. In this case, the thickness of the resist on the base film is adjusted to 2 to 200 μm. The compound and composition of the present invention used to form a dry film resist may be any of those described above as long as they contain the compound, but the composition of the first aspect described above is preferred. Examples of the base film and cover film include films made of polyester, polypropylene, polyethylene, TAC, polyimide, and the like. These films may be treated with a silicone (registered trademark)-based release treatment agent or a non-silicone (registered trademark)-based release treatment agent, as needed. Supplying the composition as a dry film resist eliminates the steps of coating and drying on a substrate, making it easier to use the composition of the present invention.

[0048] The cured film containing the compound of the present invention can be used in electronic components such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, the cured film is suitably used for applications such as a passivation film for semiconductors, a surface protection film for semiconductor elements, an interlayer insulating film, an interlayer insulating film for multilayer wiring for high-density packaging, an insulating film for redistribution layers, an interlayer insulating film for electronic components such as inductors and SAW filters, and an insulating film or planar layer for organic electroluminescent devices, but is not limited thereto, and can have various structures. [Example]

[0049] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "parts" means parts by mass, and "%" means % by mass. The weight-average molecular weight of the synthesized polymer was determined in terms of standard polystyrene using gel permeation chromatography (GPC, apparatus manufactured by Tosoh Corporation, column manufactured by Tosoh Corporation). Unless otherwise specified, commercially available reagents were used.

[0050] Example 1 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-1) A flask equipped with a thermometer, a condenser, an air inlet tube, and a stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 15.6 parts (120 mmol) of 2-hydroxymethyl methacrylate, and 33 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 8.53 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours. Subsequently, 12.1 parts (60 mmol) of 4,4′-dihydroxydiphenyl ether and 24 parts of anisole were added, followed by the dropwise addition of a mixture of 17.1 parts (132 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole. The mixture was stirred at 100°C for 3 hours while blowing air into the solution. The reaction mixture was then cooled to room temperature and added dropwise to 1500 mL of methanol, and the precipitated solid was collected. The recovered solid was redissolved in 40 parts of anisole, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was recovered by filtration and dried at 50°C for 24 hours to obtain 16.1 parts of the compound of the present invention having the structure represented by the following formula (A-1). The weight-average molecular weight was 4,310.

[0051] [ka]

[0052] Example 2 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-2) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 10.7 parts (60 mmol) of 4-hydroxyphenyl methacrylate, and 66 parts of anisole, and the mixture was ice-cooled while stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 90 minutes. Subsequently, 20.2 parts (60 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 61 parts of anisole were added, followed by the dropwise addition of a mixture of 17.1 parts (132 mmol) of N,N-dipropylethylamine and 34.1 parts of anisole. The mixture was stirred at 100°C for 3 hours while blowing air into the solution. The reaction mixture was then cooled to room temperature and added dropwise to 1500 mL of methanol, and the precipitated solid was collected by filtration. The recovered solid was redissolved in 90 parts of anisole, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was recovered by filtration and dried at 50°C for 24 hours to obtain 22.2 parts of the compound of the present invention having the structure represented by the following formula (A-2). The weight-average molecular weight was 10,600.

[0053] [ka]

[0054] Example 3 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-3) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 2.67 parts (15 mmol) of 4-hydroxyphenyl methacrylate, 5.50 parts (45 mmol) of 4-ethylphenol, and 58 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 45 minutes. Subsequently, 20.2 parts (60 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 61 parts of anisole were added, followed by the dropwise addition of a mixture of 17.1 parts (132 mmol) of N,N-dipropylethylamine and 34.1 parts of anisole. The mixture was stirred at 100°C for 3 hours while blowing air into the solution. The reaction mixture was then cooled to room temperature and added dropwise to 1500 ml of methanol, and the precipitated solid was collected by filtration. 120 parts of anisole was added to the collected solid to redissolve it, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was collected by filtration and dried at 50°C for 24 hours to obtain 15.6 parts of the compound of the present invention having a structure represented by the following formula (A-3). The compound had a weight-average molecular weight of 7,140.

[0055] [ka]

[0056] Example 4 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-4) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 2.67 parts (15 mmol) of 4-hydroxyphenyl methacrylate, 6.04 parts (45 mmol) of 2-allylphenol, and 59 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 80 minutes. Subsequently, 13.4 parts (40 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 26.9 parts of anisole were added, followed by the dropwise addition of a mixture of 11.4 parts (88 mmol) of N,N-dipropylethylamine and 11.4 parts of anisole. After the addition, the mixture was stirred at room temperature for 100 minutes. After that, 6.17 parts (20 mmol) of 2,2'-diallylbisphenol A and 12.3 parts of anisole were added, and a mixture of 5.69 parts (44 mmol) of N,N-dipropylethylamine and 5.69 parts of anisole was added dropwise. The mixture was stirred at 100 ° C for 3 hours while blowing air into the solution. The reaction solution was then cooled to room temperature and added dropwise to 1500 ml of methanol, and the precipitated solid was collected by filtration. 120 parts of anisole was added to the collected solid to redissolve it, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was collected by filtration and dried at 50 ° C for 24 hours to obtain 12.6 parts of a compound of the present invention having a structure represented by the following formula (A-4). The weight-average molecular weight was 7,890.

[0057] [ka]

[0058] Example 5 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-5) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 10.7 parts (60 mmol) of 4-hydroxyphenyl methacrylate, and 65 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 8.5 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 60 minutes. Subsequently, 12.6 parts (15 mmol) of KF-8010 (manufactured by Shin-Etsu Silicones Co., Ltd.) and 12.6 parts of anisole were added, followed by the dropwise addition of a mixture of 4.26 parts (33 mmol) of N,N-dipropylethylamine and 4.26 parts of anisole. After the addition, the mixture was stirred at room temperature for 90 minutes. After that, 15.1 parts (45 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 30.3 parts of anisole were added, and a mixture of 12.8 parts (99 mmol) of N,N-dipropylethylamine and 12.8 parts of anisole was added dropwise. The mixture was stirred at 100 ° C for 3 hours while air was blown into the solution. The reaction solution was then cooled to room temperature and added dropwise to 2300 ml of methanol. The precipitated solid was collected by filtration and dried at 50 ° C for 24 hours to obtain 1.2 parts of the compound of the present invention having the structure represented by the following formula (A-5). The weight-average molecular weight was 8,370.

[0059] [ka]

[0060] Example 6 (Synthesis of compounds of the present invention) Synthesis of the compound of the present invention represented by the following formula (A-6) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 2.67 parts (15 mmol) of 4-hydroxyphenyl methacrylate, 7.29 parts (45 mmol) of 3-hydroxybenzotrifluoride, and 63 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 60 minutes. Subsequently, 7.01 parts (20 mmol) of 9,9-bis(4-hydroxyphenyl)fluorene and 14.0 parts of anisole were added, followed by the dropwise addition of a mixture of 5.69 parts (44 mmol) of N,N-dipropylethylamine and 5.69 parts of anisole. After the addition, the mixture was stirred at room temperature for 30 minutes. The solution was then stirred at 100°C for 1 hour while blowing air into it. The reaction mixture was then cooled to room temperature, and 13.4 parts (40 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 26.9 parts of anisole were added. A mixture of 11.4 parts (88 mmol) of N,N-dipropylethylamine and 11.4 parts of anisole was then added dropwise. The mixture was stirred at 100°C for 3 hours while blowing air into the solution. The reaction mixture was then cooled to room temperature and added dropwise to 1500 ml of methanol, and the precipitated solid was collected by filtration. The collected solid was redissolved in 90 parts of anisole, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was collected by filtration and dried at 50°C for 24 hours to obtain 18.6 parts of a compound of the present invention having the structure represented by formula (A-6) below. The weight-average molecular weight was 11,200.

[0061] [ka]

[0062] Example 7 (Synthesis of Compounds of the Present Invention) Synthesis of the compound of the present invention represented by the following formula (A-7) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 2.67 parts (15 mmol) of 4-hydroxyphenyl methacrylate, 6.04 parts (45 mmol) of 2-allylphenol, and 59 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 60 minutes. Subsequently, 13.4 parts (40 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 26.9 parts of anisole were added, followed by the dropwise addition of a mixture of 11.4 parts (88 mmol) of N,N-dipropylethylamine and 11.4 parts of anisole. After the addition, the mixture was stirred at room temperature for 60 minutes. After that, 3.20 parts (20 mmol) of 2,7-dihydroxynaphthalene and 6.41 parts of anisole were added, and a mixture of 5.69 parts (44 mmol) of N,N-dipropylethylamine and 5.69 parts of anisole was added dropwise. The mixture was stirred at 100 ° C for 3 hours while blowing air into the solution. The reaction solution was then cooled to room temperature and added dropwise to 1500 ml of methanol, and the precipitated solid was collected by filtration. The collected solid was redissolved in 90 parts of anisole, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was collected by filtration and dried at 50 ° C for 24 hours to obtain 12.8 parts of a compound of the present invention having a structure represented by the following formula (A-7). The weight-average molecular weight was 7,700.

[0063] [ka]

[0064] Example 8 (Synthesis of compounds of the present invention) Synthesis of the compound of the present invention represented by the following formula (A-8) A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 2.67 parts (15 mmol) of 4-hydroxyphenyl methacrylate, 6.04 parts (45 mmol) of 2-allylphenol, and 59 parts of anisole, and the mixture was ice-cooled with stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 60 minutes. Subsequently, 6.29 parts (20.4 mmol) of 2,2'-diallylbisphenol A and 17.1 parts of anisole were added, followed by the dropwise addition of a mixture of 6.29 parts (20.4 mmol) of N,N-dipropylethylamine and 12.6 parts of anisole. After the addition, the mixture was stirred at 70°C for 70 minutes. Next, 14.4 parts (40.8 mmol) of 4,4'-dihydroxytetraphenylmethane and 28.8 parts of anisole were added, followed by dropwise addition of a mixture of 11.6 parts (89.8 mmol) of N,N-dipropylethylamine and 11.6 parts of anisole. The mixture was stirred at 100 °C for 3 hours while blowing air into the solution. The reaction solution was then cooled to room temperature and added dropwise to 1800 ml of methanol, and the precipitated solid was collected by filtration. 70 parts of anisole was added to the collected solid to redissolve it, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was collected by filtration and dried at 50 °C for 24 hours to obtain 22.6 parts of a compound of the present invention having a structure represented by the following formula (A-8). The weight-average molecular weight was 4,000.

[0065] [ka]

[0066] Comparative Example 1 Synthesis of a compound represented by the following formula (B-1): A flask equipped with a thermometer, a condenser, an air inlet tube, and a stirrer was charged with 2.77 parts (15 mmol) of cyanuric chloride, 10.7 parts (60 mmol) of 2-hydroxymethyl methacrylate, 27 parts of 4-methyltetrahydropyran, and 3.11 parts (22.5 mmol) of potassium carbonate, and the mixture was stirred at 80 ° C. for 1 hour. After stirring at 100 ° C. for 1 hour, 24 parts of 1-methyl-2-pyrrolidone was added, and the mixture was stirred at 120 ° C. for 2 hours. After that, 200 parts of water was added to the reaction liquid cooled to room temperature, and the solid was collected by filtration. 80 parts of methanol was added to the collected solid, and the mixture was stirred and washed. The solid was then collected by filtration and dried at 50 ° C. for 24 hours to obtain 5.6 parts of a compound represented by the following formula (B-1).

[0067] [ka]

[0068] Comparative Example 2 Synthesis of a compound represented by the following formula (B-2): A flask equipped with a thermometer, condenser, air inlet, and stirrer was charged with 11.1 parts (60 mmol) of cyanuric chloride, 7.33 parts (60 mmol) of 4-ethylphenol, and 54 parts of anisole, and the mixture was ice-cooled while stirring. A mixture of 8.53 parts (66 mmol) of N,N-dipropylethylamine and 17.1 parts of anisole was added dropwise to the ice-cooled anisole solution at a rate such that the temperature did not exceed 10°C. After the addition, the mixture was stirred at room temperature for 60 minutes. Subsequently, 20.2 parts (60 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 61 parts of anisole were added, followed by the dropwise addition of a mixture of 17.1 parts (132 mmol) of N,N-dipropylethylamine and 34.1 parts of anisole. The mixture was stirred at 100°C for 3 hours while blowing air into the solution. The reaction mixture was then cooled to room temperature and added dropwise to 1500 mL of methanol, and the precipitated solid was collected by filtration. The recovered solid was redissolved in 120 parts of anisole, and the resulting solution was added dropwise to 1000 ml of methanol. The precipitated solid was recovered by filtration and dried at 50°C for 24 hours to obtain 14.6 parts of a compound having the structure represented by the following formula (B-2). The weight-average molecular weight was 7,210.

[0069] [ka]

[0070] Examples 9 to 16 and Comparative Examples 3 to 4 (Preparation of Compositions of the Present Invention) The components were blended in the component ratios (parts by mass) shown in Table 1 to prepare compositions of the present invention. The materials used in preparing the compositions are shown below. (triazine compounds) Compounds synthesized in Examples 1 to 8 and Comparative Examples 1 and 2. (Photopolymerization initiator) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (BASF Japan, "IRGACURE OXE-02") (solvent) Anisole, 4-formylmorpholine and 1-methyl-2-pyrrolidone

[0071] The compositions of Examples 9 to 16 and Comparative Examples 3 and 4 were evaluated as follows. The results are summarized in Table 1.

[0072] (Evaluation of film-forming properties of the composition) Using a spin coater, each of the compositions obtained in Examples 9 to 16 and Comparative Examples 3 and 4 was applied to a silicon substrate and dried at 95°C for 2 minutes to form a composition layer having a thickness of 5 to 20 μm on the silicon substrate. ◯: The surface was smooth. ×: The surface was not smooth.

[0073] (Evaluation of photocurability of composition) The silicon substrate having the composition layer obtained in the previous section was exposed to 300 mJ / cm using an ultraviolet light exposure device (USHIO, ultra-high pressure mercury lamp). 2After exposure at 400°C, the substrate was further heated at 95°C for 5 minutes. The silicon substrate was cooled to room temperature and immersed in propylene glycol monomethyl ether acetate, and the surface of the composition layer was visually inspected to evaluate the photocurability according to the following evaluation criteria. ◯: The exposed area did not dissolve. ×: The exposed area was dissolved.

[0074] (Preparation of the composition film of the present invention) Each of the compositions of Examples 9 to 16 and Comparative Example 4 was applied to a copper foil having a thickness of 18 μm using an applicator, and then dried at 100° C. for 5 minutes to form a composition layer having a thickness of 10 to 20 μm on the copper foil. The composition layer on the copper foil thus obtained was then exposed to light at a wavelength of 365 nm using a conveyor UV irradiation device CS30L-1-1 manufactured by GS Yuasa Corporation at an exposure dose of 350 to 400 mJ / cm. 2 Then, the copper foil was heated at 200° C. for 60 minutes to form a polymer film on the copper foil. The copper foil was then removed by etching to obtain the cured film of the present invention.

[0075] (Evaluation of the glass transition temperature (Tg) of the cured film) Measurements were performed using a dynamic viscoelasticity measuring device (DMA) (TA Instruments RSA-G2) (frequency 1 Hz, tensile mode, heating rate 3°C / min), and the glass transition temperature was determined from the maximum value of the loss tangent (tanδ). 〇: 200℃ or higher ×: Less than 200℃

[0076] (Evaluation of the dielectric properties of the cured film (dielectric constant: Dk, dielectric loss tangent: Df)) The cured film was dried at 120°C for 1 hour and then measured using a split cylinder resonator CR-710 (manufactured by EM Lab Co., Ltd.) under the measurement conditions of a frequency of 10 GHz and a temperature of 25°C. 〇: Dk less than 3.3, Df less than 0.01 ×: Dk 3.3 or more, Df 0.01 or more

[0077] [Table 1]

[0078] As is clear from the results shown in Table 1, the compound of the present invention having a structural unit represented by formula (1) can be photocured, and the cured product exhibits excellent heat resistance and dielectric properties.

Claims

1. A compound having a structure represented by the following formula (1): 【Chemical 1】 (In formula (1), R １ represents a divalent linking group, and R １ If there are multiple R １ may be the same or different. ２ represents a monovalent linking group, and R ２ If there are multiple R ２ may be the same or different, and at least one of them contains an acrylate group or a methacrylate group. １ , X ２ and Y １ represents a direct bond or a divalent linking group, and when a plurality of X's are present in a compound, they may be the same or different. １ , X ２ and at least one of Y1 contains an oxygen atom. １ and Z ２ represents a monovalent linking group.

2. X １ , X ２ and Y １ The compound according to claim 1, wherein is —O— or —NH—.

3. R ２ The compound according to claim 1, wherein at least one of the following is a structure selected from the following formulas (a), (b), (c), and (d): 【Chemistry 2】

4. A composition comprising the compound of claim 4.

5. A dry film comprising a composition comprising the compound according to any one of claims 1 to 3.

6. A cured product of a composition comprising the composition according to claim 4 or the cured product according to claim 6.

7. A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film for a rewiring layer, which comprises the composition according to claim 4 or the cured product according to claim 6.

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