Resin compositions, cured products, and electronic components

Abstract

The present invention provides a resin component that exhibits various properties when applied to a resin composition, a resin composition containing the resin component, and a cured product and electronic component obtained from the resin composition. [Solution] A resin composition according to one aspect of the present invention is a polyimide sulfide having the structure shown in the following formula (1). [Formula 1] TIFF2026119955000028.tif47170{In formula (1), R1 and R2 each represent independent groups, and R2 is a group having an ethylenically unsaturated double bond.}

Description

[Technical Field]

[0001] This invention relates to resin compositions, cured products, and electronic components. [Background technology]

[0002] Bismaleimide-derived resins are used in a variety of applications due to their high heat resistance and low dielectric properties. They have been used conventionally. As an example of such a resin, Non-Patent Document 1 discloses a polyimide sulfide (polyimide thioether) having a predetermined structure and excellent transparency and solvent solubility. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] J.Mater.Chem.,2010,20,4080-4084 [Overview of the initiative] [Problems that the invention aims to solve]

[0004] However, when conventional polyimide sulfides were incorporated into resin compositions, their performance (for example, solvent resistance or mechanical strength of the cured product obtained from the resin composition) was sometimes insufficient.

[0005] The present invention addresses the above-mentioned problems and aims to provide a resin component that exhibits various properties when applied to a resin composition, a resin composition containing the resin component, and a cured product and electronic component obtained from the resin composition. [Means for solving the problem]

[0006] One aspect of the present invention is polyimide sulfide. The aforementioned polyimide sulfide includes the structure shown in formula (1) below. [ka] {In formula (1), R1 and R2 each represent an independent group, and R2 is a group having an ethylenically unsaturated double bond.}

[0007] Preferably, R2 has a structure represented by the following formula (2).

Chemical formula

[0008] Another aspect of the present invention is a resin composition comprising the polyimide sulfide and a radical generator.

[0009] Preferably, the radical generator is a photo radical generator.

[0010] Preferably, the resin composition contains a crosslinking agent.

[0011] Yet another aspect of the present invention is a cured product obtained by curing the resin composition.

[0012] Yet another aspect of the present invention is an electronic component comprising a resin layer obtained from the resin composition or the cured product.

Advantages of the Invention

[0013] According to the present invention, it is possible to provide technologies related to resin components that exhibit various performances when applied to a resin composition, the resin composition containing the resin components, and cured products and electronic components obtained from the resin composition.

Brief Description of the Drawings

[0014] [Figure 1] 1H NMR chart of polyimide sulfide 1 synthesized in the examples. [Figure 2] 1H NMR chart of polyimide sulfide 2 synthesized in the examples. [Figure 3] This is the 1H NMR chart of polyimide sulfide 3 synthesized in the example. [Figure 4] This is the 1H NMR chart of polyimide sulfide 4 synthesized in the example. [Figure 5] This is the 1H NMR chart of polyimide sulfide 6 synthesized in the example. [Modes for carrying out the invention]

[0015] In this disclosure, if isomers exist for the compounds described, all possible stereoisomers are available for use in this disclosure unless otherwise specified.

[0016] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined by gel permeation chromatography (GPC). More specifically, the measurement is performed under the following conditions, for example. (Measurement conditions) Device name: e2695 (manufactured by Waters) Mobile phase: Chloroform Column: Shodex K-805L Column temperature: 40℃ Flow rate: 1.0mL / min Detector: 2414 (RI detector, Waters, wavelength 410nm) Sample concentration: 1.0 mg / mL Sample solvent: Same as the mobile phase. STD reagent: Standard polystyrene STD concentration: 1.0mg / mL STD solvent: Same as mobile phase. Analysis time: 20min

[0017] Where the upper and lower limits of a numerical range are described separately in this disclosure, all combinations of each lower limit and each upper limit shall be substantially described to the extent that they are not inconsistent.

[0018] In this disclosure, when multiple compounds that can be used as a component are given as examples, this includes both forms in which one selected from the multiple compounds is used alone, and forms in which two or more arbitrary compounds selected from the multiple compounds are used in combination.

[0019] The following describes the polyimide sulfide relating to this disclosure, the resin composition containing the polyimide sulfide relating to this disclosure, and the cured products obtained using the resin composition.

[0020] <<<Polyimide sulfide>>> Polyimide sulfides include structures represented by the following formula (1).

[0021] [ka]

[0022] In formula (1), R1 and R2 represent independent groups, and R2 is a group having an ethylenically unsaturated double bond.

[0023] Thus, the polyimide sulfide according to this disclosure has a predetermined backbone and includes a group having an ethylenically unsaturated double bond. By using such a polyimide sulfide, it becomes possible to crosslink the group having an ethylenically unsaturated double bond, so that when used in a resin composition, it is possible to obtain a resin composition that exhibits various properties, such as excellent solvent resistance or mechanical strength, while maintaining the excellent properties of the polyimide sulfide. Furthermore, such a polyimide sulfide is preferably applicable as a thermosetting resin composition or a photocurable resin composition.

[0024] In addition, the polyimide sulfide may contain a structure other than the structure represented by the formula (1). For example, it may contain a structure similar to the structure represented by the formula (1) except that R2 is a group having no ethylenically unsaturated double bond. When the polyimide sulfide contains a structure other than the structure represented by the formula (1), the ratio of the number of structural units represented by the formula (1) in the repeating units contained in the polyimide sulfide is preferably 30% or more, 50% or more, 70% or more, 90% or more, or 95% or more.

[0025] Next, specific examples of R1 and R2 will be described.

[0026] R1 is a residue of bismaleimide and is preferably a structure represented by the following formula (3). Further, R1 may be a structure in which the aromatic ring in the following formula (3) is hydrogenated (the aromatic ring bonded to R , A , A , , , I , E , ,

[0028] , , , B , A , A ,

[0027] , , F , , ~R E and the aromatic ring bonded to R F ~R I are substituted with cyclohexyl rings).

[0027]

Chemical formula

[0028] In the formula (3), R A is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, or an organic group having 1 to 15 carbon atoms. R A is, for example, a hydrocarbon group having 1 to 15 carbon atoms which may contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom). R A may contain a ring structure (aromatic ring, aliphatic ring, heterocyclic ring). R A is preferably a hydrocarbon group having 1 to 5 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, a hydrocarbon group having 1 to 2 carbon atoms, or a methylene group. In the formula (2), R B , R E , R F , R IEach of these is independently hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and hydrogen is preferred. In formula (2), R C , R D , R G , R H Each of these is independently hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 2 carbon atoms. * indicates a bond.

[0029] R A ~R I If the hydrocarbon group is a hydrocarbon group, these hydrocarbon groups may have an ethylenically unsaturated double bond.

[0030] R2 is preferably a group having an ethylenically unsaturated double bond with 1 to 25 carbon atoms (preferably 1 to 20 or 1 to 15), which may contain a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom).

[0031] More specifically, R2 is preferably the structure shown in formula (2) below.

[0032] [ka] In formula (2), R3 represents a monovalent group having an ethylenically unsaturated double bond, and * represents a bond.

[0033] R3 is a group having an ethylenically unsaturated double bond, which may contain, for example, a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom). In this case, the number of carbon atoms in R3 is preferably 2 or more, 3 or more, or 5 or more, and preferably 20 or less, 15 or less, or 12 or less.

[0034] In formula (2), R3 is preferably the group shown in formula (4) below.

[0035] [ka]

[0036] In formula (4), R X , R Y Each of these is independently a hydrocarbon group having a structure in which the terminal end of an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 or 2 to 4 carbon atoms), an alkenyl group having 1 to 10 carbon atoms (preferably 2 to 4 carbon atoms), or an alkyl group having 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms) is substituted with a styryl group or an allylphenyl group, R X , R Y At least one of these is a hydrocarbon group having a structure in which the terminal of an alkyl group having 1 to 10 carbon atoms (preferably 2 to 4 carbon atoms) is substituted with a styryl group or an allylphenyl group. From the viewpoint of improving the i-ray permeability of polyimide sulfide, X , R Y Each of these is preferably an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 or 2 to 4 carbon atoms) or an alkenyl group having 1 to 10 carbon atoms (preferably 2 to 4 carbon atoms).

[0037] Thus, the inclusion of a 1,3,5-triazine ring structure in polyimide sulfide can result in superior performance, such as i-ray permeability. Furthermore, the inclusion of a 1,3,5-triazine ring structure in polyimide sulfide can improve heat resistance.

[0038] The weight-average molecular weight of the polyimide sulfide is preferably 1,000 or more, 3,000 or more, or 5,000 or more, and also preferably 200,000 or less, 100,000 or less, or 50,000 or less. Furthermore, the number-average molecular weight of the polyimide sulfide is preferably 1,000 or more, 2,000 or more, or 3,000 or more, and also preferably 100,000 or less, 50,000 or less, or 20,000 or less.

[0039] <<Synthesis of Polyimide Sulfides>> The polyimide sulfide relating to this disclosure can be synthesized using a bismaleimide represented by the following formula (5) and a compound having two thiol groups (a difunctional thiol) represented by the following formula (6) as raw materials.

[0040] [ka]

[0041] In equation (5), R1 is the same as R1 in equation (1).

[0042] [ka]

[0043] In equation (6), R2 is the same as R2 in equation (1).

[0044] Thus, R1 and R2 in formula (1) can also be expressed as residues in bismaleimide and a difunctional thiol used in the synthesis of polyimide sulfides, respectively. Therefore, in other words, the polyimide sulfide according to this disclosure can also be expressed as a compound obtained by reacting bismaleimide with a difunctional thiol having an ethylenically unsaturated double bond. Furthermore, the polyimide sulfide may also be a compound obtained by further reacting a difunctional thiol that does not have an ethylenically unsaturated double bond.

[0045] The following describes bismaleimide and difunctional thiols, which are the raw materials for polyimide sulfide, as well as the synthesis conditions for polyimide sulfide.

[0046] <Bismareimide> Specific examples of bismaleimides include 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, triethylene glycol bis(maleimide ethyl carbonate), bis(3-ethyl-5-methyl-4-maleimoidphenyl)methane, 4,4-bismaleimide diphenyl ether, 2,2-bis[4-(4-maleimoidphenoxy)phenyl]propane, 4,4'-bismaleimide diphenylamine, N,N'-dodecamethylenebismaleimide, 1-maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane, N,N' -p-phenylenebismaleimide, 1,1'-(cyclohexane-1,3-diylbis(methylene))bis(1H-pyrrole-2,5-dione), 1,1'-(4,4'-methylenebis(cyclohexane-4,1-diyl))bis(1H-pyrrole-2,5-dione), 1,1'-(3,3'-(piperazine-1,4-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2, Examples include 5-dione, 1,2-bis(maleimide)ethane, N-succinimidyl-3-maleimidepropionate, succinimidyl-4-(N-maleimidemethyl)cyclo-hexane-1-carboxylate, 1,2-bis(maleimide)butane, 1,2-bis(maleimide)hexane, N,N'-1,4-phenylenedimaleimide, and bis(2-maleimideethyl)disulfide. Maleimide compounds described in Japanese Patent Application Publication No. 2022-99579 can also be used.

[0047] Furthermore, by substituting or modifying any part of such bismaleimide with a group having an ethylenically unsaturated double bond, it is also possible to obtain a bismaleimide with an ethylenically unsaturated double bond.

[0048] In other words, bismaleimide may be a compound represented by the following formula (7). Also, bismaleimide may be a structure in which the aromatic ring in the following formula (7) is hydrogenated (R B ~R E The aromatic ring and R that are bonded to it F ~R I The compound may also have a structure in which the aromatic ring bonded to it is replaced by a cyclohexyl ring.

[0049] [ka]

[0050] In formula (7), R A ~R I This is as previously stated.

[0051] <Bifunctional Thiol> A difunctional thiol is a compound having two thiol groups in one molecule. Difunctional thiols are not particularly limited and include alkyl thiol compounds; polyethers having terminal thiol groups; polythioethers having terminal thiol groups; thiol compounds obtained by the reaction of epoxy compounds with hydrogen sulfide; thiol compounds obtained by the reaction of polythiol compounds with epoxy compounds; ester compounds of polyols and mercapto organic acids; mercapto-modified (meth)acrylates; and the like.

[0052] Specific examples of difunctional thiols that do not have a group with an ethylenically unsaturated double bond include 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 2,2'-thiobisethanethiol, ethylene glycol bisthioglycolate, tetraethylene glycol bis(3-mercaptopropionate), 1,4-benzenedithiol, p-xylenedithiol, m-xylenedithiol, 4,4'-biphenyldithiol, bis(4-mercaptophenyl) sulfide, 5-dimethyl-o-xylenedithiol, and 1,5-naphthalenedithiol.

[0053] Furthermore, by substituting or modifying any part of such a difunctional thiol with a group having an ethylenically unsaturated double bond, a difunctional thiol with an ethylenically unsaturated double bond can also be obtained.

[0054] Alternatively, the difunctional thiol may be a compound represented by the following formula (8) or (9).

[0055] [ka]

[0056] In formula (8), R3 is as described above. The compound represented by formula (8) corresponds to a difunctional thiol having an ethylenically unsaturated double bond.

[0057] [ka]

[0058] In formula (9), R4 is a monovalent group that does not have an ethylenically unsaturated double bond, for example, the group represented by formula (4) and R X , R Y However, it is preferable that both are alkyl groups. The compound represented by formula (9) corresponds to a difunctional thiol that does not have an ethylenically unsaturated double bond.

[0059] <Synthesis conditions> The synthesis of polyimide sulfides (reaction of bismaleimide with a difunctional thiol) can be carried out in an organic solvent.

[0060] The organic solvent is not particularly limited, and known organic solvents can be used. Examples include amide organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF); alcohol organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester organic solvents such as ethyl acetate, butyl acetate, and ethyl lactate; ether organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon compound organic solvents such as benzene, toluene, and xylene.

[0061] The reaction between bismaleimide and a difunctional thiol can be carried out, for example, in the presence of a base and a nucleophile at 0-50°C for 1 minute to 10 hours. Examples of bases include amines (e.g., triethylamine, n-hexylamine), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), and alkoxide salts (e.g., sodium methoxide). Examples of nucleophiles include phosphines (e.g., triphenylphosphine, dimethylphenylphosphine, tributylphosphine).

[0062] <<<Resin composition>>> The resin composition according to this disclosure comprises a polyimide sulfide. Preferably, the resin composition according to this disclosure further comprises a radical generator. The resin composition according to this disclosure may also contain other components.

[0063] <<Polyimide sulfide>> As previously mentioned, polyimide sulfides are as described above, so a detailed explanation will be omitted.

[0064] The polyimide sulfide content in the resin composition is, for example, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total solid content of the resin composition (excluding the content of fillers if the resin composition contains fillers).

[0065] <<Radical Generator>> When the resin composition is a photocurable resin composition, it is preferable that the resin composition contains a radical generator. A photoradical generator is a compound that generates radicals when irradiated with light such as ultraviolet light.

[0066] Examples of photoradical generators include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; Alpha-hydroxy ketones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; Alpha-aminoketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; Oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octadione-2-(benzoyl)oxime; Phosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4- Benzophenone compounds such as toxic-4'-dimethylaminobenzophenone; Quinone compounds such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; Benzyl compounds such as benzyldimethyl ketal; Acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-phenylglycine; Coumarin; and others are examples.

[0067] The amount of photoradical generator is preferably 0.01 to 20 parts by mass, 0.05 to 10 parts by mass, or 0.10 to 5 parts by mass per 100 parts by mass of the solid content of polyimide sulfide in the resin composition.

[0068] Furthermore, when the resin composition is a thermosetting resin composition, it is preferable that the resin composition contains a thermal radical generator. A thermal radical generator is a compound that generates radicals when heated.

[0069] Examples of thermal radical generators include peroxides. Peroxides include methyl ethyl ketone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, 2,5- Examples include dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-butene, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxydicarbonate, t-butylene peroxybenzoate, di-t-butyl peroxide, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy-m-isopropyl)benzene.

[0070] The amount of thermal radical generator is preferably 0.01 to 20 parts by mass, 0.05 to 10 parts by mass, or 0.10 to 5 parts by mass per 100 parts by mass of the solid content of polyimide sulfide in the resin composition.

[0071] <<Crosslinking agent>> The resin composition relating to this disclosure preferably contains a crosslinking agent. The crosslinking agent is not particularly limited, but examples include one or more selected from compounds having two or more thiol groups (polyfunctional thiols) and compounds having two or more vinyl groups (polyfunctional vinyl compounds).

[0072] When the resin composition is a photocurable resin composition, it is preferable to include a polyfunctional thiol as a crosslinking agent from the viewpoint of improving solvent resistance after curing.

[0073] Polyfunctional thiols are not particularly limited as long as they are compounds having two or more thiol groups in a single molecule. Examples of difunctional thiols among polyfunctional thiols include the same difunctional thiols used in the synthesis of polyimide sulfides described above. The polyfunctional thiol may be the same compound as the difunctional thiol that constitutes the polyimide sulfide, or it may be a different compound.

[0074] Examples of polyfunctional thiols with three or more functions include 1,3,5-trimercaptobenzene, trimethylolpropanetris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritoltetrakis(3-mercaptopropionate), and dipentaerythritolhexakis(3-mercaptopropionate).

[0075] The polyfunctional thiol is preferably a compound containing an ester bond. Furthermore, the polyfunctional thiol is preferably a compound with three or more functions.

[0076] The polyfunctional thiol is particularly preferably trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropineauto), or dipentaerythritolhexakis(3-mercaptopropionate).

[0077] The polyfunctional thiol content is preferably 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, and also preferably 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less, based on the solid content of polyimide sulfide in the resin composition.

[0078] Furthermore, the ratio [(C=C) / SH] of the number of ethylenically unsaturated double bond functional groups in the polyimide sulfide bismaleimide in the resin composition to the number of thiol functional groups in the polyfunctional thiol in the resin composition is preferably 0.50 or more, 0.60 or more, or 0.75 or more, and preferably 20 or less, 10 or less, or 5 or less.

[0079] When the resin composition is a thermosetting resin composition, it is preferable to include a polyfunctional vinyl compound as a crosslinking agent from the viewpoint of obtaining a cured product with excellent mechanical strength.

[0080] Preferred polyfunctional vinyl compounds include aromatic vinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl; vinylbenzyl ether compounds synthesized from the reaction of phenol and vinylbenzyl chloride; styrene monomers; allyl ether compounds synthesized from the reaction of phenol and allyl chloride; and trialkenyl(iso)cyanurate. As a crosslinking agent, trialkenyl(iso)cyanurate is preferred, and among these, triallyl isocyanurate (hereinafter referred to as TAIC®) and triallyl cyanurate are particularly preferred. These exhibit low dielectric properties and can enhance heat resistance.

[0081] The content of the polyfunctional vinyl compound is preferably 1 to 100 parts by mass, and more preferably 20 to 80 parts by mass, based on the solid content of polyimide sulfide in the resin composition.

[0082] <<Other ingredients>> Other components may include photosensitive agents (photoacid generators, photobase generators), fillers, adhesives, surfactants, plasticizers, thermoacid generators, sensitizers, leveling agents, colorants, fibers, etc.

[0083] Furthermore, the resin composition may contain a solvent. In addition to the organic solvents that can be used in the reaction between bismaleimide and difunctional thiols described above, examples of conventionally known solvents include chloroform, methylene chloride, propylene glycol monomethyl ether acetate (PMA), and diethylene glycol monoethyl ether acetate (CA).

[0084] The filler may include organic or inorganic fillers. Examples of organic fillers include imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; and organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyoxybenzoate, and polyoxybenzoate. Examples of inorganic fillers include clay minerals such as talc, mica, sericite, and montmorillonite; metal oxides such as silica, alumina, and titanium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; fillers having a ferrobskite-type crystal structure such as barium titanate and strontium titanate; and boron nitride, aluminum borate, barium sulfate, and calcium carbonate. The filler is preferably silica.

[0085] If the resin composition contains fillers, the filler content is, for example, 1 to 99% by mass, 10 to 90% by mass, or 20 to 80% by mass, relative to the total solid content of the resin composition.

[0086] <<Dry Film>> The resin composition relating to this disclosure is suitable for coating in the form of a varnish, and a dry film can be produced by applying the varnish onto a substrate and drying it to form a resin layer.

[0087] As a base material, for example, a polyester film such as polyethylene terephthalate can be used. Furthermore, the thickness of the resin layer of the dry film can be, for example, 1 to 100 μm.

[0088] <<Cured film>> The cured film according to this disclosure can be formed by heat curing or photocuring, etc., after applying and drying the resin composition described above, or after laminating the dry film onto a substrate.

[0089] <<Electronic Components>> The electronic component relating to this disclosure has a resin layer obtained from the cured product or resin composition described above. Because the resin layer obtained from the cured product or resin composition relating to this disclosure exhibits low dielectric properties, it can be used as a material for electronic components in various applications. Furthermore, because the cured product relating to this disclosure has excellent solvent resistance, it can also be used for pattern formation applications using photolithography.

[0090] The applications of the electronic components relating to this disclosure are not particularly limited, but preferably include insulating materials in electronic components such as high-capacity, high-speed communication systems like fifth-generation communication systems (5G) and millimeter-wave radar for automotive ADAS (Advanced Driver-Assistance Systems).

[0091] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. [Examples]

[0092] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0093] <<<Synthesis of polyimide sulfides>>> <<Raw materials>> <Bismareimide> • Bismaleimide 1: BMI-70 Bismaleimide represented by the following formula (10), manufactured by K.I. Chemicals Co., Ltd. [ka]

[0094] <Bifunctional Thiol> • 2 functional thiol 1: VBATDT A dithiol containing a 1,3,5-triazine ring, represented by the following formula (11), manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0095] • 2 functional thiols: DATD A dithiol containing a 1,3,5-triazine ring, represented by the following formula (12), manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0096] • 2 functional thiols 3: MPS Dithiol [bis(4-mercaptophenyl) sulfide] represented by the following formula (13), manufactured by Tokyo Chemical Industry Co., Ltd. [ka]

[0097] • 2 functional thiols 4: IBSH A dithiol containing a 1,3,5-triazine ring, represented by the following formula (14), manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0098] <<Synthesis of Polyimide Sulfides>> <Polyimide sulfide 1> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 1 (VBATDT) was used as the difunctional thiol. VBATDT 1.45 g (4.55 mmol), BMI-70 (manufactured by K.I. Chemicals Co., Ltd.) 2.03 g (4.58 mmol), THF 28 mL as solvent, and Et3N 0.10 mL as base were prepared and mixed in a 120 mL vial, and the reaction described below was carried out. After stirring at room temperature for 4.4 hours, the mixture was diluted with 18 mL of THF and reprecipitation was performed using 400 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum dried (70°C, 8 hours) to obtain 3.12 g (90% yield) of pale yellow polyimide sulfide (solid). The obtained polyimide sulfide 1 had a weight-average molecular weight of 38,400 and a number-average molecular weight of 11,500. 1 The 1H NMR chart is shown in Figure 1.

[0099] [ka]

[0100] <Polyimide Sulfide 2> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 2 (DATD) was used as the difunctional thiol. 0.64 g (2.66 mmol) of DATD, 1.20 g (2.71 mmol) of BMI-70 (manufactured by K.I. Chemicals Co., Ltd.), 15 mL of THF as solvent, and 0.03 mL of Et3N as base were prepared and mixed in a 50 mL vial, and the reaction described below was carried out. After stirring at room temperature for 4.5 hours, the mixture was diluted with 11 mL of THF and reprecipitation was performed using 180 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum dried (90°C, 15 hours) to obtain 1.69 g (91% yield) of pale yellow polyimide sulfide (solid). The obtained polyimide sulfide 2 had a weight-average molecular weight of 49,000 and a number-average molecular weight of 16,000. 1 The 1H NMR chart is shown in Figure 2.

[0101] [ka]

[0102] <Polyimide Sulfide 3> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 2 (DATD) and difunctional thiol 3 (MPS) were used as the difunctional thiols. 0.74 g (2.94 mmol) of bis(4-mercaptophenyl) sulfide, 1.63 g (3.68 mmol) of BMI-70 (manufactured by K.I. Chemicals Co., Ltd.), 12 mL of THF as solvent, and 0.03 mL of Et3N as base were prepared and mixed in a 50 mL vial, and the reaction described below was carried out. The mixture was stirred at room temperature for 4.2 hours. Then, 0.16 g (0.53 mmol) of VBATDT was stirred at room temperature for 3.1 hours, diluted with 20 mL of THF, and reprecipitation was performed using 350 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum dried (40°C, 4 hours) to obtain 2.15 g (83% yield) of pale yellow polyimide sulfide (solid). The obtained polyimide sulfide 3 had a weight-average molecular weight of 27,200 and a number-average molecular weight of 98,000. 1 The 1H NMR chart is shown in Figure 3.

[0103] [ka]

[0104] In equation (17), m / n is 4.9.

[0105] <Polyimide Sulfide 4> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 3 (DATD) and difunctional thiol 3 (MPS) were used as the difunctional thiols. 0.72 g (2.88 mmol) of bis(4-mercaptophenyl) sulfide, 1.59 g (3.59 mmol) of BMI-70 (manufactured by K.I. Chemicals Co., Ltd.), 12 mL of THF as solvent, and 0.03 mL of Et3N as base were prepared and mixed in a 50 mL vial, and the reaction described below was carried out. The mixture was stirred at room temperature for 4.2 hours. Then, 0.17 g (0.69 mmol) of DATD was stirred at room temperature for 2.8 hours, diluted with 23 mL of THF, and reprecipitation was performed using 350 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum dried (40°C, 4 hours) to obtain 1.95 g (79% yield) of pale yellow polyimide sulfide (solid). The obtained polyimide sulfide 4 had a weight-average molecular weight of 39,100 and a number-average molecular weight of 15,900. 1 The 1H NMR chart is shown in Figure 4.

[0106] [ka]

[0107] In equation (18), m / n is 4.6.

[0108] <Polyimide sulfide 5> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 3 (MPS) was used as the difunctional thiol. 5.00 g (11.3 mmol) of BMI-70, 2.75 g (11.0 mmol) of MPS, 64 mL of THF as solvent, and 0.40 mL of Et3N as base were prepared. The starting materials were mixed in a 120 mL vial, and the reaction described below was carried out. After stirring at room temperature for 4.1 hours, the mixture was diluted with 15 mL of THF and reprecipitation was performed using 500 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum-dried (90°C, 16 hours) to obtain 7.38 g (95% yield) of pale yellow polyimide sulfide 4 (solid) represented by formula (16). The obtained polyimide sulfide 5 had a weight-average molecular weight of 25,400 and a number-average molecular weight of 9,100.

[0109] [ka]

[0110] <Polyimide sulfide 6> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and difunctional thiol 4 (IBSH) was used as the difunctional thiol. 1.24 g (4.55 mmol) of IBSH, 2.05 g (4.63 mmol) of BMI-70 (manufactured by K.I. Chemicals Co., Ltd.), 26 mL of THF as solvent, and 0.10 mL of Et3N as base were prepared and mixed in a 120 mL vial, and the reaction described below was carried out. After stirring at room temperature for 4.7 hours, the mixture was diluted with 7 mL of THF and reprecipitation was performed using 400 mL of MeOH. After filtration using a Kiriyama funnel, the mixture was vacuum dried (70°C, 8 hours) to obtain 2.98 g (91% yield) of pale yellow polyimide sulfide (solid). The obtained polyimide sulfide 6 had a weight-average molecular weight of 25,400 and a number-average molecular weight of 10,900. 1 The 1H NMR chart is shown in Figure 5.

[0111] [ka]

[0112] <<<Thermosetting resin composition>>> <<Raw materials>> <Thermal radical generator> • Perbutyl P40 (manufactured by NOF Corporation, peroxide)

[0113] <Crosslinking agent> TAIC (manufactured by Mitsubishi Chemical Corporation)

[0114] <Solvent> Cyclohexanone

[0115] <<Preparation of Thermosetting Resin Compositions>> As shown in Table 1, a cyclohexanone solution was prepared using only polyimide sulfide, and varnishes of the resin compositions according to Example 1 and Comparative Example 1 were prepared.

[0116] Furthermore, as shown in Table 2, 100 parts by mass of polyimide sulfide, 5 parts by mass of a thermal radical generator, and 50 parts by mass of a crosslinking agent were mixed and stirred in cyclohexanone to prepare varnishes of thermosetting resin compositions according to Examples 2-5 and Comparative Examples 2 and 3.

[0117] <<Evaluation of Thermosetting Resin Compositions>> <Film forming properties> The film-forming properties were evaluated as follows. A resin composition or thermosetting resin composition varnish was applied to copper foil using an applicator with a gap of 200 μm. Next, it was dried in a hot air circulating drying oven at 90°C for 5 minutes. After that, the temperature was raised to 200°C in an inert oven under a well-purged nitrogen atmosphere and cured for 1 hour to obtain a cured film on the copper foil. The copper foil was removed from the obtained cured film on the copper foil by etching to obtain a self-supporting cured film. The film formation performance of the process for obtaining the self-supporting cured film was evaluated according to the following criteria. ○: No cracks or unevenness were observed in the self-supporting hardened film. ×: Cracks occurred in the hardened film on the copper foil, making it impossible to obtain a self-supporting film.

[0118] In Comparative Example 1, the cured film cracked, and a self-supporting film could not be obtained, so no further evaluation was performed.

[0119] <Dielectric properties> The relative permittivity Dk and dielectric loss tangent Df were measured according to the following method. For the film formation evaluation, self-supporting cured films were cut into 80 mm length and 45 mm width sections and measured using the SPDR (Split Post Dielectric Resonator) method. The measurement equipment used was a Keysight Technologies LLC E5071C vector network analyzer, an SPDR resonator, and a calculation program from QWED. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0120] <modulus of elasticity> In the film formation evaluation, a self-supporting cured film was cut to a length of 7 cm and a width of 0.5 cm, and the stress-strain diagram was measured under the following conditions. The elastic modulus was determined from the slope of the strain in the obtained stress-strain diagram at stresses from 5 MPa to 10 MPa. [Measurement conditions] Testing machine: Tensile testing machine EZ-SX (manufactured by Shimadzu Corporation) Chuck spacing: 50mm Test speed: 1 mm / min

[0121] <tg> In the film formation evaluation, a self-supporting cured film was cut to a length of 30 mm and a width of 5 mm, and the glass transition temperature (Tg) was measured using an RSA-G2 (TA Instruments). The temperature range was 30 to 280°C, the heating rate was 5°C / min, the frequency was 1 Hz, the strain was 0.1%, the load was 0.5 N, and the distance between the grips was 10 mm. The glass transition temperature (Tg) was defined as the temperature at which tanδ showed a maximum.

[0122] [Table 1]

[0123] [Table 2]

[0124] From the above, it is understood that by using the polyimide sulfide according to this disclosure, it is possible to improve performance such as elastic modulus while maintaining excellent heat resistance and dielectric properties.

[0125] <<<Photocurable resin composition>>> <<Raw materials>> <Photoradical Generator> NCL-730 Oxime ester-based photoradical generator, manufactured by ADEKA Corporation.

[0126] <Crosslinking agent> ·TMMP Trimethylolpropanetris (3-mercaptopropionate)

[0127] <Solvent> Cyclopentanone

[0128] <<<Preparation of Photocurable Resin Composition>>> Varnishes of photocurable resin compositions according to Example AG and Comparative Examples A and B were prepared according to the components and formulations shown in Table 3. Note that the amounts in Table 3 represent parts by mass.

[0129] <<Evaluation of Photocurable Resin Compositions>> Each photocurable resin composition varnish was spin-coated onto a silicon substrate to a dry film thickness of approximately 3 μm, and then heat-dried at 90°C for 3 minutes. Subsequently, a contact exposure machine (UVE-251S + EL-100 (manufactured by San-ei Electric Works Co., Ltd.)) was used to expose the entire dry coating film at 2000 mJ / cm². 2 A cured product was obtained by irradiating the silicon substrate with ultraviolet light at a wavelength of 365 nm using the specified exposure dose. Subsequently, the cured product on the silicon substrate was immersed in cyclopentanone for 10 seconds and blow-dried, then immersed again in cyclopentanone for 5 seconds and blow-dried. After the second blow-drying, the solvent resistance was evaluated based on whether or not a cured film remained on the silicon substrate.

[0130] [Table 3]

[0131] From the above, it is understood that by using the polyimide sulfide relating to this disclosure, it is possible to obtain a cured product with excellent solvent resistance. [Industrial applicability]

[0132] By using the polyimide sulfide of this disclosure, a cured product with excellent performance can be obtained. For this reason, it can be suitably used as a forming material for electronic components.< / tg>

Claims

1. A polyimide sulfide containing the structure shown in formula (1) below. 【Chemistry 1】 {In formula (1), R １ , R ２ Each of these represents an independent group, R ２ This is a group having an ethylenically unsaturated double bond.

2. The aforementioned R ２ The polyimide sulfide according to claim 1, wherein the structure is represented by the following formula (2). 【Chemistry 2】 {In formula (2), R ３ * indicates a monovalent group having an ethylenically unsaturated double bond, and * indicates a bond.

3. A resin composition comprising the polyimide sulfide described in claim 1 and a radical generating agent.

4. The resin composition according to claim 3, wherein the radical generating agent is a photoradical generating agent.

5. A resin composition according to claim 3, comprising a crosslinking agent.

6. A cured product obtained by curing the resin composition according to claim 3.

7. An electronic component comprising a resin layer obtained from the resin composition according to claim 3, or a cured product according to claim 6.

Images