Resin compositions, cured products, and electronic components

Abstract

The present invention provides a polyimide sulfide having excellent i-ray permeability, a resin composition containing the polyimide sulfide, 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). [Case 1] TIFF2026119954000021.tif44170{In formula (1), R1 is a divalent organic group, and R2 is a hydrogen atom, a halogen atom, or a monovalent organic group.}

Description

[Technical Field]

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

[0002] Resins derived from bismaleimide exhibit high heat resistance and low dielectric properties, and are therefore used in a variety of applications. 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 project] [Problems that the invention aims to solve]

[0004] However, conventional polyimide sulfides did not have sufficient ultraviolet light transmittance, particularly the 365 nm wavelength ultraviolet light (i-ray) commonly used in pattern formation using photolithography. Therefore, when pattern formation was performed using a resin composition containing polyimide sulfide, there was a risk that the desired pattern shape could not be formed.

[0005] The present invention addresses the above-mentioned problems and aims to provide a polyimide sulfide having excellent i-ray permeability, a resin composition containing the polyimide sulfide, 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 polyimide sulfide contains a structure represented by the following formula (1). [Chemical formula] {In formula (1), R1 is a divalent organic group, and R2 is a hydrogen atom, a halogen atom, or a monovalent organic group.}

[0007] Another aspect of the present invention is a resin composition containing a polyimide sulfide.

[0008] The resin composition preferably contains a photosensitive agent.

[0009] Still another aspect of the present invention is a cured product obtained by curing the resin composition.

[0010] Still another aspect of the present invention is an electronic component including a resin layer obtained from the resin composition or the cured product. [Advantages of the Invention]

[0011] According to the present invention, it is possible to provide technologies related to a polyimide sulfide having excellent i-line transparency, a resin composition containing the polyimide sulfide, and a cured product and an electronic component obtained from the resin composition. [Brief Description of the Drawings]

[0012] [Figure 1] It is a 1H NMR chart of polyimide sulfide 1 synthesized in an example. [Figure 2] It is a 1H NMR chart of polyimide sulfide 2 synthesized in an example. [Figure 3] It is a 1H NMR chart of polyimide sulfide 3 synthesized in an example.

[0013] In the present disclosure, when isomers exist in the described compounds, unless otherwise specified, all possible stereoisomers that can exist are usable in the present disclosure.

[0014] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by gel permeation chromatography (GPC). More specifically, the measurement may be carried out 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

[0015] 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.

[0016] Where the present disclosure provides examples of multiple compounds that can be used as a component, this includes both forms in which one of the multiple compounds is used alone, and forms in which two or more arbitrary compounds selected from the multiple compounds are used in combination.

[0017] 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.

[0018] <<Polyimide sulfide>>> The polyimide sulfide relating to this disclosure includes a structure represented by the following formula (1).

[0019] [ka]

[0020] In formula (1), R1 is a divalent organic group, and R2 is a hydrogen atom, a halogen atom, or a monovalent organic group. The monovalent organic group may contain, for example, a heteroatom (e.g., a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom) and may have a hydrocarbon group. The number of carbon atoms in R2 is preferably 2 or more, 3 or more, or 5 or more, and preferably 20 or less, 15 or less, or 12 or less.

[0021] Thus, the polyimide sulfide according to this disclosure contains a 1,3,5-triazine ring structure. By introducing such a structure, the i-line transmittance of the polyimide sulfide can be increased. Although the mechanism is not clear, it is thought that the presence of the electron-withdrawing triazine skeleton changes the energy levels of the HOMO and LUMO, causing a lower wavelength shift in the absorption band and thus improving i-line transmittance. Furthermore, the introduction of such a rigid structure may improve heat resistance.

[0022] Herein, the polyimide sulfide according to the present disclosure may have an ethylenically unsaturated double bond in its repeating unit structure. More specifically, the polyimide sulfide according to the present disclosure may have any of the following structures as represented by formula (1): (Structure I) a structure in which R1 is a group without an ethylenically unsaturated double bond and R2 is a group with an ethylenically unsaturated double bond; (Structure II) a structure in which R1 is a group with an ethylenically unsaturated double bond and R2 is a group without an ethylenically unsaturated double bond; (Structure III) a structure in which both R1 and R2 are groups with an ethylenically unsaturated double bond; or (Structure IV) a structure in which both R1 and R2 are groups without an ethylenically unsaturated double bond.

[0023] When the polyimide sulfide according to the present disclosure has an ethylenically unsaturated double bond, it is easy to form a cured product excellent in solvent resistance, mechanical strength, etc. Further, such a polyimide sulfide is preferably applicable as a photocurable resin composition, and particularly preferably applicable as a resin composition combined with a photosensitizer or the like.

[0024] R1 is not particularly limited, and for example, it is an organic group having 1 to 25 carbon atoms which may contain a hetero atom (nitrogen atom, oxygen atom, sulfur atom, fluorine atom, etc.). R1 may contain a ring structure (aromatic ring, aliphatic ring, heterocyclic ring).

[0025] R1 is a residue of bismaleimide, and preferably has a structure represented by the following formula (2). Further, R1 may be a structure in which the aromatic rings in the following formula (2) are hydrogenated (the aromatic rings bonded to R B ~R E and the aromatic rings bonded to R F ~R I are substituted with cyclohexyl rings).

[0026]

Chemical formula

[0027] In formula (2), 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, nitrogen atom, oxygen atom, sulfur atom, or 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 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.

[0028] Returning to formula (1), if R2 is a monovalent organic group, it is preferable that R2 is the group shown in formula (3) below.

[0029] [ka]

[0030] In formula (3), 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. From the viewpoint of further improving the i-ray permeability of polyimide sulfide, R 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).

[0031] Furthermore, polyimide sulfides may contain structural units other than those shown in formula (1). For example, polyimide sulfides may contain structural units shown in formula (4) below.

[0032] [ka]

[0033] In formula (4), R 11, R 12 R is a divalent organic group. 12 It does not contain a 1,3,5-triazine ring structure. R 11 It may have the same structure as R1 in equation (1). R 12 For example, it may not contain a 1,3,5-triazine ring structure and may contain heteroatoms (e.g., nitrogen, oxygen, sulfur, or halogen atoms), and may have a hydrocarbon group having 1 to 25 carbon atoms (preferably 1 to 20 or 1 to 15 carbon atoms).

[0034] If the polyimide sulfide contains structures other than the structure shown in formula (1) (for example, the structure shown in formula (4)), it is preferable that the proportion of the repeating units in the polyimide sulfide that are structural units shown in formula (1) is 30% or more, 50% or more, 70% or more, 90% or more, or 95% or more.

[0035] 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.

[0036] <<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.

[0037] [ka]

[0038] In equation (5), R1 is the same as R1 in equation (1).

[0039] [ka]

[0040] In equation (6), R2 is the same as R2 in equation (1).

[0041] Thus, R1 and R2 in formula (1) can also be expressed as residues in bismaleimide and a difunctional thiol, respectively, used in the synthesis of polyimide sulfides.

[0042] 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.

[0043] 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.

[0044] [ka]

[0045] In formula (7), R A ~R I This is as previously stated.

[0046] <Synthesis conditions> The synthesis of polyimide sulfides (reaction of bismaleimide with a difunctional thiol) can be carried out in an organic solvent.

[0047] 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.

[0048] 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).

[0049] <<<Resin composition>>> The resin composition relating to this disclosure contains polyimide sulfide. The resin composition relating to this disclosure may also contain other components.

[0050] As previously mentioned, polyimide sulfides are as described above, so a detailed explanation will be omitted.

[0051] 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).

[0052] Other components include photosensitive agents (photoradical generators, photoacid generators, photobase generators), compounds having two or more thiol groups (polyfunctional thiols), thermal radical generators, crosslinking agents, fillers, adhesives, surfactants, plasticizers, thermal acid generators, sensitizers, leveling agents, colorants, fibers, etc.

[0053] When the resin composition is a photocurable resin composition, it is preferable that the other components include a photoradical generator. A photoradical generator is a compound that generates radicals when irradiated with light such as ultraviolet light.

[0054] 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.

[0055] 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.

[0056] 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 compounds selected from compounds having two or more thiol groups (polyfunctional thiols) and compounds having two or more vinyl groups (polyfunctional vinyl compounds).

[0057] Polyfunctional thiols are not particularly limited as long as they are compounds having two or more thiol groups in a single molecule.

[0058] The solvent resistance of the resulting cured product can be improved by using polyimide sulfide in combination with a polyfunctional thiol. The polyfunctional thiol is preferably used in the photocurable resin composition together with a photosensitive agent.

[0059] The polyfunctional thiol may be a compound containing an ester bond. Furthermore, it is preferable that the polyfunctional thiol is a compound with three or more functions. It is also preferable that the polyfunctional thiol does not contain a group having an ethylenically unsaturated double bond.

[0060] Polyfunctional thiols 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, 1,5- Examples include naphthalenedithiol, 1,3,5-trimercaptobenzene, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropineauto), or dipentaerythritol hexakis (3-mercaptopropionate), and it is preferable that one or more selected from trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropineauto), and dipentaerythritol hexakis (3-mercaptopropionate).

[0061] 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 preferably 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less, based on 100 parts by mass of the solid content of polyimide sulfide in the resin composition.

[0062] By using polyimide sulfide in combination with a polyfunctional vinyl compound, the mechanical strength and other properties of the resulting cured product can be improved.

[0063] 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.

[0064] 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.

[0065] Furthermore, the resin composition may contain a solvent. In addition to the organic solvents that can be used in the reaction between bismaleimide and polyfunctional 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).

[0066] <<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.

[0067] 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.

[0068] <<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.

[0069] <<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 polyimide sulfide relating to this disclosure has excellent i-line transparency, it can also be used for pattern formation applications using photolithography.

[0070] 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).

[0071] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. [Examples]

[0072] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0073] <<<Synthesis of polyimide sulfides>>> <<Raw materials>> <Bismareimide> • Bismaleimide 1: BMI-70 Bismaleimide represented by the following formula (8), manufactured by K.I. Chemicals Co., Ltd. [ka]

[0074] <Bifunctional Thiol> • Polyfunctional Thiol 1: VBATDT A dithiol containing a 1,3,5-triazine ring, represented by formula (9) below, manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0075] • Polyfunctional Thiol 2: DATD A dithiol containing a 1,3,5-triazine ring, represented by the following formula (10), manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0076] • Polyfunctional Thiol 3: IBSH A dithiol containing a 1,3,5-triazine ring, represented by the following formula (11), manufactured by Kawaguchi Chemical Industry Co., Ltd. [ka]

[0077] • Polyfunctional Thiol 4:MPS Dithiol [bis(4-mercaptophenyl) sulfide] represented by the following formula (12), manufactured by Tokyo Chemical Industry Co., Ltd. [ka]

[0078] <<Synthesis of Polyimide Sulfides>> <Polyimide sulfide 1> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and polyfunctional thiol 1 (VBATDT) was used as the polyfunctional 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.

[0079] [ka]

[0080] <Polyimide sulfide 2> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and polyfunctional thiol 2 (DATD) was used as the polyfunctional thiol. 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.

[0081] [ka]

[0082] <Polyimide Sulfide 3> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and polyfunctional thiol 3 (IBSH) was used as the polyfunctional 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 3 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 3.

[0083] [ka]

[0084] <Polyimide Sulfide 4> Bismaleimide 1 (BMI-70) was used as the bismaleimide, and polyfunctional thiol 4 (MPS) was used as the polyfunctional 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 4 had a weight-average molecular weight of 25,400 and a number-average molecular weight of 9,100.

[0085] [ka]

[0086] <<<Evaluation of Polyimide Sulfides>>> The i-ray transmittance of each polyimide sulfide was measured. Cyclopentanone solutions of each polyimide sulfide were applied to quartz glass and heated and dried on a hot plate at 90°C for 3 minutes to form a dried coating. The transmission spectrum of the dried coating was measured using a UV-Vis spectrophotometer (Jasco V-570, JASCO Corporation), and the measured values ​​were normalized to a film thickness of 3 μm. The above transmission spectra were measured under the following conditions: bandwidth of 5 nm, scanning speed of 400 nm / min, and data reading interval of 1 nm. Table 1 shows the results of the transmittance evaluation for the i-line (wavelength 365 nm), which is a common exposure wavelength in photolithography.

[0087] [Table 1]

[0088] From the above results, it can be understood that polyimide sulfides 1-3 according to this disclosure, which have a 1,3,5-triazine ring in their main chain, exhibit improved i-ray permeability compared to polyimide sulfide 4.

[0089] <<<Preparation of Photocurable Resin Composition>>> Next, using polyimide sulfides 1, 2, and 4 as the polyimide sulfides, varnishes of the photocurable resin compositions according to Examples 1 and 2 and Comparative Example 1 were prepared according to the components and formulations shown in Table 2. Note that the amounts in Table 2 are expressed in parts by mass.

[0090] <<Raw materials>> <Photoradical Generator> NCL-730 Oxime ester-based photoradical generator, manufactured by ADEKA Corporation.

[0091] <Crosslinking agent> ·TMMP Trimethylolpropanetris (3-mercaptopropionate)

[0092] <Solvent> Cyclopentanone

[0093] <<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.

[0094] [Table 2] [Industrial applicability]

[0095] 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.

Claims

1. A polyimide sulfide containing the structure shown in formula (1) below. 【Chemistry 1】 {In formula (1), R １ R is a divalent organic group, ２ This is a hydrogen atom, a halogen atom, or a monovalent organic group.

2. A resin composition comprising the polyimide sulfide described in claim 1.

3. The resin composition according to claim 2, comprising a photosensitive agent.

4. A cured product obtained by curing the resin composition according to claim 2.

5. An electronic component comprising a resin layer obtained from the resin composition according to claim 2, or a cured product according to claim 4.

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