Polyhydroxyamide compound, resin composition, dry film, cured product, and electronic component

Abstract

To provide a new polyhydroxyamide compound which is usable for a resin composition such as a photosensitive resin composition.SOLUTION: A polyhydroxyamide compound has a structural unit represented by formula (1), and a structural unit including isosorbide-derived and isomannide-derived structures. In the formula, R1 is a divalent organic group, and R2 is a tetravalent organic group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyhydroxyamide compound, a resin composition, a dry film, a cured product, and an electronic component. [Background technology]

[0002] Photosensitive resin compositions containing a polyhydroxyamide compound, which is a polybenzoxazole precursor, exhibit excellent properties such as insulating properties, heat resistance, and mechanical strength, and are therefore widely used as insulating films in various fields such as semiconductors and electronic components.

[0003] For example, Patent Document 1 discloses the use of a photosensitive resin composition containing a specific polyamide derivative, which is a photosensitive polybenzoxazole precursor, a compound that generates an acid upon irradiation with radiation, and a compound that can crosslink the specific polyamide derivative. According to the disclosure of Patent Document 1, a pattern with a good shape that is excellent in sensitivity, resolution, and heat resistance, and highly reliable electronic components are provided.

[0004] Patent Document 2 discloses the use of a photosensitive resin composition containing a polybenzoxazole precursor, a photosensitizer, and a compound having an oxacene group. According to the disclosure of Patent Document 2, a photosensitive resin composition is provided that has excellent lithography performance and stability, and is cured at a low temperature and has excellent mechanical properties, heat resistance, and substrate adhesion. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2001-125267 A [Patent Document 2] JP 2008-224970 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] In recent years, there has been a demand for higher integration of semiconductor elements in response to the demand for higher performance and smaller size of electronic components and electrical equipment. To meet these demands, technologies for higher performance and smaller size in the field of semiconductor element packaging, such as wafer level packaging (WLP), have been developed, and insulating films used in redistribution layers are now required to have various characteristics that are compatible with these higher performance and smaller size technologies, in addition to finer pattern formation.

[0007] Therefore, an object of the present disclosure is to provide a novel polyhydroxyamide compound that can be used in resin compositions such as photosensitive resin compositions. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that a polyhydroxyamide compound having a specific structure as a skeleton can solve the above problems, and have completed the present invention. That is, according to one aspect of the disclosed technique, It is possible to provide a polyhydroxyamide compound having a structural unit represented by formula (1) and a structural unit containing a structure represented by formula (2). [ka] (R in the formula 1 is a divalent organic group, and R 2 is a tetravalent organic group. [ka] (In the formula, * indicates a bond.) The structure represented by the formula (2) preferably includes a structure represented by the following formula (3): [ka] (In the formula, * indicates a bond.) The structural unit containing the structure represented by formula (2) preferably contains a structural unit represented by formula (4). [ka] (R in the formula 3 is a divalent organic group. According to another aspect of the disclosed technique, there can be provided a resin composition comprising the polyhydroxyamide compound. According to another aspect of the disclosed technique, a dry film can be provided, comprising a resin layer formed from the resin composition. According to another aspect of the disclosed technique, a cured product of the resin composition or a cured product of the resin layer of the dry film can be provided. According to another aspect of the disclosed technique, it is possible to provide an electronic component comprising the cured product. Effect of the Invention

[0009] According to the disclosed technique, it is possible to provide a novel polyhydroxyamide compound that can be used in a resin composition such as a photosensitive resin composition. [Brief description of the drawings]

[0010] [Figure 1] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 1. [Diagram 2] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 2. [Diagram 3] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 3. [Figure 4] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 4. [Diagram 5] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 5. [Figure 6] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 6. [Figure 7] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 7. [Figure 8]1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 8. [Figure 9] 1 is a 1H-NMR spectrum of the polyhydroxyamide compound of Example 9. [Figure 10] 1 shows transmission spectra of light of 200 to 500 nm for polyhydroxyamide compounds of Examples 1 to 3 and Comparative Example 1. [Figure 11] 1 shows transmission spectra of light of 200 to 500 nm for polyhydroxyamide compounds of Examples 4 to 6 and Comparative Example 1. [Figure 12] 1 shows transmission spectra of light in the range of 200 to 500 nm for polyhydroxyamide compounds of Examples 7 to 9 and Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expression "p to q" in the description of a numerical range means p or more and q or less, unless otherwise specified.

[0012] When isomers exist in the described compounds, all possible isomers can be used in the disclosed technology unless otherwise specified.

[0013] 1. Polyhydroxyamide compounds As the polyhydroxyamide compound of the present disclosure, any compound having a structural unit represented by formula (1) can be used without any particular limitation. [ka] (R in the formula 1 is a divalent organic group, and R 2 is a tetravalent organic group. The polyhydroxyamide compound further has a structural unit including a structure represented by formula (2). Examples of the structure represented by formula (2) include a skeleton derived from isosorbide and a skeleton derived from isomannide. [ka] (In the formula, * indicates a bond.)

[0014] Among the polyhydroxyamide compounds having structures represented by formula (2), those having an isosorbide-derived skeleton represented by formula (3) are preferred, from the viewpoint of being able to obtain polyhydroxyamide compounds having excellent reactivity and high molecular weights, and those having a structural unit represented by formula (4) are particularly preferred. When natural (plant-derived) components such as starch and sugar, which are renewable resources, are used as isosorbide, a polyhydroxyamide compound with superior sustainability can be obtained. [ka] (In the formula, * indicates a bond.) [ka] (R in the formula 3 is a divalent organic group.

[0015] When a polyhydroxyamide compound has a structural unit containing a structure represented by formula (2), when the polyhydroxyamide compound is used in a curable resin composition, the cured product has a lower glass transition temperature than the cured product of a curable resin composition containing a conventional polyhydroxyamide compound. This is believed to be due to the fact that, while conventional polyhydroxyamide compounds contain structural units having many reactive groups such as hydroxyl groups, the polyhydroxyamide compound of the present disclosure has a structural unit containing a structure represented by formula (2) that does not contain reactive groups such as hydroxyl groups, which replaces some of the structural units having many reactive groups such as hydroxyl groups. It is presumed that this reduces the crosslinking points (reactive groups such as hydroxyl groups) of the polyhydroxyamide compound, and reduces the crosslinking density of the cured product, thereby lowering the glass transition temperature. In addition, since the structural unit containing the structure represented by formula (2) itself is considered to be a highly flexible structure, it is presumed that this also reduces the glass transition temperature of the cured product. When such a polyhydroxyamide compound capable of giving a cured product having a low glass transition temperature is used as a photosensitive resin composition, the acid generated from the photoacid generator becomes more easily diffused in the post exposure bake (PEB) process described later, and therefore a photosensitive resin composition having superior resolution can be obtained.

[0016] Here, R 1 is not particularly limited as long as it is a divalent organic group, and examples thereof include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group, and an ester group. Among these, divalent aromatic hydrocarbon groups having a skeleton such as benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, diphenyl hexafluoropropane, and benzophenone, or divalent aliphatic hydrocarbon groups having a skeleton such as butane and cyclobutane are preferred. For example, from the viewpoint of resolution when the polyhydroxyamide compound is used in a photosensitive resin composition, and from the viewpoint of obtaining a cured product having excellent insulation reliability when used as a curable resin composition, R 1The carbon number of R is preferably 4 to 30, and phenyl, biphenyl, diphenyl ether, and diphenylhexafluoropropane are preferred. 1 It is also possible to contain two or more of the groups exemplified above as .

[0017] R 2 is not particularly limited as long as it is a tetravalent organic group, but is preferably a tetravalent aromatic hydrocarbon group having a skeleton such as diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide, diphenyl sulfone, biphenyl, or benzene, and more preferably an organic group having a structure represented by formula (5). [ka] (In the formula, a is an integer of 0 to 3, and * indicates a bond.)

[0018] Here, R 3 is not particularly limited as long as it is a divalent organic group, and examples thereof include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group, and an ester group. Among these, a divalent aromatic hydrocarbon group having a skeleton such as benzene, naphthalene, perylene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, diphenyl hexafluoropropane, or benzophenone, or a divalent aliphatic hydrocarbon group having a skeleton such as butane or cyclobutane, is preferred. For example, from the viewpoint of resolution when the polyhydroxyamide compound is used in a photosensitive resin composition, and from the viewpoint of obtaining a cured product having excellent insulation reliability when used as a curable resin composition, R 3 The carbon number of R is preferably 4 to 30, and phenyl, biphenyl, diphenyl ether, and diphenylhexafluoropropane are preferred. 3 It is also possible to contain two or more of the groups exemplified above as R 3 is R 1 may be the same organic group as or different from.

[0019] The polyhydroxyamide compound may have a terminal structure in which the molecular chain terminal is blocked with a terminal blocking agent. From the viewpoint of obtaining a superior resolution of the polyhydroxyamide compound, it is preferable that the terminal structure does not have a carboxyl group. Moreover, from the viewpoint of obtaining a superior solubility in a developer, it is preferable that the terminal structure has a hydroxyl group, and it is particularly preferable that the terminal structure has a phenolic hydroxyl group. In order to improve the i-line (365 nm light) transmittance of the resin composition (or a dried coating film of the resin composition described below), the terminal structure preferably has a carboxyl group.

[0020] The weight average molecular weight (Mw) of the polyhydroxyamide compound is not particularly limited, but when used in a photosensitive resin composition, it can be, for example, 2,000 to 100,000, preferably 2,000 to 60,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, and particularly preferably 4,000 to 10,000. The number average molecular weight (Mn) of the polyhydroxyamide compound is not particularly limited, but when used in a photosensitive resin composition, it can be, for example, 1,000 to 30,000, preferably 1,000 to 20,000, and more preferably 1,500 to 7,000. The polydispersity index (PDI) of the polyhydroxyamide compound is not particularly limited, but when used in a photosensitive resin composition, it can be, for example, 1.5 to 4.0, and preferably 1.5 to 3.5. When the weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity index (PDI) of the polyhydroxyamide compound are within the above ranges, a photosensitive resin composition having superior resolution can be obtained. In this specification, the weight average molecular weight and number average molecular weight are values ​​measured by gel permeation chromatography (GPC) and converted into standard polystyrene. In this specification, the polydispersity index (PDI) is calculated by the following formula (X). PDI = Mw / Mn (X)

[0021] The hydroxyl equivalent of the polyhydroxyamide compound is not particularly limited, but may be, for example, 100 to 800 g / eq, and is preferably 150 to 700 g / eq, more preferably 200 to 700 g / eq, from the viewpoint of lowering the glass transition temperature of the cured product. When the polyhydroxyamide compound is used as a photosensitive resin composition, the hydroxyl equivalent is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, from the viewpoint of obtaining a photosensitive resin composition with excellent developability.

[0022] 2. Method for synthesizing polyhydroxyamide compounds The method for synthesizing the polyhydroxyamide compound is not particularly limited, but for example, a method of copolymerizing a hydroxyamino compound represented by formula (6), a dicarbonyl dichloride compound represented by formula (7), and a compound represented by formula (8) can be used. Note that these compounds can also be further copolymerized with other compounds that are copolymerizable therewith. [ka] (R in the formula 2 is a tetravalent organic group. [ka] (R in the formula 1 is a divalent organic group. [ka]

[0023] The polyhydroxyamide compound obtained by copolymerization as described above is a copolymer represented by formula (9) having a structural unit represented by formula (1) and a structural unit containing a structure represented by formula (2). When other compounds copolymerizable with the compounds represented by formulas (6) to (8) are further added and copolymerized, the copolymer can further contain other structural units different from the structural unit represented by formula (1) and the structural unit containing a structure represented by formula (2). The other compounds can be used alone or in combination in any ratio. The copolymer in the present disclosure includes both random copolymers and block copolymers. [ka] (In the formula, m and n are natural numbers, R 1 is a divalent organic group, and R 2 is a tetravalent organic group.

[0024] When the compound of formula (10) is used as the compound of formula (8), the copolymer of formula (9) is represented by formula (11). 1 and R 3 are considered to be identical, the formula (11) is a structure containing a structural unit represented by the formula (1) and a structural unit represented by the formula (4). [ka] [ka] (In the formula, m and n are natural numbers, R 1 is a divalent organic group, and R 2 is a tetravalent organic group.

[0025] In formula (9) and formula (11), the ratio of m to n in the molecule of the polyhydroxyamide compound is not particularly limited, but can be m:n=1:99 to 99:1, and preferably m:n=5:95 to 80:20. From the viewpoint of obtaining a resin composition (or a dried coating film of the resin composition described later) with excellent i-line (365 nm light) transmittance, m:n=20:80 to 75:25 is particularly preferred. The ratio of m and n can be adjusted by the blending ratio of each raw material during copolymerization.

[0026] As described above, when the compounds represented by formulae (6) to (8) are copolymerized with other copolymerizable compounds, a copolymer having other structural units different from the structural unit represented by formula (1) and the structural unit containing the structure represented by formula (2) is obtained. When the number of other structural units contained in the molecule of the polyhydroxyamide compound is l (l is a natural number, and when a plurality of other structural units are present, it is the total number of the units), the ratio of l to (m+n) is not particularly limited, but when the polyhydroxyamide compound is used in a photosensitive resin composition, it can be l:(m+n)=0.1:99.9 to 30:70.

[0027] The ratio of l, m, and n can be adjusted by the blending ratio of each raw material during copolymerization.

[0028] 3. Uses of polyhydroxyamide compounds The polyhydroxyamide compound of the present disclosure can be used in resin compositions such as thermosetting resin compositions and photosensitive resin compositions (photocurable resin compositions, etc.), and dry films having a resin layer formed from the resin composition. The polyhydroxyamide compound can be used as a curable resin composition or dry film to obtain a cured product with a low glass transition temperature, and can also be used as a curable resin composition (or a dried coating film of a resin composition described later) with excellent i-line transparency. Therefore, as a material for forming semiconductor elements, electronic components, etc., a fine wiring pattern can be formed. Examples of materials for forming semiconductor elements include resist materials, buffer coat films, and insulating films for rewiring layers of wafer-level packages (e.g., insulating films for a rewiring layer formation process using a damascene method). Examples of materials for forming electronic components include printed wiring boards, interlayer insulating films, wiring coating films, etc.

[0029] Furthermore, as described above, the curable resin composition using the polyhydroxyamide compound of the present disclosure can provide a cured product having a lower glass transition temperature than curable resin compositions using conventional polyhydroxyamide compounds.

[0030] The resin composition containing a polyhydroxyamide compound is not particularly limited in terms of the components to be mixed. For example, a thermosetting resin composition can be prepared by blending a crosslinking agent, other additives, etc. with a polyhydroxyamide compound, and a cured product can be formed by heating. In addition, a photosensitive resin composition can be prepared by blending a photoacid generator, a photobase generator, a photopolymerization initiator, or other photosensitizer, and if necessary, a crosslinking agent or other additives, etc. with a polyhydroxyamide compound, and a pattern can be formed by photolithography by irradiating the composition with light of a predetermined wavelength and developing the composition with a chemical solution such as tetramethylammonium hydroxide.

[0031] 3-1.Thermosetting resin composition The amount of the polyhydroxyamide compound (solid content) can be 50 to 90 mass % when the total mass of the solid content of the thermosetting resin composition is taken as 100 mass %.

[0032] The crosslinking agent is not particularly limited as long as it has two or more functional groups in one molecule that can react with the hydroxyl group contained in the polyhydroxyamide compound. Examples of the crosslinking agent include a crosslinking agent having a cyclic ether group such as an epoxy group or a cyclic thioether group such as an episulfide group, a crosslinking agent having an alcoholic hydroxyl group in which a hydroxyl group is bonded to an alkylene group having 1 to 12 carbon atoms such as a methylol group, a compound having an ether bond such as an alkoxymethyl group, a crosslinking agent having a triazine ring structure, and a urea-based crosslinking agent. Among them, a crosslinking agent having an epoxy group, a crosslinking agent having a methylol group, and a crosslinking agent having a methoxymethyl group are preferred. In addition, it is more preferred that the heterocycle is in the molecular structure because it provides low thermal expansion (thermal dimensional stability), and that the heterocycle is a triazine ring because it is excellent in low dielectric properties. In addition, it is more preferred that the functional group capable of reacting with the hydroxyl group is a methylol group or a methoxymethyl group because it provides excellent toughness. The crosslinking agents may be used alone or in any combination in any ratio.

[0033] The amount of the crosslinking agent is, for example, 0.01 parts by mass or more and 50 parts by mass or less, preferably 0.05 parts by mass or more and 45 parts by mass or less, and more preferably 0.1 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the total amount (based on solid content) of the thermosetting resin such as the polyhydroxyamide compound.

[0034] As other additives, components other than the above-mentioned components, for example, conventional additives, can be used depending on the application. The conventional additives are not particularly limited, but examples thereof include resins and elastomers, inorganic fillers, curing catalysts, colorants, dispersants, defoamers / leveling agents, thixotropic agents, coupling agents, flame retardants, organic solvents, etc.

[0035] 3-2. Photosensitive resin composition The amount of the polyhydroxyamide compound (solid content) can be 50 to 90% by mass, assuming that the total mass of the solid content of the photosensitive resin composition is 100% by mass.

[0036] The photosensitive resin composition contains a polyhydroxyamide compound, a photoacid generator, a photobase generator, a photosensitizer such as a photopolymerization initiator, and further contains a crosslinking agent and other additives as necessary. For example, in a photosensitive resin composition using a photoacid generator, the photoacid generator is not particularly limited as long as it is a compound that generates an acid by irradiation with light such as ultraviolet light or visible light, and specifically, naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, oximesulfonates, naphthalimides, benzoquinone diazosulfonic acid esters, and the like can be mentioned. These can be used alone or in combination in any ratio. When used as a positive-type photosensitive resin composition, the photoacid generator is preferably a dissolution inhibitor, and is preferably a naphthoquinone diazide compound. When used as a negative-type photosensitive resin composition, the photoacid generator is preferably used in combination with the above-mentioned crosslinking agent, and the photoacid generator is more preferably an oxime sulfonate compound.

[0037] Examples of naphthoquinone diazide compounds that can be used include naphthoquinone diazide adducts of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (e.g., TKF-520, TKF-528, TKF-420, and TKF-428 manufactured by Sanbo Chemical Laboratory Co., Ltd.) and naphthoquinone diazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, and BS599 manufactured by Sanbo Chemical Laboratory Co., Ltd.). Here, the addition of naphthoquinone diazide can be achieved by reacting, for example, o-quinone diazide sulfonyl chlorides with a hydroxy compound or an amino compound. These can be used alone or in combination in any ratio.

[0038] Examples of the oxime sulfonate compound include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203 manufactured by BASF. These can be used alone or in combination in any ratio.

[0039] The amount of the photoacid generator (solid content) can be 3 to 20% by mass, assuming that the total mass of the solid content in the photosensitive resin composition is 100% by mass.

[0040] The photosensitive resin composition may be made into a photosensitive thermosetting resin composition by blending the crosslinking agent and other additives as the above-mentioned thermosetting resin composition.

[0041] The dry film and cured product of the present disclosure will be described below using as an example a case in which a photosensitive resin composition containing the polyhydroxyamide compound of the present disclosure is used.

[0042] 3-3. Dry film The dry film of the present disclosure includes a substrate and a resin layer formed on the substrate from a photosensitive resin composition. In addition, a protective film may be laminated on the surface of the resin layer to protect the resin layer.

[0043] The substrate is not particularly limited, but examples thereof include metal foils such as copper foil; polyester films such as polyethylene terephthalate (PET) film and polyethylene naphthalate (PEN) film; and films such as polyimide film.

[0044] The protective film is not particularly limited, but polyethylene film, polytetrafluoroethylene film, polypropylene film, paper, etc. can be used. It is preferable to select a protective film in which the adhesive strength between the protective film and the resin layer is lower than that between the substrate and the resin layer. In order to make the adhesive strength between the protective film and the resin layer lower than that between the substrate and the resin layer, a protective film having a release treatment applied to its surface can be used.

[0045] The thickness of the resin layer is not particularly limited, but can be 1 to 150 μm depending on the application. The resin layer can be obtained, for example, by applying a photosensitive resin composition onto a substrate, adjusting the thickness of the resin layer using a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and drying the resin layer.

[0046] 3-4.Cured product The cured product of the present disclosure is a product obtained by curing a resin composition or a resin layer of a dry film. In the present disclosure, the cured product includes both a product in which a polyhydroxyamide compound is cyclized to become a polybenzoxazole, and a product in which a polyhydroxyamide compound reacts with a crosslinking agent to be crosslinked as described below. That is, the polyhydroxyamide compound of the present disclosure can be used as a curable resin that is cured by cyclization even when used alone. The cured product may be a patterned cured product. The following method can be given as an example of a method for producing a patterned cured product.

[0047] 3-4-1. Dry coating film formation process The dry coating film forming step is a step of applying a photosensitive resin composition onto a substrate to form a coating film, and then drying the coating film. In the dry coating film forming step, a resin layer of a dry film can be transferred onto the substrate to form a dry coating film on the substrate.

[0048] The method for applying the photosensitive resin composition onto a substrate is not particularly limited, and examples thereof include a method of applying the composition using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, a spray coating method using a spray coater, an inkjet method, and the like.

[0049] The method for drying the coating film is not particularly limited, and examples thereof include air drying, heat drying in an oven or a hot plate, vacuum drying, etc. Conditions for heat drying are, for example, a heating temperature of 70 to 140° C. and a drying time of 1 to 30 minutes.

[0050] The method for transferring the resin layer of the dry film onto the substrate is preferably vacuum lamination under pressure and heat using a vacuum laminator, etc. The heating temperature can be, for example, 60 to 100°C.

[0051] The substrate is not particularly limited, and may be, for example, a printed wiring board on which a circuit is formed, a flexible printed wiring board, or a wafer on which a semiconductor element is formed.

[0052] 3-4-2. Exposure process The exposure step is a step in which the dried coating film formed in the dry coating film forming step is irradiated with radiation through a photomask capable of forming a desired pattern, thereby sensitizing the photosensitizer in the exposed area and generating active species. If patterning is not required, there is no need to use a photomask. Alternatively, a pattern may be directly drawn with a laser using a direct drawing device.

[0053] The wavelength of the radiation is such that the photosensitizer can be activated, and in order to perform fine patterning, the maximum wavelength is preferably 410 nm or less. The irradiation energy can be adjusted depending on the thickness of the formed dry coating film, and is, for example, 10 to 1000 mJ / cm. 2 As the exposure light source, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, a KRF laser, or the like can be used.

[0054] 3-4-3.PEB process The PEB process is a process in which the dried coating film exposed in the exposure process is heat-treated to activate the acid, base, etc. generated from the photosensitizer. When the photosensitive resin composition of the present disclosure is used as a negative photosensitive resin composition, this is a process in which development resistance is imparted to the exposed part of the dried coating film (hereinafter, may be abbreviated as the exposed part), and the reaction between the polyhydroxyamide compound and the crosslinking agent etc. proceeds with the acid, base, etc. generated from the photosensitizer in the exposed part as the active species, and the exposed part becomes insoluble in the developer. The heating temperature in the PEB process can be 90 to 150°C, and the heating time can be 0.5 to 10 minutes. Heating can be performed by a known method such as a hot plate or a heating furnace.

[0055] 3-4-4.Developing process The developing step is a step in which the dried coating film heated in the PEB step is treated with a developer to dissolve and remove the unexposed parts of the dried coating film (exposed parts of the dried coating film in the case of a positive photosensitive resin composition) in the developer, thereby obtaining a patterned coating film. As the developing method, a known method can be used, for example, a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, etc. can be mentioned.

[0056] The developer may be a known one, and examples of the developer include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, etc. If necessary, a water-soluble organic solvent such as methanol, ethanol, and isopropyl alcohol, or a surfactant may be added.

[0057] After the treatment with the developer, the coating film can be washed with a rinse liquid as necessary to obtain a patterned coating film. The rinse liquid is not particularly limited, and examples thereof include pure water, methanol, ethanol, isopropyl alcohol, etc. These can be used alone or in combination in any ratio.

[0058] 3-4-5. Post-development heating process The post-development heating step is a step of heating the patterned coating film formed in the development step to complete the curing of the patterned coating film and obtain a cured patterned coating film (cured product). The heating temperature can be 150 to 200°C, and the heating time can be 1 to 120 minutes. Heating can be performed by a known method such as a hot plate or an inert oven, and heating is preferably performed under a nitrogen atmosphere. EXAMPLES

[0059] The present disclosure will be described in more detail using examples, but the present disclosure is not limited to the examples.

[0060] <Synthesis of polyhydroxyamide compounds> (Synthesis Example 1: Synthesis Example of Polyhydroxyamide Compound of Example 1) In a 125 mL vial equipped with a stirrer and a thermometer, 0.28 g (1.95 mmol) of isosorbide (ISB) was sonicated in 30 g of N-methylpyrrolidone (NMP) until it was completely dissolved. 12.10 g (41.01 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added thereto and stirred at 80°C for 18 hours. Then, 13.56 g (37.03 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 1.55 g (14.20 mmol) of 3-aminophenol (3-AP) were completely dissolved in 35 g of N-methylpyrrolidone (NMP) and the solution was added dropwise and stirred at 25°C for 18 hours. The stirred solution was poured into a large amount of ion-exchanged water and the precipitate was collected. The obtained solid was dissolved in 64 g of ethyl acetate. 14 g of anion exchange resin (Amberlyst B-20, manufactured by Organo Corporation) was added thereto and vigorously stirred for 1 hour. The stirred solution was filtered to remove the anion exchange resin, and the filtrate was concentrated and then added to a large amount of ion exchange water to recover the precipitate. The precipitated solid was recovered and then dried under reduced pressure to obtain a polyhydroxyamide compound having a phenolic hydroxyl group terminal. The resulting polyhydroxyamide compound had a weight average molecular weight (Mw) of 9,100, a number average molecular weight (Mn) of 3,300, a polydispersity index (PDI) of 2.8, and a phenolic hydroxyl group equivalent of 261 g / eq.

[0061] (Synthesis Examples 2 to 6: Synthesis Examples of Polyhydroxyamide Compounds of Examples 2 to 6) The phenolic hydroxyl group-terminated polyhydroxyamide compounds of each Example were obtained in the same manner as in Synthesis Example 1, except that the amounts (molar ratios) of isosorbide (ISB), 4,4'-oxybis(benzoyl chloride) (DEDC), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), and 3-aminophenol (3-AP) used were as shown in Table 1.

[0062] (Synthesis Example 7: Synthesis Example of Polyhydroxyamide Compound of Example 7) In a 125 mL vial equipped with a stirrer and a thermometer, 1.43 g (3.79 mmol) of isosorbide (ISB) was sonicated in 30 g of N-methylpyrrolidone (NMP) until it was completely dissolved. 12.08 g (40.95 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added thereto and stirred at 80°C for 18 hours. Then, 10.73 g (29.29 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was added dropwise to a solution in which 35 g of N-methylpyrrolidone (NMP) had been completely dissolved, and the solution was stirred at 25°C for 18 hours. The stirred solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 64 g of ethyl acetate. 14 g of anion exchange resin (Amberlyst B-20, manufactured by Organo Corporation) was added thereto and vigorously stirred for 1 hour. The stirred solution was filtered to remove the anion exchange resin, and the filtrate was concentrated and then added to a large amount of ion exchange water to recover the precipitate. The precipitated solid was recovered and then dried under reduced pressure to obtain a polyhydroxyamide compound having a carboxyl group terminal.

[0063] (Synthesis Examples 8 and 9: Synthesis Examples of Polyhydroxyamide Compounds of Examples 8 and 9) The carboxyl-terminated polyhydroxyamide compounds of each Example were obtained in the same manner as in Synthesis Example 7, except that the amounts (molar ratios) of isosorbide (ISB), 4,4'-oxybis(benzoyl chloride) (DEDC), and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) used were as shown in Table 1.

[0064] (Synthesis Example 10: Synthesis Example of Polyhydroxyamide Compound of Comparative Example 1) In a 500 mL flask equipped with a stirrer and a thermometer, 14.93 g (44.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) and 2.45 g (22.42 mmol) of 3-aminophenol were stirred and dissolved in 79 g of N-methylpyrrolidone (NMP). The flask was then immersed in an ice bath, and while keeping the temperature in the flask at 0-5°C, 16.41 g (55.61 mmol) of 4,4'-oxybis(benzoyl chloride) (DEDC) was added as a solid over a period of 10 minutes, and the mixture was stirred in an ice bath for 30 minutes. After stirring at room temperature for 18 hours, the solution was poured into a large amount of ion-exchanged water, and the precipitate was collected. The obtained solid was dissolved in 79 g of ethyl acetate. 17 g of anion-exchange resin (Amberlyst B-20, manufactured by Organo Corporation) was poured in, and the mixture was stirred vigorously for 1 hour. The stirred solution was filtered to remove the anion exchange resin, and the filtrate was concentrated and then poured into a large amount of ion exchange water to recover the precipitate. The precipitated solid was recovered and then dried under reduced pressure to obtain a polyhydroxyamide compound having a hydroxyl group terminal. The resulting polyhydroxyamide compound had a weight average molecular weight (Mw) of 9,200, a number average molecular weight (Mn) of 3,500, a polydispersity index (PDI) of 2.6, and a phenolic hydroxyl group equivalent of 252 g / eq.

[0065] ( 1 H-NMR measurement) The polyhydroxyamide compounds obtained in Examples 1 to 9 1The measurement results of 1H-NMR are shown in FIGS. 1 to 9, respectively. From the results, it was confirmed that the polyhydroxyamide compounds of Examples 1 to 9 are polyhydroxyamide compounds having an isosorbide skeleton having structural units represented by the following formulas (12) and (13) (the structural units are described in each figure). In addition, m:n of each example is shown in Table 1. m:n was calculated as the ratio of the integrated value of the peak of a (corresponding to n) to the integrated value of the peak of b (corresponding to m) in the 1H-NMR spectrum. Note that 1 in the 1H-NMR spectrum, it was calculated as the ratio of the integrated value of the peak of a to the integrated value of the peak of b. Note that 1 the peaks of a and b shown in the 1H-NMR spectrum are derived from the structures of part a and part b shown in the structural formulas of FIGS. 1 to 9. [Chemical formula] [Chemical formula]

[0066] [Glass transition temperature (Tg) evaluation] After drying the polyhydroxyamide compounds of Examples 1 to 9 and the polyhydroxyamide of the comparative example, a powder sample was obtained. Using about 5 mg of the obtained powder sample, differential scanning calorimetry (DSC, manufactured by TA Instruments, product name Q100) was performed. Specifically, the temperature was raised from 40°C to 350°C (heating rate 10°C / min), held for 1 hour to cure (cyclize) the polyhydroxyamide compound, then cooled to 40°C (cooling rate 10°C / min), and the glass transition temperature of each sample in the second heating (heating rate 10°C / min) was measured. The obtained results are shown in Table 1.

[0067] [i-line transmittance evaluation] The polyhydroxyamide compounds of Examples 1 to 9 and the polyhydroxyamide of Comparative Example were spin-coated on a quartz glass substrate so that the film thickness after drying was 3 μm. Then, the coating was dried at 90° C. for 180 seconds to prepare a sample for measuring light transmittance. Each sample for measuring light transmittance was subjected to absorption spectrum analysis at wavelengths of 200 to 500 nm using a spectrophotometer (manufactured by JASCO Corporation, product name: UV-Visible-Near-Infrared Spectrophotometer V-570). The results are shown in FIGS. 10 to 12. The results of measuring the transmittance for light (i-line) with a wavelength of 365 nm in each Example and Comparative Example are shown in Table 1.

[0068] [Table 1]

Claims

1. A polyhydroxyamide compound having a structural unit represented by formula (1) and a structural unit containing a structure represented by formula (2). 【Chemical 1】 (In the formula R １ is a divalent organic group, and R ２ is a tetravalent organic group. 【Chemistry 2】 (In the formula, * indicates a bond.)

2. The polyhydroxyamide compound according to claim 1, wherein the structure represented by formula (2) includes a structure represented by formula (3). 【Chemistry 3】 (In the formula, * indicates a bond.)

3. 2. The polyhydroxyamide compound according to claim 1, wherein the structural unit containing the structure represented by formula (2) contains a structural unit represented by formula (4). 【Chemistry 4】 (In the formula R ３ is a divalent organic group.

4. A resin composition comprising the polyhydroxyamide compound according to any one of claims 1 to 3.

5. A dry film comprising a resin layer formed from the resin composition according to claim 4.

6. A cured product of the resin composition according to claim 4.

7. A cured product of the resin layer of the dry film according to claim 5.

8. An electronic component comprising the cured product according to claim 6.

9. An electronic component comprising the cured product according to claim 7.

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