Photosensitive polymer, photosensitive resin composition, and cured film

Abstract

The present disclosure relates to a photosensitive polymer which contains a constituent unit represented by formula (1), wherein X represents a tetravalent organic group having 6-40 carbon atoms, Y represents a divalent organic group having 6-40 carbon atoms, R1 and R2 each independently represent a carboxy group or a monovalent organic group represented by formula (2), at least one of R1 or R2 represents a monovalent organic group represented by formula (2), L1 represents an organic group having 2-10 carbon atoms, Rx represents a photosensitive group, and n represents 1 or 2.　

Description

Photosensitive polymer, photosensitive resin composition, and cured film

[0001] The present disclosure relates to a photosensitive polymer, a photosensitive resin composition, and a cured film.

[0002] It is known that a protective film and an insulating film of a semiconductor device are formed using a photosensitive resin composition containing a polyimide precursor having a photosensitive group (for example, Patent Documents 1 and 2).

[0003] JP 2021-196482 A JP 2020-122875 A

[0004] While conventional polyimide precursors having photosensitive groups (e.g., polyamic acid esters) are insoluble in alkaline aqueous solutions, the present disclosure aims to provide a photosensitive polymer that is soluble in alkaline aqueous solutions.

[0005] The present disclosure includes the following [1] to [5]. [1] The following formula (1): X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and R １ and R ２ are each independently a carboxy group or a group represented by the following formula (2): R represents a monovalent organic group represented by １ or R ２ At least one of L is a monovalent organic group represented by formula (2), １ represents an organic group having 2 to 10 carbon atoms, Rx represents a photosensitive group, and n is 1 or 2. [2] A photosensitive polymer, wherein the photosensitive group is represented by the following formula (2a): is a group represented by R ３ , R ４ and R ５ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [3] The photosensitive polymer according to [1] or [2] above, wherein the structural unit represented by formula (1) is a structural unit derived from a reaction product of a tetracarboxylic dianhydride, a diamine, and a (meth)acrylate compound having an isocyanate group. [4] A photosensitive resin composition containing the photosensitive polymer according to any one of [1] to [3] above. [5] A photosensitive polymer according to the following formula (3): X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and L １ [6] A cured film, wherein Z represents an organic group having 2 to 10 carbon atoms, and Z represents a crosslinking bond. R ３ , R ４ and R ５ [5] The cured film according to the above [4], wherein each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0006] According to the present disclosure, it is possible to provide a photosensitive polymer that is soluble in an alkaline aqueous solution and a photosensitive resin composition containing the photosensitive polymer.

[0007] 1 is a process diagram showing an example of a method for producing a cured film. 2 is an NMR spectrum of the polyamic acid of Example 1. 3 is an NMR spectrum of the polyamide-imide precursor of Example 1.

[0008] The present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiments. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. In this specification, the term "layer" includes a structure having a shape formed on the entire surface as well as a structure having a shape formed on a portion thereof when observed in a plan view.

[0009] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, in numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in a certain stage may be replaced with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. When referring to the amount of each component in a composition in this specification, if the composition contains multiple substances corresponding to each component, the total amount of the multiple substances present in the composition is meant, unless otherwise specified.

[0010] In this specification, the term "solid content" refers to the non-volatile content excluding volatile substances such as water and solvents contained in the photosensitive resin composition, and refers to components that remain without volatilizing when the resin composition is dried, and also includes liquid, starch syrup-like, and wax-like components at room temperature around 25°C.

[0011] An example of the photosensitive polymer according to the present disclosure is a polymer (polyamideimide precursor) containing a constitutional unit represented by the following formula (1):

[0012] In formula (1), X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and R １ and R ２ each independently represents a carboxy group or a monovalent organic group represented by the following formula (2), and R １ or R ２ At least one of the structural units represented by formula (1) contained in the photosensitive polymer is a monovalent organic group represented by formula (2). １ , R ２ , X and Y may be the same or different.

[0013] In formula (2), L １ represents an organic group having 2 to 10 carbon atoms, Rx represents a photosensitive group, and n is 1 or 2. １ may be an alkylene group or alkylene ether group having 2 to 10 carbon atoms. The photosensitive group represented by Rx may be a group represented by the following formula (2a):

[0014] In formula (2a), R ３ , R ４ and R ５ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ may be a hydrogen atom or a methyl group. ４ and R ５ may be a hydrogen atom.

[0015] All R in the structural unit represented by formula (1) contained in the photosensitive polymer １ and R ２Among these, the proportion of the monovalent organic group represented by formula (2) (introduction rate of the photosensitive group) may be 30 mol % or more, 40 mol % or more, or 45 mol % or more from the viewpoint of heat resistance and dielectric properties, and may be 80 mol % or less, 70 mol % or less, or 60 mol % or less from the viewpoint of alkali developability.

[0016] The tetravalent organic group represented by X in formula (1) may contain an optionally substituted aromatic group, an optionally substituted cycloaliphatic group, or a combination thereof.

[0017] X in formula (1) may be a tetravalent group represented by the following formula (a2), (a3), (a4) or (a5).

[0018] In formulas (a2) to (a5), R １０ represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; m1 represents 1 or 2; m2 represents an integer of 1 to 3; m3 represents an integer of 1 to 4; and multiple R １０ In formula (a3), m1 and m2 may be the same or different. １ represents a direct bond, a methanediyl group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, a carbonyl group, a sulfonyl group, a thio group, a carbonyloxy group, an oxy group, or a fluorene-9,9-diyl group, and k represents an integer of 0 to 2. １ may be the same or different. １０ may be a fluorine atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group), or a fluorinated alkyl group having 1 to 10 carbon atoms (for example, a trifluoromethyl group).

[0019] The divalent organic group represented by Y in formula (1) may contain an optionally substituted aromatic group, an optionally substituted cycloaliphatic group, a siloxane group, or a combination thereof. Y in formula (1) may also be a divalent group represented by the following formula (a6), (a7), or (a8):

[0020] In formulas (a6) to (a7), R １１ represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; m1 represents 1 or 2; m2 represents an integer of 1 to 3; m3 represents an integer of 1 to 4; and multiple R １１ , m1 and m2 may be the same or different.

[0021] In formula (a7), Z ２ represents a direct bond, a methanediyl group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, a carbonyl group, a sulfonyl group, a thio group, a carbonyloxy group, an oxy group, a fluorene-9,9-diyl group, or an amide group, and k represents an integer of 0 to 2. ２ may be the same or different. １１ may be a fluorine atom, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group), or a fluorinated alkyl group having 1 to 10 carbon atoms (for example, a trifluoromethyl group).

[0022] In formula (a8), Z ３ represents an oxy group or an arylene group (e.g., a phenylene group), and R １２ represents an alkyl group having 1 to 10 carbon atoms (for example, a methyl group), and p and q each independently represent an integer of 1 to 10. １２ may be the same or different, and p and q may be integers of 1 to 3.

[0023] The structural unit represented by formula (1) may be a structural unit derived from a reaction product of a tetracarboxylic dianhydride, a diamine, and a (meth)acrylate compound having an isocyanate group.

[0024] Examples of the (meth)acrylate compound having an isocyanate group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2-acryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 2-(2-acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bismethacryloyloxymethyl)ethyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0025] A photosensitive polymer (polyamideimide precursor) having a structural unit represented by formula (1) can be produced, for example, by a method comprising: polycondensing a tetracarboxylic dianhydride with a diamine compound to form a polyamic acid having carboxy groups; and converting at least a portion of the carboxy groups in the polyamic acid to amide groups by reacting the polyamic acid with a (meth)acrylate compound having an isocyanate group. In the polyamideimide precursor obtained by this method, X is usually a residue derived from the tetracarboxylic dianhydride, and Y is a residue derived from the diamine compound.

[0026] An example of a method for synthesizing a photosensitive polymer is a method in which a polyamic acid having a structural unit represented by the following formula (A) is reacted with a compound represented by the following formula (B) with a carboxy group in the polyamic acid.

[0027] In formula (A), X and Y have the same meanings as X and Y in formula (1), and L in formula (B) １ and n is L in formula (2). １ and n, R ３ , R ４ , and R ５ is R in formula (2a) ３ , R ４ , and R ５ is synonymous with.

[0028] A catalyst may be added when reacting a polyamic acid with a (meth)acrylate compound having an isocyanate group, such as 4-dimethylaminopyridine, dibutyltin dilaurate, diazabicyclo(5,4,0)udecene, diisopropoxytitanium bis(ethylacetoacetate), and triphenylphosphine.

[0029] The photosensitive polymer may be synthesized by reacting a polyamic acid having a structural unit represented by formula (A) with an amine compound having a functional group and a compound represented by formula (B). Examples of the amine compound having a functional group include 4-aminobenzoic acid, 3-aminophenol, O-phosphoriethanolamine, and 5-aminobenzimidazole.

[0030] In addition to the constitutional unit represented by formula (1), the photosensitive polymer may contain a constitutional unit represented by formula (A) from the viewpoint of alkali developability.

[0031] The acid value of the photosensitive polymer may be 80 to 130 mgKOH / g, 85 to 120 mgKOH / g, 90 to 115 mgKOH / g, or 95 to 110 mgKOH / g from the viewpoint of alkali solubility.

[0032] The weight average molecular weight (Mw) of the photosensitive polymer may be 8,000 to 150,000, 9,000 to 50,000, 10,000 to 40,000, or 12,000 to 30,000. Mw here refers to a value measured by gel permeation chromatography and converted into standard polystyrene.

[0033] For example, a patterned cured film can be formed using a photosensitive resin composition containing the photosensitive polymer according to this embodiment as component (A). The cured film may contain a constitutional unit represented by the following formula (3):

[0034] In formula (3), X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and L １ represents an organic group having 2 to 10 carbon atoms, and Z represents a cross-linking bond.

[0035] Z may be a crosslinked bond formed by polymerization of two or more monovalent organic groups represented by formula (2), or may be a crosslinked bond formed by polymerization of a monovalent organic group represented by formula (2) with a photopolymerizable monomer described later.

[0036] The cross-linking bond represented by Z in formula (3) may include a structure represented by the following formula (4):

[0037] In formula (4), R ３ , R ４ and R ５ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ may be a hydrogen atom or a methyl group. ４ and R ５ may be a hydrogen atom.

[0038] Fig. 1 is a process diagram showing an example of a method for producing a cured film. The method shown in Fig. 1 includes forming a photosensitive resin film 10A containing a photosensitive resin composition on a substrate 20, irradiating a portion of the photosensitive resin film 10A with actinic light hν (e.g., ultraviolet light), removing a portion of the photosensitive resin film 10A to form a patterned resin film 10B, and heating the resin film 10B to form a cured film 10 containing a polyamideimide resin containing structural units having an amide group and an imide group.

[0039] The photosensitive resin film 10A can be formed by applying a photosensitive resin composition to a substrate 20 and removing the solvent from the coating film as necessary. By irradiating the photosensitive resin film 10A with actinic rays hν through a mask 15 having a light-transmitting portion, a portion of the photosensitive resin film 10A is irradiated with the actinic rays hν. A patterned resin film 10B is then formed by a conventional development method. The resin film 10B is heated by a heating device 30 to promote imidization, thereby forming a cured film 10 containing an imide-based resin. The heating device 30 can be, for example, a heating furnace.

[0040] By heating the resin film 10B at a relatively low temperature, imidization proceeds, and a cured film 10 containing a polyamide-imide resin can be formed. The heating temperature for imidization may be, for example, 350° C. or less, 320° C. or less, 300° C. or less, 280° C. or less, or 260° C. or less, or may be 180° C. or more, 200° C. or more, 220° C. or more, or 230° C. or more. The heating time for imidization may be, for example, 30 minutes or more and 180 minutes or less.

[0041] The photosensitive resin composition may further contain a photopolymerizable monomer as component (B). This photopolymerizable monomer is a compound having k of 1 or greater and is selected from compounds different from component (A). The photopolymerizable group of the photopolymerizable monomer may be, for example, a methacryloyl group or an acryloyl group. The photopolymerizable monomer may be one or more selected from acrylic acid esters of alcohol compounds, methacrylic acid esters of alcohol compounds, acrylamide and its derivatives, and methacrylamide and its derivatives. The acrylic acid ester may be a monoacrylate or polyacrylate (e.g., diacrylate, triacrylate, tetraacrylate). The methacrylic acid ester may be a monomethacrylate or polymethacrylate (e.g., dimethacrylate, trimethacrylate, tetramethacrylate).

[0042] Examples of alcohol compounds that form acrylic acid esters or methacrylic acid esters include alkyl alcohols, alkane polyols, polyether polyols, aromatic polyols, and ethylene oxide or propylene oxide adducts of these alcohol compounds. An example of an alkyl alcohol is isoborneol. Examples of alkane polyols include ethylene glycol, propylene glycol, neopentyl glycol, glycerol, 1,4-butanediol, 1,6-hexanediol, cyclohexanediol, trimethylolpropane, and pentaerythritol. Examples of polyether polyols include polyethylene glycols (e.g., diethylene glycol, tetraethylene glycol) and polypropylene glycol. Examples of aromatic polyols include bisphenol A and trihydroxybenzene.

[0043] The content of the component (B) in the photosensitive resin composition may be 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the component (A). The content of the component (B) may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more per 100 parts by mass of the component (A), and may be 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less.

[0044] The photopolymerization initiator of component (C) may be a photoradical polymerization initiator. Examples of photoradical polymerization initiators include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; and benzoin derivatives such as benzoin and benzoin methyl ether. oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; and titanocenes. Component (C) may be a photoacid generator. An example of the photoacid generator is α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0045] The content of the (C) component may be 0.1 parts by mass or more, 0.5 parts by mass or more, 0.8 parts by mass or more, or 1.0 part by mass or more, and may be 10.0 parts by mass or less, 8.0 parts by mass or less, 6.0 parts by mass or less, or 4.0 parts by mass or less, per 100 parts by mass of the (A) component.

[0046] The photosensitive resin composition may further contain a sensitizer as component (D). By containing component (D), the photosensitive resin composition according to this embodiment can effectively utilize the absorption wavelength of actinic rays used for exposure.

[0047] Examples of component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. From the viewpoint of further improving resolution and adhesion, component (D) may contain a pyrazoline compound or a dialkylaminobenzophenone compound.

[0048] Examples of the pyrazoline compound include 1-(4-methoxyphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1,5-bis-(4-methoxyphenyl)-3-(4-methoxystyryl)-pyrazoline, 1-(4-isopropylphenyl)-3-styryl-5-phenyl-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1,5-bis-(4-isopropylphenyl)-3-(4- isopropylstyryl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(4-isopropyl-styryl)-5-(4-isopropyl 1-(4-methoxyphenyl)-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5 -(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2,4-dimethoxystyryl)-5-(2 ,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,5-dimethoxystyryl)-5 -(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-(4-tert-butyl-phenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3,4-dimethoxystyryl)-5- (3,4-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, and 1-(4-isopropyl-phenyl)-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline.

[0049] Examples of dialkylaminobenzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide.

[0050] From the viewpoint of improving photosensitivity and resolution, the content of the component (D) may be 0.01 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, or 0.1 parts by mass or more, and may be 1.5 parts by mass or less, 1.3 parts by mass or less, 1.0 part by mass or less, or 0.7 parts by mass or less, relative to 100 parts by mass of the component (A).

[0051] The photosensitive resin composition may contain a solvent as component (E) from the viewpoint of adjusting the handleability, viscosity, and storage stability of the photosensitive resin composition. The solvent can be selected from those that dissolve the polyamide precursor well, and may be a polar organic solvent. Examples of solvents include 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and 2-octanone. These may be used alone or in combination of two or more.

[0052] The amount of the component (E) relative to 100 parts by mass of the component (A) may be 30 parts by mass or more and 1,500 parts by mass or less, 100 parts by mass or more and 1,000 parts by mass or less, or 100 parts by mass or more and 500 parts by mass or less.

[0053] A semiconductor device having an insulating resin layer formed from a photosensitive resin composition includes, for example, a semiconductor chip and a wiring layer provided on the semiconductor chip. The wiring layer includes a conductive layer having a wiring pattern and an insulating resin layer that provides insulation between the conductive layers. The insulating resin layer may be a cured product of the photosensitive resin composition according to the present disclosure. The semiconductor device may be a fan-out semiconductor package having a rewiring layer as a wiring layer.

[0054] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0055] Example 1: To a solution of 18.82 g of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA) dissolved in 210.53 g of N-methyl-2-pyrrolidone (NMP), a solution of 10.41 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) dissolved in 60.55 g of NMP was added dropwise and stirred at 30°C for 2 hours to obtain polyamic acid. 14.82 g of 4-dimethylaminopyridine (DMAP) was added thereto at 30°C or below, and the mixture was stirred at room temperature for 30 minutes. 9.46 g of 2-isocyanatoethyl methacrylate (manufactured by Resonac Corporation, trade name "Karenz MOI") was then added over 30 minutes without exceeding 30°C, and the mixture was stirred for 2 hours. 65 g of 2 mol / L hydrochloric acid and 65 g of NMP were added to the reaction solution, and the mixture was stirred for 1 hour. This reaction solution was added dropwise to distilled water to produce a precipitate. The produced polymer was filtered off and dissolved in 75.33 g of NMP and 25.86 g of tetrahydrofuran (THF) to obtain a polymer solution. The polymer solution was added dropwise to 4.0 L of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain a powdery polyamideimide precursor (A1). The Mw of (A1) was 16,000.

[0056] Example 2: A solution of 4.76 g of m-TB in 27.64 g of NMP was added dropwise to a solution of 8.62 g of ODPA in 96.41 g of NMP and stirred at 30°C for 2 hours to obtain a polyamic acid solution. Next, 1.48 g of 4-aminobenzoic acid was added and stirred at 30°C for 1 hour, 6.05 g of DMAP was added and stirred at room temperature for 30 minutes, after which 7.67 g of 2-isocyanatoethyl methacrylate was added over 30 minutes so as not to exceed 30°C, and the reaction was carried out by stirring for 2 hours. 25 g of a 2 mol / L aqueous hydrochloric acid solution and 25 g of NMP were added to the reaction solution and stirred for 1 hour. This reaction solution was added dropwise to distilled water to produce a precipitate. The produced polymer was filtered off and dissolved in 25.37 g of NMP and 10.50 g of THF to obtain a polymer solution. The polymer solution was added dropwise to 4.0 L of water to precipitate the polymer, and the resulting precipitate was filtered and dried in vacuum to obtain a powdery polyamideimide precursor (A2). Mw of (A2) was 18,000.

[0057] Comparative Example 3: 9.07 g of ODPA was placed in a separable flask, and 7.83 g of 2-hydroxyethyl methacrylate (HEMA) and 26.34 g of γ-butyrolactone were added. 4.62 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, under ice cooling, a solution of 12.03 g of dicyclocarbodiimide (DCC) dissolved in 21.85 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, and a suspension of 5.43 g of m-TB in 23.06 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 1.38 g of ethanol was added, and the mixture was stirred for 1 hour, after which 26.34 g of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction mixture. The resulting reaction solution was added to 1.0 L of ethanol to produce a crude polymer precipitate. The crude polymer was collected by filtration and dissolved in 75 g of THF to produce a crude polymer solution. The crude polymer solution was added dropwise to 2.0 L of distilled water to precipitate the polymer. The resulting precipitate was collected by filtration and vacuum dried to produce powdered polyamic acid ester (A3). The Mw of (A3) was 39,500.

[0058] (Weight-average molecular weight) 0.5 mg of polymer (polyamideimide precursor or polyamic acid ester) was dissolved in 1 mL of solvent (tetrahydrofuran / dimethylformamide = 1 / 1 (volume ratio)) to prepare a solution for measuring the weight-average molecular weight (Mw). Mw was measured by gel permeation chromatography (GPC) using the following equipment and conditions, and calculated using a calibration curve of standard polystyrene. Detector: L4000UV (UV 270 nm, manufactured by Hitachi, Ltd.) Pump: L-6000 (manufactured by Hitachi, Ltd.) Data processing device: C-R4A Chromatopac (manufactured by Shimadzu Corporation) Column: Gelpack GL-S300MDT-5 x 2 (Resonac Corporation) Eluent: LiBr (0.03 mol / L) and H ３ P.O. ４ (0.06 mol / L) in tetrahydrofuran / dimethylformamide (volume ratio: 1 / 1) Flow rate: 1.0 mL / min

[0059] (NMR) NMR measurements were carried out on the polyamic acid and polyamideimide precursor, and the introduction of photosensitive groups derived from 2-isocyanatoethyl methacrylate was identified under the following conditions. Figure 2 shows the NMR spectrum of the polyamic acid of Example 1, and Figure 3 shows the NMR spectrum of the polyamideimide precursor. Apparatus: FT-NMR AV400M (manufactured by Bruker Biospin Co., Ltd.) Magnetic field strength: 400 MHz Reference substance: tetramethylsilane (TMS) Solvent: dimethyl sulfoxide (DMSO)

[0060] (Acid Value) The introduction rate of the photosensitive group was calculated by measuring the acid value of the polymer before and after the introduction of the photosensitive group using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., product name "COM-1750S") using a 0.05 mol / L aqueous potassium hydroxide solution as a standard substance. Since the acid value of the polyamic acid before the reaction with 2-isocyanatoethyl methacrylate was 220 mg KOH / g and the acid values ​​of the polyamideimide precursors (A1) and (A2) were 110 mg KOH / g, the introduction rate of the photosensitive group in Examples 1 and 2 was 50 mol%.

[0061] [Photosensitive Resin Composition] Photosensitive resin compositions of Examples and Comparative Examples were prepared using the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of component (A).

[0062] Component (A): Photosensitive polymer A-1: ​​Polyamideimide precursor (A1) A-2: Polyamideimide precursor (A2) A-3: Polyamic acid ester (A3)

[0063] Component (B): Polymerizable monomer B-1: Tetraethylene glycol dimethacrylate (TEGDMA, manufactured by Shin-Nakamura Chemical Co., Ltd.) B-2: Ethoxylated pentaerythritol tetraacrylate (ATM-4E, manufactured by Shin-Nakamura Chemical Co., Ltd.) B3: Bisphenol A epoxy acrylate (Viscoat #540, manufactured by Osaka Organic Chemical Industry Ltd.) Component (C): Photopolymerization initiator C-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02, manufactured by BASF Japan Ltd.) Component (D): Sensitizer D-1: 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Co., Ltd.) Component (E): Solvent E-1: N-methyl-2-pyrrolidone (NMP) E-2: 3-methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals Co., Ltd., trade name "KJCMPA-100")

[0064] [Patterned Cured Film] (Examples 1 and 2) A photosensitive resin composition was spin-coated onto a 6-inch diameter silicon wafer using a coating device (manufactured by Mikasa Co., Ltd., trade name "MS-A200"), and heated at 100°C for 2 minutes, followed by heating at 110°C for 2 minutes to form a photosensitive resin film. The photosensitive resin film was exposed to broadband (BB) light using a mask aligner (manufactured by Mikasa Co., Ltd., trade name "ML-320FSAT") in a predetermined pattern (a strip-shaped pattern with a width of 10 mm). The exposed photosensitive resin film was paddle-developed with 2.38% tetramethylammonium hydroxide (TMAH) using a developing machine (Takizawa Sangyo Co., Ltd., trade name "AD-3000"), and then rinsed with pure water to obtain a patterned resin film. The patterned resin film was heated in a high-temperature clean oven (manufactured by JTEKT Corporation, trade name "CLH-35CD") at 230°C for 2 hours in a nitrogen atmosphere to obtain a patterned cured film (thickness 10 µm).

[0065] Comparative Example 1 A patterned cured film was obtained in the same manner as in Examples 1 and 2, except that the exposed photosensitive resin film was paddle-developed with cyclopentanone and rinsed with propylene glycol monomethyl ether acetate.

[0066] [Evaluation] (Glass transition temperature) A silicon wafer with a patterned cured film was immersed in a 5.0 mass% hydrofluoric acid aqueous solution for 15 minutes, and the cured film was peeled off from the silicon wafer to obtain a cured film having a width of 10 mm, a length of 30 mm, and a thickness of 10 μm. Using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Corporation), the temperature was increased from 30° C. to 380° C. at a rate of 5° C. / min, and the glass transition temperature (Tg) was calculated from the peak of tan δ.

[0067] (5% Weight Loss Temperature) Using a thermogravimetric analyzer (manufactured by Hitachi High-Technologies Corporation, product name "STA7300"), the temperature was increased from room temperature at a rate of 10°C / min. The weight of the cured film when it reached 100°C was taken as 100%, and the temperature at which the weight decreased by 5% was measured as the 5% weight loss temperature (5% Td).

[0068] (Linear expansion coefficient) A silicon wafer with a patterned cured film was immersed in a 5.0 mass% hydrofluoric acid aqueous solution for 15 minutes, and the cured film was peeled off from the silicon wafer to obtain a cured film having a width of 4 mm, a length of 30 mm, and a thickness of 10 μm. Using a thermomechanical analyzer (manufactured by Hitachi High-Technologies Corporation, product name "TMA7100"), the temperature was raised from 30°C to 380°C at a rate of 5°C / min in a tensile mode under atmospheric conditions, and the linear expansion coefficient (CTE) of the cured film from 100 to 150°C was calculated.

[0069] (Dielectric Properties) A ​​photosensitive resin composition was spin-coated onto a 6-inch silicon wafer using a coating device (MS-A200) so that the film thickness after curing would be approximately 10 μm, and the wafer was pre-baked on a hot plate at 100° C. for 2 minutes and then at 110° C. for 2 minutes. The wafer was then exposed to light at an exposure dose of 500 mJ / cm using a mask aligner (manufactured by Mikasa Co., Ltd., product name "ML-320FSAT"). ２ After that, the film was heated at 230° C. for 2 hours in a nitrogen atmosphere using a high-temperature clean oven CLH-35CD (manufactured by JTEKT Corporation) to obtain a cured film.

[0070] The silicon wafer on which the cured film was formed was immersed in a 5.0% by mass hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer to obtain a test piece for dielectric properties. The dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece at 10 GHz at 25°C were measured by a cavity resonator perturbation method using a split cylinder resonator. A network analyzer (MS46122B, manufactured by Anritsu Corporation) was used as the measuring device. The dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample were measured in the 10 GHz band at an ambient temperature of 25°C according to the cavity resonator perturbation method.

[0071]

[0072] It was confirmed that the photosensitive resin films formed from the photosensitive resin compositions containing the photosensitive polymers of Examples 1 and 2 can be developed in an alkaline environment, and the cured photosensitive resin films have excellent heat resistance and dielectric properties.

[0073] 10A...photosensitive resin film, 10B...resin film, 10...cured film, 15...mask, 20...substrate, 30...heating device.

Claims

1. The following formula (1): X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and R １ and R ２ are each independently a carboxy group or a group represented by the following formula (2): R represents a monovalent organic group represented by １ or R ２ At least one of L is a monovalent organic group represented by the formula (2), １ represents an organic group having 2 to 10 carbon atoms, Rx represents a photosensitive group, and n is 1 or 2.

2. The photosensitive group is represented by the following formula (2a): is a group represented by R ３ , R ４ and R ５ 2. The photosensitive polymer according to claim 1, wherein each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

3. The photosensitive polymer according to claim 1, wherein the structural unit represented by formula (1) is a structural unit derived from a reaction product of a tetracarboxylic dianhydride, a diamine, and a (meth)acrylate compound having an isocyanate group.

4. A photosensitive resin composition containing the photosensitive polymer according to any one of claims 1 to 3.

5. The following formula (3): X represents a tetravalent organic group having 6 to 40 carbon atoms, Y represents a divalent organic group having 6 to 40 carbon atoms, and L １ represents an organic group having 2 to 10 carbon atoms, and Z represents a crosslinking bond.

6. The cross-linking bond is represented by the following formula (4): R ３ , R ４ and R ５ The cured film according to claim 5, wherein each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

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