TW202413490A - Photosensitive resin composition for forming insulating film - Google Patents

Abstract

A photosensitive resin composition for forming an insulating film, the composition comprising a solvent and at least one polymer from among polyimides, polyamic acids, and polyamic acid esters, said polymer including a photopolymerizable group, an aromatic group, and an alkyl group with 5 or more carbon atoms.

Description

Photosensitive resin composition for forming insulating film

The present invention relates to a photosensitive resin composition for forming an insulating film, an insulating film obtained from the composition, a photosensitive resist film using the composition, a method for manufacturing a substrate with a hardened relief pattern, and a semiconductor device having a hardened relief pattern.

In the past, polyimide resins with excellent heat resistance, electrical properties and mechanical properties were used in insulating materials for electronic parts, passivation films, surface protection films and interlayer insulation films of semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors in particular can easily form heat-resistant relief pattern coatings through thermal imidization treatments such as coating, exposure, development and curing of the precursors. Compared with conventional non-photosensitive polyimide resins, this photosensitive polyimide precursor has the characteristic of greatly reducing the number of steps.

Patent Documents 1 and 2 propose a photosensitive resin composition containing polyamide or polyimide using a diamine having a (meth)acryloxy group. In addition, since the passivation film, surface protection film, interlayer insulation film, etc. of the semiconductor device are made thicker and have a higher elastic modulus, the stress increases, the warp of the semiconductor wafer increases, and defects may occur during transportation and wafer fixing. Therefore, it is desired to develop a polyimide resin with low residual stress. As for the method of reducing the residual stress of polyimide resin, there can be cited a method of setting the molecular chain of polyimide into a rigid skeleton in order to make the thermal expansion coefficient of polyimide close to the thermal expansion coefficient of silicon wafer (for example, patent document 3). [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2000-347404 [Patent Document 2] Japanese Patent Publication No. 2012-516927 [Patent Document 3] Japanese Patent Publication No. 5-295115

[The problem that the invention wants to solve]

In recent years, semiconductor devices must transmit and process large amounts of information at high speed, so the frequency of electrical signals has been increasing. Since high-frequency electrical signals are prone to attenuation, transmission loss must be reduced. Therefore, low dielectric loss tangent is required for insulating films used in semiconductor devices.

When the hardened relief pattern is formed, development is performed with a developer, but generally an alkaline aqueous developer or an organic solvent developer is used. The photosensitive resin used to obtain the hardened relief pattern is divided into a positive type in which the photosensitive resin in the exposed part is dissolved in the developer and the photosensitive resin in the unexposed part remains, and a negative type in which the photosensitive resin in the unexposed part is dissolved in the developer and the photosensitive resin in the exposed part remains. In particular, although the negative type has poorer resolution than the positive type, it is easy to make thicker or thinner films and has excellent reliability, and is used in the manufacture of semiconductor devices that require such characteristics. On the other hand, in the case of a negative photosensitive resin containing polyimide, there is a problem that the development time is long when developing with an organic solvent. In addition, in order to reduce the warp of the semiconductor wafer, it is desirable that the residual stress of the negative photosensitive resin be low, especially when the film thickness is increased.

Therefore, a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent in the obtained insulating film, a short developing time during organic solvent development, and low residual stress is sought. However, the photosensitive resin compositions described in Patent Documents 1 to 3 do not satisfy all of these characteristics.

The purpose of the present invention is to provide, in view of the above circumstances, a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent in the obtained insulating film, a short developing time in organic solvent development, and low residual stress; an insulating film obtained from the composition; a photosensitive resist film using the composition; a method for manufacturing a substrate with a hardened relief pattern; and a semiconductor device having a hardened relief pattern. [Means for solving the problem]

The inventors of this case have continued to work hard to achieve the above-mentioned problems and have found that by including a specific polymer in the photosensitive resin composition for forming an insulating film, a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent, a short developing time during organic solvent development, and low residual stress can be obtained, thereby completing the present invention.

[1] A photosensitive resin composition for forming an insulating film, comprising a polymer of at least one of polyimide, polyamic acid, and polyamic acid ester, and a solvent, wherein the polymer has a photopolymerizable group, an aromatic group, and an alkyl group having 5 or more carbon atoms. [2] A photosensitive resin composition for forming an insulating film as described in [1], wherein the polyimide is the following polyimide (1), the polyamic acid is the following polyamic acid (2), and the polyamic acid ester is the following polyamic acid ester (3), wherein the polyimide (1) is a polyimide having structural units represented by the following formula (1-a), the following formula (1-b), and the following formula (1-c), the polyamic acid (2) is a polyamic acid having structural units represented by the following formula (2), the following formula (1-b), and the following formula (1-c), and the polyamic acid ester (3) is at least one of the following polyamic acid esters (3a) to (3b), Polyamic acid ester (3a): a polyamic acid ester having structural units represented by the following formula (3-a) and the following formula (1-b), Polyamic acid ester (3b): a polyamic acid ester having structural units represented by the following formula (3-b), the following formula (1-b), and the following formula (1-c), [Chemical 1] In formula (1-a), _Ar1 represents a tetravalent organic group, in formula (1-b), X represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms, in formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group, [Chemical 2] In formula (2), _Ar2 represents a tetravalent organic group, [Chemical 3] In formula (3-a), Ar ₃ represents a tetravalent organic group, L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group. In formula (3-b), Ar ₄ represents a tetravalent organic group, R ₁ and R ₂ each independently represent a monovalent organic group. [3] The photosensitive resin composition for forming an insulating film according to [2], wherein in formula (1-b), X represents a divalent organic group represented by any one of the following formulas (V-1) to (V-6), [Chemical 4] In formula (V-1), ^Xv1 represents -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, and ^Rv1 represents an alkyl group having 5 to 20 carbon atoms. In formulas (V-2) to (V-5), ^Xv2 to ^Xv5 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^Rv2 to ^Rv5 each independently represent an alkyl group having 5 to 20 carbon atoms. In formula (V-6), _Xa represents a single bond, -O-, -NH-, -O-( _CH2 ) _m -O-, -C( _CH3 ) _2- , -CO-, -( _CH2 ) _m -, _-SO2- , -OC( _CH3 ) _2- , -CO-(CH2) _m- , -NH-( _CH2 )m-, -SO2-( _CH2 )m-, -CONH-(CH2) _m- , -CONH-( _CH2 ) _m -NHCO- _{, -COO-} (CH2)m-OCO-, -CONH-, -NH-( _CH2 ) _m -NH-, or _-SO2- (CH2) _m -SO2-, wherein m represents an integer of 1 to 6, Xp1 and _Xp2 each independently represent -( _CH2 ) _a- , -CONH-, _-NHCO- , -CON( _CH3 )-, -NH-, -O-, -CH2-O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^R1a and ^R2 are independently -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, -CH2-O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^R1a and R2 are independently -( _CH2 )a-, -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2-O-, _-CH2- OCO-, -COO-, or -OCO-. ^1b each independently represents an alkyl group having 5 to 20 carbon atoms, k1 and k2 each independently represent an integer of 0 to 2, In formulas (V-1) to (V-6), * represents an atomic bond. [4] A photosensitive resin composition for forming an insulating film as described in [2] or [3], wherein in the formula (1-c), Y represents a divalent organic group represented by the following formula (9-a), In the formula (3-a), _L1 and _L2 each independently represent a monovalent organic group represented by the following formula (9-b), [Chemistry 5] In formula (9-a), V ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, or a urea bond, W ₁ represents an oxygen atom or an NH group, R ₁₅ represents an alkylene group having 2 to 6 carbon atoms which is a direct bond or may be substituted with a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents an atomic bond. [Chemistry 6] In formula (9-b), _W2 represents an oxygen atom or an NH group, _R17 represents an alkylene group having 2 to 6 carbon atoms which is directly bonded or optionally substituted by a hydroxyl group, _R18 represents a hydrogen atom or a methyl group, and * represents an atomic bond. [5] The photosensitive resin composition for forming an insulating film as described in [4], wherein _V1 in the formula (9-a) represents an ester bond and _W1 represents an oxygen atom. [6] The photosensitive resin composition for forming an insulating film as described in [4] or [5], wherein _R15 in the formula (9-a) represents a 1,2-ethylene group. [7] The photosensitive resin composition for forming an insulating film as described in any one of [1] to [6], further comprising a photoradical polymerization initiator. [8] The photosensitive resin composition for forming an insulating film as described in any one of [1] to [7], further comprising a crosslinking compound. [9] The photosensitive resin composition for forming an insulating film as described in any one of [1] to [8] is a negative photosensitive resin composition. [10] An insulating film is a calcined product of a coating film of the photosensitive resin composition for forming an insulating film as described in any one of [1] to [9]. [11] A photosensitive resist film comprising: a substrate film, a photosensitive resin layer formed by the photosensitive resin composition for forming an insulating film as described in any one of [1] to [9], and a cover film. [12] A method for manufacturing a substrate with a hardened relief pattern, comprising the following steps: (1) applying a photosensitive resin composition for forming an insulating film as described in any one of claims 1 to 9 onto a substrate to form a photosensitive resin layer on the substrate, (2) exposing the photosensitive resin layer, (3) developing the exposed photosensitive resin layer to form a relief pattern, and (4) heating the relief pattern to form a hardened relief pattern. [13] A method for manufacturing a substrate with a hardened relief pattern as described in [12], wherein the developer used in the developing is an organic solvent. [14] A substrate with a hardened relief pattern is manufactured by the method for manufacturing a substrate with a hardened relief pattern as described in [12] or [13]. [15] A semiconductor device comprising a semiconductor element and a cured film disposed on the upper part or the lower part of the semiconductor element, wherein the cured film is a cured relief pattern formed by the photosensitive resin composition for forming an insulating film as described in any one of [1] to [9]. [Effects of the Invention]

According to the present invention, a photosensitive resin composition for forming an insulating film having a low dielectric loss tangent, a short developing time during organic solvent development, and low residual stress can be obtained; an insulating film obtained from the composition; a photosensitive resist film using the composition; a method for manufacturing a substrate with a hardened relief pattern; and a semiconductor device having a hardened relief pattern.

(Photosensitive resin composition for forming insulating film) The photosensitive resin composition for forming insulating film of the present invention contains at least a polymer and a solvent, and may contain other components as needed.

<Polymer> The polymer is at least one of polyimide, polyamic acid, and polyamic acid ester. Hereinafter, the polymer may be referred to as a "specific polymer". The specific polymer has a photopolymerizable group. The specific polymer has an aromatic group. The specific polymer has an alkyl group having 5 or more carbon atoms.

The inventors of this case speculate that the reasons why the effects of the present invention are exerted by the photosensitive resin composition for forming an insulating film of the present invention are as follows. By making the specific polymer have a photopolymerizable group, photosensitivity is imparted to the resin composition containing the specific polymer. By making the specific polymer have an alkyl group with more than 5 carbon atoms and an aromatic group, the dielectric loss tangent of the insulating film is reduced. By making the specific polymer have an alkyl group with more than 5 carbon atoms and an aromatic group, the developing time during development with an organic solvent can be shortened. By making the specific polymer have an alkyl group with more than 5 carbon atoms, the residual stress can be reduced.

As for the polyimide, the following polyimide (1) is more preferable. As for the polyamine, the following polyamine (2) is more preferable. As for the polyamic acid ester, the following polyamic acid ester (3) is more preferable. Polyimide (1) is a polyimide having structural units represented by the following formula (1-a), the following formula (1-b), and the following formula (1-c). Polyamic acid (2) is a polyamic acid having structural units represented by the following formula (2), the following formula (1-b), and the following formula (1-c). Polyamic acid ester (3) is at least one of the following polyamic acid esters (3a) to (3b). Polyamic acid ester (3a) is a polyamic acid ester having structural units represented by the following formula (3-a) and the following formula (1-b). Polyamic acid ester (3b) is a polyamic acid ester having structural units represented by the following formula (3-b), the following formula (1-b), and the following formula (1-c).

[Chemistry 7] In formula (1-a), _Ar1 represents a tetravalent organic group. In formula (1-b), X represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms. In formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group.

[Chemistry 8] In formula (2), _Ar2 represents a tetravalent organic group.

[Chemistry 9] In formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group. In formula (3-b), Ar ₄ represents a tetravalent organic group, and R ₁ and R ₂ each independently represent a monovalent organic group.

＜＜Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ ＞＞ Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent a tetravalent organic group. The tetravalent organic group is not particularly limited, but a tetravalent organic group having two or more aromatic rings is preferred from the viewpoint of lowering the dielectric loss shear of the insulating film.

The number of aromatic rings possessed by the tetravalent organic group having two or more aromatic rings is not particularly limited as long as it is two or more, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, eight or less, or six or less.

Regarding the counting method of the aromatic rings in "two or more aromatic rings", polycyclic aromatic rings formed by condensing two or more aromatic rings such as the naphthalene ring and the anthracene ring are counted as one aromatic ring. Therefore, the naphthalene ring is counted as one aromatic ring. On the other hand, the biphenyl ring is counted as two aromatic rings because it is not a condensed ring. In addition, the perylene ring is regarded as a structure formed by two naphthalene rings bonded together and is counted as two aromatic rings. As for the aromatic rings, there are aromatic hydrocarbon rings, aromatic heterocyclic rings, etc.

From the viewpoint of appropriately obtaining the effects of the present invention, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are preferably tetravalent organic groups represented by the following formula (4). In formula (4), _X1 and _X2 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a carbamate bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond ( _-SO2- ). _Ra1 and _Ra2 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. _Z1 represents a divalent organic group represented by the following formula (5-a), the following formula (5-b), the following formula (5-c) or the following formula (5-d). n1 and n2 each independently represent an integer of 0 to 3. When _Ra1 is plural, the plural _Ra1s may be the same or different. When _Ra2 is plural, the plural _Ra2s may be the same or different. * indicates an atomic bond.

As for the alkyl group having 1 to 6 carbon atoms which may be substituted in R _a1 and R _a2 in formula (4), for example, an alkyl group having 1 to 6 carbon atoms may be exemplified. As for the alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. may be exemplified. In the present specification, unless the structure of the alkyl group or the alkylene group is particularly mentioned, the alkyl group or the alkylene group may be a linear chain, a branched group, a cyclic group, or a combination of two or more thereof. As for the substituent in the alkyl group having 1 to 6 carbon atoms which may be substituted, for example, a halogen atom, a hydroxyl group, a thiol group, a carboxyl group, a cyano group, a formyl group, a halogenated formyl group, a sulfonic acid group, an amino group, a nitro group, a nitroso group, a pendyl group, a thioxy group, an alkoxy group having 1 to 6 carbon atoms, etc. may be exemplified. In addition, the "carbon number of 1 to 6" in the "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the carbon number of the "alkyl group" excluding the substituent. The number of substituents is not particularly limited.

[Chemistry 11] In formula (5-a), R ₃ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m ₁ represents an integer of 0 to 4. When m ₁ is 2 or more, R ₃ may be the same or different. In formula (5-b), Z ₂ represents a direct bond, or a divalent organic group represented by the following formula (6-a) or the following formula (6-b), R ₄ and R ₅ each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m ₂ and m ₃ each independently represent an integer of 0 to 4. When m ₂ is 2 or more, R ₄ may be the same or different. When m ₃ is 2 or more, R ₅ may be the same or different. In formula (5-c), R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m ₄ represents an integer of 0 to 6. When m ₄ is 2 or more, R ₆ may be the same or different. In formula (5-d), Z ₃ represents a direct bond, or a divalent organic group represented by the following formula (6-a) or the following formula (6-b). * represents an atomic bond.

[Chemistry 12] In formula (6-a), R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. In formula (6-b), R ₉ and R ₁₀ each independently represent an alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom or an arylene group having 6 to 12 carbon atoms which may be substituted with a substituted alkylene group. * represents an atomic bond.

From the viewpoint of obtaining the effect of the present invention, Z ₁ is preferably a divalent organic group represented by formula (5-b). From the viewpoint of obtaining the effect of the present invention, Z ₂ in formula (5-b) is preferably a direct bond. From the viewpoint of obtaining the effect of the present invention, R ₄ and R ₅ in formula (5-b) are preferably methyl groups.

As for the alkyl group with 1 to 6 carbon atoms which may be substituted with a halogen atom in _R7 and _R8 , there can be mentioned an alkyl group with 1 to 6 carbon atoms, a halogenated alkyl group with 1 to 6 carbon atoms, etc. As for the alkyl group with 1 to 6 carbon atoms, there can be mentioned a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. As for the halogenated atom in the halogenated alkyl group with 1 to 6 carbon atoms, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. The halogenated atom in the halogenated alkyl group with 1 to 6 carbon atoms may be a part or all.

As for the substituent in the alkylene group having 1 to 6 carbon atoms which may be substituted in _R9 and _R10 , for example, a halogen atom, a hydroxyl group, a thiol group, a carboxyl group, a cyano group, a formyl group, a halogenated formyl group, a sulfonic acid group, an amino group, a nitro group, a nitroso group, a pendoxy group, a thioxy group, an alkoxy group having 1 to 6 carbon atoms, etc. As for the alkylene group having 1 to 6 carbon atoms which may be substituted, for example, an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, etc. As for the alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, etc. In addition, the "carbon number 1 to 6" in the "alkylene group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms of the "alkylene group" excluding the substituent. Furthermore, there is no particular limitation on the number of substituents.

As for the substituent in the arylene group having 6 to 10 carbon atoms which may be substituted in R ₉ and R ₁₀ , there can be exemplified a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be halogenated, an alkoxy group having 1 to 6 carbon atoms which may be halogenated, etc. In addition, the halogenation may be partial or complete. As for the arylene group, there can be exemplified a phenylene group, a naphthylene group, etc. In addition, the "6 to 10 carbon atoms" in the "arylene group having 6 to 10 carbon atoms which may be substituted" refers to the number of carbon atoms of the "arylene group" excluding the substituent. In addition, there is no particular limitation as to the number of substituents.

The divalent organic group represented by the formula (6-a) includes the divalent organic group represented by the following formula. [Chemistry 13] In the formula, * represents an atomic bond.

As the divalent organic group represented by the formula (6-b), the divalent organic group represented by the following formula can be cited. In the formula, R ₃₁ to R ₃₃ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. n31 represents an integer of 0 to 5. n32 and n33 each independently represent an integer of 0 to 4. When R ₃₁ is plural, the plural R _31s may be the same or different. When R ₃₂ is plural, the plural R _32s may be the same or different. When R ₃₃ is plural, the plural R _33s may be the same or different. * represents an atomic bond.

Specific examples of the alkyl group with 1 to 6 carbon atoms which may be substituted with a halogen atom in R ₃₁ to R ₃₃ include alkyl groups with 1 to 6 carbon atoms and halogenated alkyl groups with 1 to 6 carbon atoms. Examples of the alkyl group with 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. Examples of the halogenated atom in the halogenated alkyl group with 1 to 6 carbon atoms include fluorine, chlorine, bromine, and iodine. The halogenated atom in the halogenated alkyl group with 1 to 6 carbon atoms may be partially or completely halogenated. Specific examples of the alkoxy group with 1 to 6 carbon atoms which may be substituted with a halogen atom in R ₃₁ to R ₃₃ include the alkyl group with 1 to 6 carbon atoms which may be substituted with a halogen atom and replaced with an alkoxy group.

As the tetravalent organic group having two or more aromatic rings, the tetravalent organic group represented by the following formula can be cited. [Chemistry 15] [Chemistry 16] In the formula, * represents an atomic bond.

＜＜X＞＞ X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms. The alkyl group with 5 or more carbon atoms may be directly bonded to the aromatic ring of the divalent aromatic group or may be bonded via other linking groups. The number of carbon atoms in the alkyl group is not particularly limited as long as it is 5 or more, and may be, for example, 40 or less, 35 or less, or 30 or less. The number of carbon atoms in the alkyl group is preferably 8 or more and 40 or less, more preferably 10 or more and 35 or less, and particularly preferably 12 or more and 30 or less. The alkyl group may be a straight chain, a branched chain, a ring, or a combination of two or more thereof.

As for X, from the viewpoint of ideally obtaining the effect of the present invention, a divalent aromatic group represented by any one of formulae (V-1) to (V-6) is more ideal. [Chem. 17] In formula (V-1), ^Xv1 represents -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, and ^Rv1 represents an alkyl group having 5 to 20 carbon atoms. In formulas (V-2) to (V-5), ^Xv2 to ^Xv5 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^Rv2 to ^Rv5 each independently represent an alkyl group having 5 to 20 carbon atoms. In formula (V-6), _Xa represents a single bond, -O-, -NH-, -O-( _CH2 ) _m -O-, -C( _CH3 ) _2- , -CO-, -( _CH2 ) _m- , _-SO2- , -OC( _CH3 ) _2- , -CO-( _CH2 ) _m- , -NH-( _CH2 ) _m- , _-SO2- ( _CH2 ) _m- , -CONH-( _CH2 ) _m- , -CONH-( _CH2 ) _m -NHCO-, -COO-( _CH2 ) _m -OCO-, -CONH-, -NH-( _CH2 ) _m -NH-, or _-SO2- ( _CH2 ) _m - _SO2- , wherein m represents an integer of 1 to 6, and ^Xp1 and ^Xp2 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON(CH2)m- ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms, and k1 and k2 each independently represent an integer of 0 to 2. In formulas (V-1) to (V-6), * represents an atomic bond.

^Xv1 to ^Xv5 preferably represent -O-. ^Xp1 and ^Xp2 preferably represent _-CH2 -O-. _Xa preferably represents a single bond.

＜＜Y＞＞ Y represents a divalent aromatic group having a photopolymerizable group. As for the photopolymerizable group, free radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups can be listed. Among these, free radical polymerizable groups are more desirable. As for the free radical polymerizable group, acryl group, methacryl group, acryl ether group, vinyl ether group, vinyl group, etc. can be listed.

Examples of the aromatic ring in the divalent aromatic group having a photopolymerizable group include a benzene ring, a naphthalene ring, an anthracene ring and the like.

The divalent aromatic group having a photopolymerizable group is, for example, a residue formed by removing two amine groups from an aromatic diamine compound having a photopolymerizable group.

The divalent aromatic group having a photopolymerizable group is preferably a divalent organic group represented by the following formula (9-a). In formula (9-a), _V1 represents a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, or a urea bond, _W1 represents an oxygen atom or an NH group, _R15 represents an alkylene group having 2 to 6 carbon atoms which is a direct bond or may be substituted with a hydroxyl group, _R16 represents a hydrogen atom or a methyl group, and * represents an atomic bond.

The two atomic bonds in formula (9-a) are, for example, atomic bonds to nitrogen atoms.

In the present specification, examples of the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group include 1,1-ethylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,2-butylene, 2,3-butylene, 1,2-pentylene, 2,4-pentylene, 1,2-hexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, and alkylene groups in which at least a part of the hydrogen atoms are substituted with a hydroxyl group (e.g., 2-hydroxy-1,3-propylene).

V ₁ preferably represents an ester bond (-COO-). W ₁ preferably represents an oxygen atom. R ₁₅ preferably represents a 1,2-ethylene group.

As the divalent organic group represented by formula (9-a), the divalent organic group represented by the following formula can be cited. In the formula, * represents an atomic bond. For example, two atomic bonds are located at the meta position relative to the substituent having a photopolymerizable group.

＜＜L ₁ 、和L ₂ ＞＞ L ₁ 、和L ₂ each independently represent a monovalent organic group having a photopolymerizable group. Examples of the photopolymerizable group include free radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, free radical polymerizable groups are preferred. Examples of the free radical polymerizable group include acryloyl group, methacryloyl group, acryloyl ether group, vinyl ether group, and vinyl group.

As the monovalent organic group having a photopolymerizable group, a monovalent organic group represented by the following formula (9-b) is preferred. In formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents an alkylene group having 2 to 6 carbon atoms which is directly bonded or optionally substituted by a hydroxyl group, R ₁₈ represents a hydrogen atom or a methyl group, and * represents an atomic bond.

_W2 preferably represents an oxygen atom. _R17 preferably represents a 1,2-ethylene group.

<<R ₁ , and R ₂ >> R ₁ , and R ₂ each independently represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group. Examples of the linear alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group (lauryl group), a tridecyl group, a tetradecyl group (myristyl group), a pentadecyl group, a hexadecyl group (palmityl group), a heptadecyl group (margaryl group), an octadecyl group (stearyl group), a nonadecyl group, an arachyl group, a heneicosyl group, a behenyl group, a tricosyl group, a tetracosyl group (lignoceryl group), a pentacosyl group, a hexacosyl group, a heptacosyl group, and the like. As for the branched chain alkyl group having 1 to 30 carbon atoms, there may be mentioned isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, d-isopentyl, isohexyl, neohexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-ethylpentyl, heptane-3-yl, heptane-4-yl, 4-methylhexane-2-yl, 3-methylhexane-3-yl, 2,3-dimethylpentane-2-yl, 2,4-dimethylpentane-2-yl, 4,4-dimethylpentane-2-yl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-ethylpentyl, heptane-3-yl, heptane-4-yl, 4-methylhexane-2-yl, 3-methylhexane-3-yl, 2,3-dimethylpentane-2-yl, 2,4-dimethylpentane-2-yl, 4,4-dimethylpentane-2-yl, 6-methylheptyl, 2-ethylhexyl, 2-Methylhexyl, octane-2-yl, 6-methylheptane-2-yl, 6-methyloctane, 3,5,5-trimethylhexyl, nonane-4-yl, 2,6-dimethylheptane-3-yl, 3,6-dimethylheptane-3-yl, 3-ethylheptane-3-yl, 3,7-dimethyloctane, 8-methylnonyl, 3-methylnonane-3-yl, 4-ethyloctane-4-yl, 9-methyldecyl, undecane-5-yl, 3-ethylnonane-3-yl, 5-ethylnonane-5-yl, 2,2,4,5,5-pentamethylhexane-4-yl, 10-methylundecyl, 11-methyldodecyl, tridecane -6-yl, tridecane-7-yl, 7-ethylundecane-2-yl, 3-ethylundecane-3-yl, 5-ethylundecane-5-yl, 12-methyltridecyl, 13-methyltetradecyl, pentadecane-7-yl, pentadecane-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, heptadecan-8-yl, heptadecan-9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundecane-5-yl, 16-methylheptadecyl, 17-methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10 ,14-tetramethylpentadecan-7-yl, 18-methylnonadecan-7-yl, 19-methyleicosyl, heneicosyl, 20-methylheneicosyl, 21-methyldocosyl, tricosan-11-yl, 22-methyltricosanyl, 23-methyltetracosyl, pentacosan-12-yl, pentacosan-13-yl, 2,22-dimethyltricosan-11-yl, 3,21-dimethyltricosan-11-yl, 9,15-dimethyltricosan-11-yl, 24-methylpentacosanyl, 25-methylhexacosanyl, heptacosan-13-yl, etc. Examples of the alicyclic alkyl group having 1 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1,6-dimethylcyclohexyl, mentholyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptan-2-yl, bornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclo[5.2.1.0 ^2,6 ]decan-4-yl, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl, and cyclododecyl.

Polyamic acid ester (3) may also be the following polyamic acid ester (3c). Polyamic acid ester (3c): A polyamic acid ester having structural units represented by the above formula (3-b), the following formula (3-c), and the above formula (1-b). However, in formula (3-b), the tetravalent organic group in Ar ₄ represents a tetravalent organic group having two or more aromatic rings. [Chemistry 21] In formula (3-c), Ar ₅ represents a tetravalent organic group, and L ₃ and L ₄ each independently represent a monovalent organic group having a photopolymerizable group.

Examples of the monovalent organic group having a photopolymerizable group in L ₃ and L ₄ include the monovalent organic groups having a photopolymerizable group exemplified in the description of L ₁ and L ₂ .

＜＜Ar ₅ ＞＞ Ar ₅ represents a tetravalent organic group. The tetravalent organic group is not particularly limited, and examples thereof include tetravalent organic groups other than tetravalent organic groups having two or more aromatic rings. Examples of such a tetravalent organic group include a tetravalent organic group represented by the following formula. [Chem. 22] [Chemistry 23] In the formula, * represents an atomic bond.

<<Other tetravalent organic groups>> The specific polymer may also have a tetravalent organic group other than the tetravalent organic groups exemplified so far.

＜＜Other divalent organic groups＞＞ The specific polymer may also have divalent organic groups other than X and Y. For example, in view of obtaining a lower dielectric loss tangent in the obtained insulating film, a divalent organic group having three or more aromatic rings is more desirable. The divalent organic group having three or more aromatic rings is, for example, a residue obtained by removing two amine groups from an aromatic diamine compound having three or more aromatic rings.

The number of aromatic rings in the divalent organic group having 3 or more aromatic rings is not particularly limited if it is 3 or more, and may be, for example, 4 or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, 8 or less, or 6 or less.

The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (13). In formula (13), _X21 and _X22 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a carbamate bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond ( _-SO2- ). _R21 and _R22 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. _Y20 represents a divalent organic group represented by the above formula (5-a), the above formula (5-b) or the above formula (5-c). n21 and n22 each independently represent an integer of 0 to 4. When _R21 is plural, the plural _R21s may be the same or different. When _R22 is plural, the plural _R22s may be the same or different. * indicates an atomic bond.

As for the alkyl group having 1 to 6 carbon atoms which may be substituted in R ₂₁ and R ₂₂ in formula (13), for example, an alkyl group having 1 to 6 carbon atoms may be exemplified. As for the alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. may be exemplified. In the present specification, unless the structure of the alkyl group or the alkylene group is particularly mentioned, the alkyl group or the alkylene group may be a linear chain, a branched group, a cyclic group, or a combination of two or more thereof. As for the substituent in the alkyl group having 1 to 6 carbon atoms which may be substituted, for example, a halogen atom, a hydroxyl group, a thiol group, a carboxyl group, a cyano group, a formyl group, a halogenated formyl group, a sulfonic acid group, an amino group, a nitro group, a nitroso group, a pendyl group, a thioxy group, an alkoxy group having 1 to 6 carbon atoms, etc. may be exemplified. In addition, the "carbon number of 1 to 6" in the "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the carbon number of the "alkyl group" excluding the substituent. There is no particular limitation on the number of substituents.

As the divalent organic group having three or more aromatic rings, the divalent organic group represented by the following formula can be cited. [Chemistry 25] [Chemistry 26] In the formula, * represents an atomic bond.

As for other divalent organic groups, the divalent organic groups represented by the following formulas can be listed. These divalent organic groups are, for example, residues formed by removing two amino groups from diamine. [Chemistry 27] In the formula, * represents an atomic bond.

Polyimide is, for example, an imide product of polyamic acid which is a reaction product of a diamine component and a tetracarboxylic acid derivative. The imidization rate of polyimide does not necessarily have to be 100%. The imidization rate of polyimide may be, for example, 90% or more, 95% or more, or 98% or more.

Polyamic acid is, for example, a reaction product of a diamine component and a tetracarboxylic acid derivative. Polyamic acid ester is, for example, a reaction product of a diamine component and a tetracarboxylic acid diester.

Here, as the tetracarboxylic acid derivative, there can be listed, for example, tetracarboxylic acid, tetracarboxylic acid diester, tetracarboxylic acid dihalide, tetracarboxylic acid dianhydride and the like.

The tetracarboxylic acid derivative preferably includes a tetracarboxylic acid derivative having two or more aromatic rings. Ar ₁ in formula (1-a), Ar ₂ in formula (2), Ar ₃ in formula (3-a), and Ar ₄ in formula (3-b) are preferably a tetravalent organic group, for example, a residue obtained by removing a carboxyl group, a carboxylate group, or a carboxylic dianhydride group from a tetracarboxylic acid derivative having two or more aromatic rings.

As for the tetracarboxylic acid derivative having two or more aromatic rings, the tetracarboxylic dianhydride represented by the following formula (4-Z) is more preferable. [Chem. 28] In formula (4-Z), _X1 and _X2 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a carbamate bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond ( _-SO2- ). _Ra1 and _Ra2 each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. _Z1 represents a divalent organic group represented by the above formula (5-a), the above formula (5-b), the above formula (5-c) or the above formula (5-d). n1 and n2 each independently represent an integer of 0 to 3. When _Ra1 is plural, the plural _Ra1s may be the same or different. When _Ra2 is plural, the plural _Ra2s may be the same or different.

The diamine component includes an aromatic diamine compound having an alkyl group with 5 or more carbon atoms. The diamine component preferably includes an aromatic diamine compound having a photopolymerizable group. X in formula (1-b) is a divalent aromatic group having an alkyl group with 5 or more carbon atoms, for example, a residue obtained by removing two amine groups from an aromatic diamine compound having an alkyl group with 5 or more carbon atoms. Y in formula (1-c) is a divalent aromatic group having a photopolymerizable group, for example, a residue obtained by removing two amine groups from an aromatic diamine compound having a photopolymerizable group.

As for the aromatic diamine compound having an alkyl group with 5 or more carbon atoms, the diamine compound represented by the following formula (V-1a) to (V-6a) is more preferable. [Chemistry 29] In formula (V-1a), ^Xv1 represents -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-. ^Rv1 represents an alkyl group having 5 to 20 carbon atoms. In formulas (V-2a) to (V-5a), ^Xv2 to ^Xv5 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15. ^Rv2 to ^Rv5 each independently represent an alkyl group having 5 to 20 carbon atoms. In formula (V-6a), _Xa represents a single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-, -C(CH ₃ ) ₂ -, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, -CONH-, -NH-(CH ₂ ) _m -NH-, or -SO ₂ -(CH ₂ ) _{m -SO 2 -} , wherein _m represents an integer of 1 to 6. ^Xp1 and ^Xp2 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, -CH2 _- O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15. ^R1a and ^R1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer of 0 to 2.

Specific examples of aromatic diamine compounds having an alkyl group having 5 or more carbon atoms are shown below.

As for the aromatic diamine compound having a photopolymerizable group, an aromatic diamine compound represented by the following formula (9-A) is more preferable. V ₁ , W ₁ , R ₁₅ , and R ₁₆ in formula (9-A) have the same meanings as V ₁ , W ₁ , R ₁₅ , and R ₁₆ in formula (9-a).

The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivatives constituting the polyimide is not particularly limited, but from the viewpoint of ideally obtaining the effect of the present invention, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is more ideal. The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivatives constituting the polyamide is not particularly limited, but from the viewpoint of ideally obtaining the effect of the present invention, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is more ideal. The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to the total tetracarboxylic acid derivatives constituting the polyamide is not particularly limited, but from the perspective of ideally achieving the effect of the present invention, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is even more ideal.

The ratio of the aromatic diamine compound having an alkyl group with 5 or more carbon atoms to the total diamine components constituting the polyimide is not particularly limited, but from the viewpoint of ideally obtaining the effect of the present invention, 5 mol% to 80 mol% is more ideal, 10 mol% to 70 mol% is more ideal, and 15 mol% to 65 mol% is particularly ideal. The ratio of the aromatic diamine compound having an alkyl group with 5 or more carbon atoms to the total diamine components constituting the polyimide is not particularly limited, but from the viewpoint of ideally obtaining the effect of the present invention, 5 mol% to 80 mol% is more ideal, 10 mol% to 70 mol% is more ideal, and 15 mol% to 65 mol% is particularly ideal. The ratio of the aromatic diamine compound having an alkyl group with 5 or more carbon atoms to the total diamine components constituting the polyamide ester is not particularly limited, but from the perspective of ideally achieving the effect of the present invention, 5 mol% to 80 mol% is more ideal, 10 mol% to 70 mol% is more ideal, and 15 mol% to 65 mol% is particularly ideal.

The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine components constituting the polyimide is not particularly limited, but from the perspective of obtaining sufficient photosensitivity, 10 mol% to 90 mol% is more ideal, 15 mol% to 75 mol% is more ideal, and 20 mol% to 60 mol% is particularly ideal. The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine components constituting the polyimide is not particularly limited, but from the perspective of obtaining sufficient photosensitivity, 10 mol% to 90 mol% is more ideal, 15 mol% to 75 mol% is more ideal, and 20 mol% to 60 mol% is particularly ideal. The ratio of the aromatic diamine compound having a photopolymerizable group to the total diamine components constituting the polyamide ester is not particularly limited, but from the perspective of obtaining sufficient photosensitivity, 10 mol% to 90 mol% is more ideal, 15 mol% to 75 mol% is more ideal, and 20 mol% to 60 mol% is particularly ideal.

The molar ratio (A:B) of the aromatic diamine compound (A) having a photopolymerizable group and the aromatic diamine compound (B) having an alkyl group having 5 or more carbon atoms in polyimide, polyamic acid, and polyamic acid ester is not particularly limited, but 3:1 to 0.3:1 is more ideal, 2:1 to 0.5:1 is more ideal, and 1.5:1 to 0.5:1 is particularly ideal.

As for the molar ratio of the total of the aromatic diamine compound having a photopolymerizable group and the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to the total diamine components constituting the polyimide, polyamic acid, and polyamic acid ester, it is more preferably 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more, from the viewpoint of ideally obtaining the effect of the present invention. There is no particular limitation on the upper limit of the total molar ratio, but the total molar ratio may be 100 mol% or less, or 90 mol% or less.

The ratio of the aromatic diamine compound having three or more aromatic rings to the total diamine components constituting the polyamide is not particularly limited, but from the perspective of ideally achieving the effect of the present invention, 5 mol% to 60 mol% is more ideal, 10 mol% to 55 mol% is more ideal, and 15 mol% to 50 mol% is particularly ideal.

The weight average molecular weight of the specific polymer is not particularly limited, but the weight average molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC in this specification) in terms of polyethylene oxide is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

<<Method for producing specific polymer>> The method for producing specific polymer is not particularly limited, and examples thereof include a known method of reacting a diamine component with a tetracarboxylic acid derivative to obtain polyamic acid, polyamic acid ester, or polyimide. Polyamic acid, polyamic acid ester, and polyimide can be synthesized by a known method such as that described in WO2013/157586.

The production of polyamic acid or polyamic acid ester can be carried out, for example, by allowing a diamine component and a tetracarboxylic acid derivative to undergo a (polycondensation) reaction in a solvent.

Specific examples of the above-mentioned solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used. [Chemistry 32] In formula [D-1], ^D1 represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], ^D2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], ^D3 represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. Even a solvent that does not dissolve polyamine acid or polyamine ester may be mixed with the above solvents for use as long as the polyamine acid or polyamine ester does not precipitate.

When the diamine component and the tetracarboxylic acid derivative are reacted in a solvent, the reaction can be carried out at any concentration, but the most ideal concentration is 1% to 50% by mass, and the most ideal concentration is 5% to 30% by mass. The reaction can also be carried out at a high concentration at the beginning, and then the solvent is added. In the reaction, the ratio of the total molar number of the diamine component to the total molar number of the tetracarboxylic acid derivative is preferably 0.8 to 1.2. Similarly to the general polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the generated polyamine or polyamine ester will be.

When the diamine component and the tetracarboxylic acid derivative are reacted, a thermal polymerization inhibitor may be added to the reaction system to avoid polymerization of the photopolymerizable group. As for the thermal polymerization inhibitor, hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, tert-butyl o-catechol, phenothiol, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol bisaminoethyl ether tetraacetic acid, 2,6-di-tert-butyl p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. can be listed. As for the amount of the thermal polymerization inhibitor used, there is no particular limitation.

Polyimide can be obtained by dehydrating and ring-closing the polyamide obtained by the above reaction. As for the method of obtaining polyimide, there can be listed such as thermal imidization in which the solution of the polyamide obtained by the above reaction is heated in its original state, or chemical imidization in which a catalyst is added to the solution of the polyamide. The temperature for thermal imidization in the solution is 100℃~400℃, preferably 120℃~250℃, and it is more ideal to remove the water generated by the imidization reaction from the system while performing the thermal imidization.

The chemical imidization can be carried out by adding an alkaline catalyst and an acid anhydride to the polyamide solution obtained by the reaction, and stirring at -20°C to 250°C, preferably 0°C to 180°C. The amount of the alkaline catalyst is 0.1 to 30 moles of the amide group, preferably 0.2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles of the amide group, preferably 1.5 to 30 moles. As for the alkaline catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. can be listed, among which triethylamine is more ideal because it is not easy to generate polyisoimide as a by-product. As for the acid anhydride, acetic anhydride, trimellitic anhydride, pyromelite anhydride, etc. can be cited. Among them, if acetic anhydride is used, purification after the reaction is terminated will be easier and therefore more ideal. The imidization rate (the ratio of the closed-ring repeating units relative to the total repeating units of the polyimide precursor, also called the closed-ring rate) of chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When the imide product is recovered from the reaction solution of the imidization, the reaction solution is put into a solvent for precipitation. As for the solvent used for precipitation, methanol, ethanol, isopropanol, acetone, hexane, butyl cellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. can be listed. The polymer obtained by putting into the solvent and precipitating can be filtered and recovered, and then dried under normal pressure or reduced pressure, at room temperature or by heating.

The specific polymer may also be terminal-capped. The terminal-capping method is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

<Solvent> As for the solvent contained in the photosensitive resin composition for forming the insulating film, it is more desirable to use an organic solvent from the viewpoint of solubility for a specific polymer. Specifically, there can be mentioned N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyramide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethoxy-1,2-diolactone ... Methyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate or solvents represented by the following formulas [D-1] to [D-3], etc. These can be used alone or in combination of two or more. [Chemistry 33] In formula [D-1], ^D1 represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], ^D2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], ^D3 represents an alkyl group having 1 to 4 carbon atoms.

The solvent may be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, based on 100 parts by mass of the specific polymer, depending on the desired coating thickness and viscosity of the photosensitive resin composition for forming an insulating film.

<Other components> In the embodiment, the photosensitive resin composition for forming the insulating film may also contain other components besides the specific polymer and the solvent. As for other components, they may include photo radical polymerization initiator (also called "photo radical initiator"), crosslinking compound (also called "crosslinking agent"), thermosetting agent, other resin components, filler, sensitizer, adhesive aid, thermal polymerization inhibitor, azole compound, hindered phenol compound, etc.

＜＜Photoradical polymerization initiator＞＞ The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used in photocuring, and examples thereof include tert-butyl peroxy isobutyrate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)isopropoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)isopropyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)pentylene, Organic peroxides such as butyl peroxide, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone ; Benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin and other benzoin derivatives; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propane-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-linoylpropane-1-one, 2-benzyl- Alkyl phenyl ketone compounds such as 2-dimethylamino-1-(4-oxo-1-phenyl)-1-butanone and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-oxo-1-phenyl)-butane-1-one; acyl phosphine oxide compounds such as bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide; oxime ester compounds such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3-yl]ethanone. Oxime ester compounds are particularly ideal from the perspective of i-ray curability.

The photoradical polymerization initiator can be obtained as a commercial product, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (all manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (all manufactured by STAUFFER Co., Ltd.), ESACURE KIP150, same as TZT, same as 1001, same as KTO46, same as KB1, same as KL200, same as KS300, same as EB3, triazine-PMS, triazine A, triazine B (all from Nihon Siber Hegner Co., Ltd.), ADEKA OPTOMER N-1717, same as N-1414, same as N-1606, ADEKA ARKLS N-1919T, same as NCI-831E, same as NCI-930, same as NCI-730 (all from ADEKA Co., Ltd.). These photoradical polymerization initiators may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polymer, and is more preferably 0.5 to 15 parts by mass in view of photosensitivity characteristics. When the photoradical polymerization initiator is contained in an amount of 0.1 parts by mass or more relative to 100 parts by mass of the specific polymer, the photosensitivity of the photosensitive resin composition for forming an insulating film is easily improved, while when the photoradical polymerization initiator is contained in an amount of 20 parts by mass or less, the thick film curing property of the photosensitive resin composition for forming an insulating film is easily improved.

<<Crosslinking compound>> In the embodiment, in order to improve the resolution of the relief pattern, a monomer having an unsaturated bond that is photo-radical polymerizable (crosslinking compound) may be arbitrarily contained in the photosensitive resin composition for forming the insulating film. As for such a crosslinking compound, a compound containing a polymerizable group that undergoes a radical polymerization reaction due to a photo-radical polymerization initiator is more desirable, and examples thereof include (meth)acrylic acid compounds and maleimide compounds, but are not particularly limited to the following. As the (meth)acrylic acid compound, for example, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate, propylene glycol or polypropylene glycol mono- or di(meth)acrylate, glycerol mono-, di- or tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, di(meth)acrylate of 1,10-decanediol, di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate of dioxanediol, mono- or di(meth)acrylate of bisphenol A, di(meth)acrylate of bisphenol F, di(meth)acrylate of hydrogenated bisphenol A meth)acrylate, benzyl trimethacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, isobornyl(meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trihydroxymethylpropane tri(meth)acrylate, glycerol di- or tri(meth)acrylate, pentaerythritol di-, tri- , or tetra(meth)acrylate, and compounds such as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanateethyl(meth)acrylate or isocyanate-containing(meth)acrylate, and compounds obtained by adding blocking agents such as methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol, etc. Moreover, as for the maleimide compound, for example, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,4-phenylene dimaleimide, N,N'-1,3-phenylene dimaleimide, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(2-maleimidoethyl)disulfide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and the like can be cited. Commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more. In this specification, (meth)acrylate refers to acrylate and methacrylate.

The content of the crosslinking compound is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the specific polymer.

<<Thermosetting agent>> As for the thermosetting agent, hexamethoxymethyl melamine, tetramethoxymethyl glycoluril, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetrakis(methoxymethyl) glycoluril, 1,3,4,6-tetrakis(butoxymethyl) glycoluril, 1,3,4,6-tetrakis(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea can be listed. The content of the thermosetting agent in the photosensitive resin composition for forming the insulating film is not particularly limited.

<<Filler>> As fillers, inorganic fillers can be cited, and specifically, sols of silicon dioxide, aluminum nitride, boron nitride, zirconium dioxide, aluminum oxide, etc. can be cited. The content of the filler in the photosensitive resin composition for forming an insulating film is not particularly limited.

＜＜Other resin components＞＞ In the embodiment, the photosensitive resin composition for forming an insulating film may also contain resin components other than the specific polymer. As for the resin components that may be contained in the photosensitive resin composition for forming an insulating film, polyimide, polyazole, polyazole precursor, phenolic resin, polyamide, epoxy resin, silicone resin, acrylic resin, etc. other than the specific polymer can be listed. The content of these resin components is not particularly limited, and is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the specific polymer.

<<Sensitizer>> In the embodiment, a sensitizer may be arbitrarily blended into the photosensitive resin composition for forming an insulating film in order to improve photosensitivity. As for the sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylamine phenylallylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminobenzylidene)acetone, 3-Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These may be used alone or in combination of plural numbers.

The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the specific polymer.

<<Adhesive aid>> In the embodiment, in order to improve the adhesion between the film formed using the photosensitive resin composition for forming an insulating film and the substrate, an adhesive aid may be optionally mixed into the photosensitive resin composition for forming an insulating film. As the bonding agent, there can be mentioned γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-butyl propyl methyl dimethoxysilane, 3-(meth)acryloxypropyl dimethoxymethyl silane, 3-(meth)acryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropyl methyl silane, N-(3-diethoxymethylsilylpropyl) succinyl Silane coupling agents such as silane amine, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesive agents such as tris(ethyl acetylacetate)aluminum, tris(ethyl acetylacetone)aluminum, and ethyl acetylacetate diisopropylaluminum.

Among these bonding agents, silane coupling agents are more ideal from the perspective of bonding strength.

The content of the adhesive agent is not particularly limited, but is preferably in the range of 0.5 to 25 parts by weight relative to 100 parts by weight of the specific polymer.

<<Thermal polymerization inhibitor>> In the embodiment, a thermal polymerization inhibitor may be optionally blended in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition for forming an insulating film when stored in a solution containing a solvent. As thermal polymerization inhibitors, hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, tert-butyl o-catechol, phenothiol, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol bisaminoethyl ether tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. can be used.

The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the specific polymer.

<<Azole compound>> For example, when a substrate made of copper or a copper alloy is used, an azole compound can be arbitrarily mixed into a photosensitive resin composition for forming an insulating film in order to suppress discoloration of the substrate. As the azole compound, there can be mentioned 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl] -benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like. Particularly desirable examples include 4-carboxyl-1H-benzotriazole and 5-carboxyl-1H-benzotriazole. In addition, these azole compounds may be used alone or as a mixture of two or more.

The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polymer, and more preferably 0.5 to 5 parts by mass in view of photosensitivity characteristics. When the content of the azole compound is 0.1 parts by mass or more relative to 100 parts by mass of the specific polymer, discoloration of the surface of copper or copper alloy is suppressed when the photosensitive resin composition for forming an insulating film is formed on copper or copper alloy, while when the content is 20 parts by mass or less, photosensitivity is excellent and therefore it is more preferable.

<<Hindered phenol compound>> In the embodiment, a hindered phenol compound can be arbitrarily blended into the photosensitive resin composition for forming an insulating film in order to suppress discoloration on copper. As for the hindered phenol compound, there can be listed 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3- 6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl 6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris-(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1, 3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri-(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri-[4-(1-ethylpropyl)-3- 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[3-hydroxy-2,6-dimethyl-4-phenylbenzyl]-1,3,5-tris[2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[2,4,6-(1H,3H,5H)-trione, -tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione 6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2- 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di ...

The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polymer, and more preferably 0.5 to 10 parts by mass in view of photosensitivity characteristics. When the content of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the specific polymer, for example, when a photosensitive resin composition for forming an insulating film is formed on copper or a copper alloy, discoloration and corrosion of the copper or the copper alloy can be prevented, while when the content is 20 parts by mass or less, it is more preferable because the photosensitivity is excellent.

The insulating film-forming photosensitive resin composition can be preferably used as a negative-type insulating film-forming photosensitive resin composition for producing a hardened relief pattern described later.

(Insulating film) The insulating film of the present invention is a calcined product of a coating film of the insulating film-forming photosensitive resin composition of the present invention. As for the coating method, the coating method used in the past for the insulating film-forming photosensitive resin composition can be used, such as a coating method using a spin coater, a coating bar, a doctor blade coater, a curtain coater, a screen printer, etc., and a spray coating method using a spray coater. As a calcination method when obtaining the calcined product, various methods can be selected, such as a method using a hot plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program. Calcination can be performed at 130°C to 250°C for 30 minutes to 5 hours. Air can be used as the ambient gas during heat curing, or a passive gas such as nitrogen or argon can be used. The thickness of the insulating film is not particularly limited, but 1μm to 100μm is ideal, and 2μm to 50μm is even more ideal.

(Photosensitive Resist Film) The photosensitive resin composition for insulating film formation of the present invention can be used in a photosensitive resist film (so-called dry film resist). The photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed by the photosensitive resin composition for insulating film formation of the present invention, and a cover film. Usually, the photosensitive resin layer and the cover film are laminated in this order on the base film.

The photosensitive resist film can be manufactured, for example, by coating a photosensitive resin composition for forming an insulating film on a substrate film, drying it to form a photosensitive resin layer, and then laminating a covering film on the photosensitive resin layer. As for the coating method, the coating method used in the past for the photosensitive resin composition for forming an insulating film can be used, for example, a coating method using a spin coater, a coating bar, a doctor blade coater, a curtain coater, a screen printer, etc., and a spray coating method using a spray coater, etc. can be used. As for the drying method, the conditions of 20°C to 200°C and 1 minute to 1 hour can be listed. The thickness of the obtained photosensitive resin layer is not particularly limited, but 1μm~100μm is ideal, and 2μm~50μm is even more ideal.

The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2μm to 150μm. The covering film may be a known film, such as a polyethylene film, a polypropylene film, etc. As for the covering film, a film having a smaller adhesive force with the photosensitive resin layer than the substrate film is more desirable. The thickness of the covering film is preferably 2μm to 150μm, more preferably 2μm to 100μm, and particularly preferably 5μm to 50μm. The so-called substrate film and the covering film may be made of the same film material, or different films may be used.

(Method for manufacturing a substrate with a hardened relief pattern) The method for manufacturing a substrate with a hardened relief pattern of the present invention comprises the following steps: (1) applying the photosensitive resin composition for forming an insulating film of the present invention on a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate, (2) exposing the photosensitive resin layer, (3) developing the exposed photosensitive resin layer to form a relief pattern, (4) heating the relief pattern to form a hardened relief pattern.

The following describes each step.

(1) A step of applying the insulating film-forming photosensitive resin composition of the present invention on a substrate to form a photosensitive resin layer on the substrate In this step, the insulating film-forming photosensitive resin composition of the present invention is applied on a substrate and then dried as needed to form a photosensitive resin layer. As for the coating method, the method used in the past for coating the insulating film-forming photosensitive resin composition can be used, for example, a method of coating by a spin coater, a coating bar, a doctor blade coater, a curtain coater, a screen printer, etc., and a method of spray coating by a spray coater, etc. can be used.

If necessary, the coating film formed of the insulating film-forming photosensitive resin composition can be dried, and as for the drying method, for example, air drying, heat drying in an oven or a heating plate, vacuum drying, etc. can be used. Specifically, when air drying or heat drying is performed, the drying can be performed at 20°C to 200°C and for 1 minute to 1 hour. In the above manner, a photosensitive resin layer can be formed on the substrate.

(2) Exposure of the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed to a UV light source through a photomask or reticle with a pattern or directly using an exposure device such as a contact exposure machine, a mirror projection exposure machine, or a stepper. The light source used for exposure includes g-ray, h-ray, i-ray, ghi-ray broadband, and KrF excimer laser. The exposure amount is expected to be 25mJ/ ^cm2 ~2000mJ/ ^cm2 .

Afterwards, for the purpose of improving photosensitivity, a post-exposure bake (PEB) and/or a pre-development bake at any combination of temperature and time may be performed as needed. The baking conditions are preferably in the range of 50°C to 200°C and 10 seconds to 600 seconds, but are not limited to this range if the properties of the photosensitive resin composition for forming the insulating film are not impeded.

(3) Developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As for the developing method for developing the exposed (irradiated) photosensitive resin layer, any of the previously known photoresist developing methods can be used, such as a rotary spray method, an immersion method, an immersion method accompanied by ultrasonic treatment, etc. After development, rinsing can be performed for the purpose of removing the developer. In addition, for the purpose of adjusting the shape of the relief pattern, post-development baking with any combination of temperature and time can be performed as needed. As for the developer used in the development, an organic solvent is more ideal. As for the organic solvent, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are more ideal. Moreover, two or more solvents may be used in combination, for example, several types may be used in combination. As for the rinse solution used in the rinse, it is more ideal to use an organic solvent that will mix with the developer and has low solubility in the photosensitive resin composition for forming the insulating film. As for the rinse solution, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, xylene, etc. are more ideal. Furthermore, two or more solvents may be used in combination, for example, several types may be used in combination.

(4) Step of heating the relief pattern to form a hardened relief pattern In this step, the relief pattern obtained by the above-mentioned development is heated to be converted into a hardened relief pattern. As for the method of heat hardening, various methods can be selected, such as using a heating plate, using an oven, and using a temperature-raising oven with a settable temperature program. Heating can be performed at 130°C to 250°C for 30 minutes to 5 hours. As for the ambient gas during heat hardening, air can be used, and a passive gas such as nitrogen or argon can also be used.

The thickness of the hardened relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

(Semiconductor device) In an embodiment, a semiconductor device having a semiconductor element and a hardened film disposed on the upper part or the lower part of the semiconductor element is also provided. The hardened film is a hardened relief pattern formed by the photosensitive resin composition for forming an insulating film of the present invention. The hardened relief pattern can be obtained, for example, by steps (1) to (4) in the above-mentioned method for manufacturing a substrate with a hardened relief pattern. In addition, the present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a substrate with a hardened relief pattern as one of the steps. The semiconductor device of the present invention can be manufactured by forming the hardened relief pattern into a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device with a bump structure, etc., and combining it with a known semiconductor device manufacturing method.

(Display device) In an embodiment, a display device is provided, which has a display element and a hardened film disposed on the upper part of the display element, and the hardened film is the hardened relief pattern. Here, the hardened relief pattern can be laminated directly in contact with the display element, or can be laminated with other layers sandwiched therebetween. For example, the hardened film can be a surface protection film, an insulating film, and a flattening film of a TFT (Thin Film Transistor) liquid crystal display element and a color filter element, a protrusion for an MVA (Multi-domain Vertical Alignment) type liquid crystal display device, and a partition for a cathode of an organic EL (Electro-Luminescence) element.

The photosensitive resin composition for forming an insulating film of the present invention is not only applicable to the semiconductor devices as described above, but is also useful in interlayer insulating films of multilayer circuits, surface coatings of flexible copper-clad boards, solder resists, and liquid crystal alignment films. [Example]

Next, embodiments are listed to specifically illustrate the content of the present invention, but the present invention is not limited to these.

The compounds shown in the following synthesis examples and comparative synthesis examples are as follows: BEM-S: 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (manufactured by Samsung Chemical Industries, Ltd.) [Chemical 34]

BAPP: 2,2-Bis[4-(4-aminophenoxy)phenyl]propane[Chemical 35]

HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane[Chemical 36]

APC-14: 4-Tetradecyloxy-1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical 37]

APC-16: 4-hexadecyloxy-1,3-phenylenediamine (produced by Wakayama Seika Co., Ltd.) [Chemical 38]

DAB-C18: 4-octadecyloxy-1,3-phenylenediamine (produced by Wakayama Seika Co., Ltd.) [Chemical 39]

BPADA: 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride [Chemical 40]

TMPBP-TME: 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diyl-bis(1,3-dioxy-1,3-dihydroisophenylfuran-5-carboxylate) (manufactured by Honshu Chemical Industry Co., Ltd.) [Chemical 40]

6FDA: 4,4'-[perfluoro(propane-2,2-diyl)]diphthalic anhydride (manufactured by Daikin Industries, Ltd.) [Chemical 41]

The weight average molecular weight (Mw) shown in the following synthesis examples is the result of gel permeation chromatography (hereinafter referred to as GPC in this manual). The measurement was performed using a GPC device (HLC-8320GPC (manufactured by Tosoh Co., Ltd.)) and the measurement conditions were as follows. ･Column: Shodex [registered trademark] KD-805/Shodex [registered trademark] KD-803 (manufactured by Showa Denko Co., Ltd.) ･Column temperature: 50°C ･Flow rate: 1 mL/min ･Solvent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM)/phosphoric acid (30 mM)/tetrahydrofuran (1%) ･Standard sample: polyethylene oxide

The chemical imidization rate shown in the following synthesis example is the result of measurement by a nuclear magnetic resonance device (hereinafter referred to as NMR in this manual). The measurement was performed using an NMR device (JNM-ECA500) (manufactured by JEOL Ltd.), and the measurement conditions were as follows. ･Measurement temperature: room temperature ･Measurement solvent: deuterated tetrahydrofuran (THF-d8) In addition, the chemical imidization rate is calculated by using the peak accumulation value of the proton from the structure that does not change before and after the imidization as the reference proton and the peak accumulation value of the proton from the NH group of the amide appearing around 9.5ppm~11.0ppm according to the following formula. Chemical imidization rate (%) = (1-α･x/y) × 100 In the above formula, x is the peak accumulation value of the protons from the NH group of the acylamidin, y is the peak accumulation value of the reference proton, and α is the ratio of the reference proton number to the NH group proton of one acylamidin in the case of polyacylamidin (acylamidization rate is 0%).

<Synthesis Example 1> Synthesis of polyimide (P-1) 5.50 g (20.81 mmol) of BEM-S, 14.56 g (38.65 mmol) of DAB-C18, and 211.43 g of N-ethyl-2-pyrrolidone were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, 14.86 g (28.54 mmol) of BPADA, 18.39 g (29.73 mmol) of TMPBP-TME, and 90.61 g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50°C for 20 hours to obtain a polyimide solution. Next, 177.65 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. Then, 532.95 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 25,770, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 2> Synthesis of polyimide (P-2) BEM-S 5.10 g (19.30 mmol), DAB-C18 10.38 g (27.57 mmol), HFBAPP 4.29 g (8.27 mmol) and N-ethyl-2-pyrrolidone 200.71 g were added to a 4-necked flask and stirred at room temperature under air to dissolve. Then, BPADA 13.78 g (26.47 mmol), TMPBP-TME 17.05 g (27.57 mmol) and N-ethyl-2-pyrrolidone 86.02 g were added to the flask and stirred at 50°C for 20 hours to obtain a polyamide solution. Next, 168.65 g of N-ethyl-2-pyrrolidone, 16.89 g of acetic anhydride, and 2.79 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. Then 505.95 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 32,863, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 3> Synthesis of polyimide (P-3) 5.40 g (20.43 mmol) of BEM-S, 14.29 g (37.95 mmol) of DAB-C18, and 200.02 g of N-ethyl-2-pyrrolidone were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, 8.51 g (16.35 mmol) of BPADA, 14.45 g (23.35 mmol) of TMPBP-TME, 7.78 g (17.51 mmol) of 6FDA, and 85.72 g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50°C for 20 hours to obtain a polyamide solution. Next, 168.10 g of N-ethyl-2-pyrrolidone, 17.88 g of acetic anhydride, and 2.95 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. Then 504.30 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 28,569, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 4> Synthesis of polyimide (P-4) 5.50 g (20.81 mmol) of BEM-S, 12.39 g (38.65 mmol) of APC-14, and 195.12 g of N-ethyl-2-pyrrolidone were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, 7.92 g (17.84 mmol) of BPADA, 14.71 g (23.78 mmol) of TMPBP-TME, 8.67 g (16.65 mmol) of 6FDA, and 83.62 g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50°C for 20 hours to obtain a polyamide solution. Next, 163.97 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. Then 491.91 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 32,929, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 5> Synthesis of polyimide (P-5) 5.50 g (20.81 mmol) of BEM-S, 13.47 g (38.65 mmol) of APC-16, and 199.43 g of N-ethyl-2-pyrrolidone were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, 7.92 g (17.84 mmol) of BPADA, 14.71 g (23.78 mmol) of TMPBP-TME, 8.67 g (16.65 mmol) of 6FDA, and 85.47 g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50°C for 20 hours to obtain a polyamide solution. Next, 167.58 g of N-ethyl-2-pyrrolidone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. Then, 502.76 g of N-ethyl-2-pyrrolidone was added and added dropwise to methanol. The resulting precipitate was filtered and dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 30,568, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 6> Synthesis of polyimide (P-6) BEM-S 7.05g (26.68mmol), BAPP 4.38g (10.67mmol), DAB-C18 6.03g (16.01mmol), and N-ethyl-2-pyrrolidone 98.95g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, BPADA 7.22g (13.87mmol), TMPBP-TME 13.20g (21.35mmol), 6FDA 7.11g (16.01mmol), and N-ethyl-2-pyrrolidone 156.05g were added to the flask and stirred at 50°C for 19 hours to obtain a polyamide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.34 g of acetic anhydride, and 2.79 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 22,930, and the chemical imidization rate obtained by NMR (THF-d8) was 98%.

<Synthesis Example 7> Synthesis of polyimide (P-7) BEM-S 6.96g (26.34mmol), BAPP 4.32g (10.53mmol), DAB-C18 5.95g (15.80mmol), and N-ethyl-2-pyrrolidone 97.67g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, BPADA 7.40g (14.22mmol), TMPBP-TME 13.03g (21.07mmol), 6FDA 7.02g (15.80mmol), maleic anhydride 0.31g (3.16mmol), and N-ethyl-2-pyrrolidone 157.33g were added to the flask and stirred at 50°C for 19 hours to obtain a polyimide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.13 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 22,959, and the chemical imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 8> Synthesis of polyimide (P-8) BEM-S 6.95g (26.31mmol), BAPP 4.32g (10.52mmol), DAB-C18 5.95g (15.79mmol), and N-ethyl-2-pyrrolidone 97.57g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, BPADA 7.39g (14.21mmol), TMPBP-TME 13.02g (21.05mmol), 6FDA 7.01g (15.79mmol), itaconic anhydride 0.35g (3.16mmol), and N-ethyl-2-pyrrolidone 157.43g were added to the flask and stirred at 50°C for 19 hours to obtain a polyimide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.12 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 26,102, and the chemical imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 9> Synthesis of polyimide (P-9) In a 4-necked flask, add 6.93 g (26.21 mmol) of BEM-S, 4.30 g (10.49 mmol) of BAPP, 5.92 g (15.73 mmol) of DAB-C18, and 97.22 g of N-ethyl-2-pyrrolidone, and stir under air at room temperature to dissolve. Then, BPADA 7.37 g (14.16 mmol), TMPBP-TME 12.97 g (20.97 mmol), 6FDA 6.99 g (15.73 mmol), 5-norbornene-2,3-dicarboxylic anhydride 0.52 g (3.15 mmol) and N-ethyl-2-pyrrolidone 157.78 g were added to the flask and stirred at 50° C. for 19 hours to obtain a polyamide solution. Next, N-ethyl-2-pyrrolidone 150.00 g, acetic anhydride 16.06 g, and triethylamine 2.65 g were added to the flask and stirred at 60° C. for 3 hours to perform chemical imidization. N-ethyl-2-pyrrolidone 192.86 g was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 26,096, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 10> Synthesis of polyimide (P-10) BEM-S 6.80 g (25.72 mmol), BAPP 4.22 g (10.29 mmol), DAB-C18 5.81 g (15.43 mmol), and N-ethyl-2-pyrrolidone 95.37 g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, TMPBP-TME 21.32 g (34.46 mmol), 6FDA 6.85 g (15.43 mmol), and N-ethyl-2-pyrrolidone 159.63 g were added to the flask, and stirred at 50°C for 22 hours to obtain a polyamide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 15.75 g of acetic anhydride, and 2.60 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 33,309, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 11> Synthesis of polyimide (P-11) BEM-S 6.75g (25.54mmol), BAPP 4.19g (10.22mmol), DAB-C18 5.77g (15.33mmol), and N-ethyl-2-pyrrolidone 94.73g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, TMPBP-TME 21.17g (34.23mmol), 6FDA 6.81g (15.33mmol), maleic anhydride 0.30g (3.07mmol), and N-ethyl-2-pyrrolidone 160.27g were added to the flask and stirred at 50°C for 19 hours to obtain a polyimide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 15.65 g of acetic anhydride, and 2.58 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 29,575, and the chemical imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 12> Synthesis of polyimide (P-12) BEM-S 10.09 g (38.18 mmol), DAB-C18 6.16 g (16.36 mmol), and N-ethyl-2-pyrrolidone 92.09 g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, BPADA 7.66 g (14.73 mmol), TMPBP-TME 13.49 g (21.82 mmol), 6FDA 7.27 g (16.36 mmol), maleic anhydride 0.32 g (3.27 mmol), and N-ethyl-2-pyrrolidone 162.91 g were added to the flask and stirred at 50°C for 19 hours to obtain a polyamide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.70 g of acetic anhydride, and 2.76 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 22,161, and the chemical imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 13> Synthesis of polyimide (P-13) BEM-S 8.43g (38.18mmol), BAPP 5.46g (13.30mmol), DAB-C18 3.01g (7.98mmol), and N-ethyl-2-pyrrolidone 95.76g were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, BPADA 6.92g (13.30mmol), TMPBP-TME 16.45g (26.60mmol), 6FDA 4.73g (10.64mmol), and N-ethyl-2-pyrrolidone 159.24g were added to the flask and stirred at 50°C for 19 hours to obtain a polyamide solution. Next, 150.00 g of N-ethyl-2-pyrrolidone, 16.29 g of acetic anhydride, and 2.69 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 192.86 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was filtered, washed with methanol, and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 23,237, and the chemical imidization rate obtained by NMR (THF-d8) was 98%.

<Comparative Synthesis Example 1> Synthesis of Polyimide (P-14) 2.81 g (10.62 mmol) of BEM-S, 10.23 g (19.72 mmol) of HFBAPP, and 96.15 g of N-ethyl-2-pyrrolidone were added to a 4-necked flask, and stirred at room temperature under air to dissolve. Then, 7.58 g (14.57 mmol) of BPADA, 9.39 g (15.17 mmol) of TMPBP-TME, and 73.85 g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at room temperature for 39 hours to obtain a polyamide solution. Next, 100.00 g of N-ethyl-2-pyrrolidone, 9.29 g of acetic anhydride, and 1.54 g of triethylamine were added to the flask and stirred at 60°C for 3 hours to perform chemical imidization. 128.57 g of N-ethyl-2-pyrrolidone was added to the reaction solution for dilution, and the diluted solution was added dropwise to methanol. The resulting precipitate was washed with methanol and then dried under reduced pressure at 60°C to obtain polyimide powder. The weight average molecular weight (Mw) obtained by GPC was 44,173, and the chemical imidization rate obtained by NMR (THF-d8) was 99%.

The compounds shown in the Examples and Comparative Examples are as follows. NK ESTER A-DOD-N: 1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) BMI-689: a maleimide compound represented by the following formula (manufactured by Designer Molecules Inc.) [Chemical 41]

･CaA-BTZ: 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) ･CBT-SG: A mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.) ･KBM-5103: 3-Acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

<Example 1> 5.81 g of polyimide (P-1) obtained in Synthesis Example 1, 0.58 g of NK ESTER A-DOD-N as a crosslinking agent, 0.12 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.17 g of CaA-BTZ, 0.11 g of KBM-5103, 3.96 g of N-ethyl-2-pyrrolidone, and 9.24 g of cyclopentanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 2> 5.32g of polyimide (P-2) obtained in Synthesis Example 2, 0.80g of NK ESTER A-DOD-N as a crosslinking agent, 0.21g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.16g of CaA-BTZ, 0.11g of KBM-5103, 7.02g of N-ethyl-2-pyrrolidone, 9.36g of γ-butyrolactone, and 7.02g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 3> 7.66g of polyimide (P-2) obtained in Synthesis Example 2, 1.15g of NK ESTER A-DOD-N as a crosslinking agent, 0.31g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.23g of CaA-BTZ, 0.15g of KBM-5103, 12.15g of N-ethyl-2-pyrrolidone, 16.20g of γ-butyrolactone, and 12.15g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 4> 7.02 g of polyimide (P-3) obtained in Synthesis Example 3, 1.05 g of NK ESTER A-DOD-N as a crosslinking agent, 0.28 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.21 g of CaA-BTZ, 0.14 g of KBM-5103, 6.39 g of N-ethyl-2-pyrrolidone, 8.52 g of γ-butyrolactone, and 6.39 g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 5> 10.08g of the polyimide (P-3) obtained in Synthesis Example 3, 1.51g of NK ESTER A-DOD-N as a crosslinking agent, 0.40g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.30g of CaA-BTZ, 0.20g of KBM-5103, 11.25g of N-ethyl-2-pyrrolidone, 15.00g of γ-butyrolactone, and 11.25g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 6> 8.06g of polyimide (P-4) obtained in Synthesis Example 4, 1.21g of NK ESTER A-DOD-N as a crosslinking agent, 0.32g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.24g of CaA-BTZ, 0.16g of KBM-5103, 9.00g of N-ethyl-2-pyrrolidone, 12.00g of γ-butyrolactone, and 9.00g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 7> 8.06g of polyimide (P-5) obtained in Synthesis Example 5, 1.21g of NK ESTER A-DOD-N as a crosslinking agent, 0.32g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.24g of CaA-BTZ, 0.16g of KBM-5103, 9.00g of N-ethyl-2-pyrrolidone, 12.00g of γ-butyrolactone, and 9.00g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 8> 8.82g of polyimide (P-6) obtained in Synthesis Example 6, 1.32g of NK ESTER A-DOD-N and 0.88g of BMI-689 as crosslinking agents, 0.26g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.13g of CBT-SG, 0.18g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 9> 8.82g of polyimide (P-7) obtained in Synthesis Example 7, 1.32g of NK ESTER A-DOD-N and 0.88g of BMI-689 as crosslinking agents, 0.26g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.13g of CBT-SG, 0.18g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 10> 8.56g of polyimide (P-7) obtained in Synthesis Example 7, 1.28g of NK ESTER A-DOD-N and 0.86g of BMI-689 as crosslinking agents, 0.09g of ADEKA ARKLS NCI-930 as a photoradical initiator, 0.51g of IRGACURE [registered trademark] 819, 0.13g of CBT-SG, 0.17g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 11> 8.82g of polyimide (P-8) obtained in Synthesis Example 8, 1.32g of NK ESTER A-DOD-N and 0.88g of BMI-689 as crosslinking agents, 0.26g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.13g of CBT-SG, 0.18g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 12> 8.82g of polyimide (P-9) obtained in Synthesis Example 9, 1.32g of NK ESTER A-DOD-N and 0.88g of BMI-689 as crosslinking agents, 0.26g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.13g of CBT-SG, 0.18g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 13> Mixed with 9.23g of polyimide (P-10) obtained in Synthesis Example 10, 1.38g of NK ESTER A-DOD-N and 0.92g of BMI-689 as crosslinking agents, 0.09g of ADEKA ARKLS NCI-930 and 0.55g of IRGACURE [registered trademark] 819 as photoradical initiators, 0.14g of CBT-SG, and KBM-5103 0.18g, 11.25g of N-ethyl-2-pyrrolidone, 15.00g of γ-butyrolactone, and 11.25g of cyclohexanone were dissolved and filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 14> 7.97 g of polyimide (P-11) obtained in Synthesis Example 11, 1.20 g of NK ESTER A-DOD-N and 0.80 g of BMI-689 as crosslinking agents, 0.08 g of ADEKA ARKLS NCI-930 and 0.48 g of IRGACURE [registered trademark] 819 as photoradical initiators, 0.12 g of CBT-SG, 0.16 g of KBM-5103, 8.76 g of N-ethyl-2-pyrrolidone, 11.68 g of γ-butyrolactone, and 8.76 g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 15> 8.56g of polyimide (P-12) obtained in Synthesis Example 12, 1.28g of NK ESTER A-DOD-N and 0.86g of BMI-689 as crosslinking agents, 0.09g of ADEKA ARKLS NCI-930 and 0.51g of IRGACURE [registered trademark] 819 as photoradical initiators, 0.13g of CBT-SG, 0.17g of KBM-5103, 8.52g of N-ethyl-2-pyrrolidone, 11.36g of γ-butyrolactone, and 8.52g of cyclohexanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Example 16> Mixed with 10.70g of polyimide (P-13) obtained in Synthesis Example 13, 1.61g of NK ESTER A-DOD-N and 1.07g of BMI-689 as crosslinking agents, 0.11g of ADEKA ARKLS NCI-930 and 0.64g of IRGACURE [registered trademark] 819 as photoradical initiators, 0.16g of CBT-SG, and KBM-5103 0.21g, 10.65g of N-ethyl-2-pyrrolidone, 14.20g of γ-butyrolactone, and 10.65g of cyclohexanone were dissolved and filtered using a polypropylene filter with a pore size of 5μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Comparative Example 1> 10.00 g of polyimide (P-14) obtained in Comparative Synthesis Example 1, 1.50 g of NK ESTER A-DOD-N as a crosslinking agent, 0.40 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 0.30 g of CaA-BTZ, 0.20 g of KBM-5103, 12.45 g of N-ethyl-2-pyrrolidone, 16.61 g of γ-butyrolactone, and 12.45 g of cyclopentanone were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition for forming an insulating film.

<Comparative Example 2> 32.89 g of the negative photosensitive resin composition for forming an insulating film obtained in Comparative Example 1 was mixed with 4.32 g of N-ethyl-2-pyrrolidone, 5.76 g of γ-butyrolactone, and 4.32 g of cyclopentanone for dilution.

[Evaluation of electrical properties] The negative photosensitive resin composition for forming an insulating film prepared in Example 1, Example 2, Example 4, Examples 6 to 16 and Comparative Example 1 was spin-coated on a 4-inch silicon wafer covered with a 20 μm thick aluminum foil, and calcined on a hot plate at 115°C for 270 seconds to form a photosensitive resin film of approximately 25 μm on the aluminum foil. The obtained photosensitive resin film was fully exposed on the wafer at 500 mJ/ ^cm2 using an i-line exposure machine (PLA-501, manufactured by Canon Co., Ltd.), and then calcined at 230°C for 2 hours in a nitrogen environment using a high-temperature dust-free oven (CLH-21CD(V)-S, manufactured by KOYO THERMO SYSTEMS Co., Ltd.). Then, the calcined aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil, thereby obtaining a thin film. The dielectric loss tangent of the obtained thin film was measured at 60 GHz using a split cylinder resonator. The measurement conditions of the dielectric loss tangent are as described above. ･Measurement method: Split cylinder resonator ･Vector network analyzer: FieldFox N9926A (Keysight Technologies, Inc.) ･Resonator: CR-760 (EM labs, Inc.) ･Measurement frequency: Approximately 60 GHz The measurement results of the dielectric loss tangent of the film at 60 GHz are shown in Table 1.

[Table 1] Resin Dielectric loss tangent (60GHz) Embodiment 1 Polyimide (P-1) 0.0055 Embodiment 2 Polyimide (P-2) 0.0061 Embodiment 4 Polyimide (P-3) 0.0061 Embodiment 6 Polyimide (P-4) 0.0066 Embodiment 7 Polyimide (P-5) 0.0064 Embodiment 8 Polyimide (P-6) 0.0060 Embodiment 9 Polyimide (P-7) 0.0057 Embodiment 10 Polyimide (P-7) 0.0056 Embodiment 11 Polyimide (P-8) 0.0059 Embodiment 12 Polyimide (P-9) 0.0058 Embodiment 13 Polyimide (P-10) 0.0055 Embodiment 14 Polyimide (P-11) 0.0055 Embodiment 15 Polyimide (P-12) 0.0061 Embodiment 16 Polyimide (P-13) 0.0061 Comparison Example 1 Polyimide (P-14) 0.0079 According to the results in Table 1, the thin films obtained from the negative photosensitive resin composition for forming the insulating film of Examples 1, 2, 4, 6 to 16 show a lower dielectric loss tangent at 60 GHz than the thin film obtained from the negative photosensitive resin composition for forming the insulating film of Comparative Example 1.

[Photosensitivity Evaluation] The negative photosensitive resin composition for forming an insulating film prepared in Examples 3, 5 to 16, and Comparative Example 2 was coated on an 8-inch silicon wafer using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Electron Co., Ltd.), and then calcined at 115°C for 270 seconds to form a photosensitive resin film with a film thickness of about 6.5 μm on the wafer. An exposure pattern of 7 mm square was prepared on the obtained photosensitive resin film using an i-ray stepper (NSR-2205i12D, manufactured by Nikon Co., Ltd.) (exposure dose: 300 mJ/cm ² ). After exposure, an automatic developing device (AD-1200, manufactured by MIKASA Co., Ltd.) was used to spray develop with cyclopentanone as a developer, and propylene glycol monomethyl ether acetate (PGMEA) was used as a rinse solution for spray rinsing. The developing time with cyclopentanone was set to the time until the unexposed part (0 mJ/cm ² ) was completely developed, and the rinsing time with PGMEA was set to 10 seconds. The film thickness immediately after film formation and the film thickness after development in the unexposed part and the exposed part (300 mJ/cm ² ) were measured using an interference film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.), and the ratio of the film thickness remaining in the exposed part without development (residual film ratio (%)) was calculated using the following formula. Residual film rate (%) = [(film thickness of unexposed part) or (film thickness of exposed part)] / (film thickness just after film formation) × 100. That is, if the residual film rate is 80%, it means that the film thickness after development is 80% of the film thickness just after film formation and remains undeveloped. The test results of the developing time and residual film rate after development are shown in Table 2.

[Table 2] Resin Development time (seconds) Residual film rate after development (%) Unexposed area (0mJ/cm2) Exposure part (300mJ/cm2) Embodiment 3 Polyimide (P-2) 120 ＜1 90 Embodiment 5 Polyimide (P-3) 75 ＜1 92 Embodiment 6 Polyimide (P-4) 90 ＜1 94 Embodiment 7 Polyimide (P-5) 70 ＜1 93 Embodiment 8 Polyimide (P-6) 40 ＜1 89 Embodiment 9 Polyimide (P-7) 40 ＜1 89 Embodiment 10 Polyimide (P-7) 30 ＜1 88 Embodiment 11 Polyimide (P-8) 45 ＜1 90 Embodiment 12 Polyimide (P-9) 50 ＜1 90 Embodiment 13 Polyimide (P-10) 120 ＜1 89 Embodiment 14 Polyimide (P11) 80 ＜1 89 Embodiment 15 Polyimide (P-12) 35 ＜1 93 Embodiment 16 Polyimide (P-13) 50 ＜1 86 Comparison Example 2 Polyimide (P-14) 500 ＜1 84

According to the results in Table 2, after developing the negative photosensitive resin composition for insulating film formation of Example 3, Example 5 to Example 16, and Comparative Example 2, the photosensitive resin film of the unexposed part is completely developed, while the photosensitive resin film of the exposed part is almost not developed. Then, the photosensitive resin film obtained from the negative photosensitive resin composition for insulating film formation of Comparative Example 2 has a longer developing time with cyclopentanone than the photosensitive resin film obtained from the negative photosensitive resin composition for insulating film formation of Example 3 and Example 5 to Example 16. That is, the photosensitive resin film obtained by using the negative photosensitive resin composition for insulating film formation in Examples 3 and 5 to 16 has high solubility in the developer, which is effective in shortening the development time of the development step and reducing the amount of developer used.

[Residual Stress Evaluation] The negative photosensitive resin composition for insulating film formation prepared in Example 3, Example 5, and Comparative Example 2 was applied to a new 8-inch silicon wafer with a thickness of 724 μm using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Electron Co., Ltd.), and then calcined at 115°C for 270 seconds to form a photosensitive resin film with a thickness of about 6.5 μm on the wafer. Then, an i-ray stepper (NSR-2205i12D, manufactured by Nikon Co., Ltd.) was used for full exposure at 500 mJ/ ^cm2 . Then, the film was calcined at 230°C for 2 hours in a nitrogen atmosphere using a high temperature dust-free oven (CLH-21CD(V)-S, KOYO THERMO SYSTEMS (Co., Ltd.)) to obtain a polyimide cured film. The residual stress of the obtained polyimide film was measured at room temperature using a thin film stress measuring device (FLX-3300-T: manufactured by KLA-Tencor (Co., Ltd.)). The results of the residual stress measurement are shown in Table 3. The obtained measured value of 25 MPa or less was defined as "good", and the value of 30 MPa or more was defined as "bad".

[table 3] Resin Residual stress(MPa) Embodiment 3 Polyimide (P-2) Good (22.9) Embodiment 5 Polyimide (P-3) Good (20.7) Comparison Example 2 Polyimide (P-6) Bad (31.3)

According to the results in Table 3, the polyimide cured film obtained from the negative photosensitive resin composition for insulating film formation of Examples 3 and 5 has a smaller residual stress than the polyimide cured film obtained from the negative photosensitive resin composition for insulating film formation of Comparative Example 2, so the silicon wafer is not easy to warp, and defects are not easy to occur during transportation and wafer fixing.

That is, the negative photosensitive resin composition for forming the insulating film of Examples 1 to 16 can not only produce relief patterns with a short development time, but also because of its low dielectric loss tangent and small residual stress, it can be ideally used in the manufacture of electronic materials that require excellent electrical properties.

Claims (12)

A photosensitive resin composition for forming an insulating film, comprising a polymer of at least one of polyimide, polyamine, and polyamic acid ester, a photo-radical polymerization initiator, a cross-linking compound containing a polymerizable group that undergoes a radical polymerization reaction due to the photo-radical polymerization initiator, and a solvent, wherein the polymer has a photo-polymerizable group, an aromatic group, and an alkyl group having 5 or more carbon atoms. A photosensitive resin composition for forming an insulating film as claimed in claim 1, wherein the polyimide is the following polyimide (1), the polyamic acid is the following polyamic acid (2), the polyamic acid ester is the following polyamic acid ester (3), polyimide (1): a polyimide having structural units represented by the following formula (1-a), the following formula (1-b) and the following formula (1-c), polyamic acid (2): a polyamic acid having structural units represented by the following formula (2), the following formula (1-b) and the following formula (1-c), polyamic acid ester (3): at least one of the following polyamic acid esters (3a) to (3b), Polyamic acid ester (3a): a polyamic acid ester having structural units represented by the following formula (3-a) and the following formula (1-b), Polyamic acid ester (3b): a polyamic acid ester having structural units represented by the following formula (3-b), the following formula (1-b), and the following formula (1-c), In formula (1-a), _Ar1 represents a tetravalent organic group, in formula (1-b), X represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms, in formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group, In formula (2), _Ar2 represents a tetravalent organic group, In formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a monovalent organic group having a photopolymerizable group. In formula (3-b), Ar ₄ represents a tetravalent organic group, and R ₁ and R ₂ each independently represent a monovalent organic group. The photosensitive resin composition for forming an insulating film as claimed in claim 2, wherein in the formula (1-b), X represents a divalent organic group represented by any one of the following formulas (V-1) to (V-6), In formula (V-1), ^Xv1 represents -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, and ^Rv1 represents an alkyl group having 5 to 20 carbon atoms. In formulas (V-2) to (V-5), ^Xv2 to ^Xv5 each independently represent -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, _-CH2 -O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^Rv2 to ^Rv5 each independently represent an alkyl group having 5 to 20 carbon atoms. In formula (V-6), _Xa represents a single bond, -O-, -NH-, -O-( _CH2 ) _m -O-, -C( _CH3 ) _2- , -CO-, -( _CH2 ) _m -, _-SO2- , -OC( _CH3 ) _2- , -CO-(CH2) _m- , -NH-( _CH2 )m-, -SO2-( _CH2 )m-, -CONH-(CH2) _m- , -CONH-( _CH2 ) _m -NHCO- _{, -COO-} (CH2)m-OCO-, -CONH-, -NH-( _CH2 ) _m -NH-, or _-SO2- (CH2) _m -SO2-, wherein m represents an integer of 1 to 6, Xp1 and _Xp2 each independently represent -( _CH2 ) _a- , -CONH-, _-NHCO- , -CON( _CH3 )-, -NH-, -O-, -CH2-O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^R1a and ^R2 are independently -( _CH2 ) _a- , -CONH-, -NHCO-, -CON( _CH3 )-, -NH-, -O-, -CH2-O-, _-CH2 -OCO-, -COO-, or -OCO-, wherein a is an integer of 1 to 15, and ^R1a and R2 are independently -( _CH2 )a-, -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2-O-, _-CH2- OCO-, -COO-, or -OCO-. ^1b each independently represents an alkyl group having 5 to 20 carbon atoms, k1 and k2 each independently represent an integer of 0 to 2, and in formulas (V-1) to (V-6), * represents an atomic bond. The photosensitive resin composition for forming an insulating film as claimed in claim 2, wherein in the formula (1-c), Y represents a divalent organic group represented by the following formula (9-a), and in the formula (3-a), _L1 and _L2 each independently represent a monovalent organic group represented by the following formula (9-b), In formula (9-a), _V1 represents a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, or a urea bond, _W1 represents an oxygen atom or an NH group, _R15 represents an alkylene group having 2 to 6 carbon atoms which is a direct bond or may be substituted with a hydroxyl group, _R16 represents a hydrogen atom or a methyl group, * represents an atomic bond, In formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents an alkylene group having 2 to 6 carbon atoms which is directly bonded or optionally substituted by a hydroxyl group, R ₁₈ represents a hydrogen atom or a methyl group, and * represents an atomic bond. A photosensitive resin composition for forming an insulating film as claimed in claim 4, wherein _V1 in the formula (9-a) represents an ester bond and _W1 represents an oxygen atom. The photosensitive resin composition for forming an insulating film as claimed in claim 4, wherein R ₁₅ in the formula (9-a) represents a 1,2-ethylene group. The photosensitive resin composition for forming an insulating film as claimed in claim 1, wherein the polymer is polyimide. The photosensitive resin composition for forming an insulating film as claimed in claim 1, wherein the crosslinking compound comprises two or more compounds selected from the group consisting of (meth)acrylic acid compounds and maleimide compounds. The photosensitive resin composition for forming an insulating film as claimed in claim 1 is a negative photosensitive resin composition. An insulating film is a calcined product of a coating film of the photosensitive resin composition for forming an insulating film as described in any one of claims 1 to 9. A photosensitive resist film comprising: a base film, a photosensitive resin layer formed by a photosensitive resin composition for forming an insulating film as recited in any one of claims 1 to 9, and a cover film. A semiconductor device comprises a semiconductor element and a cured film disposed on the upper part or the lower part of the semiconductor element, wherein the cured film is a cured relief pattern formed by the photosensitive resin composition for forming an insulating film as described in any one of claims 1 to 9.