TW202344569A - 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 insulating film formation

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

In the past, polyimide resin, which has excellent heat resistance, electrical properties, and mechanical properties, has been used as insulating materials for electronic parts and passivation films, surface protective films, interlayer insulating films, etc. of semiconductor devices. Among the polyimide resins, especially those provided in the form of a photosensitive polyimide precursor, thermal imidization treatment can be performed by coating, exposing, developing, and hardening the precursor. And easily form a heat-resistant embossed pattern coating. This kind of photosensitive polyimide precursor has the characteristic of significantly reducing the number of steps compared to conventional non-photosensitive polyimide resins.

Patent Document 1 and Patent Document 2 propose a photosensitive resin composition containing polyamide or polyimide using a diamine having a (meth)acryloxy group. In addition, because the passivation film, surface protection film, interlayer insulating film, etc. of the semiconductor device are thickened and the elastic modulus is high, the stress increases, the warpage of the semiconductor wafer becomes larger, and there are problems during transportation and wafer fixing. When defects occur. Therefore, it is desired to develop a polyimide resin with low residual stress. Methods for reducing the residual stress of polyimide resin include, for example, setting the molecular chains of the polyimide into a rigid skeleton in order to bring the thermal expansion coefficient of the polyimide close to that of the silicon wafer. (For example, Patent Document 3). [Prior technical literature] [Patent Document]

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

[Problem to be solved by the invention]

In recent years, it is necessary to transmit and process large-capacity information at high speed in semiconductor devices, so there has been progress in increasing the frequency of electrical signals. Because high-frequency electrical signals are easily attenuated, transmission losses must be reduced. Therefore, insulating films used in semiconductor devices are required to have a low dielectric loss tangent.

In addition, when forming a hardened relief pattern, development is performed using a developer, but generally an alkali aqueous solution developer or an organic solvent developer is used. The photosensitive resin used to obtain a 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 through exposure and development, and the photosensitivity of the unexposed part A negative type in which the resin is dissolved in the developer and the photosensitive resin remains in the exposed area. In particular, although the negative type has poorer resolution than the positive type, it is easy to thicken and thin the film 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 of long development time during organic solvent development. In addition, in order to reduce the warpage of the semiconductor wafer, especially when the film thickness of the negative photosensitive resin is increased, it is desired to have a low residual stress.

Therefore, a photosensitive resin composition for forming an insulating film that has a low dielectric loss tangent in the obtained insulating film, a short development time when developed with an organic solvent, and a low residual stress has been sought. However, the photosensitive resin compositions described in Patent Documents 1 to 3 cannot satisfy all of these characteristics.

In view of the above, an object of the present invention is to provide a photosensitive resin composition for forming an insulating film that has a low dielectric loss tangent in the obtained insulating film, a short development time when developed with an organic solvent, and a low residual stress. object; an insulating film obtained from the composition; a photoresist film using the composition; a method for manufacturing a substrate with a hardened relief pattern; and a semiconductor device with a hardened relief pattern. [Means to solve the problem]

The inventors of the present invention continued their research in order to achieve the above-mentioned subject, and found that by including a specific polymer in a photosensitive resin composition for forming an insulating film, it is possible to obtain an insulating film having a low dielectric loss tangent. , the present invention is completed by providing a photosensitive resin composition for forming an insulating film that has a short development time and low residual stress during development with an organic solvent.

[1] A photosensitive resin composition for forming an insulating film, comprising a polymer of at least one of polyimide, polyamide acid, and polyamide ester, and a solvent, the polymer having photopolymerizability groups, aromatic groups and alkyl groups with more than 5 carbon atoms. [2] The photosensitive resin composition for forming an insulating film according to [1], wherein the polyamide imide is the following polyamide (1), and the polyamide acid is the following polyamide (2) ), the polyamide ester is the following polyamide ester (3), polyimide (1): having the following formula (1-a), the following formula (1-b) and the following formula (1- c) A polyimide having a structural unit represented by the following formula (2), polyamide acid (2): a polyimide having a structural unit represented by the following formula (2), the following formula (1-b), and the following formula (1-c) Amino acid, polyamic acid ester (3): at least one of the following polyamic acid esters (3a) ~ (3b), polyamic acid ester (3a): having the following formula (3-a), and a polyamide ester having a structural unit represented by the following formula (1-b), polyamide ester (3b): having the following formula (3-b), the following formula (1-b), and the following formula (1 The polyamide ester of the structural unit represented by -c), [Chemical 1] In the formula (1-a), Ar ₁ represents a tetravalent organic group. In the formula (1-b), X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms. In the formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group, [Chemical 2] In formula (2), Ar ₂ represents a tetravalent organic group, [Chemical 3] In the formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a univalent organic group having a photopolymerizable group. In the formula (3-b), Ar ₄ represents a tetravalent organic group. The organic group, R ₁ and R ₂ each independently represents a monovalent organic group. [3] The photosensitive resin composition for forming an insulating film according to [2], wherein in the formula (1-b), X represents any one of the following formulas (V-1) to (V-6) The divalent organic radical, [Chemical 4] In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, and R ^v1 represents an alkyl group with 5 to 20 carbon atoms. , in formulas (V-2) ~ (V-5), X ^v2 ~ X ^v5 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH -, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15, R ^v2 ~ R ^v5 each independently represents the number of carbon atoms 5~20 alkyl group, in formula (V-6), X _a 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 -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, -CONH-, -NH-(CH ₂ ) _m -NH-, or -SO ₂ -(CH ₂ ) _m -SO ₂ -, where m represents an integer from 1 to 6, X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a -, -CONH -, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is 1~ An integer of 15, R ^1a and R ^1b each independently represent an alkyl group with 5 to 20 carbon atoms, k1 and k2 each independently represent an integer of 0 to 2, in formulas (V-1) to (V-6), * indicates atomic bond. [4] The photosensitive resin composition for forming an insulating film according to [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), L ₁ and L ₂ each independently represent a monovalent organic group represented by the following formula (9-b), [Chemical 5] In formula (9-a), V ₁ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W ₁ represents an oxygen atom or an NH group, and R ₁₅ represents a direct bond. , or an alkylene group with 2 to 6 carbon atoms that may be substituted by a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, * represents an atomic bond, [Chemical 6] In formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents an alkylene group with 2 to 6 carbon atoms that is directly bonded or may be substituted with a hydroxyl group, and R ₁₈ represents a hydrogen atom or a methyl group. , ＊represents atomic bonds. [5] The photosensitive resin composition for forming an insulating film according to [4], wherein V ₁ in the formula (9-a) represents an ester bond, and W ₁ represents an oxygen atom. [6] The photosensitive resin composition for forming an insulating film according to [4] or [5], wherein R ₁₅ in the formula (9-a) represents a 1,2-ethylidene group. [7] The photosensitive resin composition for forming an insulating film according to any one of [1] to [6], further comprising a photoradical polymerization initiator. [8] The photosensitive resin composition for forming an insulating film according to any one of [1] to [7], further containing a crosslinking compound. [9] The photosensitive resin composition for forming an insulating film according to any one of [1] to [8], which is a negative photosensitive resin composition. [10] An insulating film which is a calcined product of a coating film of the photosensitive resin composition for forming an insulating film according to any one of [1] to [9]. [11] A photoresist film comprising: a base film, a photosensitive resin layer formed of the photosensitive resin composition for forming an insulating film according to any one of [1] to [9], and a cover film . [12] A method of manufacturing a substrate with a hardened relief pattern, including the following steps: (1) Coating the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 9 on the substrate, and A photosensitive resin layer is formed on the substrate, (2) the photosensitive resin layer is exposed, (3) the exposed photosensitive resin layer is developed to form a relief pattern, (4) the relief pattern is heated , forming a hardened relief pattern. [13] The method of manufacturing a substrate with a hardened relief pattern according to [12], wherein the developer used in the development is an organic solvent. [14] A substrate with a hardened relief pattern, manufactured by the method of manufacturing a substrate with a hardened relief pattern as in [12] or [13]. [15] A semiconductor device including a semiconductor element and a cured film provided on or below the semiconductor element, and the cured film is made of the photosensitive resin for forming an insulating film according to any one of [1] to [9] The hardened relief pattern formed by the composition. [Effects of the invention]

According to the present invention, it is possible to obtain a photosensitive resin composition for forming an insulating film that has a low dielectric loss tangent in the obtained insulating film, a short development time when developed with an organic solvent, and a low residual stress; obtained from the composition An insulating film; a photoresist film using the composition; a method for manufacturing a substrate with a hardened relief pattern; and a semiconductor device with a hardened relief pattern.

(Photosensitive resin composition for insulating film formation) The photosensitive resin composition for forming an insulating film of the present invention contains at least a polymer and a solvent, and optionally further contains other components.

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

The inventors of the present invention speculate that the effect of the present invention is exerted by the photosensitive resin composition for forming an insulating film of the present invention for the following reasons. By providing a specific polymer with a photopolymerizable group, photosensitivity is imparted to the resin composition containing the specific polymer. By making the specific polymer have an alkyl group and an aromatic group having 5 or more carbon atoms, the dielectric loss tangent of the insulating film can be reduced. By having a specific polymer having an alkyl group and an aromatic group having 5 or more carbon atoms, the development time in organic solvent development can be shortened. By having a specific polymer have an alkyl group having 5 or more carbon atoms, the residual stress can be reduced.

As for the polyimide, the following polyimide (1) is preferred. As for the polyamide, the following polyamide (2) is preferred. As for the polyamide ester, the following polyamide ester (3) is preferred. 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). The polyamide ester (3) is at least one of the following polyamide esters (3a) to (3b). Polyamic acid ester (3a) is a polyamic acid ester having a structural unit 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).

[Chemical 7] In formula (1-a), Ar ₁ 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 8] In formula (2), Ar ₂ represents a tetravalent organic group.

[Chemical 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. There is no particular limitation on the tetravalent organic group, but it is preferable to use a tetravalent organic group having two or more aromatic rings from the viewpoint of lowering the dielectric loss tangent change of the insulating film.

The number of aromatic rings of a tetravalent organic group having two or more aromatic rings is not particularly limited as long as it is two or more, and it may be four or more, for example. The upper limit of the number of aromatic rings is not particularly limited, and may be 8 or less, or 6 or less, for example.

Regarding the counting method of aromatic rings in "two or more aromatic rings", polycyclic aromatic ring systems formed by the condensation of two or more aromatic rings such as naphthalene rings and anthracene rings are counted as one aromatic ring . Therefore, the naphthalene ring system counts as 1 aromatic ring. On the other hand, since the biphenyl ring is not a condensed ring, it is counted as two aromatic rings. In addition, the perylene ring system is regarded as a structure in which two naphthalene rings are bonded, and is counted as two aromatic rings. Examples of the aromatic ring include aromatic hydrocarbon rings, aromatic heterocyclic rings, and the like.

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). [Chemical 10] In formula (4), X ₁ and X ₂ each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), or a urethane bond. bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R _a1 and R _a2 each independently represent an alkyl group having 1 to 6 carbon atoms that may be substituted. Z ₁ 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 from 0 to 3. When R _a1 is a plural number, the plural R _a1 may be the same or different. When R _a2 is a plural number, the plural R _a2 may be the same or different. * indicates atomic bond.

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in R _a1 and R _a2 in formula (4) include an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. In this specification, an alkyl group and an alkylene group may be linear, branched, cyclic, or a combination of two or more thereof, unless their structure is specifically mentioned. Examples of substituents in the alkyl group having 1 to 6 carbon atoms that may be substituted include halogen atom, hydroxyl group, thiol group, carboxyl group, cyano group, formyl group, haloformyl group, sulfonate group, etc. Acid group, amine group, nitro group, nitroso group, side oxygen group, thioxy group, alkoxy group with 1 to 6 carbon atoms, etc. In addition, the "carbon number 1 to 6" of the "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms of the "alkyl group" excluding the substituent. In addition, the number of substituents is not particularly limited.

[Chemical 11] In formula (5-a), R ₃ represents an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, or an alkoxy group with 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 the 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), and R ₄ and R ₅ each independently represent the number of carbon atoms. For an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, m ₂ and m ₃ each independently represent an integer from 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 with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, or an alkoxy group with 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 the 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). * indicates atomic bond.

[Chemical 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 that 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 that may be substituted or an aryl group having 6 to 12 carbon atoms that may be substituted. * indicates atomic bond.

Z ₁ , from the viewpoint that the effects of the present invention can be ideally obtained, preferably represents a divalent organic group represented by formula (5-b). From the viewpoint that the effects of the present invention can be ideally obtained, in formula (5-b), Z ₂ represents direct bonding which is ideal. From the viewpoint that the effects of the present invention can be ideally obtained, in formula (5-b), R ₄ and R ₅ preferably represent a methyl group.

As for the alkyl group with 1 to 6 carbon atoms in R ₇ and R ₈ that may be substituted by a halogen atom, examples include alkyl groups with 1 to 6 carbon atoms and halogenated alkyl groups with 1 to 6 carbon atoms. wait. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be part or all of it.

Examples of substituents in the alkylene group having 1 to 6 carbon atoms in R ₉ and R ₁₀ that may be substituted include halogen atoms, hydroxyl groups, thiol groups, carboxyl groups, cyano groups, and carboxyl groups. , halogenated formyl group, sulfonate group, amine group, nitro group, nitroso group, side oxy group, thioxy group (thioxy), alkoxy group with 1 to 6 carbon atoms, etc. Examples of the optionally substituted alkylene group having 1 to 6 carbon atoms include an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, and the like. Examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, propylene, and butylene. In addition, the "carbon number 1 to 6" of 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. In addition, the number of substituents is not particularly limited.

As for the substituents in the optionally substituted aryl group with 6 to 10 carbon atoms in R ₉ and R ₁₀ , examples thereof include halogen atoms and alkyl groups with 1 to 6 carbon atoms that may also be halogenated. , alkoxy groups with 1 to 6 carbon atoms that may also be halogenated, etc. In addition, halogenation may be part or all of it. Examples of the aryl group include phenylene group, naphthylene group, and the like. In addition, the "carbon number of 6 to 10" of 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, the number of substituents is not particularly limited.

Examples of the divalent organic group represented by formula (6-a) include divalent organic groups represented by the following formula. [Chemical 13] In the formula, * represents atomic bond.

Examples of the divalent organic group represented by formula (6-b) include divalent organic groups represented by the following formula. [Chemical 14] In the formula, R ₃₁ ~ R ₃₃ each independently represents a halogen atom, an alkyl group with 1 to 6 carbon atoms that may be substituted by a halogen atom, or an alkoxy group with 1 to 6 carbon atoms that may be substituted with a halogen atom. . n31 represents an integer from 0 to 5. n32 and n33 each independently represent an integer from 0 to 4. When R ₃₁ is a plural number, the plural R ₃₁ may be the same or different. When R ₃₂ is a plural number, the plural R ₃₂ may be the same or different. When R ₃₃ is a plural number, the plural R ₃₃ may be the same or different. * indicates atomic bond.

Specific examples of the alkyl group having 1 to 6 carbon atoms in R ₃₁ to R ₃₃ that may be substituted with a halogen atom include an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms. Halogenated alkyl. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be part or all of it. Specific examples of the alkoxy group having 1 to 6 carbon atoms in R ₃₁ to R ₃₃ that may be substituted with a halogen atom include an alkyl group with 1 to 6 carbon atoms that may be substituted with a halogen atom. The group is set to an alkoxy group.

Examples of the tetravalent organic group having two or more aromatic rings include tetravalent organic groups represented by the following formula. [Chemical 15] [Chemical 16] In the formula, * represents atomic bond.

＜＜X＞＞ X represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms. The alkyl group having 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 of the alkyl group is not particularly limited as long as it is 5 or more. For example, it may be 40 or less, 35 or less, or 30 or less. The number of carbon atoms of the alkyl group is preferably from 8 to 40, more preferably from 10 to 35, and particularly preferably from 12 to 30. The alkyl group may be linear, branched, cyclic, or a combination of two or more thereof.

Regarding X, from the viewpoint that the effects of the present invention can be ideally obtained, a divalent aromatic group represented by any one of formulas (V-1) to (V-6) is preferred. [Chemical 17] In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, and R ^v1 represents an alkyl group with 5 to 20 carbon atoms. . In the formulas (V-2) to (V-5), X ^v2 to X ^v5 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15, R ^v2 ~ R ^v5 each independently represents the number of carbon atoms 5 ~20 alkyl groups. In formula (V-6), X _a 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 -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, -CONH-, -NH-(CH ₂ ) _m -NH-, Or -SO ₂ -(CH ₂ ) _m -SO ₂ -, where m represents an integer from 1 to 6, X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, - CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15, R ^1a and R ^1b each independently represents 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.

As far as X ^v1 ~X ^v5 is concerned, it means -O- is more ideal. For X ^p1 and X ^p2 , it is ideal to represent -CH ₂ -O-. In the case of X _a , it is ideal to represent a single bond.

＜＜Y＞＞ Y represents a divalent aromatic group having a photopolymerizable group. Examples of the photopolymerizable group include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, radically polymerizable groups are preferred. Examples of the radically polymerizable group include an acryl group, a methacryloyl group, an acryl ether group, a vinyl ether group, and a vinyl group.

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 obtained 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). [Chemical 18] In formula (9-a), V ₁ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W ₁ represents an oxygen atom or an NH group, and R ₁₅ represents a direct bond. , or an alkylene group with 2 to 6 carbon atoms that may be substituted by a hydroxyl group, R ₁₆ represents a hydrogen atom or a methyl group, and * represents an atomic bond.

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

In this specification, examples of alkylene groups having 2 to 6 carbon atoms that may be substituted with hydroxyl groups include 1,1-ethylene group, 1,2-ethylene group, and 1,2-propylene group. , 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, Alkylene groups in which at least part of their hydrogen atoms are substituted with hydroxyl groups (for example, 2-hydroxy-1,3-propylene group), etc.

V ₁ represents an ester bond (-COO-) which is ideal. W ₁ represents an oxygen atom which is ideal. R ₁₅ preferably represents 1,2-ethylidene group.

Examples of the divalent organic group represented by formula (9-a) include divalent organic groups represented by the following formula. [Chemical 19] In the formula, * represents atomic bond. The two atomic bonds are, for example, at a meta position relative to the substituent having a photopolymerizable group.

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

The monovalent organic group having a photopolymerizable group is preferably a monovalent organic group represented by the following formula (9-b). [Chemistry 20] In formula (9-b), W ₂ represents an oxygen atom or an NH group, R ₁₇ represents an alkylene group with 2 to 6 carbon atoms that is directly bonded or may be substituted with a hydroxyl group, and R ₁₈ represents a hydrogen atom or a methyl group. , * represents atomic bond.

W ₂ represents an oxygen atom, which is ideal. R ₁₇ preferably represents 1,2-ethylidene 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 linear alkyl groups, branched chain alkyl groups, alicyclic alkyl groups, and the like. Examples of linear alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, and decyl. , undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmyl), heptadecyl (margaryl) ), octadecyl (stearyl), nonadecyl, arachyl, behenyl, behenyl, tridecyl, tetracosyl Lignoceryl, pentadecyl, hexadecyl, heptadecyl, etc. Examples of branched chain alkyl groups having 1 to 30 carbon atoms include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, Second isopentyl, isohexyl, neohexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2- Ethylpentyl, heptan-3-yl, heptan-4-yl, 4-methylhexan-2-yl, 3-methylhexan-3-yl, 2,3-dimethylpentane -2-yl, 2,4-dimethylpentan-2-yl, 4,4-dimethylpentan-2-yl, 6-methylheptyl, 2-ethylhexyl, octane-2 -yl, 6-methylheptan-2-yl, 6-methyloctyl, 3,5,5-trimethylhexyl, nonan-4-yl, 2,6-dimethylheptan-3 -yl, 3,6-dimethylheptan-3-yl, 3-ethylheptan-3-yl, 3,7-dimethyloctyl, 8-methylnonyl, 3-methylnonyl Alk-3-yl, 4-ethyloctan-4-yl, 9-methyldecyl, undecyl-5-yl, 3-ethylnonan-3-yl, 5-ethylnonan- 5-yl, 2,2,4,5,5-pentamethylhexane-4-yl, 10-methylundecyl, 11-methyldodecyl, tridecyl-6-yl, Tridecan-7-yl, 7-ethylundecan-2-yl, 3-ethylundecan-3-yl, 5-ethylundecan-5-yl, 12-methyltridecane Alkyl, 13-methyltetradecyl, pentadecyl-7-yl, pentadecyl-8-yl, 14-methylpentadecyl, 15-methylhexadecyl, heptadecan- 8-yl, heptadecan-9-yl, 3,13-dimethylpentadecan-7-yl, 2,2,4,8,10,10-hexamethylundecan-5-yl, 16-methylheptadecanyl, 17-methyloctadecyl, nonadecan-9-yl, nonadecan-10-yl, 2,6,10,14-tetramethylpentadecan-7 -yl, 18-methylnonadecyl, 19-methyleicosanyl, hecosan-10-yl, 20-methyleicosanyl, 21-methyleicosanyl, Tricosyl-11-yl, 22-methyltricosyl, 23-methyltetracosyl, pentacos-12-yl, pentacos-13-yl, 2,22 -Dimethyltricosan-11-yl, 3,21-dimethyltricosan-11-yl, 9,15-dimethyltricosan-11-yl, 24-methyldi Pentadecyl, 25-methylhexadecyl, heptadecan-13-yl, etc. Examples of alicyclic alkyl groups having 1 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, and 1,6-dimethyl. Cyclohexyl, 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, cyclododecyl, etc.

The polyamide ester (3) may also be the following polyamide 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 group having a photopolymerizable group as 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 tetravalent organic groups include tetravalent organic groups represented by the following formula. [Chemistry 22] [Chemistry 23] In the formula, * represents atomic bond.

＜＜Other 4-valent organic groups＞＞ The specific polymer may 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. Regarding such a divalent organic group, for example, from the viewpoint of obtaining a lower dielectric loss tangent in the insulating film obtained, a divalent organic group having three or more aromatic rings is ideal. 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 a divalent organic group having three or more aromatic rings is not particularly limited as long as it is three or more. For example, it may be four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be 8 or less, or 6 or less, for example.

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). [Chemistry 24] In formula (13), X ₂₁ and X ₂₂ each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), or a urethane bond ( -NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₂₁ and R ₂₂ each independently represent an alkyl group having 1 to 6 carbon atoms which may be substituted. Y ₂₀ 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 from 0 to 4. When R ₂₁ is a plural number, the plural R ₂₁ may be the same or different. When R ₂₂ is a plural number, the plural R ₂₂ may be the same or different. * indicates atomic bond.

Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in R ₂₁ and R ₂₂ in formula (13) include an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. In this specification, an alkyl group and an alkylene group may be linear, branched, cyclic, or a combination of two or more thereof unless their structure is specifically mentioned. Examples of substituents in the alkyl group having 1 to 6 carbon atoms that may be substituted include halogen atom, hydroxyl group, thiol group, carboxyl group, cyano group, formyl group, haloformyl group, sulfonate group, etc. Acid group, amine group, nitro group, nitroso group, side oxygen group, thioxy group, alkoxy group with 1 to 6 carbon atoms, etc. In addition, the "carbon number 1 to 6" of the "alkyl group having 1 to 6 carbon atoms which may be substituted" refers to the number of carbon atoms of the "alkyl group" excluding the substituent. In addition, the number of substituents is not particularly limited.

Examples of the divalent organic group having three or more aromatic rings include divalent organic groups represented by the following formula. [Chemical 25] [Chemical 26] In the formula, * represents atomic bond.

Examples of other divalent organic groups include those represented by the following formula. These divalent organic groups are, for example, residues obtained by removing two amine groups from diamine. [Chemical 27] In the formula, * represents atomic bond.

Polyamide imide is, for example, an amide imide of polyamide acid which is a reaction product of a diamine component and a tetracarboxylic acid derivative. The imidization rate of polyimide does not necessarily need to be 100%. The imidization rate of the 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. The polyamide ester is, for example, a reaction product of a diamine component and a tetracarboxylic acid diester.

Here, examples of the tetracarboxylic acid derivative include tetracarboxylic acid, tetracarboxylic acid diester, tetracarboxylic acid dihalide, tetracarboxylic dianhydride, and the like.

The tetracarboxylic acid derivative preferably contains a tetracarboxylic acid derivative having two or more aromatic rings. It is a tetravalent organic group of Ar ₁ in formula (1-a), Ar ₂ in formula (2), Ar ₃ in formula (3-a), and Ar ₄ in formula (3-b), for example A residue obtained by removing a carboxyl group, a carboxylic acid ester group, or a carboxylic acid dianhydride group from a tetracarboxylic acid derivative having two or more aromatic rings is preferred.

The tetracarboxylic acid derivative having two or more aromatic rings is preferably a tetracarboxylic dianhydride represented by the following formula (4-Z). [Chemical 28] In formula (4-Z), X ₁ and X ₂ each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), or a urethane bond. bond (-NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R _a1 and R _a2 each independently represent an alkyl group having 1 to 6 carbon atoms that may be substituted. Z ₁ 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 from 0 to 3. When R _a1 is a plural number, the plural R _a1 may be the same or different. When R _a2 is a plural number, the plural R _a2 may be the same or different.

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

The aromatic diamine compound having an alkyl group having 5 or more carbon atoms is preferably a diamine compound represented by the following formulas (V-1a) to (V-6a). [Chemical 29] In formula (V-1a), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-. R ^v1 represents an alkyl group with 5 to 20 carbon atoms. In the formulas (V-2a) to (V-5a), X ^v2 to X ^v5 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH- , -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15. R ^v2 to R ^v5 each independently represent an alkyl group having 5 to 20 carbon atoms. In formula (V-6a), X _a 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 -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, -CONH-, -NH-(CH ₂ ) _m -NH-, Or -SO ₂ -(CH ₂ ) _m -SO ₂ -, where m represents an integer from 1 to 6. X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15. R ^1a and R ^1b each independently represent an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represent an integer from 0 to 2.

Specific examples of aromatic diamine compounds having an alkyl group having 5 or more carbon atoms are as follows. [Chemical 30]

The aromatic diamine compound having a photopolymerizable group is preferably an aromatic diamine compound represented by the following formula (9-A). [Chemical 31] V ₁ , W ₁ , R ₁₅ and R ₁₆ in the formula (9-A) are each synonymous with V ₁ , W ₁ , R ₁₅ and R ₁₆ in the formula (9-a).

The ratio of the aromatic tetracarboxylic acid derivatives having two or more aromatic rings to all the tetracarboxylic acid derivatives constituting the polyimide is not particularly limited, but it is considered that the ratio of the aromatic tetracarboxylic acid derivatives having two or more aromatic rings to the present invention can be obtained ideally. From the viewpoint of effect, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is even more ideal. The ratio of the aromatic tetracarboxylic acid derivatives having two or more aromatic rings to all the tetracarboxylic acid derivatives constituting the polyamide acid is not particularly limited, but it is considered that the ratio of the aromatic tetracarboxylic acid derivatives having two or more aromatic rings to the present invention can be obtained ideally. From the viewpoint of effect, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is even more ideal. The ratio of the aromatic tetracarboxylic acid derivatives having two or more aromatic rings to all the tetracarboxylic acid derivatives constituting the polyamide ester is not particularly limited, but it is considered that the present invention can be obtained ideally. From the perspective of the effect, 20 mol% to 100 mol% is more ideal, and 40 mol% to 100 mol% is more ideal.

The ratio of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to all the diamine components constituting the polyimide is not particularly limited, but it is considered from the viewpoint that the effects of the present invention can be optimally obtained. , 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 having 5 or more carbon atoms to all the diamine components constituting the polyamide acid is not particularly limited, but it is considered from the viewpoint that the effects of the present invention can be optimally obtained. , 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 having 5 or more carbon atoms to all the diamine components constituting the polyamide ester is not particularly limited, but it is considered to be such that the effects of the present invention can be ideally obtained. From a viewpoint, 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 proportion of the aromatic diamine compound having a photopolymerizable group relative to all the diamine components constituting the polyimide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is 10 mol%~ 90 mol% is more ideal, 15 mol% to 75 mol% is more ideal, and 20 mol% to 60 mol% is particularly ideal. The proportion of the aromatic diamine compound having a photopolymerizable group relative to all the diamine components constituting the polyamide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is 10 mol%~ 90 mol% is more ideal, 15 mol% to 75 mol% is more ideal, and 20 mol% to 60 mol% is particularly ideal. The proportion of the aromatic diamine compound having a photopolymerizable group relative to all the diamine components constituting the polyamide ester is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is 10 mol % ~90 mol% is more ideal, 15 mol% ~ 75 mol% is more ideal, and 20 mol% ~ 60 mol% is particularly ideal.

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

The total amount of the aromatic diamine compound having a photopolymerizable group and the aromatic diamine compound having an alkyl group having 5 or more carbon atoms is relative to the total amount of the aromatic diamine compound that constitutes the polyimide, polyamide acid, and polyamide ester. In terms of the molar ratio of all diamine components, from the viewpoint of ideally obtaining the effects of the present invention, it is more preferably 30 mol% or more, more preferably 40 mol% or more, and particularly 50 mol% or more. ideal. The upper limit of the total molar ratio is not particularly limited, 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 all the diamine components constituting the polyamide acid is not particularly limited, but it is considered from the viewpoint that the effects of the present invention can be ideally obtained. It is more ideal that it is 5 mol% to 60 mol%, it is more ideal that it is 10 mol% to 55 mol%, and it is especially ideal that it is 15 mol% to 50 mol%.

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

＜＜Production method of specific polymer＞＞ The method for producing a specific polymer is not particularly limited, but may include known methods such as 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 described in WO2013/157586, for example.

Polyamic acid or polyamic acid ester can be produced, for example, by reacting a diamine component and a tetracarboxylic acid derivative in a solvent (condensation polymerization).

Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and N,N-dimethylformamide. , N,N-dimethylacetylamide, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, dimethylserioxide, 1,3-dimethyl-2 -Imidazolidinone. In addition, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] ~ formula [D -3] Solvents shown. [Chemical 32] In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents can be used individually or in mixture. Then, even if it is a solvent that does not dissolve polyamic acid or polyamic acid ester, it can be mixed with the above-mentioned solvent and used as long as the polyamic acid or polyamic acid 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 it is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%. The reaction may be initially carried out at a high concentration, and the solvent may be added later. In the reaction, the ratio of the total molar number of the diamine components to the total molar number of the tetracarboxylic acid derivatives is preferably 0.8 to 1.2. The same is true for general condensation polymerization reactions. The closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic acid or polyamic acid ester produced.

When the diamine component and the tetracarboxylic acid derivative are reacted, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group. Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiol, and N-benzene. Naphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol bisaminoethyl ether tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-phenylene glycol Nitro-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropyl Amino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. The usage amount of the thermal polymerization inhibitor is not particularly limited.

Polyimide can be obtained by subjecting the polyamide acid obtained by the above reaction to dehydration and ring-closure. Examples of methods for obtaining polyimide include thermal imidization by heating the polyamide acid solution obtained by the above reaction as it is, or adding a catalyst to the polyamide acid solution. Chemical imidization. The temperature when performing thermal imidization in a solution is 100°C to 400°C, preferably 120°C to 250°C. It is ideal to perform the process while removing water generated by the acyl imidization reaction out of the system.

For the above-mentioned chemical imidization, an alkaline catalyst and an acid anhydride can be added to the polyamic acid solution obtained by the reaction, and stirred at -20°C to 250°C, preferably 0°C to 180°C. Use this to proceed. The amount of alkaline catalyst is 0.1 mole times to 30 mole times of the amide acid group, preferably 0.2 mole times to 20 mole times, and the amount of acid anhydride is 1 mole times to 50 mole times of the amide acid group. Molar times, preferably 1.5 molar times to 30 molar times. Examples of alkaline catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferable because it is less likely to generate polyisoamide as a by-product. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, pyromelite anhydride, and the like. Among them, acetic anhydride is preferably used because purification after termination of the reaction becomes easier. The imidization rate of chemical imidization (the ratio of the closed repeating units relative to all the repeating units of the polyimide precursor, also called the loop closing rate.) can be adjusted by adjusting the amount of catalyst and The reaction temperature and reaction time are controlled.

When recovering the generated imide from the reaction solution of the above-mentioned imidization, the reaction solution may be put into a solvent to precipitate. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butylcellulose, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer obtained by putting it into a solvent and precipitating it can be dried under normal pressure or reduced pressure, at normal temperature or by heating after being filtered and recovered.

Certain polymers can also be end-capped. The terminal blocking method is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

<Solvent> Regarding the solvent contained in the photosensitive resin composition for forming an insulating film, it is preferable to use an organic solvent from the viewpoint of solubility with respect to a specific polymer. Specific examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. , N,N-dimethylpropylpropamide, N,N-dimethylisobutylamine, dimethyltrisoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butylene Ester, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidinone, 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 the following formula [D-1] ~ formula [D-3 ] represents solvents, etc. These can be used alone or in combination of two or more. [Chemical 33] In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms. In formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms. In formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

Depending on the desired coating film thickness and viscosity of the photosensitive resin composition for forming an insulating film, the solvent may be in the range of, for example, 30 parts by mass to 1,500 parts by mass relative to 100 parts by mass of the specific polymer, and preferably 100 parts by mass. Use within the range of ~1000 parts by mass.

＜Other ingredients＞ In the embodiment, the photosensitive resin composition for forming an insulating film may further contain other components other than the specific polymer and the solvent. Examples of other components include photo-radical polymerization initiators (also called "photo radical initiators"), cross-linking compounds (also called "cross-linking agents"), thermosetting agents, and others. Resin components, fillers, sensitizers, adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, 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 for photocuring. Examples thereof include tert-butylperoxyisobutyrate, 2,5-dibutyl Methyl-2,5-bis(benzyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)isopropoxy]benzene, di-tert-butyldioxy Oxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)isopropyl hydroperoxide, No. Tributyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy) Oxy)butyl valerate, cyclohexanone peroxide, 2,2',5,5'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4' -Tetrakis(tertiary butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tertiary pentylperoxycarbonyl)benzophenone, 3,3',4, 4'-Tetrakis(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butyl organic peroxides such as hydroxyperoxybenzoate and di-tert-butyl diperoxyisophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, eight Quinones such as methylanthraquinone and 1,2-benzoanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, etc.; 2,2-Dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-( 2-Hydroxy-2-methyl-propyl)benzyl}-phenyl]-2-methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4- (Methylthio)phenyl]-2-𠰌linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)-1-butanone, Alkylphenyl ketone compounds such as 2-dimethylamino-2-(4-methylbenzyl)-1-(4-𠰌lin-4-yl-phenyl)-butan-1-one; Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other hydroxylphosphine oxides Compounds; 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)- oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone. From the viewpoint of i-ray curability, oxime ester-based compounds are particularly ideal.

Photoradical polymerization initiators can be obtained in the form of commercial products, such as IRGACURE [registered trademark] 651, Tong 184, Tong 2959, Tong 127, Tong 907, Tong 369, Tong 379EG, Tong 819, Tong 819DW, Tong 1800 , Same as 1870, Same as 784, Same as OXE01, Same as OXE02, Same as OXE03, Same as OXE04, Same as 250, Same as 1173, Same as MBF, Same as TPO, Same as 4265, Same as TPO (the above, made by BASF Corporation), KAYACURE [registered trademark] DETX -S, same as MBP, same as DMBI, same as EPA, same as OA (above, Nippon Kayaku Co., Ltd.)), VICURE-10, same as 55 (above, manufactured by STAUFFER Co. LTD), ESACURE KIP150, same as TZT, same as 1001 , the same as KTO46, the same as KB1, the same as KL200, the same as KS300, the same as EB3, triazine-PMS, triazine A, triazine B (above, Nihon Siber Hegner (share)), ADEKA OPTOMER N-1717, the same as N-1414, the same as N- 1606. ADEKA ARKLS N-1919T, same as NCI-831E, same as NCI-930, same as NCI-730 (above, ADEKA (stock) system). 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. It is ideally 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polymer. From the viewpoint of photosensitivity characteristics, it is 0.5 to 15 parts by mass. More ideal. When the photoradical polymerization initiator is contained at 0.1 parts by mass or more relative to 100 parts by mass of the specific polymer, it is easy to improve the photosensitivity of the photosensitive resin composition for forming an insulating film. On the other hand, when it is contained at 20 parts by mass or less, it is easy to Improves the thick film curability of the photosensitive resin composition for insulating film formation.

＜＜Crosslinking compound＞＞ In the embodiment, in order to improve the resolution of the relief pattern, a monomer (crosslinking compound) having a photoradically polymerizable unsaturated bond may be optionally contained in the photosensitive resin composition for forming an insulating film. Such a cross-linked compound is preferably a compound containing a polymerizable group that undergoes a radical polymerization reaction due to a photoradical polymerization initiator. Examples thereof include (meth)acrylic acid compounds and maleimide compounds. , are not particularly limited to the following. Examples of the (meth)acrylic compound include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate. acrylate, mono- or di(meth)acrylate of propylene glycol or polypropylene glycol, mono-, di- or tri(meth)acrylate of glycerol, di(meth)acrylate of 1,4-butanediol, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl Diol di(meth)acrylate, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate , Dimethanediol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate ) Acrylate, benzenetrimethacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]benzobis(meth)acrylate, ginseng(2-hydroxyethyl)isocyanate Uric acid ester bis(meth)acrylate, isobornyl(meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(methyl) Compounds such as acrylate, glycerol di- or tri-(meth)acrylate, neopentylerythritol di-, tri-, or tetra-(meth)acrylate, and ethylene oxide or propylene oxide adducts of these compounds , 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and to them are added methyl ethyl ketoxime, ε-caprolactam, γ-caprolactam, 3,5- Compounds made of blocking agents such as dimethylpyrazole, diethyl malonate, ethanol, isopropyl alcohol, n-butanol, and 1-methoxy-2-propanol. Examples of the maleimide compound include 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, and 1,6-bis(maleimide)butane. (Maleimide)hexane, N,N'-1,4-benzenedimaleimide, N,N'-1,3-phenylenedismaleimide, 4,4' -Bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(2-maleimideethyl)disulfide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane wait. Examples of commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (manufactured by Designer Molecules Inc.). Moreover, these compounds can also be used individually, and 2 or more types can be used in combination. In addition, in this specification, (meth)acrylate means acrylate and methacrylate.

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

＜＜Thermal hardener＞＞ Examples of the thermal hardener include hexamethoxymethyl melamine, tetramethoxymethyl glycoluril, tetramethoxymethyl benzoguanamine, 1,3,4,6-methoxymethyl methyl) glycoluril, 1,3,4,6-fourth (butoxymethyl) glycoluril, 1,3,4,6-fourth (hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl) glycoluril ) urea, 1,1,3,3-fourth (butoxymethyl) urea and 1,1,3,3-fourth (methoxymethyl) urea, etc. The content of the thermosetting agent in the photosensitive resin composition for forming an insulating film is not particularly limited.

＜＜Padding＞＞ Examples of fillers include inorganic fillers, and specific examples include sols such as silica, aluminum nitride, boron nitride, zirconium dioxide, and alumina. The content of the filler in the photosensitive resin composition for forming an insulating film is not particularly limited.

＜＜Other resin ingredients＞＞ In the embodiment, the photosensitive resin composition for forming an insulating film may further contain a resin component other than the specific polymer. Examples of resin components that may be contained in the photosensitive resin composition for forming an insulating film include polyimide, polyethylene, polyethazole precursor, phenolic resin, polyamide, and cyclic resin other than the specific polymer. Oxygen resin, siloxane resin, acrylic resin, etc. The content of these resin components is not particularly limited, but 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 can be optionally blended into the photosensitive resin composition for forming an insulating film in order to improve the photosensitivity. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, and 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-dimethylaminophenylene Indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene) base) benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3- Bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylamine Coumarin, 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-𠰌linyl benzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoethazole, 2-(p-dimethylaminostyryl)benzene Thiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These may be used individually or in plural combination.

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

＜＜Adhesion aids＞＞ In the embodiment, in order to improve the adhesion between a film formed using the photosensitive resin composition for forming an insulating film and a substrate, an adhesion aid may be optionally blended into the photosensitive resin composition for forming an insulating film. . Examples of adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ- Glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyldimethoxymethylsilane Methylacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(3 -Diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamide, benzophenone-3,3' -Bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl] Silane coupling agents such as propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, and ginseng ( Aluminum-based adhesion aids such as aluminum acetate (ethyl acetate), aluminum ginseng (acetyl acetone), aluminum diisopropoxide (ethyl acetate), etc.

Among these adhesion aids, silane coupling agents are more ideal from the viewpoint of adhesion.

The content of the adhesion aid is not particularly limited, but is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the specific polymer.

＜＜Thermal polymerization inhibitor＞＞ In the embodiment, a thermal polymerization inhibitor may be optionally blended in order to improve the viscosity and photosensitivity stability 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, p-tert-butylcatechol, phenothiol, N-phenyl can be used Naphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol bisaminoethyl ether tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-phenylene glycol Nitro-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropyl Amino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

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 compounds＞＞ For example, when using a substrate made of copper or a copper alloy, an azole compound can be optionally blended into the photosensitive resin composition for forming an insulating film in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-benzene. Base-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) methyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- Hydroxy-5'-tertiary octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole Triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole , 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred examples include 4-carboxy-1H-benzotriazole and 5-carboxy-1H-benzotriazole. In addition, these azole compounds may be used alone or as a mixture of two or more types.

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. Considering the light sensitivity characteristics, it is more preferably 0.5 to 5 parts by mass. When the content of the specific polymer per 100 parts by mass of the azole compound is 0.1 part by mass or more, when the photosensitive resin composition for forming an insulating film is formed on copper or a copper alloy, discoloration of the surface of the copper or copper alloy is suppressed, and the discoloration of the surface of the copper or copper alloy is suppressed. On the other hand, when the content is 20 parts by mass or less, the light sensitivity is excellent, so it is preferable.

＜＜Hindered phenol compounds＞＞ In the embodiment, a hindered phenol compound may be optionally blended into the photosensitive resin composition for forming an insulating film in order to suppress discoloration of copper. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and octadecyl-3- (3,5-Di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylene bis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4 '-Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propanol acid ester], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenediol Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylene bis(3,5-di-tert-butyl-4- Hydroxy-hydrocinamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6 -Tertiary butylphenol), neopentylerythritol-4 [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], ginseng-(3,5-di-tert-butylphenol), Tributyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tributyl(3,5-di-tert-butyl-4-hydroxybenzyl) 1,3,5-benzene, 1,3,5-hydroxy-2,6-dimethyl-4-isopropylbenzyl-1,3,5-tribenzyl-2,4,6-(1H ,3H,5H)-triketone, 1,3,5-triketone (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triketone-2, 4,6-(1H,3H,5H)-trione, 1,3,5-shen(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5 -Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethyl Benzyl]-1,3,5-triethylmethyl-2,4,6-(1H,3H,5H)-trione, 1,3,5-triethylmethyl-3-hydroxy -2,6-Dimethylbenzyl]-1,3,5-tristrione-2,4,6-(1H,3H,5H)-trione, 1,3,5-shen(3-hydroxy- 2,6-Dimethyl-4-phenylbenzyl)-1,3,5-tristrione-2,4,6-(1H,3H,5H)-trione, 1,3,5-trione ( 4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-Shen(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tributyl-2,4,6- (1H,3H,5H)-trione, 1,3,5-triketone (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triketone 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-triketone, 4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethyl Benzyl)-1,3,5-tributyl-2,4,6-(1H,3H,5H)-trione, 1,3,5-tributyl-5,6-dione Ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-trihydroxy-2,4,6-(1H,3H,5H)-trione, 1,3,5-triketone (4 -Tertibutyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5- Ginseng(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-Shen(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H, 5H)-triketone, etc., but are not limited to these. Among these, 1,3,5-shen(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6 -(1H,3H,5H)-trione is particularly ideal.

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. Considering the light sensitivity characteristics, it is more preferably 0.5 to 10 parts by mass. When the content of the specific polymer of the hindered phenol compound is 0.1 parts by mass or more based on 100 parts by mass of the specific polymer, for example, when forming a photosensitive resin composition for forming an insulating film on copper or copper alloys, discoloration and corrosion of copper or copper alloys can be prevented. , on the other hand, when it is 20 parts by mass or less, the light sensitivity is excellent, so it is preferable.

The photosensitive resin composition for insulating film formation can be suitably used as a negative photosensitive resin composition for insulating film formation that is used for production of a cured relief pattern described below.

(insulation film) The insulating film of the present invention is a calcined product of the coating film of the photosensitive resin composition for forming the insulating film of the present invention. As the coating method, methods conventionally used for coating photosensitive resin compositions for forming insulating films can be used, such as spin coaters, smear rods, blade coaters, curtain coaters, screen printing machines, etc. Coating method, and spray coating method with a sprayer, etc. As a method of calcining to obtain a calcined product, various methods can be selected, such as using a hot plate, using an oven, or using a temperature-raising oven with a programmable temperature. Calcining can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As the ambient gas during heating and hardening, air can be used, and inert gases such as nitrogen and argon can also be used. The thickness of the insulating film is not particularly limited, but it is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

(Photoresist film) The photosensitive resin composition for forming an insulating film of the present invention can be used in a photosensitive resist film (so-called dry film resist). The photoresist film includes a base film, a photosensitive resin layer (photosensitive resin film) formed of the photosensitive resin composition for forming an insulating film of the present invention, and a cover film. Usually, a photosensitive resin layer and a cover film are laminated in this order on a base film.

The photoresist film can be produced, for example, by coating a base film with a photosensitive resin composition for forming an insulating film, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. . As the coating method, methods conventionally used for coating photosensitive resin compositions for forming insulating films can be used. For example, spin coaters, smear rods, blade coaters, curtain coaters, and screens can be used. Methods of coating with printing machines, etc., and methods of spray coating with a sprayer, etc. As for the drying method, conditions such as 20°C to 200°C and 1 minute to 1 hour can be cited. The thickness of the obtained photosensitive resin layer is not particularly limited, but it is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

As the base film, a known one can be used, and for example, a thermoplastic resin film or the like can be used. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the base film is ideally 2 μm to 150 μm. As the cover film, a known one can be used, for example, a polyethylene film, a polypropylene film, etc. can be used. As for the cover film, it is ideal that the adhesive force with the photosensitive resin layer is smaller than that of the base film. The thickness of the covering film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm. The base film and the cover film may be the same film material, or different films may be used.

(Method for manufacturing substrate with hardened relief pattern) The method for manufacturing a substrate with a hardened relief pattern of the present invention includes the following steps: (1) Coating 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) Expose the photosensitive resin layer, (3) Develop the exposed photosensitive resin layer to form a relief pattern, (4) Heat the relief pattern to form a hardened relief pattern.

Each step is explained below.

(1) The step of applying the photosensitive resin composition for forming an insulating film of the present invention on a substrate and forming a photosensitive resin layer on the substrate In this step, the photosensitive resin composition for forming an insulating film of the present invention is applied to a substrate, and then dried if necessary to form a photosensitive resin layer. As the coating method, methods conventionally used for coating the photosensitive resin composition for forming an insulating film can be used. For example, a spin coater, a smear bar, a blade coater, a curtain coater, and a mesh can be used. Methods for coating with plate printing machines, etc., and methods for spray coating with a spray applicator, etc.

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

(2) Step of exposing the photosensitive resin layer. In this step, the photosensitive resin layer formed in the above step (1) is exposed using exposure devices such as a contact exposure machine, mirror projection exposure machine, and stepper machine. A photomask or reticle with a pattern can be exposed directly, using an ultraviolet light source or the like. As for the light source used during exposure, examples include g-line, h-line, i-ray, ghi-ray broadband, and KrF excimer laser. The expected exposure amount is 25mJ/cm ² ~2000mJ/cm ² .

After that, for the purpose of improving the light sensitivity, post-exposure baking (PEB) and/or pre-development baking using any combination of temperature and time can be implemented as needed. The range of baking conditions, the temperature is preferably 50°C to 200°C, and the time is preferably 10 seconds to 600 seconds, but it is not limited to this range as long as it does not interfere with the characteristics of the photosensitive resin composition for forming the insulating film.

(3) The step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a development method for developing the photosensitive resin layer after exposure (irradiation), conventionally known photoresist development methods can be used, such as rotary spray method, immersion method, and immersion with ultrasonic treatment. Any method among other methods. In addition, after development, rinsing may be performed for the purpose of removing the developer. In addition, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking using any combination of temperature and time can be performed as needed. The developer used in development is preferably an organic solvent. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and N,N-dimethylacetyl. Amine, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. Moreover, two or more types of each solvent may be used in combination, for example, several types may be used in combination. The rinse liquid used for rinse is preferably an organic solvent that mixes with the developer and has low solubility in the photosensitive resin composition for forming an insulating film. As the rinse liquid, for example, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, xylene, etc. are preferred. Moreover, two or more types of each solvent may be used in combination, for example, several types may be used in combination.

(4) The step of heating the relief pattern to form a hardened relief pattern In this step, the relief pattern obtained by the above development is heated and transformed into a hardened relief pattern. As for the heat hardening method, various methods can be selected, such as using a heating plate, using an oven, and using a temperature-raising oven with a programmable temperature. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. As for the ambient gas during heating and hardening, air can be used, or inert gases such as nitrogen and argon can 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 including a semiconductor element and a cured film provided on the upper part or lower part of the semiconductor element is also provided. The cured film is a cured relief pattern formed from 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 manufacturing method of a substrate with a hardened relief pattern. Furthermore, the present invention is also applicable to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a hardened relief pattern as a part of the steps. The semiconductor device of the present invention can be formed into a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a semiconductor device having a bump structure by forming the hardened relief pattern. protective film, etc., and combined with known manufacturing methods of semiconductor devices to manufacture.

(display device) In an embodiment, a display device is provided, including a display element and a cured film provided on an upper part of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the hardened relief pattern can be laminated in direct contact with the display element, or can be laminated with other layers sandwiched between them. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, and MVA (Multi-domain Vertical Alignment) liquid crystals. Protrusions for display devices, and partition walls for cathodes of organic EL (Electro-Luminescence) devices.

The photosensitive resin composition for forming an insulating film of the present invention is suitable for use in, in addition to the above-mentioned semiconductor devices, interlayer insulating films of multilayer circuits, surface coatings of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films. Also useful in. [Example]

Next, the contents of the present invention will be described in detail using examples, 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: 3,5-diaminobenzoic acid 2-(methacryloxy)ethyl (manufactured by Samsung Chemical Industries Co., 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 (manufactured by Wakayama Seika Industry Co., Ltd.) [Chemical 38]

DAB-C18: 4-octadecyloxy-1,3-phenylenediamine (manufactured by Wakayama Seika Industry 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-bis Oxy-1,3-dihydroisofuran-5-carboxylate) (manufactured by Honshu Chemical Industry Co., Ltd.) [Chemical 40]

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

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

The chemical acyl imidization rates shown in the following synthesis examples are the results of measurements using a nuclear magnetic resonance instrument (hereinafter, abbreviated to NMR in this specification). The measurement system used 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 uses protons derived from a structure that does not change before and after imidization as a reference proton, and uses the peak accumulation value of this proton and the protons derived from amide acid that appear around 9.5 ppm to 11.0 ppm. The cumulative value of the proton peak of the NH group is calculated by the following formula. Chemical acyl imidization rate (%) = (1-α･x/y)×100 In the above formula, x is the accumulated value of the proton peak derived from the NH group of amide, y is the accumulated value of the peak of the reference proton, and α is the case of polyamic acid (imidization rate 0%) The ratio of the base protons to the number of NH protons in one amide.

<Synthesis Example 1> Synthesis of polyimide (P-1) Add 5.50g (20.81mmol) of BEM-S, 14.56g (38.65mmol) of DAB-C18, and 211.43g of N-ethyl-2-pyrrolidinone to a 4-neck flask, and stir under air and room temperature. It dissolves. Then, 14.86g (28.54mmol) of BPADA, 18.39g (29.73mmol) of TMPBP-TME, and 90.61g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50° C. for 20 hours to obtain a polyamide. Amino acid solution. Next, 177.65 g of N-ethyl-2-pyrrolidinone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask, and the mixture was stirred at 60° C. for 3 hours to perform chemical imidization. Then, 532.95 g of N-ethyl-2-pyrrolidinone was added and dropped into 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 2> Synthesis of polyimide (P-2) Add BEM-S 5.10g (19.30mmol), DAB-C18 10.38g (27.57mmol), HFBAPP 4.29g (8.27mmol) and N-ethyl-2-pyrrolidinone 200.71g in a 4-neck flask, under air , stir at room temperature to dissolve. Then, 13.78g (26.47mmol) of BPADA, 17.05g (27.57mmol) of TMPBP-TME, and 86.02g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50° C. for 20 hours to obtain a polyamide. Amino acid 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 the mixture was stirred at 60° C. for 3 hours to perform chemical imidization. Then, 505.95 g of N-ethyl-2-pyrrolidinone was added and dropped into 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 3> Synthesis of polyimide (P-3) Add BEM-S 5.40g (20.43mmol), DAB-C18 14.29g (37.95mmol), and N-ethyl-2-pyrrolidinone 200.02g into a 4-neck flask, and stir under air and room temperature. It dissolves. Then, BPADA 8.51g (16.35mmol), TMPBP-TME 14.45g (23.35mmol), 6FDA 7.78g (17.51mmol), and N-ethyl-2-pyrrolidinone 85.72g were added to the flask, and stirred at 50°C. This took 20 hours to obtain a polyamic acid solution. Next, 168.10 g of N-ethyl-2-pyrrolidinone, 17.88 g of acetic anhydride, and 2.95 g of triethylamine were added to the flask, and the mixture was stirred at 60° C. for 3 hours to perform chemical imidization. Then, 504.30 g of N-ethyl-2-pyrrolidinone was added and dropped into 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 4> Synthesis of polyimide (P-4) Add 5.50g of BEM-S (20.81mmol), 12.39g of APC-14 (38.65mmol), and 195.12g of N-ethyl-2-pyrrolidinone to a 4-neck flask, and stir under air and room temperature. It dissolves. Then, BPADA 7.92g (17.84mmol), TMPBP-TME 14.71g (23.78mmol), 6FDA 8.67g (16.65mmol), and N-ethyl-2-pyrrolidinone 83.62g were added to the flask, and stirred at 50°C. This took 20 hours to obtain a polyamic acid solution. Next, 163.97 g of N-ethyl-2-pyrrolidinone, 18.21 g of acetic anhydride, and 3.01 g of triethylamine were added to the flask, and the mixture was stirred at 60° C. for 3 hours to perform chemical imidization. Then, 491.91 g of N-ethyl-2-pyrrolidinone was added and dropped into 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 5> Synthesis of polyimide (P-5) Add 5.50g (20.81mmol) of BEM-S, 13.47g (38.65mmol) of APC-16, and 199.43g of N-ethyl-2-pyrrolidinone to a 4-neck flask, and stir under air and room temperature. It dissolves. Then, BPADA 7.92g (17.84mmol), TMPBP-TME 14.71g (23.78mmol), 6FDA 8.67g (16.65mmol), and N-ethyl-2-pyrrolidinone 85.47g were added to the flask, and stirred at 50°C. This took 20 hours to obtain a polyamic acid 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 the mixture was stirred at 60° C. for 3 hours to perform chemical imidization. Then, 502.76 g of N-ethyl-2-pyrrolidinone was added and dropped into 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 6> Synthesis of polyimide (P-6) Add BEM-S 7.05g (26.68mmol), BAPP 4.38g (10.67mmol), DAB-C18 6.03g (16.01mmol), and N-ethyl-2-pyrrolidinone 98.95g in a 4-neck flask, and add it in the air Stir at room temperature to dissolve. Then, BPADA 7.22g (13.87mmol), TMPBP-TME 13.20g (21.35mmol), 6FDA 7.11g (16.01mmol) and N-ethyl-2-pyrrolidinone 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 the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 98%.

<Synthesis Example 7> Synthesis of polyimide (P-7) Add BEM-S 6.96g (26.34mmol), BAPP 4.32g (10.53mmol), DAB-C18 5.95g (15.80mmol), and N-ethyl-2-pyrrolidinone 97.67g in a 4-neck flask, and add it in the air Stir at room temperature 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-pyrrolidinone 157.33 g was 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, 16.13 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask, and the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 8> Synthesis of polyimide (P-8) Add 6.95g of BEM-S (26.31mmol), 4.32g of BAPP (10.52mmol), 5.95g of DAB-C18 (15.79mmol), and 97.57g of N-ethyl-2-pyrrolidinone in a 4-neck flask. Stir at room temperature 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-pyrrolidinone 157.43 g was 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, 16.12 g of acetic anhydride, and 2.66 g of triethylamine were added to the flask, and the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 9> Synthesis of polyimide (P-9) Add BEM-S 6.93g (26.21mmol), BAPP 4.30g (10.49mmol), DAB-C18 5.92g (15.73mmol), and N-ethyl-2-pyrrolidinone 97.22g in a 4-neck flask, and add it in the air Stir at room temperature to dissolve. Then, BPADA 7.37g (14.16mmol), TMPBP-TME 12.97g (20.97mmol), 6FDA 6.99g (15.73mmol), 5-norbornene-2,3-dicarboxylic anhydride 0.52g (3.15mmol) and N -Ethyl-2-pyrrolidone 157.78g was 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-pyrrolidinone, 16.06 g of acetic anhydride, and 2.65 g of triethylamine were added to the flask, and the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 10> Synthesis of polyimide (P-10) Add BEM-S 6.80g (25.72mmol), BAPP 4.22g (10.29mmol), DAB-C18 5.81g (15.43mmol), and N-ethyl-2-pyrrolidinone 95.37g in a 4-neck flask, and add it in the air Stir at room temperature to dissolve. Then, 21.32g (34.46mmol) of TMPBP-TME, 6.85g (15.43mmol) of 6FDA and 159.63g of N-ethyl-2-pyrrolidone were added to the flask, and stirred at 50°C for 22 hours to obtain polyamide. acid 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 the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

<Synthesis Example 11> Synthesis of polyimide (P-11) Add BEM-S 6.75g (25.54mmol), BAPP 4.19g (10.22mmol), DAB-C18 5.77g (15.33mmol), and N-ethyl-2-pyrrolidinone 94.73g in a 4-neck flask, and add it in the air Stir at room temperature to dissolve. Then, 21.17g (34.23mmol) of TMPBP-TME, 6.81g (15.33mmol) of 6FDA, 0.30g (3.07mmol) of maleic anhydride and 160.27g of N-ethyl-2-pyrrolidinone were added to the flask and heated at 50°C. Stir for 19 hours to obtain a polyamide 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 the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 12> Synthesis of polyimide (P-12) Add 10.09g (38.18mmol) of BEM-S, 6.16g (16.36mmol) of DAB-C18, and 92.09g of N-ethyl-2-pyrrolidinone to a 4-neck flask, and stir under air and room temperature. It dissolves. Then, BPADA 7.66g (14.73mmol), TMPBP-TME 13.49g (21.82mmol), 6FDA 7.27g (16.36mmol), maleic anhydride 0.32g (3.27mmol) and N-ethyl-2-pyrrolidinone 162.91 g was 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 the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 100%.

<Synthesis Example 13> Synthesis of polyimide (P-13) Add BEM-S 8.43g (38.18mmol), BAPP 5.46g (13.30mmol), DAB-C18 3.01g (7.98mmol), and N-ethyl-2-pyrrolidinone 95.76g in a 4-neck flask, in the air Stir at room temperature to dissolve. Then, BPADA 6.92g (13.30mmol), TMPBP-TME 16.45g (26.60mmol), 6FDA 4.73g (10.64mmol) and N-ethyl-2-pyrrolidinone 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 the mixture was 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 to dilute it, 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 acyl imidization rate obtained by NMR (THF-d8) was 98%.

<Comparative synthesis example 1> Synthesis of polyimide (P-14) Add 2.81g (10.62mmol) of BEM-S, 10.23g (19.72mmol) of HFBAPP, and 96.15g of N-ethyl-2-pyrrolidinone to a 4-neck flask, and stir to dissolve under air and room temperature. . Then, 7.58g (14.57mmol) of BPADA, 9.39g (15.17mmol) of TMPBP-TME, and 73.85g of N-ethyl-2-pyrrolidinone were added to the flask, and stirred at room temperature for 39 hours to obtain a polyamide. Amino acid solution. Next, 100.00 g of N-ethyl-2-pyrrolidinone, 9.29 g of acetic anhydride, and 1.54 g of triethylamine were added to the flask, and the mixture was 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 to dilute it, and the diluted solution was added dropwise to methanol. The resulting precipitate was washed with methanol and 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 acyl imidization rate obtained by NMR (THF-d8) was 99%.

The compounds shown in 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: 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 Seongbuk Chemical Industry Co., Ltd.) ･KBM-5103: 3-propenyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

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

<Example 2> 5.32g of polyimide (P-2) obtained in Synthesis Example 2, 0.80g of NK ESTER A-DOD-N as a cross-linking agent, and 0.21g of IRGACURE [registered trademark] OXE01 as a photoradical initiator were mixed. , CaA-BTZ 0.16g, KBM-5103 0.11g, N-ethyl-2-pyrrolidinone 7.02g, γ-butyrolactone 9.36g, and cyclohexanone 7.02g and dissolved, use a polyethylene with a pore size of 5 μm. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

<Example 3> Mix 7.66g of polyimide (P-2) obtained in Synthesis Example 2, 1.15g of NK ESTER A-DOD-N as a cross-linking agent, and 0.31g of IRGACURE [registered trademark] OXE01 as a photoradical initiator. , CaA-BTZ 0.23g, KBM-5103 0.15g, N-ethyl-2-pyrrolidinone 12.15g, γ-butyrolactone 16.20g, and cyclohexanone 12.15g were dissolved, and then a polyethylene with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

<Example 4> Mix 7.02g of polyimide (P-3) obtained in Synthesis Example 3, 1.05g of NK ESTER A-DOD-N as a cross-linking agent, and 0.28g of IRGACURE [registered trademark] OXE01 as a photoradical initiator. , CaA-BTZ 0.21g, KBM-5103 0.14g, N-ethyl-2-pyrrolidinone 6.39g, γ-butyrolactone 8.52g, and cyclohexanone 6.39g were dissolved, and then a polyethylene with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

<Example 5> 10.08g of polyimide (P-3) obtained in Synthesis Example 3, 1.51g of NK ESTER A-DOD-N as a cross-linking agent, and 0.40g of IRGACURE [registered trademark] OXE01 as a photoradical initiator were mixed. , CaA-BTZ 0.30g, KBM-5103 0.20g, N-ethyl-2-pyrrolidinone 11.25g, γ-butyrolactone 15.00g, and cyclohexanone 11.25g were dissolved, and then a polyethylene with a pore size of 5 μm was used. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

<Example 6> 8.06g of polyimide (P-4) obtained in Synthesis Example 4, 1.21g of NK ESTER A-DOD-N as a cross-linking agent, and 0.32g of IRGACURE [registered trademark] OXE01 as a photoradical initiator were mixed. , CaA-BTZ 0.24g, KBM-5103 0.16g, N-ethyl-2-pyrrolidinone 9.00g, γ-butyrolactone 12.00g, and cyclohexanone 9.00g and dissolved, then use polyethylene with a pore size of 5 μm. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

<Example 7> 8.06g of polyimide (P-5) obtained in Synthesis Example 5, 1.21g of NK ESTER A-DOD-N as a cross-linking agent, and 0.32g of IRGACURE [registered trademark] OXE01 as a photoradical initiator were mixed. , CaA-BTZ 0.24g, KBM-5103 0.16g, N-ethyl-2-pyrrolidinone 9.00g, γ-butyrolactone 12.00g, and cyclohexanone 9.00g and dissolved, then use polyethylene with a pore size of 5 μm. A negative photosensitive resin composition for forming an insulating film was prepared by filtering through a filter material made of acrylic.

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

<Example 9> Mix 8.82g of polyimide (P-7) obtained in Synthesis Example 7, 1.32g of NK ESTER A-DOD-N as a cross-linking agent and 0.88g of BMI-689, and IRGACURE as a photoradical initiator. Registered trademark] OXE01 0.26g, CBT-SG 0.13g, KBM-5103 0.18g, N-ethyl-2-pyrrolidinone 8.52g, γ-butyrolactone 11.36g, and cyclohexanone 8.52g and dissolved , using a polypropylene filter material with a pore size of 5 μm to filter, thereby preparing a negative photosensitive resin composition for forming an insulating film.

<Example 10> Mix 8.56g of polyimide (P-7) obtained in Synthesis Example 7, 1.28g of NK ESTER A-DOD-N as a cross-linking agent and 0.86g of BMI-689, and ADEKA ARKLS as a photoradical initiator. NCI-930 0.09g, IRGACURE [registered trademark] 819 0.51g, CBT-SG 0.13g, KBM-5103 0.17g, N-ethyl-2-pyrrolidinone 8.52g, γ-butyrolactone 11.36g, and ring After dissolving 8.52 g of hexanone, the mixture was filtered using a polypropylene filter material with a pore size of 5 μm, thereby preparing 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 as a cross-linking agent and 0.88g of BMI-689, and IRGACURE as a photoradical initiator were mixed. Registered trademark] OXE01 0.26g, CBT-SG 0.13g, KBM-5103 0.18g, N-ethyl-2-pyrrolidinone 8.52g, γ-butyrolactone 11.36g, and cyclohexanone 8.52g and dissolved , using a polypropylene filter material with a pore size of 5 μm to filter, thereby preparing 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 as a cross-linking agent and 0.88g of BMI-689, and IRGACURE as a photoradical initiator were mixed. Registered trademark] OXE01 0.26g, CBT-SG 0.13g, KBM-5103 0.18g, N-ethyl-2-pyrrolidinone 8.52g, γ-butyrolactone 11.36g, and cyclohexanone 8.52g and dissolved , using a polypropylene filter material with a pore size of 5 μm to filter, thereby preparing a negative photosensitive resin composition for forming an insulating film.

<Example 13> Mix 9.23g of polyimide (P-10) obtained in Synthesis Example 10, 1.38g of NK ESTER A-DOD-N as a cross-linking agent and 0.92g of BMI-689, and ADEKA ARKLS as a photoradical initiator. NCI-930 0.09g and IRGACURE [registered trademark] 819 0.55g, CBT-SG 0.14g, KBM-5103 0.18g, N-ethyl-2-pyrrolidinone 11.25g, γ-butyrolactone 15.00g, and ring After dissolving 11.25 g of hexanone, the mixture was filtered using a polypropylene filter material with a pore size of 5 μm, thereby preparing a negative photosensitive resin composition for forming an insulating film.

<Example 14> Mix 7.97g of polyimide (P-11) obtained in Synthesis Example 11, 1.20g of NK ESTER A-DOD-N as a cross-linking agent and 0.80g of BMI-689, and ADEKA ARKLS as a photoradical initiator. NCI-930 0.08g and IRGACURE [registered trademark] 819 0.48g, CBT-SG 0.12g, KBM-5103 0.16g, N-ethyl-2-pyrrolidone 8.76g, γ-butyrolactone 11.68g, and ring After dissolving 8.76 g of hexanone, the mixture was filtered using a polypropylene filter material with a pore size of 5 μm, thereby preparing a negative photosensitive resin composition for forming an insulating film.

<Example 15> Mix 8.56g of polyimide (P-12) obtained in Synthesis Example 12, 1.28g of NK ESTER A-DOD-N as a cross-linking agent and 0.86g of BMI-689, and ADEKA ARKLS as a photoradical initiator. NCI-930 0.09g and IRGACURE [registered trademark] 819 0.51g, CBT-SG 0.13g, KBM-5103 0.17g, N-ethyl-2-pyrrolidinone 8.52g, γ-butyrolactone 11.36g, and ring After dissolving 8.52 g of hexanone, the mixture was filtered using a polypropylene filter material with a pore size of 5 μm, thereby preparing a negative photosensitive resin composition for forming an insulating film.

<Example 16> Mix 10.70g of polyimide (P-13) obtained in Synthesis Example 13, 1.61g of NK ESTER A-DOD-N as a cross-linking agent and 1.07g of BMI-689, and ADEKA ARKLS as a photoradical initiator. NCI-930 0.11g and IRGACURE [registered trademark] 819 0.64g, CBT-SG 0.16g, KBM-5103 0.21g, N-ethyl-2-pyrrolidinone 10.65g, γ-butyrolactone 14.20g, and ring After dissolving 10.65 g of hexanone, the mixture was filtered using a polypropylene filter material with a pore size of 5 μm, thereby preparing a negative photosensitive resin composition for forming an insulating film.

＜Comparative example 1＞ 10.00g of polyimide (P-14) obtained in Comparative Synthesis Example 1, 1.50g of NK ESTER A-DOD-N as a cross-linking agent, and IRGACURE [registered trademark] OXE01 0.40 as a photoradical initiator were mixed. g, CaA-BTZ 0.30g, KBM-5103 0.20g, N-ethyl-2-pyrrolidinone 12.45g, γ-butyrolactone 16.61g, and cyclopentanone 12.45g and dissolved, use a pore size 5 μm A negative photosensitive resin composition for forming an insulating film was prepared by filtering the filter material made of polypropylene.

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

[Evaluation of Electrical Properties] The negative photosensitive resin composition for forming an insulating film prepared in Example 1, Example 2, Example 4, Example 6 to Example 16 and Comparative Example 1 was spin-coated on a 20 μm-coated surface. A 4-inch silicon wafer with thick aluminum foil was fired on a hot plate at 115°C for 270 seconds to form a photosensitive resin film of about 25 μm on the aluminum foil. The obtained photosensitive resin film was fully exposed on the wafer using an i-line exposure machine (PLA-501, manufactured by Canon Co., Ltd.) at 500 mJ/cm ² , and then a high-temperature dust-free oven (CLH-21CD(V)) was used. -S, KOYO THERMO SYSTEMS (Co., Ltd.), calcined at 230°C for 2 hours in a nitrogen atmosphere. Then, the calcined aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil, thereby obtaining a thin film. A split cylinder resonator was used to measure the dielectric loss tangent of the obtained film at 60GHz. The measurement conditions of dielectric loss tangent are as described above. ･Measurement method: Split cylinder resonator ･Vector network analyzer: FieldFox N9926A (manufactured by Keysight Technologies, Inc.) ･Resonator: CR-760 (manufactured by EM labs, Inc.) ･Measurement frequency: Approximately 60GHz 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) Example 1 Polyimide (P-1) 0.0055 Example 2 Polyimide(P-2) 0.0061 Example 4 Polyimide(P-3) 0.0061 Example 6 Polyimide (P-4) 0.0066 Example 7 Polyimide (P-5) 0.0064 Example 8 Polyimide (P-6) 0.0060 Example 9 Polyimide (P-7) 0.0057 Example 10 Polyimide (P-7) 0.0056 Example 11 Polyimide (P-8) 0.0059 Example 12 Polyimide (P-9) 0.0058 Example 13 Polyimide (P-10) 0.0055 Example 14 Polyimide (P-11) 0.0055 Example 15 Polyimide (P-12) 0.0061 Example 16 Polyimide (P-13) 0.0061 Comparative example 1 Polyimide (P-14) 0.0079 According to the results in Table 1, the film obtained from the negative photosensitive resin composition for forming an insulating film of Examples 1, 2, 4, 6 to 16 is different from the insulating film of Comparative Example 1. The dielectric loss tangent at 60 GHz shows a lower value than a film formed using a negative photosensitive resin composition.

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

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

According to the results in Table 2, after development of the negative photosensitive resin composition for forming an insulating film of Example 3, Example 5 to Example 16, and Comparative Example 2, all the photosensitive resin films in the unexposed portions were developed. The photosensitive resin film in the exposed part is almost not developed. Then, the photosensitive resin film obtained from the negative photosensitive resin composition for forming an insulating film of Comparative Example 2 is compared with the negative photosensitive resin for forming an insulating film of Example 3 and Examples 5 to 16. The photosensitive resin film obtained from the composition has a longer development time using cyclopentanone. That is, the photosensitive resin film obtained from the negative photosensitive resin composition for forming an insulating film of Example 3 and Example 5 to Example 16 has high solubility in the developer, and the development time of the development step is shortened, Reducing the amount of developer used is effective.

[Evaluation of Residual Stress] The negative photosensitive resin composition for forming an insulating film 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). After coating with ACT-8, Tokyo Electronics Co., Ltd., it was fired at 115°C for 270 seconds to form a photosensitive resin film with a film thickness of about 6.5 μm on the wafer. Next, the entire surface was exposed at 500 mJ/cm ² using an i-ray stepper (NSR-2205i12D, manufactured by Nikon Co., Ltd.). Then, a high-temperature dust-free oven (CLH-21CD(V)-S, KOYO THERMO SYSTEMS Co., Ltd.) was used to calcine in a nitrogen environment at 230°C for 2 hours to obtain a polyimide cured film. The residual stress of the obtained polyimide film was measured at room temperature using a film stress measuring device (FLX-3300-T: manufactured by KLA-Tencor Co., Ltd.). The results of measuring the residual stress are shown in Table 3. The measured value obtained is defined as "good" if it is 25 MPa or less, and "poor" if it is 30 MPa or more.

[table 3] Resin Residual stress (MPa) Example 3 Polyimide(P-2) Good(22.9) Example 5 Polyimide (P-3) Good(20.7) Comparative 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 is better than the negative photosensitive resin composition for insulating film formation of Comparative Example 2. The polyimide cured film obtained from the photosensitive resin composition has a small residual stress, so the silicon wafer is less likely to warp, and defects during transportation and wafer fixing are less likely to occur.

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

Claims (15)

A photosensitive resin composition for forming an insulating film, including a polymer of at least one of polyimide, polyamide acid, and polyamide ester, and a solvent, This polymer has a photopolymerizable group, an aromatic group, and an alkyl group having 5 or more carbon atoms. The photosensitive resin composition for forming an insulating film according to claim 1, wherein the polyamide imide is the following polyamide imide (1), the polyamide acid is the following polyamide acid (2), and the The polyamide ester is the following polyamide ester (3), polyamide imide (1): represented by the following formula (1-a), the following formula (1-b) and the following formula (1-c) Polyimide having structural units, polyamide acid (2): polyamic acid having structural units represented by the following formula (2), the following formula (1-b), and the following formula (1-c), Polyamide ester (3): at least one of the following polyamide esters (3a) to (3b), Polyamide ester (3a): having the following formula (3-a), and the following formula Polyamic acid ester of the structural unit represented by (1-b), polyamic acid ester (3b): having the following formula (3-b), the following formula (1-b), and the following formula (1-c) The structural unit represented by the polyamide ester, In the formula (1-a), Ar ₁ represents a tetravalent organic group. In the formula (1-b), X represents a divalent aromatic group having an alkyl group with 5 or more carbon atoms. In the formula (1-c), Y represents a divalent aromatic group having a photopolymerizable group, In formula (2), Ar ₂ represents a tetravalent organic group, In the formula (3-a), Ar ₃ represents a tetravalent organic group, and L ₁ and L ₂ each independently represent a univalent organic group having a photopolymerizable group. In the formula (3-b), Ar ₄ represents a tetravalent organic group. The organic group, R ₁ and R ₂ each independently represents a monovalent organic group. The photosensitive resin composition for forming an insulating film according to claim 2, wherein in the formula (1-b), organic base, In formula (V-1), X ^v1 represents -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, and R ^v1 represents an alkyl group with 5 to 20 carbon atoms. , in formulas (V-2) ~ (V-5), X ^v2 ~ X ^v5 each independently represent -(CH ₂ ) _a -, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH -, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is an integer from 1 to 15, R ^v2 ~ R ^v5 each independently represents the number of carbon atoms 5~20 alkyl group, in formula (V-6), X _a 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 -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, -CONH-, -NH-(CH ₂ ) _m -NH-, or -SO ₂ -(CH ₂ ) _m -SO ₂ -, where m represents an integer from 1 to 6, X ^p1 and X ^p2 each independently represent -(CH ₂ ) _a -, -CONH -, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ -O-, -CH ₂ -OCO-, -COO-, or -OCO-, where a is 1~ An integer of 15, R ^1a and R ^1b each independently represent an alkyl group with 5 to 20 carbon atoms, k1 and k2 each independently represent an integer of 0 to 2, in formulas (V-1) to (V-6), * indicates atomic bond. The photosensitive resin composition for forming an insulating film according to 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) , L ₁ and L ₂ each independently represent a monovalent organic group represented by the following formula (9-b), In formula (9-a), V ₁ represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W ₁ represents an oxygen atom or an NH group, and R ₁₅ represents a direct bond. , or an alkylene group with 2 to 6 carbon atoms that may be substituted by a hydroxyl group, R ₁₆ 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 with 2 to 6 carbon atoms that is directly bonded or may be substituted with a hydroxyl group, and R ₁₈ represents a hydrogen atom or a methyl group. , * represents atomic bond. The photosensitive resin composition for forming an insulating film according to claim 4, wherein V ₁ in the formula (9-a) represents an ester bond, and W ₁ represents an oxygen atom. The photosensitive resin composition for forming an insulating film according to claim 4, wherein R ₁₅ in the formula (9-a) represents a 1,2-ethylidene group. The photosensitive resin composition for forming an insulating film according to claim 1 further contains a photoradical polymerization initiator. The photosensitive resin composition for forming an insulating film according to claim 1 further contains a crosslinking compound. The photosensitive resin composition for forming an insulating film according to 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 according to any one of claims 1 to 9. A photosensitive resist film having: base film, A photosensitive resin layer formed of the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 9, and Cover with film. A method of manufacturing a substrate with a hardened relief pattern, including the following steps: (1) Coating the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 9 on a substrate to form a photosensitive resin layer on the substrate, (2) Expose the photosensitive resin layer, (3) Develop the exposed photosensitive resin layer to form a relief pattern, (4) Heat the relief pattern to form a hardened relief pattern. The method for manufacturing a substrate with a hardened relief pattern according to claim 12, wherein the developer used in the development is an organic solvent. A substrate with a hardened relief pattern is manufactured by the manufacturing method of a substrate with a hardened relief pattern according to claim 12. A semiconductor device including a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, and the cured film is formed of the photosensitive resin composition for forming an insulating film according to any one of claims 1 to 9. Hardened relief pattern.