TW201936722A - Photosensitive resin composition, method for producing cured embossed pattern and semiconductor device capable of suppressing the occurrence of voids at an interface between a Cu layer and a cured photosensitive resin layer - Google Patents

Abstract

The present invention provides a photosensitive resin composition with which, after a high-temperature storage test, voids are unlikely to occur at an interface of a Cu layer where the Cu layer makes contact with a cured photosensitive resin layer, and with which a highly adhesive resin layer is obtained; a method for forming a cured embossed pattern by using the photosensitive resin composition; and a semiconductor device having the cured embossed pattern. By deploying a cyclic compound having carbonyl groups into a photosensitive resin composition having a specific structure, the photosensitive resin composition of the present invention can form a cured film in which the void generated at the interface where the Cu layer makes contact with the photosensitive resin layer after the high-temperature storage test is suppressed.

Description

Photosensitive resin composition, method for producing cured embossed pattern, and semiconductor device

The present invention relates to a photosensitive resin composition for forming an insulating material such as an electronic component, and a relief pattern of a passivation film, a buffer coating film, an interlayer insulating film, or the like in a semiconductor device, and a hardened relief pattern using the same. a forming method and a semiconductor device.

In the past, an insulating material for an electronic component, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device, a polybenzazole resin or a polybenzoxazole resin having excellent heat resistance, electrical properties, and mechanical properties. , phenol resin, etc. Among the polyimine resin, the composition is provided in the form of a photosensitive polyimide intermediate composition by coating, exposing, developing, and curing by the composition. A heat-resistant embossed pattern film can be easily formed. Such a photosensitive polyimide precursor composition has a feature that can be greatly reduced in comparison with the prior non-photosensitive polyimide pigment material.
Further, a semiconductor device (hereinafter also referred to as "element") is mounted on a printed circuit board by various methods depending on the purpose. Previous components have generally been fabricated by wire bonding using thin wires from external terminals (pads) of the component to the leadframe. However, today, the speed of the components has increased and the operating frequency has reached GHz. The difference in the wiring length of each terminal in the installation may even affect the operation of the components. Therefore, in the installation of components for high-end applications, the length of the mounting wiring must be precisely controlled, and it is difficult to meet this requirement by wire bonding.
Therefore, flip-chip mounting has been proposed, that is, a rewiring layer is formed on the surface of a semiconductor wafer, and bumps (electrodes) are formed thereon, and then the wafer is flipped (flip-chip) and directly mounted on a printed substrate (for example, Refer to Patent Document 1). Since the flip chip mounting is used for processing high-end signals for high-end applications due to the ability to precisely control the wiring distance, or because it is small in size, it is used for mobile phones and the like, and its demand is rapidly expanding. In the case where a material such as polyimide, polybenzoxazole, or phenol resin is used in flip chip mounting, the pattern of the resin layer is formed, and then a metal wiring layer forming step is performed. In the metal wiring layer, the surface of the resin layer is usually subjected to plasma etching to roughen the surface, and then a metal layer to be a plated seed layer is formed by sputtering to a thickness of 1 μm or less, and then the metal layer is used as an electrode. It is formed by electrolytic plating. At this time, Ti is generally used as the metal to be the seed layer, and Cu is used as the metal of the rewiring layer formed by electrolytic plating.
For such a metal rewiring layer, the adhesion between the metal layer and the resin layer requiring rewiring is high after the reliability test. For the reliability test performed here, for example, a high-temperature storage test in which air is stored at a high temperature of 125 ° C or higher for 100 hours or more, and a temperature of about 125 ° C is confirmed by applying a voltage while assembling the wiring. The high temperature operation test for the operation under the state of being stored for more than 100 hours; the temperature cycle test in which the low temperature state of about -65 to -40 ° C and the high temperature state of about 125 to 150 ° C are repeated in cycles in the air; High-temperature and high-humidity storage test stored in a water vapor environment above °C and humidity above 85%; high-temperature and high-humidity bias test for assembling the wiring and applying the voltage while performing the same test; passing 260 ° C in air or under nitrogen for several times Reflow soldering test of reflow soldering furnace, etc.
However, in the case of the high-temperature storage test in the above reliability test, there is a problem that a void is generated at the interface between the re-wiring Cu layer and the resin layer after the test. When a void is formed at the interface between the Cu layer and the resin layer, the adhesion between the two is lowered.
[Previous Technical Literature]
[Patent Literature]
[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-338947

[The problem that the invention wants to solve]
The present invention has been made in view of such prior art research, and an object thereof is to provide a gap which can be obtained at an interface between a Cu layer and a cured photosensitive resin layer after a high temperature storage test. A photosensitive resin composition of a resin layer having high adhesion, a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.
[Technical means to solve the problem]
The inventors of the present invention have found that a photosensitive resin composition capable of forming a cured film excellent in discoloration resistance even on copper or a copper alloy can be obtained by blending a cyclic compound having a carbonyl group in a photosensitive resin composition. Thus, the present invention has been completed. That is, the present invention is as follows.
[1] A photosensitive resin composition comprising:
(A) selected from the group consisting of polyaminic acid, polyglycolate, polyamidate, polyhydroxy guanamine, polyamine amide, polyamine, polyamidimide, polyimine, poly a benzoxazole, and at least one resin selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass;
(B) at least one compound selected from the group consisting of the following compounds: a cyclic compound having two or more carbonyl groups, based on 100 parts by mass of the above (A) resin, and The carbonyl group is directly bonded to the above cyclic structure, and in the case of a monocyclic compound, 1/3 or more of the atoms forming the ring structure are N atoms, and in the case of the condensed ring compound, the above ring structure having the above carbonyl group is formed. More than 1/3 of the atoms are N atoms;
(C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin.
[2] The photosensitive resin composition according to [1], wherein the (A) resin is selected from the group consisting of a polyfluorene imine precursor containing the following general formula (1) and comprising the following general formula (4) A guanamine, a polycarbazole precursor containing the following general formula (5), a polyfluorene imine comprising the following general formula (6), a novolac, a polyhydroxystyrene, and a formula (7) At least one of the group consisting of phenol resins.
The following general formula (1) is
[Chemical 1]

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom and a carbon number of 1 to 30 is saturated. An aliphatic group, an aromatic group, or the following formula (2):
[Chemical 2]

(wherein, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10), or a carbon number of 1 or a saturated aliphatic group of ～4 or the following formula (3):
[Chemical 3]

(In the formula, R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) Polyammonium precursor, polyglycolate or polyamidate,
The following general formula (4) has
[Chemical 4]

In the formula, X ₂ is an organic group having a carbon number of 6 to 15 and Y ₂ is an organic group having a carbon number of 6 to 35, and may be the same structure or have a plurality of structures, and R ₉ is at least An organic group having a carbon number of 3 to 20 radically polymerizable unsaturated bonding group, and n ₂ is an integer of 1 to 1000}
The structure of the polyamine,
The following general formula (5) has
[Chemical 5]

In the formula, Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having two or more carbon atoms, and n ₃ is an integer of from 1 to 1000. , n ₄ is an integer of 0 to _{500., n 3 / (n 3 +} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The order of the diamine units is arbitrary}
The structure of the polyhydroxy guanamine as a polycarbazole precursor,
The following general formula (6) has
[Chemical 6]

Wherein X ₅ is an organic group having a valence of 4 to 14 and Y ₅ is an organic group having a valence of 2 to 12, and R ₁₀ and R ₁₁ each independently represent at least one member selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group or a thiol group. The organic group of the group in the group, n ₅ is an integer of from 3 to 200, and m ₃ and m ₄ represent an integer of from 0 to 10}
The polyimine of the structure represented, and the following general formula (7) is
[Chemistry 7]

In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦(a+b)≦4, and R ₁₂ represents an organic group selected from a carbon number of 1 to 20, a halogen atom, and a nitro group. And a monovalent substituent in the group consisting of cyano groups. When b is 2 or 3, the plurality of R ₁₂ may be the same or different from each other, and X represents a carbon number selected from the group which may have an unsaturated bond. An aliphatic group having a valence of ～10, an alicyclic group having a carbon number of 3 to 20, and a general formula (8):
[化8]

(wherein, p is an integer of from 1 to 10), and a two-valent organic group in the group consisting of a divalent alkoxy group and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms The phenol resin represented by the base.
[3] The photosensitive resin composition according to the above [1], wherein the photosensitive resin composition contains a phenol resin having a repeating unit represented by the above formula (7), and the above formula (7) X is selected from the following formula (9):
[Chemistry 9]

In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or a carbon in which one or both of hydrogen atoms are partially substituted with a fluorine atom. In the case of an aliphatic group having a value of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 12 The organic group of the valence, at least one of R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, the plurality of R ₁₇ may be the same or different from each other; (10):
[化10]

In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or a carbon in which one or all of a hydrogen atom is partially substituted with a fluorine atom. An aliphatic group having a valence of from 1 to 10, W being a single bond, an aliphatic group selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, and a carbon number of 3 to 20 which may be substituted by a fluorine atom. Base, the following general formula (8):
[11]

(wherein, p is an integer of 1 to 10), the divalent alkoxy group represented by the formula, and the following formula (11):
[化12]

The organic group of two valences in the group consisting of the base of two valences represented by the base of two valences in the group consisting of the two valence groups.
[4] A method of manufacturing a hardened relief pattern, comprising:
(1) a step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [3] on a substrate;
(2) a step of exposing the photosensitive resin layer;
(3) a step of developing the exposed photosensitive resin layer to form a relief pattern;
(4) A step of forming a hardened embossed pattern by heat-treating the embossed pattern.
[5] The method according to [4], wherein the substrate is formed of copper or a copper alloy.
[6] A semiconductor device comprising the hardened relief pattern obtained by the production method as described in [4] or [5].
[Effects of the Invention]
According to the present invention, by combining a specific photosensitive resin with a specific compound, it is possible to provide a high temperature storage test which does not occur at the interface between the Cu layer and the polyimide layer. A photosensitive resin composition of a photosensitive resin having a high gap and good adhesion, a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.

The present invention will be specifically described below. In the present specification, when a plurality of structures represented by the same symbols in the general formula are present in the molecule, they may be the same or different.
<Photosensitive Resin Composition>
(Surface A)
The present invention has the following components as essential components, that is, (A) is selected from the group consisting of polyglycine, polyglycolate and polyamidate, polyhydroxyguanamine, polyamine amide, polyamine, poly At least one of a group consisting of amidoxime, polyimine, polybenzoxazole, and a novolac, polyhydroxystyrene, and phenol resin: 100 parts by mass, (B) a ring having a carbonyl group Compound: 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin, and (C) sensitizer: 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.
(A) Resin
The (A) resin used in the present invention will be described. The (A) resin of the present invention is selected from the group consisting of polyglycine, polyglycolate, polyamidate, polyhydroxyguanamine, polyamine amide, polyamine, polyamidimide, At least one of a group consisting of polyimine, polybenzoxazole, and a novolac, polyhydroxystyrene, and phenol resin is used as a main component. Here, the main component means that the resin is contained in an amount of 60% by mass or more based on the entire resin, and preferably 80% by mass or more. Further, other resins may be contained as needed.
The weight average molecular weight of the resin is preferably 200 or more, and more preferably 5, or more, in terms of polystyrene conversion by gel permeation chromatography, from the viewpoint of heat resistance and mechanical properties after heat treatment. The upper limit is preferably 500,000 or less, and in the case of producing a photosensitive resin composition, it is more preferably 20,000 or less from the viewpoint of solubility in a developer.
In the present invention, in order to form the embossed pattern, the (A) resin is a photosensitive resin. The photosensitive resin is a resin which is used together with the following (C) sensitizer to form a photosensitive resin composition, and which causes a phenomenon of dissolution or undissolution in the subsequent development step.
As a photosensitive resin, in polylysine, polyamidate, polyamidate, polyhydroxy guanamine, polyamine amide, polyamide, polyamidimide, polyimine, Among the polybenzoxazoles and the phenol resins containing novolacs and polyhydroxystyrenes, polyacrylamide and polyfluorene are preferably used in terms of heat resistance and mechanical properties of the resin after heat treatment. Amineates, polyamidates, polyamines, polyhydroxyguanamines, polyimines, and phenolic resins. Further, these photosensitive resins can be selected from any of the following (C) sensitizers to prepare a negative photosensitive material or a positive photosensitive resin composition according to the intended use.
[(A) Polyglycolic acid, polyamidomate, polyamidate]
In the photosensitive resin composition of the present invention, an example of the resin (A) which is optimal in terms of heat resistance and photosensitivity is the above formula (1):
[Chemistry 13]

{式,X ₁ Is a tetravalent organic base, Y ₁ Is a divalent organic group, n ₁ An integer from 2 to 150, R ₁ And R ₂ Each of them is independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or the above formula (2):
[Chemistry 14]

(where, R ₃ , R ₄ And R ₅ Each is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ The monovalent organic group represented by the monovalent organic group represented by the integer of 2 to 10 or the saturated aliphatic group having 1 to 4 carbon atoms; or the following general formula (3):
[化15]

(where, R ₆ , R ₇ And R ₈ Each is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ Polyammonium, polyglycolate or polyamidate which is a polyimine precursor represented by an ammonium ion of one of the integers of 2 to 10).
The polyimine precursor is converted to polyimine by subjecting to a cyclization treatment by heating (for example, 200 ° C or higher). The polyimide precursor is suitable for use in a negative photosensitive resin composition.
In the above formula (1), X ₁ The tetravalent organic group represented is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR, in terms of heat resistance and photosensitivity. ₁ Base and -COOR ₂ An aromatic group or an alicyclic aliphatic group in which the group and the -CONH- group are adjacent to each other. As X ₁ The tetravalent organic group represented by the above is preferably an organic group having an aromatic ring having 6 to 40 carbon atoms, more preferably the following formula (30):
[Chemistry 16]

In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, a C1 to C10 fluorine-containing hydrocarbon group, 1 is an integer selected from 0 to 2, and m is selected from 0 to 3 An integer, n is an integer selected from 0 to 4}
The structure shown is not limited to these. Again, X ₁ The structure may be one type or a combination of two or more types. X having the structure represented by the above formula ₁ The base is particularly preferable in terms of heat resistance and photosensitivity.
In the above formula (1), Y ₁ The divalent organic group is preferably an aromatic group having 6 to 40 carbon atoms in terms of heat resistance and photosensitivity, and examples thereof include the following formula (31):
[化17]

In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4}
The structure shown is not limited to these. Also, Y ₁ The structure may be one type or a combination of two or more types. Y having the structure represented by the above formula (31) ₁ The base is particularly preferable in terms of heat resistance and photosensitivity.
R in the above formula (2) ₃ Preferred is a hydrogen atom or a methyl group, R ₄ And R ₅ From the viewpoint of photosensitive characteristics, a hydrogen atom is preferred. Again, m ₁ From the viewpoint of the photosensitive property, an integer of 2 or more and 10 or less is preferably an integer of 2 or more and 4 or less.
In the case of using a polyimide precursor as the (A) resin, an ester bond type and an ionic bond type are exemplified as a method of imparting photosensitivity to the photosensitive resin composition. The former is a method in which a side chain of a polyimide precursor is introduced into a compound having a photopolymerizable group, that is, an olefinic double bond, by an ester bond, the latter of which is a carboxyl group of a polyimide precursor and an amine group. A method in which an amine group of a (meth)acrylic compound is bonded via an ionic bond to impart a photopolymerizable group.
The above-mentioned ester-bonded polyimine precursor is obtained by first, including the above-mentioned tetravalent organic group X. ₁ The tetracarboxylic dianhydride is reacted with an alcohol having a photopolymerizable unsaturated double bond and an arbitrary saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as After the acid/ester), it is made to contain the above-mentioned divalent organic group Y. ₁ The diamines are subjected to guanamine condensation polymerization.
(Preparation of acid/ester)
In the present invention, the tetravalent organic group X is contained as a polyimine precursor suitable for preparing an ester bond type. ₁ Examples of the tetracarboxylic dianhydride include a tetracarboxylic dianhydride represented by the above formula (30), for example, pyromellitic dianhydride, diphenyl ether-3,3', 4,4'-tetra. Carboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylanthracene -3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-benzene) Formic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably enumerated: pyromellitic dianhydride, Diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, but is not limited to these. Further, these may of course be used singly, or two or more types may be used in combination.
In the present invention, examples of the alcohol having a photopolymerizable unsaturated double bond which are suitable for preparing a polyester bond precursor of an ester bond type include, for example, 2-propenyloxyethanol and 1-propenyloxyl. 3-propanol, 2-propenylaminoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3- acrylate Butoxypropyl propyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-propene Hydroxy-3-cyclohexyloxypropyl ester, 2-methylpropenyloxyethanol, 1-methylpropenyloxy-3-propanol, 2-methylpropenylaminoethanol, hydroxymethylvinyl Ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Phenoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl methacrylate Propyl ester and the like.
Further, a part of the above alcohol may be used as a saturated aliphatic alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol or t-butanol.
The above-mentioned tetracarboxylic dianhydride suitable for the present invention and the above alcohol are dissolved in a solvent such as pyridine in a solvent as described below at a temperature of 20 to 50 ° C for 4 to 10 hours, The mixture is thereby subjected to an esterification reaction of an acid anhydride to obtain a desired acid/ester body.
(Preparation of polyimine precursors)
To the above acid/ester body (typically a solution in the following solvent), a suitable dehydrating condensing agent such as bicyclocarbodiimide (for example, dicyclohexylcarbodiimide) is added under ice bath cooling. , 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'- After dibutyl sulfonium imino carbonate or the like is mixed to form an acid/ester body into a polyanhydride, a divalent organic group Y which is suitably used in the present invention is added dropwise thereto. ₁ When the diamine is dissolved or dispersed in a solvent, the guanamine condensation polymerization is carried out, whereby the target polyimine precursor can be obtained. Alternatively, the acid moiety in the acid/ester body is subjected to hydrazine chlorination using sulfinium chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine, whereby a target polyimine precursor can be obtained.
As a suitable use in the present invention, a divalent organic group Y is contained. ₁ Examples of the diamines include, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 3, which are represented by a diamine having a structure represented by the above formula (31). 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3, 3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4' -diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3, 3'-Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,
1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl] Bismuth, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)benzene Ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl) Benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2 , 2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-double (3-Aminopropyldimethylmethylalkyl)benzene, o-toluidine oxime, 9,9-bis(4-aminophenyl)anthracene, and one of the hydrogen atoms on the benzene ring Substituents such as ethyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenyl Methane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl Alkyl aniline, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'- Diamino octafluorobiphenyl, etc.; preferably exemplified: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2 '-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diamino The octafluorobiphenyl or the like, and the like, etc., are not limited thereto.
Further, in order to improve the adhesion between the resin layer formed on the substrate and the various substrates by applying the photosensitive resin composition of the present invention on the substrate, it is also possible to prepare the polyimide precursor with 1,3-imine. A diamine methoxy oxane such as bis(3-aminopropyl)tetramethyldioxane or 1,3-bis(3-aminopropyl)tetraphenyldioxane is copolymerized.
After completion of the hydrazine condensation polymerization reaction, the water-absorbing by-products of the dehydration condensing agent coexisting in the reaction liquid are filtered and separated as necessary, and then water, an aliphatic lower alcohol, a mixed solution thereof, or the like is added to the obtained polymer component. The polymer is analyzed by a poor solvent, and the polymer is further subjected to re-dissolution, reprecipitation, and precipitation, whereby the polymer is purified and vacuum-dried to separate the target polyimide precursor. In order to improve the fine system, the solution of the polymer may be removed by passing through a column packed with an anion and/or a cation exchange resin swelled with a suitable organic solvent to remove ionic impurities.
On the other hand, the above ion-bonded polyimine precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, R in the above formula (1) ₁ And R ₂ At least one of them is a hydroxyl group.
The tetracarboxylic dianhydride is preferably an acid anhydride of a tetracarboxylic acid having a structure of the above formula (30), and the diamine is preferably a diamine having a structure of the above formula (31). By adding the following (meth)acrylic compound having an amine group to the obtained polyamine precursor, the photopolymerizable group is imparted by ionic bonding of a carboxyl group and an amine group.
As the (meth)acrylic compound having an amine group, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylamino methacrylate are preferable. Ethyl ester, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, methacrylic acid Dimethylaminobutyl acrylate, diethyl butyl acrylate, diethyl butyl methacrylate, a dialkylaminoalkyl acrylate or a dialkylaminoalkyl methacrylate, wherein From the viewpoint of photosensitive characteristics, a dialkylaminoalkyl acrylate or a methacrylic acid having an alkyl group having an alkyl group having 1 to 10 carbon atoms and an alkyl chain having 1 to 10 carbon atoms is preferred. Alkylaminoalkyl esters.
The amount of the (meth)acrylic compound having an amine group is from 1 to 20 parts by mass based on 100 parts by mass of the resin (A), and from the viewpoint of light sensitivity characteristics, it is preferably from 2 to 15. Parts by mass. The amount of the (meth)acrylic compound having an amine group as the (C) sensitizer is 1 part by mass or more based on 100 parts by mass of the (A) resin, and the light sensitivity is excellent, and the film is prepared by blending 20 parts by mass or less. Excellent in hardenability.
The molecular weight of the above-mentioned ester bond type and the above-mentioned ion bond type polyimine precursor is preferably 8,000 to 150,000 when measured in the form of a polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably, it is 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution of the embossed pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Further, the weight average molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.
[(A) Polyamide]
Another example of the preferred (A) resin in the photosensitive resin composition of the present invention has the following formula (4):
[化18]

{式,X ₂ It is an organic group with a carbon number of 6 to 15 and a valence of Y. ₂ It is an organic group having a carbon number of 6 to 35, and may be the same structure or have a plurality of structures, R ₉ Is an organic group having at least one radically polymerizable unsaturated bond group having a carbon number of 3 to 20, and n ₂ An integer from 1 to 1000}
The structure of the polyamine shown. The polyamide is suitable for use in a negative photosensitive resin composition.
In the above formula (4), as R ₉ The base expressed is preferably the following general formula (32) in terms of both sensitization characteristics and chemical resistance.
[Chemistry 19]

{式,R ₃₂ An organic group having at least one radical polymerizable unsaturated bond group having 2 to 19 carbon atoms}
The basis of the representation.
In the above formula (4), as X ₂ The trivalent organic group represented by carbon is preferably a trivalent organic group having 6 to 15 carbon atoms, and is preferably selected from the following formula (33):
[Chemistry 20]

The aromatic group in the group represented by the group is more preferably an aromatic group obtained by removing a carboxyl group and an amine group from the amino group-substituted isophthalic acid structure.
In the above formula (4), as Y ₂ The divalent organic group represented is preferably an organic group having 6 to 35 carbon atoms, more preferably a cyclic organic group having 1 to 4 substitutable aromatic or aliphatic rings, or no An aliphatic group or a decyloxy group of a cyclic structure. As Y ₂ Examples of the divalent organic group represented by the following formula (I) and the following formulas (34) and (35):
[Chem. 21]

[化22]

{式,R ₃₃ And R ₃₄ Separately selected from hydroxyl, methyl (-CH) ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ) or butyl (-C ₄ H ₉ a group of the group consisting of, and the propyl and butyl groups include various isomers}
[化23]

{式,m ₇ An integer from 0 to 8, m ₈ And m ₉ Independently independent of 0 to 3, m ₁₀ And m ₁₁ Independently independent of 0 to 10, and R ₃₅ And R ₃₆ Methyl (-CH) ₃ ), ethyl (-C ₂ H ₅ ), propyl (-C ₃ H ₇ ), butyl (-C ₄ H ₉ ) or such isomers}.
As the aliphatic or decyloxy group having no cyclic structure, preferred examples thereof include the following formula (36):
[Chem. 24]

{式,m ₁₂ An integer from 2 to 12, m ₁₃ An integer from 1 to 3, m ₁₄ Is an integer from 1 to 20, and R ₃₇ , R ₃₈ , R ₃₉ And R ₄₀ Each is independently an alkyl group having 1 to 3 carbon atoms or a phenyl group which may be substituted.
The polyamine resin of the present invention can be synthesized, for example, by the following manner.
(Synthesis of phthalic acid compound end caps)
The first step is to make a trivalent aromatic group X. ₂ a compound, for example, at least one selected from the group consisting of phthalic acid substituted with an amine group, phthalic acid substituted with an amine group, and terephthalic acid substituted with an amine group (hereinafter referred to as a compound) a "methic acid compound") 1 mole, and a compound 1 which reacts with an amine group, and the amine group which synthesizes the phthalic acid compound is subjected to the following radical containing a radical polymerizable unsaturated bond. A modified or blocked compound (hereinafter referred to as "phthalic acid compound capping body"). These may be used singly or in combination.
When the phthalic acid compound is terminated by the above-mentioned radical containing a radical polymerizable unsaturated bond, a negative photosensitive property (photocuring property) can be imparted to the polyamide resin.
The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radical polymerizable unsaturated bond group having 3 to 20 carbon atoms, particularly preferably a methacryl fluorenyl group or an acryl fluorenyl group. The basis.
The phthalic acid compound capping body can be obtained by using an amine group of a phthalic acid compound and a ruthenium chloride, an isocyanate or an epoxy compound having at least one radical polymerizable unsaturated bond group having 3 to 20 carbon atoms. Obtained by carrying out the reaction.
Examples of suitable ruthenium chloride include (meth)acrylofluorene chloride, 2-[(meth)acryloxyloxyethylidene chloride, 3-[(meth)acryloxyl]propyl fluorene chloride, and chlorine. 2-[(Meth)acryloxy)ethyl formate, 3-[(meth)acryloxypropyl] chloroformate, and the like. As a suitable isocyanate, 2-(methyl) propylene methoxyethyl isocyanate, 1,1-bis[(methyl) propylene methoxymethyl] ethyl isocyanate, isocyanic acid 2-[2-(Methyl)acryloxyethoxyethyl]ethyl ester or the like. As a suitable epoxy compound, glycidyl (meth)acrylate etc. are mentioned. These may be used singly or in combination, but it is especially preferred to use methacrylic acid chlorohydrin and/or 2-(methacryloxy)ethyl isocyanate.
Further, as the phthalic acid compound end-capping body, the phthalic acid compound is 5-aminoisophthalic acid, and therefore, it is preferable to obtain a polyamine which is excellent not only in photosensitive characteristics but also in film properties after heat curing. .
The capping reaction may be carried out by stirring a solution of a phthalic acid compound and a blocking agent in a solvent as described below, in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. Mix and proceed.
The hydrazine chloride or the like generates a by-product hydrogen chloride in the process of blocking the reaction depending on the type of the blocking agent. In this case, in order to prevent contamination of the subsequent steps, it is preferred to carry out the refining as appropriate, that is, to reprecipitate it in water and wash it dry, or pass it through a column packed with an ion exchange resin to remove the reduced ions. Ingredients, etc.
(synthesis of polyamine)
The above phthalic acid compound end group and the organic group Y having a divalent value ₂ The polyamine compound of the present invention can be obtained by mixing a diamine compound in the presence of a basic catalyst such as pyridine or triethylamine in a solvent as described below to carry out a guanamine condensation polymerization.
Examples of the guanamine polycondensation polymerization method include a method in which a phthalic acid compound capping agent is used as a symmetric polyanhydride after mixing with a diamine compound using a dehydrating condensing agent, or a phthalic acid compound capping body by a known method. A method of mixing a diamine compound after hydrazine chlorination, a method of reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent, and a method of mixing the diamine compound after active esterification.
As the dehydrating condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'- may be mentioned. Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-d-butylenedimino carbonate, and the like.
Examples of the chlorinating agent include sulfinium chloride and the like.
Examples of the active esterifying agent include N-hydroxybutylimine or 1-hydroxybenzotriazole, N-hydroxy-5-northene-2,3-dicarboxylimenide, and 2-hydroxyl Ethyl-2-cyanoacetate, 2-hydroxyimino-2-cyanoacetamide, and the like.
Organic group Y ₂ The diamine compound is preferably selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a decane diamine compound. At least one of the diamine compounds may be used in combination as needed.
Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-di. Aminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl hydrazine, 3,4'-diaminodiphenyl fluorene, 3,3'-diaminodiphenyl fluorene, 4,4'-diaminobiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diamine Benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-double (3-Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4 '-Bis(4-Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether , bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9 , 10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3- Aminopropyldimethylmethylalkyl)benzene, o-toluidine oxime, 9,9-bis(4-aminophenyl)anthracene, and one of the hydrogen atoms on the benzene ring are selected from the group consisting of A diamine compound substituted with one or more groups of a group consisting of a group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.
Examples of the diamine compound in which the hydrogen atom on the benzene ring is substituted include 3,3'-dimethyl-4,4'-diaminobiphenyl and 2,2'-dimethyl-4. , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodi Phenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the like.
Examples of the aromatic bisaminophenol compound include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, and 3,3'-dihydroxy-4. , 4'-diaminodiphenylphosphonium, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2, 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, bis-(3-hydroxy-4 -aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3 , 3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4- Diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene )-bis(2-aminophenol) and the like.
Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, and 1,3-diamino-1-methylcyclohexane. , 5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl- 4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethyl Cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propane Base amine, menthane diamine, isophorone diamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4 , 4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperidin, 3,9-bis(3-aminopropyl)-2, 4,8,10-tetraoxaspiro-[5,5]-undecane and the like.
The linear aliphatic diamine compound may, for example, be 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane or 1,8-diaminooctyl Hydrocarbon type diamine such as alkane, 1,10-diaminodecane, 1,12-diaminododecane, or 2-(2-aminoethoxy)ethylamine, 2,2'-( An alkylene oxide type diamine such as ethylenedioxy)diethylamine or bis[2-(2-aminoethoxy)ethyl]ether.
Examples of the oxirane diamine compound include dimethyl(poly)nonanediamine, such as those sold under the trade names of PAM-E, KF-8010, and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.
After completion of the guanamine polycondensation reaction, the precipitate derived from the dehydration condensing agent precipitated in the reaction liquid or the like is filtered and separated as necessary. Then, a poor solvent of polyamine such as water or an aliphatic lower alcohol or a mixed solution thereof is added to the reaction liquid to precipitate polyamine. Further, the precipitated polyamine is redissolved in a solvent, and a reprecipitation and precipitation operation is repeated to carry out purification, and vacuum drying is performed to separate the target polyamine. Further, in order to further improve the fine system, the solution of the polyamine can be passed through a column packed with an ion exchange resin to remove ionic impurities.
The polystyrene-equivalent weight average molecular weight of the polyamine based on gel permeation chromatography (hereinafter referred to as "GPC") is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. When the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Moreover, when the weight average molecular weight in terms of polystyrene is 70,000 or less, the development solubility at the time of forming a embossed pattern is ensured.
As a solution of GPC, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. Further, the weight average molecular weight value was determined based on a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.
[(A) Polyhydroxyguanamine]
Another example of the preferred (A) resin in the photosensitive resin composition of the present invention has the following formula (5):
[化25]

{式, Y ₃ Is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having two or more carbon atoms, Y ₄ , X ₃ And X ₄ Separately, each is a divalent organic group having two or more carbon atoms, n ₃ An integer from 1 to 1000, n ₄ An integer from 0 to 500, n ₃ /(n ₃ +n ₄ )>0.5, and contains X ₃ And Y ₃ n ₃ Dihydroxydiamine units and contain X ₄ And Y ₄ n ₄ Polyhydroxyguanamine (polycarbazole precursor) in which the order of the diamines is arranged in any order; (hereinafter, the polyhydroxyguanamine represented by the above formula (5) is sometimes abbreviated as "polycarbazole"Precursor")).
The polycarbazole precursor has n in the above formula (5) ₃ a polymer of dihydroxydiamine unit (hereinafter sometimes abbreviated as dihydroxydiamine unit), or may have n in the above formula (5) ₄ A diammonium unit (hereinafter sometimes referred to simply as a diamine unit).
X ₃ The number of carbon atoms is preferably two or more and 40 or less for the purpose of obtaining photosensitive characteristics, X ₄ The number of carbon atoms is preferably two or more and 40 or less for the purpose of obtaining photosensitive characteristics, Y ₃ The number of carbon atoms is preferably two or more and 40 or less for the purpose of obtaining photosensitive characteristics, and Y ₄ The number of carbon atoms is preferably two or more and 40 or less for the purpose of obtaining photosensitive characteristics.
The dihydroxydiamine unit can be made to have Y ₃ (NH ₂ ) ₂ (OH) ₂ a structure of a diaminodihydroxy compound (preferably a bisaminophenol) having X ₃ (COOH) ₂ The dicarboxylic acid of the structure is synthesized and formed. Hereinafter, a typical aspect will be described by taking the case where the above diaminodihydroxy compound is a bisaminophenol. The two groups of the amine group of the bisaminophenol and the hydroxyl group are in the ortho position, and the dihydroxydiamine unit is ring-closed under heating at about 250 to 400 ° C to be converted into a heat-resistant polycarbazole structure. n in the general formula (5) ₃ It is 1 or more for the purpose of obtaining photosensitive characteristics, and is 1000 or less for the purpose of obtaining photosensitive characteristics. n ₃ It is preferably in the range of 2 to 1,000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.
Condensation on polycarbazole precursors as needed ₄ One of the above diamine units. The diamine unit can be made to have Y ₄ (NH ₂ ) ₂ Structure of diamine with X ₄ (COOH) ₂ The dicarboxylic acid of the structure is synthesized and formed. n in the general formula (5) ₄ Range from 0 to 500, by n ₄ A good sensitizing property is obtained for 500 or less. n ₄ More preferably, it is in the range of 0 to 10. If the ratio of the diamine unit to the dihydroxydiamine unit is too high, the solubility in the aqueous alkaline solution used as the developer is lowered, so that n in the formula (5) ₃ /(n ₃ +n ₄ The value of more than 0.5, more preferably 0.7 or more, and most preferably 0.8 or more.
About as having Y ₃ (NH ₂ ) ₂ (OH) ₂ Examples of the bisaminophenol of the diaminodihydroxy compound of the structure include, for example, 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4, 4'-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 4,4'-diamino-3,3 '-Dihydroxydiphenyl hydrazine, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-double -(3-Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyl Phenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4' -dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6 - Dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination of two or more. As Y in the bisaminophenol ₃ The base is preferably the following formula (37) in terms of photosensitive characteristics:
[Chem. 26]

In the formula, Rs1 and Rs2 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a trifluoromethyl group.
Also, as having Y ₄ (NH ₂ ) ₂ Examples of the diamine structure include aromatic diamines and decanediamines. In addition, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diamino group. Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diamino Diphenylanthracene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2' - bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentyl Alkene,
4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, imino group Di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5 (or 6) -amino-1-(4-aminophenyl)-1,3,3-trimethylindan, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-Diaminodiphenylurea, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone Ketone, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy Benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenylanthracene, 4,4'-diaminobiphenyl ,
4,4'-diaminobenzophenone, phenylindane diamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, o-toluidine oxime, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)anthracene, bis( 4-aminophenoxyphenyl) sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9 - bis(4-aminophenyl)anthracene, 4,4'-di-(3-aminophenoxy)diphenylanthracene, 4,4'-diaminobenzimidanilide, etc., and the like The hydrogen atom of the aromatic nucleus of the aromatic diamine is substituted with at least one group or atom selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group.
Further, as the diamine, in order to improve the adhesion to the substrate, decyl diamine can be selected. Examples of the stilbene diamine include bis(4-aminophenyl)dimethyl decane, bis(4-aminophenyl)tetramethyl decane, and bis(4-aminophenyl)tetra. Methyldioxane, bis(γ-aminopropyl)tetramethyldioxane, 1,4-bis(γ-aminopropyldimethylbenzyl)benzene, bis(4-amine Butyl) tetramethyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, and the like.
Also, as having X ₃ (COOH) ₂ Or X ₄ (COOH) ₂ Preferred dicarboxylic acids of the structure can be cited as X ₃ And X ₄ They are each an aliphatic or aromatic group having a linear, branched or cyclic structure. Among them, an organic group having two or more carbon atoms and not more than 40 carbon atoms which may contain an aromatic ring or an aliphatic ring is preferable. ₃ And X ₄ Preferably, respectively, from the following formula (38):
[化27]

{式,R ₄₁ Indicated from -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ - the base of the 2 price in the group formed}
It is preferable to select among the aromatic groups represented, which is equal to the photosensitive property.
The polycarbazole precursor can also be a terminal group with a specific organic group capping. In the case of using a polycarbazole precursor which is blocked by a terminal group, it is expected that the mechanical properties (especially elongation) and the shape of the hardened relief pattern of the coating film after heat curing of the photosensitive resin composition of the present invention are changed. Good. As a preferable example of such a terminal group, the following formula (39) is mentioned:
[化28]

Represented.
The polystyrene-equivalent weight average molecular weight of the polycarbazole precursor based on gel permeation chromatography is preferably from 3,000 to 70,000, more preferably from 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the hardened relief pattern. Further, from the viewpoint of resolution, it is preferably 70,000 or less. As a developing solvent for gel permeation chromatography, tetrahydrofuran or N-methyl-2-pyrrolidone is recommended. Further, the molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.
[(A) Polyimine]
Another example of the preferred (A) resin in the photosensitive resin composition of the present invention has the above formula (6):
[化29]

{式,X ₅ Represents an organic base of 4 to 14 valence, Y ₅ Represents an organic base of 2 to 12 valence, R ₁₀ And R ₁₁ Representing an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and may be the same or different, n ₅ Is an integer from 3 to 200, and m ₃ And m ₄ An integer from 0 to 10}
The polyimine of the structure indicated. Here, the resin represented by the general formula (6) is not particularly required to undergo a chemical change when it exhibits sufficient film properties, and therefore is suitable for treatment at a lower temperature, which is particularly preferable in this respect.
X in the structural unit represented by the above formula (6) ₅ It is preferably an organic group having a carbon number of 4 to 40 and a valence of 14 to 14 in terms of heat resistance and photosensitivity, and more preferably 5 to 40 carbon atoms having an aromatic ring or an aliphatic ring. Organic base.
The polyimine represented by the above formula (6) may be a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, or trimethylnonane. The obtained diamine is obtained by carrying out a reaction. Polyimine is generally chemically treated by heating or acid or alkali by using polylysine which is one of the polyimide precursors obtained by reacting a tetracarboxylic dianhydride with a diamine. Obtained by the dehydration ring closure.
Examples of suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyl. Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2' , 3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane di-anhydride, 2,2-bis(2,3-dicarboxyphenyl) ) propane di-anhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane di-anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dihydrate, double ( 3,4-Dicarboxyphenyl)methane di-anhydride, bis(2,3-dicarboxyphenyl)methane di-anhydride, bis(3,4-dicarboxyphenyl)phosphonium anhydrate, double (3, 4-dicarboxyphenyl)ether di-anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)decanoic acid dianhydride,
9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}decanoic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6- Aromatic tetracarboxylic acid dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dihydrate, etc. An aliphatic tetracarboxylic dianhydride such as an anhydride or butane tetracarboxylic dianhydride or 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylanthracene Tetracarboxylic dianhydride and the following formula (40):
[化30]

{式,R ₄₂ Indicated from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ Or SO ₂ Base, and R ₄₃ And R ₄₄ The compounds may be the same or different and represent a compound represented by a group selected from a hydrogen atom, a hydroxyl group or a thiol group.
Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2' are preferred. , 3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenone IV Carboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane di-anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane di-anhydride, 1,1-double (3,4-dicarboxyphenyl)ethane di-anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane di-anhydride, bis(3,4-dicarboxyphenyl)methane Anhydrous, bis(2,3-dicarboxyphenyl)methane di-anhydride, bis(3,4-dicarboxyphenyl)phosphonium anhydrate,
Bis(3,4-dicarboxyphenyl)ether di-anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane di-anhydride, 3,3',4,4'-diphenyl Base tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)decanoic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} Tannic dianhydride and the following general formula (41)
[化31]

{式,R ₄₅ Indicated from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ Or SO ₂ Base, and R ₄₆ And R ₄₇ The acid dianhydrides may be the same or different and represent a structure represented by a group selected from a hydrogen atom, a hydroxyl group or a thiol group. These may be used alone or in combination of two or more.
Y of the above formula (6) ₅ The diamine is a structural component of the diamine, and the diamine represents an organic group having an aromatic ring or an aliphatic ring of 2 to 12, and among them, an organic group having 5 to 40 carbon atoms is preferred.
Specific examples of the diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 4,4. '-Diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl sulfide, 4 , 4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzyne, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2 , 6-naphthalenediamine, bis(4-aminophenoxyphenyl)fluorene, bis(3-aminophenoxyphenyl)fluorene, bis(4-aminophenoxy)biphenyl, double { 4-(4-Aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diamine linkage Benzene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis ( 4-aminophenyl)anthracene or a compound in which the aromatic ring is substituted with an alkyl group or a halogen atom, or an aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the following formula (42):
[化32]

{式,R ₄₈ Indicated from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ Or SO ₂ Base, and R ₄₉ ~R ₅₂ Diamines and the like which may be the same or different and represent a structure represented by a group selected from a hydrogen atom, a hydroxyl group or a thiol group.
Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- are preferred. Diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl sulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)茀, and the following general formula (43):
[化33]

{式,R ₅₃ Indicated from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ Or SO ₂ Base, and R ₅₄ ~R ₅₇ They may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group}
The diamine of the structure shown.
Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 1,4-bis(4-aminophenoxy)benzene, And the following general formula (44):
[化34]

{式,R ₅₈ Indicated from an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ Or SO ₂ Base, and R ₅₉ And R ₆₀ They may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group}
The diamine of the structure shown. These may be used alone or in combination of two or more.
R of the general formula (6) ₁₀ And R ₁₁ Represents a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, as R ₁₀ And R ₁₁ The phenolic hydroxyl group, the sulfonic acid group and/or the thiol group may be mixed.
By controlling R ₁₀ And R ₁₁ Since the amount of the alkali-soluble base changes in the rate of dissolution in the alkaline aqueous solution, a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.
Further, in order to improve the adhesion to the substrate, it may be in the range of not reducing the heat resistance. ₅ , Y ₅ The aliphatic group having a decane structure is copolymerized. Specific examples thereof include bis(3-aminopropyl)tetramethyldioxane and bis(p-aminophenyl)octamethylpentasiloxane as a diamine component in an amount of 1 to 10 mol%. Alkane or the like is copolymerized or the like.
The above polyimine can be obtained by a method such as the following method, in which the polyimine precursor is completely imidized by a known ruthenium imidization reaction method, or the method is stopped in the middle. a method of introducing a part of the quinone imine structure (in this case, a polyamidoximine) by amination reaction, or by blending a fully ruthenium imidized polymer with the polyimine precursor The method for introducing a part of the quinone imine structure is carried out, and the above method for obtaining a polyimine precursor is as follows: for example, a tetracarboxylic dianhydride and a diamine compound (partially substituted by a terminal blocking agent as a monoamine) are used at a low temperature. To react with a diamine compound at a low temperature with a tetracarboxylic dianhydride (a part of which is substituted as an acid anhydride or a monoterpene chlorine compound or a terminal blocking agent of a mono-active ester compound); The ester is then reacted with a diamine (partially substituted with a terminal blocking agent as a monoamine) in the presence of a condensing agent; a diester is obtained from a tetracarboxylic dianhydride and an alcohol, after which the remaining dicarboxylic acid is subjected to Chlorination, making it with diamine Substituted with a terminal capping agent of monoamine) reaction.
The polyimine is preferably a polyimide having a ruthenium iodide ratio of 15% or more with respect to the entire resin constituting the photosensitive resin composition. More preferably, it is 20% or more. Here, the term "imidization ratio" refers to the ratio of ruthenium imidization present in the entire resin constituting the photosensitive resin composition. When the imidization ratio is less than 15%, the amount of shrinkage at the time of thermosetting becomes large, and it is not suitable for thick film production.
The ruthenium amination rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer was measured, and it was confirmed that there was an absorption peak derived from the quinone imine structure of polyimine (near 1780 cm-1 and around 1377 cm-1). Then, the polymer was heat-treated at 350 ° C for 1 hour, and the infrared absorption spectrum after the heat treatment was measured, and the peak intensity near 1377 cm -1 was compared with the strength before the heat treatment, thereby calculating the polymer in the pre-heat treatment polymer. The rate of hydrazine imidization.
The molecular weight of the above polyimine is preferably 3,000 to 200,000, more preferably 5,000 to 50,000, as measured in the form of a polystyrene-equivalent weight average molecular weight by gel permeation chromatography. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in the developer is good, and the resolution of the embossed pattern is good.
As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. Further, the molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko.
Further, in the present invention, a phenol resin can also be preferably used.
[(A) Phenolic Resin]
The phenol resin in the present embodiment means a resin having a repeating unit containing a phenolic hydroxyl group. (A) The phenol resin does not undergo a structural change such as cyclization (sulfonylimidation) of the polyimide precursor during thermal curing, and therefore has an advantage of being hardenable at a low temperature (for example, 250 ° C or lower).
In the present embodiment, the weight average molecular weight of the (A) phenol resin is preferably from 700 to 100,000, more preferably from 1,500 to 80,000, still more preferably from 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the suitability of the reflow process of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
The measurement of the weight average molecular weight herein can be carried out by gel permeation chromatography (GPC) based on a calibration curve prepared using standard polystyrene.
(A) The phenol resin is preferably selected from the group consisting of novolac and polyhydroxystyrene from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress of the cured film. , having the following general formula (7):
[化35]

In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, and 1≦(a+b)≦4, R ₁₂ And a monovalent substituent selected from the group consisting of an organic group having a carbon number of 1 to 20, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁₂ X may be the same as or different from each other, and X represents an aliphatic group selected from a carbon number of 2 to 10 which may have an unsaturated bond, a alicyclic group having a carbon number of 3 to 20, and the following formula ( 8):
[化36]

(wherein, p is an integer of from 1 to 10), and a two-valent organic group in the group consisting of a divalent alkoxy group and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms base}
At least one of a phenol resin represented by the repeating unit and a phenol resin modified with a compound having a hydrocarbon group having 4 to 100 carbon atoms.
(novolac)
Herein, the term "novolak" means a whole of a polymer obtained by condensing a phenol with formaldehyde in the presence of a catalyst. In general, a novolak can be obtained by condensing 1 mol of phenol with formaldehyde which is less than 1 mol of the phenol. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylene. Phenolic, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, and the like. Specific examples of the novolak varnish include a phenol/formaldehyde condensed novolac resin, a cresol/formaldehyde condensed novolac resin, and a phenol-naphthol/formaldehyde condensed novolac resin.
The weight average molecular weight of the novolak is preferably from 700 to 100,000, more preferably from 1,500 to 80,000, still more preferably from 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the suitability of the reflow process of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
(polyhydroxystyrene)
Herein, the polyhydroxystyrene means a whole polymer containing hydroxystyrene as a polymerization unit. Preferable examples of the polyhydroxystyrene include poly-p-vinylphenol. Poly-p-vinyl phenol means the entire polymer containing p-vinylphenol as a polymer unit. Therefore, polyhydroxystyrene (for example, poly-p-vinylphenol) can be formed by using a polymerization unit other than hydroxystyrene (for example, p-vinylphenol) as long as it does not violate the object of the present invention. In the polyhydroxystyrene, the ratio of the number of moles of the hydroxystyrene unit based on the molar number of all the polymer units is preferably from 10 mol% to 99 mol%, more preferably from 20 to 97 mol%. Further preferably, it is 30 to 95% by mole. When the ratio is 10 mol% or more, it is advantageous from the viewpoint of alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, the composition containing the following copolymerization component is hardened. It is advantageous from the viewpoint of the reflowability of the cured film. The polymer unit other than the hydroxystyrene (for example, p-vinylphenol) may be any polymerized unit capable of copolymerizing with hydroxystyrene (for example, p-vinylphenol). The copolymerization component of the polymerization unit other than the hydroxystyrene (for example, p-vinylphenol) is not limited, and examples thereof include methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, and acrylic acid. Octyl ester, 2-ethoxyethyl methacrylate, tert-butyl acrylate, 1,5-pentanediol diacrylate, N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate , 1,3-propanediol diacrylate, decanediol diacrylate, decanediol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate , glycerin diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-bis(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2- 2-bis(p-hydroxyphenyl)propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyl trimethylolpropane triacrylate, ethylene glycol dimethacrylate, dibutyl Alcohol dimethacrylate, 1,3-propanediol dimethacrylate, butanediol dimethacrylate 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol Trimethacrylate, 1,2-diethyl ethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethyl Acrylates such as acrylates and 1,4-benzenediol dimethacrylate; styrene and substituted styrenes such as 2-methylstyrene and vinyltoluene; for example, vinyl acrylate and a vinyl ester monomer such as vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.
In addition, each of the novolak and the polyhydroxystyrene described above may be used alone or in combination of two or more.
The weight average molecular weight of the polyhydroxystyrene is preferably from 700 to 100,000, more preferably from 1,500 to 80,000, still more preferably from 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the suitability of the reflow process of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
(phenol resin represented by the formula (7))
In the present embodiment, the (A) phenol resin preferably further comprises the following formula (7):
[化37]

In the formula, a is an integer from 1 to 3, b is an integer from 0 to 3, and 1≦(a+b)≦4, R ₁₂ And a monovalent substituent selected from the group consisting of an organic group having a carbon number of 1 to 20, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁₂ X may be the same as or different from each other, and X represents an aliphatic group selected from a carbon number of 2 to 10 which may have an unsaturated bond, a alicyclic group having a carbon number of 3 to 20, and the following formula ( 8):
[化38]

(wherein, p is an integer of from 1 to 10), and a two-valent organic group in the group consisting of a divalent alkoxy group and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms The phenolic resin of the repeating unit represented by the base}. The phenol resin having the above repeating unit can be hardened at a low temperature as compared with, for example, a previously used polyimine resin and a polybenzoxazole resin, and can form a cured film having a good elongation, and is particularly remarkable in this respect. advantageous. The above repeating unit which is present in the phenol resin molecule may be one type or a combination of two or more types.
In the above formula (7), R ₁₂ From the viewpoint of the reactivity in synthesizing the resin of the formula (7), it is a monovalent substitution selected from the group consisting of an organic group having a carbon number of 1 to 20, a halogen atom, a nitro group and a cyano group. base. R ₁₂ From the viewpoint of alkali solubility, it is preferably selected from the group consisting of a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, and The following general formula (45):
[39]

{式,R ₆₁ , R ₆₂ And R ₆₃ Each independently represents a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, and R ₆₄ It is represented by an aliphatic group having a carbon number of 1 to 10 having an unsaturated bond, an alicyclic group having a carbon number of 3 to 20, or an aromatic group having a carbon number of 6 to 20; a one-valent substituent in the group consisting of four bases.
In the above-mentioned formula (7), a is an integer of from 1 to 3, and is preferably 2 from the viewpoint of alkali solubility and elongation. Further, in the case where a is 2, the positions at which the hydroxyl groups are substituted with each other may be any positions of the ortho, meta and para positions. Further, in the case where a is 3, the positions at which the hydroxyl groups are substituted with each other may be any positions such as 1, 2, 3-position, 1, 2, 4-position and 1, 3, 5-position.
In the above-mentioned formula (7), when a is 1 , in order to improve alkali solubility, a phenol resin having a repeating unit represented by the formula (7) (hereinafter also referred to as (a1) The resin is further mixed with a phenol resin (hereinafter also referred to as (a2) resin) selected from the group consisting of novolac and polyhydroxystyrene.
The mixing ratio of the resin (a1) to the resin (a2) is preferably in the range of (a1) / (a2) = 10 / 90 to 90/10 by mass ratio. The mixing ratio is preferably (a1) / (a2) = 10/90 to 90/10, more preferably (a1) / from the viewpoints of solubility in an alkaline aqueous solution and elongation of the cured film. (a2) = 20/80 to 80/20, and further preferably (a1) / (a2) = 30/70 to 70/30.
As the novolac and polyhydroxystyrene as the above (a2) resin, the same resins as those shown in the above (novolak) and (polyhydroxystyrene) can be used.
In the above formula, b is an integer of 0 to 3 in the above formula (7), and is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. Also, when b is 2 or 3, a plurality of R ₁₂ They may be the same or different from each other.
Further, in the present embodiment, in the above formula (7), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.
In the above-described general formula (7), X is selected from the group consisting of a fat having a carbon number of 2 to 10 which may have an unsaturated bond, from the viewpoint of the shape of the hardened relief pattern and the elongation of the cured film. a group-based, alicyclic group having a carbon number of 3 to 20, an alkylene group represented by the above formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms A two-valent organic group in the group. Among these divalent organic groups, X is preferably selected from the following general formula (9) from the viewpoint of the toughness of the film after hardening:
[化40]

{式,R ₁₃ , R ₁₄ , R ₁₅ And R ₁₆ Each of which is independently a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or an aliphatic group in which a part or all of a hydrogen atom is substituted with a fluorine atom to form a monovalent aliphatic group having 1 to 10 carbon atoms, n ₆ Is an integer from 0 to 4, and n ₆ In the case of an integer of 1 to 4, R ₁₇ Is a halogen atom, a hydroxyl group, or an organic group having a carbon number of 1 to 12, and at least one R ₁₇ Hydroxyl, n ₆ a plurality of Rs in the case of an integer of 2 to 4 ₁₇ The two-valent group represented by the same or different from each other, and the following general formula (10):
[化41]

{式,R ₁₈ , R ₁₉ , R ₂₀ And R _{twenty one} An aliphatic group having a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or a partial or all of a hydrogen atom partially substituted with a fluorine atom and having a carbon number of 1 to 10, respectively, and W is a single a bond selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, and the following general formula (8):
[化42]

(wherein, p is an integer of 1 to 10), the divalent alkoxy group represented by the formula, and the following formula (11):
[化43]

The organic group of two valences in the group consisting of the two-valent group represented by the two-valent organic group in the group consisting of the two-valent group. The carbon number of the divalent organic group X having the aromatic ring having 6 to 12 carbon atoms is preferably from 8 to 75, more preferably from 8 to 40. Further, the structure of the divalent organic group X having the aromatic ring having 6 to 12 carbon atoms is generally different from the OH group bonded to the aromatic ring in the above formula (7) and optionally R ₁₂ The structure of the base.
Furthermore, the divalent organic group represented by the above formula (10) is more preferably in the following formula (12) from the viewpoint of the pattern formation property of the resin composition and the elongation of the cured film after curing.
[化44]

The divalent organic group represented by the formula (13) is further preferably:
[化45]

The two-valent organic group represented.
In the structure represented by the formula (7), X is preferably a structure represented by the above formula (12) or (13), and the ratio of the portion represented by the structure represented by the formula (12) or (13) is From the viewpoint of elongation, it is preferably 20% by mass or more, and more preferably 30% by mass or more. The ratio is preferably 80% by mass or less, and more preferably 70% by mass or less, from the viewpoint of alkali solubility of the composition.
Further, among the phenol resins having the structure represented by the above formula (7), it is particularly preferable to have the following properties in the same resin skeleton from the viewpoint of the alkali solubility of the composition and the elongation of the cured film. The structure represented by the formula (14) and the structure represented by the following formula (15) are both structures.
[Chem. 46]

{式,R _{twenty one} Is a group having a valence of 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₇ 2 or 3, n ₈ An integer from 0 to 2, m ₅ An integer from 1 to 500, 2 ≦ (n ₇ +n ₈ )≦4,于n ₈ In the case of 2, a plurality of R _{twenty one} May be the same or different from each other}
[化47]

{式,R _{twenty two} And R _{twenty three} Each of them is independently a group having a valence of 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₉ An integer from 1 to 3, n ₁₀ An integer from 0 to 2, n ₁₁ An integer from 0 to 3, m ₆ An integer from 1 to 500, 2 ≦ (n ₉ +n ₁₀ )≦4,于n ₁₀ In the case of 2, a plurality of R _{twenty two} May be the same or different, in n ₁₁ In the case of 2 or 3, a plurality of R _{twenty three} May be the same or different from each other}
m of the above formula (14) ₅ And m of the above formula (15) ₆ Indicates the total number of repeating units in the main chain of the phenol resin. That is, in the (A) phenol resin, for example, the repeating unit in the parentheses in the structure represented by the above formula (14) and the repeating unit in the parentheses in the structure represented by the above formula (15) may be randomly and embedded. Segments or combinations of such combinations are arranged. m ₅ And m ₆ Each of them is independently an integer of from 1 to 500, and the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400, and still more preferably 350. m ₅ And m ₆ From the viewpoint of the toughness of the film after hardening, it is preferably independently 2 or more, and from the viewpoint of solubility in an alkaline aqueous solution, it is preferably 450 or less. m ₅ With m ₆ In view of the toughness of the film after hardening, it is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably from the viewpoint of solubility in an alkaline aqueous solution. It is 200 or less, more preferably 175 or less, further preferably 150 or less.
In the (A) phenol resin having the structure represented by the above formula (14) and the structure represented by the above formula (15) in the same resin skeleton, the structure represented by the above formula (14) The higher the ear ratio, the better the film physical properties after hardening and the more excellent the heat resistance. On the other hand, the higher the molar ratio of the structure represented by the above formula (15), the better the alkali solubility, and after hardening The pattern shape is more excellent. Therefore, the ratio of the structure represented by the above formula (14) to the structure represented by the above formula (15) is m. ₅ /m ₆ From the viewpoint of film properties after hardening, it is preferably 20/80 or more, more preferably 40/60 or more, and particularly preferably 50/50 or more, from the viewpoints of alkali solubility and shape of a hardened relief pattern, It is preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.
The phenol resin having a repeating unit represented by the general formula (7) typically contains a phenol compound and a copolymer component (specifically, a compound selected from an aldehyde group (including a compound which decomposes like an aldehyde compound such as trioxane) One of a group consisting of a compound having a ketone group, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule The above compound) is more preferably synthesized by subjecting a monomer component containing the same to a polymerization reaction. For example, a phenol and/or a phenol derivative (hereinafter also referred to collectively as a "phenol compound") and an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound or a haloalkyl group may be used. The copolymerization component such as a compound is polymerized to obtain (A) a phenol resin. In this case, in the above formula (7), an OH group and an arbitrary R are bonded to the aromatic ring. ₁₂ The portion indicated by the structure of the group is derived from the above phenol compound, and the portion represented by X is derived from the above copolymerized component. With respect to the reaction control and the stability of the obtained (A) phenol resin and the photosensitive resin composition, the molar ratio of the phenol compound to the above copolymerized component (phenol compound): (copolymerization component) is preferably 5:1 to 1.01:1, more preferably 2.5:1 to 1.1:1.
The weight average molecular weight of the phenol resin having a repeating unit represented by the formula (7) is preferably from 700 to 100,000, more preferably from 1,500 to 80,000, still more preferably from 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the suitability of the reflow process of the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.
Examples of the phenol compound which can be used to obtain the phenol resin having the repeating unit represented by the general formula (7) include cresol, ethyl phenol, propyl phenol, butyl phenol, amyl phenol, cyclohexyl phenol, and a hydroxyl group. Biphenyl, benzyl phenol, nitrobenzyl phenol, cyanobenzyl phenol, adamantyl phenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N-(hydroxyphenyl)- 5-northene-2,3-dicarboxy quinone imine, N-(hydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboxy quinone imine, trifluoromethylphenol , hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, Hydroquinone, xylenol, catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, Ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate Ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxydiphenyl Methyl ketone, dihydroxybenzonitrile, N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboxy quinone imine, N-(dihydroxyphenyl)-5-methyl-5- Decalene-2,3-dicarboxy quinone imine, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, Fluorine resorcinol, chlororesorcinol, bromoresorcinol, trifluoromethyl resorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzene Formic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, three Hydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile, and the like.
Examples of the aldehyde compound include acetaldehyde, propionaldehyde, trimethylacetaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, diphenylacetaldehyde, and ethyl. Butyraldehyde, benzaldehyde, glyoxylic acid, 5-northene-2-carboxyaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, and the like.
Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, dicyclohexanone, and a ring. Hexanedione, 3-butyn-2-one, 2-norbornone, adamantanone, 2,2-bis(4-oxecyclohexyl)propane, and the like.
Examples of the above methylol compound include 2,6-bis(hydroxymethyl)p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, and 2,6-bis(hydroxyl). 4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-t-butylphenol, 2,6- Bis(hydroxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-propoxyphenol, 2,6-bis(hydroxymethyl)-4-n-butoxyphenol, 2,6-bis(hydroxymethyl)-4-tributoxyphenol, 1,3-bis(hydroxymethyl)urea , ribitol, arabitol, aldol, 2,2-bis(hydroxymethyl)butyric acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol , 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-northene-2,2-dimethanol, 5 -nordecene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis(hydroxymethyl) Toluene, 2-nitro-p-phenylenediethanol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4- (hydroxymethyl)cyclohexene, 1,6-bis(hydroxymethyl)adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1 , 4-dimethoxybenzene, 2,3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'- Bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl sulfide, 4,4'-bis(hydroxyl) Benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl ester, 4-hydroxymethylbenzoic acid-4'-hydroxymethylaniline, 4,4'-bis(hydroxymethyl) Phenylurea, 4,4'-bis(hydroxymethyl)phenylcarbamate, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-Dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethyl Glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and the like.
Examples of the alkoxymethyl compound include 2,6-bis(methoxymethyl)p-cresol and 2,6-bis(methoxymethyl)-4-ethylphenol; 6-bis(methoxymethyl)-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)- 4-tert-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2, 6-bis(methoxymethyl)-4-propoxyphenol, 2,6-bis(methoxymethyl)-4-n-butoxyphenol, 2,6-bis(methoxymethyl) )-4-tert-butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis(methoxymethyl)butyric acid, 2,2-bis(methoxymethyl) 5-)nordecene, 2,3-bis(methoxymethyl)-5-norbornene, 1,4-bis(methoxymethyl)cyclohexane, 1,4-double ( Methoxymethyl)cyclohexene, 1,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl) Benzene, 2,6-bis(methoxymethyl)-1,4-dimethoxybenzene, 2,3-bis(methoxymethyl)naphthalene, 2,6-bis(methoxyl) Naphthalene, 1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl ether, 4,4'-double ( Oxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl sulfide, 4,4'-bis(methoxymethyl)benzophenone, 4-methoxy Methylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylaniline, 4,4'-bis(methoxymethyl)benzene Base urea, 4,4'-bis(methoxymethyl)phenylcarbamate, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl) Biphenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane, ethylene glycol Dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether Wait.
Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, and 1,3-butanediol. -Dimethacrylate, 2,4-hexadien-1-ol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentane Alkene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2, 5-norbornadiene, tetrahydroanthracene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diisocyanate Propyl ester, triallyl cyanurate, diallyl propyl cyanurate, and the like.
Examples of the haloalkyl compound include dichloroxylene, bischloromethyldimethoxybenzene, bischloromethyltetramethylene, bischloromethylbiphenyl, and dichloromethyl-biphenylcarboxylate. Acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, dichloromethyl hydrazine, ethylene glycol bis(chloroethyl) Ether, diethylene glycol bis(chloroethyl)ether, triethylene glycol bis(chloroethyl)ether, tetraethylene glycol bis(chloroethyl)ether, and the like.
The phenol compound and the copolymer component are condensed by dehydration, dehydrohalogenation, or dealcoholation, or polymerized while the unsaturated bond is broken, whereby (A) a phenol resin can be obtained, and a catalyst can also be used for polymerization. . Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfonic acid, acetic acid, oxalic acid, and 1-hydroxyethylene. -1,1'-bisphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, and the like. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, and 4-N,N-. Dimethylaminopyridine, piperidine, piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1 , 5-diazabicyclo[4.3.0]-5-pinene, ammonia, hexamethylenetetramine, and the like.
With respect to the amount of the catalyst used to obtain the phenol resin having the repeating structure represented by the general formula (7), the total number of moles relative to the copolymerization component (that is, the components other than the phenol compound) is preferably an aldehyde compound, The total number of moles of the ketone compound, the methylol compound, the alkoxymethyl compound, the diene compound and the haloalkyl compound is 100 mol%, preferably 0.01 mol% to 100 mol%.
In the synthesis reaction of the (A) phenol resin, the reaction temperature is usually preferably from 40 ° C to 250 ° C, more preferably from 100 ° C to 200 ° C, and the reaction time is preferably from about 1 hour to 10 hours. A solvent capable of sufficiently dissolving the resin can be used as needed.
In addition, the phenol resin having a repeating structure represented by the formula (7) may be a phenol compound in which a material which does not become a structure of the above formula (7) is polymerized in a range which does not impair the effects of the present invention. The range in which the effect of the present invention is not impaired is, for example, 30% or less of the total number of moles of the phenol compound which is the raw material of the (A) phenol resin.
(phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms)
The phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is phenol or a derivative thereof and a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes abbreviated as "an unsaturated hydrocarbon group-containing compound" The reaction product of the reaction product (hereinafter also referred to as "unsaturated hydrocarbon group-modified phenol derivative") and the condensed product of the aldehyde or the reaction product of the phenol resin and the compound containing an unsaturated hydrocarbon group.
The phenol derivative can be the same as the phenol derivative described above as a raw material of the phenol resin having a repeating unit represented by the formula (7).
The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of the residual stress of the cured film and the applicability of the reflow treatment. Further, from the viewpoint of compatibility between the resin composition and residual stress of the cured film, the unsaturated hydrocarbon group is preferably a carbon number of 4 to 100, more preferably a carbon number of 8 to 80, still more preferably a carbon number. 10 to 60.
Examples of the unsaturated hydrocarbon group-containing compound include an unsaturated hydrocarbon having 4 to 100 carbon atoms, a polybutadiene having a carboxyl group, an epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, an unsaturated fatty acid, and an unsaturated fat. Acid ester. Examples of suitable unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isooleic acid, oleic acid, sinapic acid, tetracosic acid, and linoleic acid. , α-time linoleic acid, tung acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, squid acid and docosahexaenoic acid. Among these, a vegetable oil which is an unsaturated fatty acid ester is particularly preferable from the viewpoint of the elongation of the cured film and the flexibility of the cured film.
Vegetable oils generally comprise an ester of glycerol and an unsaturated fatty acid, a non-drying oil having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Examples of the non-drying oil include olive oil, morning germination seed oil, polygonum oil, camellia oil, camellia oil, castor oil, and peanut oil. Examples of the semi-drying oil include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, hazelnut oil, and mustard oil. Further, processed vegetable oil processed from the vegetable oils may also be used.
Among the above vegetable oils, it is preferred to use a non-drying oil from the viewpoint of preventing gelation caused by excessive reaction in the reaction of phenol or a derivative thereof or a phenol resin with vegetable oil, and improving the yield. On the other hand, from the viewpoint of improving the adhesion of the resist pattern, mechanical properties, and thermal shock resistance, it is preferred to use a dry oil. Among the dry oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable, in terms of the effect of the present invention. These vegetable oils may be used alone or in combination of two or more.
The reaction of phenol or a derivative thereof with a compound containing an unsaturated hydrocarbon group is preferably carried out at 50 to 130 °C. With respect to the reaction ratio of phenol or a derivative thereof to the unsaturated hydrocarbon group-containing compound, the unsaturated hydrocarbon group-containing compound is preferably 1 in terms of reducing the residual stress of the cured film with respect to 100 parts by mass of phenol or a derivative thereof. ～100 parts by mass, more preferably 5 to 50 parts by mass. When the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and when it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst as needed.
The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is subjected to polycondensation polymerization with an aldehyde to thereby form a phenol resin modified with a compound containing an unsaturated hydrocarbon group. Aldehydes such as formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde , acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, thioglycolic acid, methyl mercaptoacetate, 2-methylmercaptopropionic acid, 2 - selected from methyl mercaptopropionate, pyruvic acid, acetopropionic acid, 4-acetic acid, acetone dicarboxylic acid and 3,3'-4,4'-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may also be used. These aldehydes may be used alone or in combination of two or more.
The reaction of the above aldehyde with the above unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and the synthesis conditions of a previously known phenol resin can be employed. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and it is more preferable to use an acid catalyst from the viewpoint of the degree of polymerization (molecular weight) of the resin. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination of two or more.
The above reaction is usually preferably carried out at a reaction temperature of from 100 to 120 °C. Further, the reaction time varies depending on the type or amount of the catalyst to be used, and is usually from 1 to 50 hours. After completion of the reaction, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is obtained by dehydrating the reaction product under reduced pressure at a temperature of 200 ° C or lower. Further, a solvent such as toluene, xylene or methanol can be used for the reaction.
The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by polycondensation of a compound other than phenol such as m-xylene and an aldehyde together with the above-mentioned unsaturated hydrocarbon group-modified phenol derivative. In this case, the addition of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.
The phenol resin modified with the unsaturated hydrocarbon group-containing compound can also be obtained by reacting a phenol resin with a compound containing an unsaturated hydrocarbon group. The phenol resin used in this case is a condensation polymerization product of a phenol compound (i.e., a phenol and/or a phenol derivative) and an aldehyde. In this case, as the phenol derivative and the aldehyde, the same as the above phenol derivative and aldehyde can be used, and the phenol resin can be synthesized under the previously known conditions as described above.
Specific examples of the phenol resin obtained from a phenol compound and an aldehyde which are suitable for forming a phenol resin modified with an unsaturated hydrocarbon group-containing compound include a phenol/formaldehyde novolac resin and a cresol/formaldehyde novolac resin. , xylenol/formaldehyde novolac resin, resorcinol/formaldehyde novolac resin and phenol-naphthol/formaldehyde novolac resin.
The unsaturated hydrocarbon group-containing compound which reacts with the phenol resin can be used in the same manner as the above-mentioned unsaturated hydrocarbon group-containing compound which is involved in the production of the aldehyde-reactive unsaturated hydrocarbon group-modified phenol derivative.
The reaction of the phenol resin with the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130 °C. In addition, the ratio of the reaction ratio of the phenol resin to the compound containing an unsaturated hydrocarbon group is preferably from the viewpoint of improving the flexibility of the cured film (resist pattern), and the compound containing an unsaturated hydrocarbon group is preferably 100 parts by mass based on 100 parts by mass of the phenol resin. It is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, still more preferably 5 to 50 parts by mass. When the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease. When the amount exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the cured film tends to be high. The tendency to reduce heat resistance. When a phenol resin is reacted with a compound containing an unsaturated hydrocarbon group, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst if necessary. Further, a solvent such as toluene, xylene, methanol or tetrahydrofuran can be used for the reaction, which will be described in detail below.
An acid-modified phenol resin can be obtained by reacting a phenolic hydroxyl group remaining in a phenol resin modified with an unsaturated hydrocarbon group-containing compound produced by the above method with a polybasic acid anhydride. The carboxyl group is introduced by acid modification using a polybasic acid anhydride, and the solubility in an alkaline aqueous solution (used as a developing solution) is further improved.
The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of a carboxyl group of a polybasic acid having a plurality of carboxyl groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, and hexahydrogen. Phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, acid anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylene Dibasic anhydrides such as methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid An aromatic tetrabasic acid dianhydride such as an anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.
The reaction of the phenolic hydroxyl group with the polybasic acid anhydride can be carried out at 50 to 130 °C. In the reaction, it is preferred to carry out a reaction of 0.10 to 0.80 mol of the polybasic acid anhydride with respect to the phenolic hydroxyl group 1 mol, more preferably 0.15 to 0.60 mol, and more preferably 0.20 to 0.40 mol. The ear reacts. When the polybasic acid anhydride is less than 0.10 mol, the developability tends to be lowered, and if it exceeds 0.80 mol, the alkali resistance of the unexposed portion tends to decrease.
Further, from the viewpoint of allowing the reaction to proceed rapidly, the above reaction may contain a catalyst as needed. Examples of the catalyst include a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine. .
Further, the acid value of the phenol resin modified with the polybasic acid anhydride is preferably from 30 to 200 mgKOH/g, more preferably from 40 to 170 mgKOH/g, still more preferably from 50 to 150 mgKOH/g. If the acid value is less than 30 mgKOH/g, the time required for alkaline development tends to be longer than when the acid value is in the above range, and if it exceeds 200 mgKOH/g, the acid value is in the above range. The development liquid resistance tends to be lower than that of the unexposed portion.
The molecular weight of the phenol resin modified with the unsaturated hydrocarbon group-containing compound is preferably from 1,000 to 100,000 in terms of weight average molecular weight, in view of solubility in an aqueous alkaline solution or a balance between photosensitive properties and physical properties of a cured film. Good for 2000 to 100000.
The phenol resin (A) of the present embodiment is preferably a phenol resin selected from the group consisting of the repeating unit represented by the above formula (7) and the above-mentioned compound modified with an unsaturated hydrocarbon group having 4 to 100 carbon atoms. A mixture of at least one phenol resin (hereinafter also referred to as (a3) resin) and a phenol resin (hereinafter also referred to as (a4) resin) selected from the group consisting of novolaks and polyhydroxystyrenes. The mixing ratio of (a3) resin to (a4) resin is in the range of (a3) / (a4) = 5/95 to 95/5 by mass ratio. The mixing ratio is preferably (a3) / (at the viewpoint of solubility in an alkaline aqueous solution, sensitivity and resolution when a resist pattern is formed, residual stress of a cured film, and applicability of a reflow process. A4) = 5/95 to 95/5, more preferably (a3) / (a4) = 10/90 to 90/10, still more preferably (a3) / (a4) = 15/85 to 85/15. As the novolak and polyhydroxystyrene as the above (a4) resin, the same resins as those shown in the above (novolak) and (polyhydroxystyrene) can be used.
(B) a cyclic compound having a carbonyl group
(B) The compound is at least one compound selected from the group consisting of a compound having two or more carbonyl groups, and the above carbonyl group is directly bonded to the above cyclic structure, and is a monocyclic compound. In the case, 1/3 or more of the atoms forming the ring structure are N atoms, and in the case of condensing the ring compound, 1/3 or more of the atoms forming the ring structure having the above carbonyl group are N atoms.
From the viewpoint of migration resistance, it is preferably at least one compound selected from the group consisting of the following compounds classified according to the ring structure, that is, a 5-membered ring compound, a 6-membered ring compound, a 5-membered ring, and a 5-membered member. A condensed ring compound of a ring, a fused ring compound of a 5-membered ring and a 6-membered ring, a condensed ring compound of a 6-membered ring and a 6-membered ring.
By having two or more carbonyl groups, the area of the voids on the copper surface can be reduced. Further, from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like, it is also preferred to have two or more carbonyl groups. When the carbonyl group is two or more, the area of the void on the copper surface is remarkably small as compared with the case where the carbonyl group is one. Moreover, from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, and the like, the case where the carbonyl group is two or more is superior to the case where the carbonyl group is one.
Specific examples of the compound (B) include, as a 5-membered ring compound, 3-pyrazolone, 5-pyrazolone, 3-methyl-5-pyrazolone, and 1,3-dimethyl Base-5-pyrazolone, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, carbendazim, allantoin, parabanic acid, etc., as 6 members Examples of the ring compound include tetrahydro-2-pyrimidinone, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-dicyclohexylbarbituric acid, and 5-aminobarbital. Acid (uramil), urethane, cyanuric acid, tris(3-hydroxyethyl) isocyanurate, etc., as a condensed ring compound of a 5-membered ring and a 5-membered ring, examples thereof include glycoluril or the like. The condensed ring compound of the ring of members and the ring of 5 members can be exemplified by: guanine, isoguanine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl) bird. Anthraquinone, N-(3-ethylphenyl)guanine, hypoxanthine, 8-azahypoxanthine, 7-deazahypoxanthine, xanthine, 1-methylxanthine, 3-methyl Astragalus, 8-bromo-3-methylxanthine, theobromine, theophylline, 7-(2-chloroethyl)theophylline, caffeine, uric acid, 8-aza-xanthine, etc., as 6 The condensed cyclic compound of the ring and the 6-membered ring may, for example, be hydrazine, dihydrotetrahydropteridine, 7,8-dimethylpyrrolidine or 1,4-dihydro-6-methylquinoxaline-2. , 3-dione, etc., may also be mentioned as a mixture thereof. Among these, a condensed ring compound is preferably used.
Further, from the viewpoint of migration resistance, the compound (B) is preferably selected from the following formula (60):
[48]

In the formula, Rs3, Rs4 and Rs5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amine group which may be substituted by an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of 1 to 10. Alkyl or aromatic group}
The compound represented by the following formula (61):
[化49]

In the formula, Rs6, Rs7 and Rs8 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amine group which may be substituted by an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of 1 to 10. Alkyl or aromatic group}
The compound represented by the following formula (62):
[化50]

In the formula, Rs9, Rs10, Rs11 and Rs12 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amine group which may be substituted by an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or a carbon number of 1 to 10 alkyl or aromatic group}
The compound represented by the following formula (63):
[化51]

{式,R _{twenty one} , R _{twenty two} , R _{twenty three} And R _{twenty four} Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group which may be substituted with an aromatic group, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group or an alkyl group having 1 to 10 carbon atoms or an aromatic group}
At least one compound of the group consisting of the compounds indicated.
Specific examples of the compound represented by the above formulas (60) to (63) include xanthine, 1-methylxanthine, 3-methylxanthine, theobromine, theophylline, caffeine, and uric acid. , 8-azaxanthine, dihydrotetrahydropteridine, and the like and derivatives thereof.
The compounding amount of the compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the (A) resin. From the viewpoint of migration resistance, it is preferably 0.01 parts by mass or more, and from the viewpoint of solubility, it is preferably less than 10 parts by mass.
It is considered that these (B) components change the surface state of copper by the coordination of the carbonyl group or the nitrogen atom contained in the ring structure with copper, thereby suppressing copper migration during the high-temperature storage test. It is considered that, particularly in the case of a condensed ring, migration resistance is improved by a synergistic action of a plurality of carbonyl groups and a nitrogen atom.
(C) sensitizer
The (C) sensitizer used in the present invention will be described. (C) Photosensitive Agent The photosensitive resin composition according to the present invention is, for example, a polyimine precursor and/or polyamine as a negative type of (A) resin, or a polycarbazole precursor, for example, mainly used. At least one of the soluble polyimine and the phenol resin differs depending on the positive type of the (A) resin and the like.
The amount of the (C) photosensitive agent to be added to the photosensitive resin composition is 1 to 50 parts by mass based on 100 parts by mass of the (A) resin. The amount of the above-mentioned compounding is 1 part by mass or more from the viewpoint of the light sensitivity or the patterning property, and is 50 parts by mass or less from the viewpoint of the curability of the photosensitive resin composition or the physical properties of the photosensitive resin layer after curing.
[(C) Negative sensitizer: photopolymerization initiator and/or photoacid generator]
First, the case where the expectation is negative is explained. In this case, a photopolymerization initiator and/or a photoacid generator are used as the (C) sensitizer, and as a photopolymerization initiator, a photoradical polymerization initiator is preferred, and a diphenyl is preferably exemplified. Benzophenone, benzophenone benzoic acid methyl ester, 4-benzylidene-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2, 2'- Acetophenone derivative such as ethoxyacetophenone, 2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl ketone, 9-oxopurine 2-methyl 9-oxothione 2-isopropyl 9-oxothiolane Diethyl 9-oxopurine 9-oxopurine Derivatives, benzoin derivatives such as benzophenone, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal,
Benzoin derivatives such as benzoin, benzoin methyl ether, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) fluorene, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, 1-phenyl-1,2-propanedione-2-(o- Benzyl hydrazino) hydrazine, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) hydrazine, 1-phenyl-3-ethoxypropanetrione-2-(o-benzamide) Anthracene, anthracene, N-arylglycine such as N-phenylglycine, peroxides such as benzamidine perchloride, aromatic biimidazole, ferrocene, α-( Photoacid generators such as n-sulfonyloxyimino)-4-methoxybenzyl cyanide, etc., but are not limited thereto. Among the above photopolymerization initiators, in particular, in terms of light sensitivity, it is more preferably an anthracene.
When a photoacid generator is used as the (C) sensitizer in the negative photosensitive resin composition, it is acidic under irradiation of active light such as ultraviolet rays, and has the following effect by the action The crosslinking agent is crosslinked with the resin as the component (A) or the crosslinking agent is polymerized with each other. As an example of the photoacid generator, a diarylsulfonium salt, a triarylsulfonium salt, a dialkyl benzamidine methyl phosphonium salt, a diarylsulfonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid can be used. Acid ester, aromatic sulfonate, nitrobenzyl ester, sulfonate, aromatic N-oxy quinone sulfonate, aromatic sulfonamide, halogenated alkyl hydrocarbon compound, halogen-containing A heterocyclic compound of an alkyl group, a naphthoquinonediazide-4-sulfonate or the like. Such a compound may be used in combination of two or more kinds as needed or in combination with other sensitizers. Among the above photoacid generators, in particular, in terms of photosensitivity, an aromatic sulfonate or an aromatic N-oxyindenine sulfonate is more preferable.
The amount of the sensitizer to be added is 1 to 50 parts by mass based on 100 parts by mass of the (A) resin, and is preferably 2 to 15 parts by mass from the viewpoint of light sensitivity characteristics. When the (C) photosensitive agent is used in an amount of 1 part by mass or more based on 100 parts by mass of the (A) resin, the photosensitivity is excellent, and when it is blended in an amount of 50 parts by mass or less, the thick film hardenability is excellent.
In the case where the resin represented by the formula (1) is an ionic bond, as described above, in order to impart a photopolymerizable group to the side chain of the (A) resin via an ionic bond, an amine group is used. (Meth)acrylic compound. In this case, a (meth)acrylic compound having an amine group is used as the (C) sensitizer, and as described above, for example, dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate is preferred. , diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethyl methacrylate Alkyl propyl acrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethyl butyl acrylate, diethyl butyl methacrylate, etc. Or a dialkylaminoalkyl methacrylate, wherein, in terms of photosensitivity, it is preferred that the alkyl group has an alkyl group having 1 to 10 carbon atoms and an alkyl chain having 1 to 10 carbon atoms. A dialkylaminoalkyl acrylate or a dialkylaminoalkyl methacrylate.
The amount of the (meth)acrylic compound having an amine group is from 1 to 20 parts by mass based on 100 parts by mass of the resin (A), and from the viewpoint of light sensitivity characteristics, it is preferably from 2 to 15. Parts by mass. When the (meth)acrylic compound having an amine group is contained in an amount of 1 part by mass or more based on 100 parts by mass of the (A) resin, the photosensitive agent is excellent in light sensitivity, and is thicker by 20 parts by mass or less. Excellent film hardenability.
Second, the case where the expectation is positive is explained. In this case, a photoacid generator is used as the (C) sensitizer, and specifically, a diazonium compound, a sulfonium salt, a halogen-containing compound, or the like can be used, from the viewpoints of solvent solubility and storage stability. A compound having a diazonium structure is preferred.
[(C) Positive sensitizer: a compound having a quinonediazide group]
(C) a compound having a quinonediazide group (hereinafter also referred to as "(C) quinonediazide compound)", a compound having a 1,2-benzoquinonediazide structure, and having 1,2 The compound of the naphthoquinone diazide structure is a known material in the specification of U.S. Patent No. 2,772,972, the specification of U.S. Patent No. 2,797,213, and the specification of U.S. Patent No. 3,669,658. The (C) quinonediazide compound is preferably a 1,2-naphthoquinonediazide-4-sulfonate selected from the polyhydroxy compounds having a specific structure described in detail below, and the polyhydroxy compound. At least one compound (hereinafter also referred to as "NQD compound") of a group consisting of 2-naphthoquinonediazide-5-sulfonate.
The NQD compound is obtained by subjecting a naphthoquinonediazidesulfonic acid compound to sulfonium sulfonation using chlorosulfonic acid or sulfinium chloride according to a conventional method to obtain the naphthoquinonediazide sulfonium chloride. The condensation reaction is carried out with a polyhydroxy compound. For example, it can be obtained by using a polyhydroxy compound with a specific amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in diterpene. Esterification is carried out by reacting in a solvent such as an alkane, acetone or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and the obtained product is washed with water and dried.
In the present embodiment, the compound having a quinonediazide group (C) is preferably represented by the following general formulae (70) to (74) from the viewpoint of sensitivity and resolution in forming a resist pattern. 1,2-naphthoquinonediazide-4-sulfonate and/or 1,2-naphthoquinonediazide-5-sulfonate of the hydroxy compound.
General formula (70)
[化52]

{式,X ₁₁ And X ₁₂ Each of which independently represents a hydrogen atom or a monovalent organic group having a carbon number of 1 to 60 (preferably, a carbon number of 1 to 30), X ₁₃ And X ₁₄ Each of the hydrogen atom or the monovalent organic group having a carbon number of 1 to 60 (preferably having a carbon number of 1 to 30) is independently represented, and r1, r2, r3 and r4 are each independently an integer of 0 to 5, and at least one of r3 and r4. It is an integer of 1 to 5, (r1+r3)≦5, and is represented by (r2+r4)≦5}.
General formula (71)
[化53]

In the formula, Z represents an organic group having a carbon number of 1 to 20, and X ₁₅ , X ₁₆ , X ₁₇ And X ₁₈ Each of the organic groups having a carbon number of 1 to 30 is independently represented, and r6 is an integer of 0 or 1, and r5, r7, r8, and r9 are each independently an integer of 0 to 3, and r10, r11, r12, and r13 are each independently 0. An integer of ～2, and r10, r11, r12, and r13 are not all represented by 0}.
And the general formula (72) consists of
[54]

In the formula, r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, and (r14 × r15) each independently represents an organic group having a carbon number of 1 to 20, and (r15) ¹ And (r15) T ² Each represents a hydrogen atom or an organic group having a monovalent number of carbon atoms of 1 to 20, respectively.
And the general formula (73) consists of
[化55]

In the formula, A represents an aliphatic organic group containing a divalent or tertiary carbon, and M represents a divalent organic group, preferably represented by the following chemical formula:
[化56]

The base of the two valences of the three kinds of bases represented by}.
Further, the general formula (74) consists of
[化57]

In the formula, r17, r18, r19 and r20 are each independently an integer of 0 to 2, and at least one of r17, r18, r19 and r20 is 1 or 2, X ₂₀ ~X ₂₉ Each of which independently represents a hydrogen atom, a halogen atom, a monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and a fluorenyl group, and Y ₁₀ , Y ₁₁ And Y ₁₂ Respectively represent a single bond, selected from -O-, -S-, -SO-, -SO ₂ -, -CO-, -CO ₂ - a 2-valent group in the group consisting of a cyclopentylene group, a cyclohexylene group, a phenylene group, and an organic group having a carbon number of 1 to 20 valence.
In another embodiment, in the above formula (74), Y ₁₀ ~Y ₁₂ Preferably, each independently from the following formula:
[化58]

[化59]

[60]

{式,X ₃₀ And X ₃₁ Each of which independently represents a hydrogen atom, at least one monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group, X ₃₂ , X ₃₃ , X ₃₄ And X ₃₅ Respectively represent a hydrogen atom or an alkyl group, respectively, r21 is an integer from 1 to 5, and X ₃₆ , X ₃₇ , X ₃₈ And X ₃₉ Respectively represent a hydrogen atom or an alkyl group, respectively}
Among the three divalent organic groups indicated, it is selected.
The compound represented by the above formula (70) includes a hydroxy compound represented by the following formulas (75) to (79).
Here, the general formula (75) is
[化61]

In the formula, r16 is independently an integer of 0 to 2, and X ₄₀ Respectively represent a hydrogen atom or an organic group having a carbon number of 1 to 20, respectively, in X ₄₀ When there are multiple cases, multiple X ₄₀ May be the same or different, and X ₄₀ Preferably, the following formula:
[化62]

(where r18 is an integer from 0 to 2, X ₄₁ A hydrogen atom, a monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and in the case where r18 is 2, 2 X ₄₁ Can be the same or different from each other)
The monovalent organic group represented by
General formula (76)
[化63]

{式,X ₄₂ The hydrogen atom is represented by a monovalent organic group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.
Also, the general formula (77) is
[化64]

In the formula, r19 is independently an integer of 0 to 2, X ₄₃ Respectively represent a hydrogen atom or a general formula:
[化65]

(where r20 is an integer from 0 to 2, X ₄₅ Selecting a group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and in the case where r20 is 2, 2 X ₄₅ 1 or more organic groups represented by each other, and X ₄₄ The group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms is selected, and the formulae (78) and (79) have the following structures.
[化66]

[67]

The compound represented by the above formula (70) is preferably a formula (80) in which the sensitivity of the NQD compound is high and the precipitation property in the photosensitive resin composition is low. a hydroxy compound represented by (82).
The structures of the formulas (80) to (82) are as follows.
[化68]

[化69]

[化70]

The compound represented by the above formula (76) is preferably a compound of the following formula (83) in that the NQD compound has a high sensitivity and a low precipitation property in the photosensitive resin composition. :
[71]

The hydroxy compound represented.
The compound represented by the above formula (77) is preferably a compound of the following formula (84) in that the NQD compound has a high sensitivity and a low precipitation property in the photosensitive resin composition. a hydroxy compound represented by ~(86).
The structures of the formulae (84) to (86) are as follows.
[化72]

[化73]

[化74]

In the above formula (71), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms, and from the viewpoint of sensitivity, it is preferred to have the following formula:
[化75]

The base of the four valences of the structure indicated.
Among the compounds represented by the above formula (71), the NQD compound is high in sensitivity and the precipitation property in the photosensitive resin composition is low, and the following formula (87) is preferred. a hydroxy compound represented by -(90).
The structures of the formulae (87) to (90) are as follows.
[化76]

[化77]

[化78]

[化79]

The compound represented by the above formula (72) is preferably a formula (91) in which the sensitivity is high when the NQD compound is formed and the precipitation property in the photosensitive resin composition is low. :
[化80]

In the formula, r40 is independently a hydroxy compound represented by an integer of 0 to 9.
The compound represented by the above formula (73) is preferably a compound of the following formula (92) in that the sensitivity is high when the NQD compound is formed and the precipitation property in the photosensitive resin composition is low. And the hydroxy compound represented by (93).
The structures of the formulas (92) and (93) are as follows.
[化81]

[化82]

The compound represented by the above formula (74) is preferably a compound of the following formula (94) in terms of high sensitivity and low precipitation in the photosensitive resin composition:
[化83]

An NQD compound of the polyhydroxy compound represented.
In the case where (C) a compound having a quinonediazide group has a 1,2-naphthoquinonediazidesulfonyl group, the group may be 1,2-naphthoquinonediazide-5-sulfonyl or 1 Any of 2-naphthoquinonediazide-4-sulfonyl. The 1,2-naphthoquinonediazide-4-sulfonyl group is capable of absorbing the i-ray region of a mercury lamp and is therefore suitable for exposure using i-rays. On the other hand, the 1,2-naphthoquinonediazide-5-sulfonyl group can absorb the g-ray region of the mercury lamp, and is therefore suitable for exposure with g rays.
In the present embodiment, it is preferred to select one of the 1,2-naphthoquinonediazide-4-sulfonate compound and the 1,2-naphthoquinonediazide-5-sulfonate compound according to the wavelength at which exposure is performed. Or both. Further, it is also possible to use a 1,2-naphthoquinone quinone having 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group in the same molecule. The sulfonate compound may also be used in combination with a 1,2-naphthoquinonediazide-4-sulfonate compound and a 1,2-naphthoquinonediazide-5-sulfonate compound.
(C) Among the compounds having a quinonediazide group, the average esterification ratio of the naphthoquinonediazidesulfonyl ester of the hydroxy compound is preferably from 10% to 100%, and further preferably from the viewpoint of development contrast. It is 20% to 100%.
In view of the physical properties of the cured film such as the sensitivity and the elongation, examples of the NQD compound include those represented by the following general formula.
[化84]

In the formula, Q is a hydrogen atom or a group of the following formula:
[化85]

Any of the naphthoquinonediazidesulfonate groups represented by any of them, but Q is not represented by a hydrogen atom at the same time.
In this case, as the NQD compound, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule can also be used. The 4-naphthoquinonediazidesulfonyl ester compound can be used in combination with a 5-naphthoquinonediazidesulfonyl ester compound.
Among the naphthoquinonediazidesulfonate groups described in the above paragraph [0196], the following formula (95) is particularly preferred:
[化86]

Represented.
Examples of the onium salt include a phosphonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, an ammonium salt, a diazonium salt, and the like, and are preferably selected from the group consisting of a diarylsulfonium salt, a triarylsulfonium salt, and a trialkylsulfonium salt. The strontium salt in the group formed.
The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound, and is preferably trichloromethyltriazine.
The amount of the photoacid generator to be added is 1 to 50 parts by mass, preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) resin. When the amount of the photo-acid generator of the (C) sensitizer is 1 part by mass or more, the patterning property of the photosensitive resin composition is good, and when it is 50 parts by mass or less, the photosensitive resin composition is cured. The tensile elongation of the film is good, and the development residue (scum) of the exposed portion is small.
The above NQD compounds may be used singly or in combination of two or more.
In the present embodiment, the compounding amount of the compound having a quinonediazide group in (C) in the photosensitive resin composition is preferably 0.1 parts by mass to 70 parts by mass based on 100 parts by mass of the (A) resin. 1 part by mass to 40 parts by mass, more preferably 3 parts by mass to 30 parts by mass, still more preferably 5 parts by mass to 30 parts by mass. When the amount is 0.1 part by mass or more, a good sensitivity is obtained. On the other hand, when the amount is 70 parts by mass or less, the mechanical properties of the cured film are good.
The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C). The preferred component is different depending on the negative type of the (A) resin, for example, a polyimine precursor and a polyamine, or a positive type such as a polycarbazole precursor and a soluble polyimine.
In the present embodiment, the polyimide precursor resin composition and the polyamide resin composition as the negative resin composition, or the polycarbazole resin composition as the positive photosensitive resin composition, soluble polyfluorene The imide resin composition and the phenol resin composition may contain a solvent for dissolving the resins.
Examples of the solvent include guanamines, guanidines, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, and the like. For example, N-methyl-2 can be used. - pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylhydrazine, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, porphyrin, dichloromethane, 1,2-dichloro Ethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like. Among them, N-methyl-2-pyrrolidone, dimethyl hydrazide, tetramethylurea are preferred from the viewpoints of solubility of the resin, stability of the resin composition, and adhesion to the substrate. , butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylethylene glycol and tetrahydrofuran methanol.
Among such solvents, it is particularly preferred to completely dissolve the resulting polymer, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethyl Mercaptoamine, dimethyl hydrazine, tetramethyl urea, γ-butyrolactone, and the like.
Examples of the solvent to be used in the above phenol resin include bis(2-methoxyethyl)ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and Ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.
In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, even more preferably 125 to 100 parts by mass of the (A) resin. A range of 500 parts by mass.
The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C).
For example, when a photosensitive resin composition of the present invention is used to form a cured film on a substrate containing copper or a copper alloy, a nitrogen-containing heterocyclic ring such as an azole compound or an anthracene derivative may be optionally disposed in order to suppress discoloration on the copper. Compound.
Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-phenyl group. -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyl triazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-di Ethyl-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-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl- 5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-p-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5 '-Third octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole , 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, and the like.
Particularly preferred are toluene triazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in combination of two or more.
Specific examples of the anthracene derivative include anthraquinone, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-A. Adenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-( 2-hydroxyethyl)adenine, guanine, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-indole, 1-ethyl Adenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N -(3-ethylphenyl)guanine, 2-azadenine, 5-azadenine, 8-azadenine, 8-azaguanine, 8-azaindole, 8-aza Astragalus, 8-azahypoxanthine and the like and derivatives thereof.
When the photosensitive resin composition of the present invention contains the above-mentioned azole compound or an anthracene derivative, the amount of the compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the resin (A), and the viewpoint of light sensitivity characteristics More preferably, it is 0.5 to 5 parts by mass. When the amount of the azole compound is 0.1 parts by mass or more based on 100 parts by mass of the (A) resin, the surface of the copper or copper alloy is suppressed when the photosensitive resin composition of the present invention is formed on the copper or copper alloy. On the other hand, when it is 20 mass parts or less, it is excellent in light sensitivity.
Further, the hindered phenol compound can be arbitrarily formulated in order to suppress discoloration on the copper surface. As the hindered phenol compound, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 3-(3,5-di-t-butyl- Octadecyl 4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylene double (2 , 6-di-t-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)propionate], 1,6-hexanediol- Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-di-extension ethyl bis[3-(3,5-di-third butyl) 4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 2,2'-Asia Methyl-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol),
Tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2 ,6-Dimethyl-4-isopropylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H) -Triketone, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triter-2,4 ,6-(1H,3H,5H)-trione,
1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-trimethyl-2,4,6-(1H,3H ,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6- (1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethyl Benzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl- 3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-third Butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-( 1H, 3H, 5H)-trione,
1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)- Triketone, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H ,3H,5H)-Trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione or the like, but is not limited thereto. Among these, it is especially preferred that 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 , 6-(1H, 3H, 5H)-trione and the like.
The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. When the amount of the hindered phenol compound to be added to 100 parts by mass of the (A) resin is 0.1 parts by mass or more, for example, when a photosensitive resin composition of the present invention is formed on copper or a copper alloy, copper or copper alloy is prevented from being produced. When the content is 20 parts by mass or less, the light sensitivity is excellent.
The photosensitive resin composition of the present invention may further contain a crosslinking agent. The crosslinking agent can be used to crosslink the (A) resin or the crosslinking agent itself to form a crosslinked network structure when the embossed pattern formed using the photosensitive resin composition of the present invention is heat-hardened. Agent. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed of the photosensitive resin composition.
Examples of the crosslinking agent include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, and 238 which are compounds containing a methylol group and/or an alkoxymethyl group. 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, Micoat 102, 105 (above, manufactured by Mitsui Cytec); NIKALAC (registered trademark) MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300, -390, -750 (above manufactured by SANWA CHEMICAL); DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML -PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM -BP, TMOM-BPA, TML-BPAF-MF (above manufactured by Honshu Chemical Industry Co., Ltd.); benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxyl) Methyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, Bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, double (a) Methyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, Bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, and the like.
Further, examples thereof include a phenol novolac type epoxy resin as an oxirane compound, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a trisphenol type epoxy resin, and a tetraphenol type epoxy resin. Phenol-benzoic epoxy resin, naphthol-benzoic epoxy resin, phenol-naphthol epoxy resin, phenol-dicyclopentadiene epoxy resin, alicyclic epoxy resin , aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra (pair Hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, o-butyl phenyl glycidyl ether, 1,6-bis(2,3-epoxypropoxy) naphthalene, diglycerol polycondensation Glycerol ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (above, trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN- 501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above is the trade name, manufactured by Nippon Kayaku Co., Ltd.), Epikote (Registrar) ) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (above, trade name, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE 3150, PLACCEL G402, PUE101 , PUE105 (above, trade name, manufactured by Diacel Chemical Industries Co., Ltd.), EPICLON (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP- 820, EXA-4850-1000 (the above is the trade name, manufactured by DIC Corporation), DENACOL (registered trademark) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411 , EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (above the trade name, manufactured by Nagase chemteX) ), Epolight (registered trademark) 70P, Epolight 100MF (above, the product name, manufactured by Kyoeisha Chemical Co., Ltd.).
Further, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,3-benzenedimethylene diisocyanate, dicyclohexylmethane-4,4'- as an isocyanate group-containing compound may be mentioned. Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (above, trade name, manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like.
Further, examples thereof include 4,4'-diphenylmethanebissuccinimide, phenylmethane maleimide, and phenyldiene as a bis-m-butylene diimine compound. Maleimide, bisphenol A diphenyl ether bis-n-butylene imide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Bis-m-butylene diimide, 4-methyl-1,3-phenylenebissuccinimide, 1,6'-bis-s-m-butyleneimine-(2,2,4 -trimethyl)hexane, 4,4'-diphenyl ether bis-n-butylene imide, 4,4'-diphenylfluorene bis-n-butylene diimide, 1,3-double (3 - maleimide phenoxy)benzene, 1,3-bis(4-methyleneimide phenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300 , BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (the above are trade names, manufactured by Daiwa Chemical Co., Ltd.), etc., but as long as The compound which is thermally crosslinked as it is is not limited to these.
The amount of the crosslinking agent in the case of using the crosslinking agent is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the (A) resin. When the amount is 0.5 parts by mass or more, it exhibits excellent heat resistance and chemical resistance. On the other hand, when it is 20 parts by mass or less, the storage stability is excellent.
The photosensitive resin composition of the present invention may also contain an organic titanium compound. When the organic titanium compound is contained, it is possible to form a photosensitive resin layer excellent in chemical resistance even when it is cured at a low temperature of about 250 °C. In addition, the photosensitive resin composition contains (B) both a cyclic compound having a carbonyl group and an organic titanium compound, and the resin layer after curing has excellent substrate adhesion and chemical resistance. effect.
Examples of the organic titanium compound which can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown in the following I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable in terms of storage stability of a negative photosensitive resin composition and obtaining a good pattern, specifically, for example, Bottom: bis(triethanolamine) titanium diisopropoxide, titanium bis(2,4-pentanedioic acid) di-n-butoxide, titanium bis(2,4-glutaric acid) diisopropoxide, bis(tetramethyl) Pimelic acid) titanium diisopropylate, bis(ethylacetamidineacetic acid) titanium diisopropylate, and the like.
II) tetraalkoxy titanium compound: for example, titanium (n-butanol), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, four Titanium methoxypropoxide, titanium tetramethyl phenol, titanium tetrakis (n-nonanol), titanium tetrakis (n-propanol), titanium tetrastearyl alcohol, tetrakis [double {2,2-(allyloxymethyl) ) Butanol}] Titanium, etc.
III) Titanocene compound: for example, (pentamethylcyclopentadienyl) trimethyl methoxide, double (η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, double (η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium or the like.
IV) Monoalkoxy titanium compound: for example, tris(dioctylphosphoric acid) titanium isopropoxide, tris(dodecylbenzenesulfonic acid) titanium isopropoxide, and the like.
V) an oxytitanium compound: for example, bis(glutaric acid) oxytitanium, bis(tetramethylpimelate)oxytitanium, phthalocyanine titanate or the like.
VI) Titanium tetraacetate pyruvate compound: for example, titanium tetraacetate pyruvate or the like.
VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate or the like.
Among them, from the viewpoint of exhibiting better chemical resistance, the organotitanium compound is preferably selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. At least one compound of the group consisting of. Especially preferred is bis(ethylacetamidineacetic acid) titanium diisopropoxide, tetra(n-butanol) titanium, and double (η ⁵ -2,4-Cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.
The blending amount in the case of blending the organotitanium compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) resin. When the amount is 0.05 parts by mass or more, it exhibits excellent heat resistance and chemical resistance. On the other hand, when it is 10 parts by mass or less, the storage stability is excellent.
Further, in order to improve the adhesion between the film formed by using the photosensitive resin composition of the present invention and the substrate, the adhesion aid can be arbitrarily formulated. Examples of the subsequent auxiliary agent include γ-aminopropyl dimethoxydecane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxydecane, and γ-glycidyloxygen. Propylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, 3-methylpropenyloxypropyldimethoxymethyldecane, 3-methylpropenyloxy Propyltrimethoxydecane, dimethoxymethyl-3-piperidinylpropylnonane, diethoxy-3-glycidoxypropylmethyldecane, N-(3-diethoxymethyl) Alkyl propyl)butanediamine, N-[3-(triethoxydecyl)propyl]benzamide, benzophenone-3,3'-bis (N-[ 3-triethoxydecyl]propyl decylamine-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxydecyl]propyl decylamine)- 2,5-dicarboxylic acid, 3-(triethoxydecyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxydecane, 3-ureidopropyltrimethoxydecane, 3- a decane coupling agent such as ureidopropyltriethoxy decane or 3-(trialkoxyindolyl)propyl succinic anhydride, and aluminum tris(ethylacetamidineacetate), aluminum tris(acetylacetonate), and Ethyl aluminum diacetate An aluminum-based auxiliary agent such as propyl ester.
Among these secondary auxiliaries, a decane coupling agent is more preferably used in terms of adhesion. In the case where the photosensitive resin composition contains a binder, the amount of the binder to be added is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the (A) resin.
Examples of the decane coupling agent include 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyl three Ethoxy decane (manufactured by Azmax Co., Ltd.: trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name: LS1375, manufactured by Azmax Co., Ltd.: commodity SIM6474.0), mercaptomethyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0) , 3-mercaptopropyldiethoxymethoxydecane, 3-mercaptopropylethoxydimethoxydecane, 3-mercaptopropyltripropoxydecane, 3-mercaptopropyldiethoxypropane Oxydecane, 3-mercaptopropylethoxydipropoxydecane, 3-mercaptopropyldimethoxypropoxydecane, 3-mercaptopropylmethoxydipropoxydecane, 2-mercaptoethyl Trimethoxy decane, 2-mercaptoethyl diethoxy methoxy decane, 2-mercapto B Ethyl ethoxy dimethoxy decane, 2-mercaptoethyl tripropoxy decane, 2-mercaptoethyl tripropoxy decane, 2-mercaptoethyl ethoxy dipropoxy decane, 2-mercapto B Dimethoxypropoxydecane, 2-mercaptoethylmethoxydipropoxydecane, 4-mercaptobutyltrimethoxydecane, 4-mercaptobutyltriethoxydecane, 4-mercaptobutyl Tripropoxydecane, N-(3-triethoxydecylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-( 3-trimethoxydecylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxydecylpropyl)urea, N-(3-ethyl Oxydimethoxydecylpropyl)urea, N-(3-tripropoxydecylpropyl)urea, N-(3-diethoxypropoxydecylpropyl)urea, N- (3-ethoxydipropoxydecylpropyl)urea, N-(3-dimethoxypropoxydecylpropyl)urea, N-(3-methoxydipropoxydecanealkyl) Propyl)urea, N-(3-trimethoxydecylethyl)urea, N-(3-ethoxydimethoxydecylethyl)urea, N -(3-tripropoxydecylethyl)urea, N-(3-tripropoxydecylethyl)urea, N-(3-ethoxydipropoxydecylethyl)urea, N-(3-Dimethoxypropoxydecylethyl)urea, N-(3-methoxydipropoxydecylethyl)urea, N-(3-trimethoxydecylbutyl) Urea, N-(3-triethoxydecylbutyl)urea, N-(3-tripropoxydecylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxy Base decane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxy decane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxydecane (Azmax) Co., Ltd. manufacture: trade name SLA0599.1), aminophenyl trimethoxy decane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxydecylethyl)pyridine (Azmax shares limited) Made by the company: trade name SIT8396.0), 2-(triethoxydecylethylethyl)pyridine, 2-(dimethoxydecylmethylethyl)pyridine, 2-(diethoxydecylalkyl) (ethyl)pyridine, (3-triethoxydecylpropyl) tert-butyl amide, (3-glycidyloxy) Propyl)triethoxydecane, tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, tetra-n-butoxydecane, tetraisobutoxydecane, tetra Third butoxydecane, tetrakis(methoxyethoxydecane), tetrakis(methoxy-n-propoxydecane), tetrakis(ethoxyethoxydecane), tetrakis(methoxyethoxyethyl) Oxydecane), bis(trimethoxydecyl)ethane, bis(trimethoxydecyl)hexane, bis(triethoxydecyl)methane, bis(triethoxydecyl)ethane, Bis(triethoxydecyl)ethylene, bis(triethoxydecyl)octane, bis(triethoxydecyl)octadiene, bis[3-(triethoxydecyl)propyl Disulfide, bis[3-(triethoxydecyl)propyl]tetrasulfide, ditributyloxydiethoxydecane, diisobutoxyaluminoxytriethoxydecane , bis(glutaric acid) titanium-O, O'-bis(oxyethyl)-aminopropyltriethoxydecane, phenyldecanetriol, methylphenyldecanediol, ethylphenyl矽 二醇 diol, n-propyl phenyl decane diol, isopropyl phenyl decane diol, n-butyl phenyl decane , isobutylphenyl decanediol, tert-butylphenyl decane diol, diphenyl decane diol, dimethoxy diphenyl decane, diethoxy diphenyl decane, dimethoxy aldehyde P-tolyl decane, ethyl methyl phenyl stanol, n-propyl methyl phenyl stanol, isopropyl methyl phenyl stanol, n-butyl methyl phenyl stanol, isobutyl methyl phenyl stanol, Third butylmethylphenyl decyl alcohol, ethyl n-propyl phenyl decyl alcohol, ethyl isopropyl phenyl stanol, n-butyl ethyl phenyl stanol, isobutyl ethyl phenyl stanol, Tributylethylphenylstanol, methyldiphenylnonanol, ethyldiphenylnonanol, n-propyldiphenylnonanol, isopropyldiphenylnonanol, n-butyldiphenyl The stanol, isobutyldiphenyl decyl alcohol, tert-butyldiphenyl decyl alcohol, triphenyl decyl alcohol, etc. are not limited to these. These may be used alone or in combination of plural kinds.
As the decane coupling agent, among the above decane coupling agents, from the viewpoint of storage stability, phenyldecanetriol, trimethoxyphenylnonane, trimethoxy(p-tolyl)decane, and diphenyl are preferable. A decane diol, dimethoxydiphenyl decane, diethoxydiphenyl decane, dimethoxydi-p-tolyl decane, triphenyl decyl alcohol, and a decane coupling agent represented by the following structure.
[化87]

The blending amount in the case of using a decane coupling agent is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the (A) resin.
The photosensitive resin composition of the present invention may further contain components other than the above components. The component is preferably a negative type such as a polyimide precursor and a polyamine, or a positive type using a polycarbazole precursor, a soluble polyimine, a phenol resin, or the like as the (A) resin. different.
When a polyimine precursor or a polyamine is used as the negative form of the (A) resin, the sensitizer can be arbitrarily prepared in order to improve the light sensitivity. As the sensitizer, for example, rice ketone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzylidene group) are exemplified. Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylamino cinnamyl indanone , p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylphenylene)benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole , 2-(p-dimethylaminophenylphenylvinyl)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-di Ethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethylindol-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylamino coumarin, 3-benzyloxycarbonyl-7-dimethylamino coumarin, 3-methoxycarbonyl-7-diethylamine coumarin , 3-ethoxycarbonyl-7-diethylamine coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluene Diethanolamine, N-phenylethanolamine, 4-carbolinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1- Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzimidyl)styrene, and the like. These may be used singly or in the form of a combination of, for example, 2 to 5.
The amount of the photosensitive resin composition in the case where the sensitizer for improving the photosensitivity is contained is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the (A) resin.
Further, in order to improve the resolution of the embossed pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily prepared. The (meth)acrylic compound which is subjected to radical polymerization by a photopolymerization initiator is preferably not limited to those listed below, and examples thereof include diethylene glycol dimethacrylate. Ethylene glycol or polyethylene glycol mono- or di-acrylate such as acrylate or tetraethylene glycol dimethacrylate, and mono or diacrylate and methacrylate of methacrylate, propylene glycol or polypropylene glycol, Mono, di or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, 1,6- Diacrylate and dimethacrylate of hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate of bisphenol A, methacrylate, benzenetrimethacrylate , isodecyl acrylate and isodecyl methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol two or three Acrylate and methacrylate, pentaerythritol a compound such as tri- or tetra-acrylate and methacrylate, and an ethylene oxide or propylene oxide adduct of the compounds.
In the case where the photosensitive resin composition contains a monomer having a photopolymerizable unsaturated bond for improving the resolution of the embossed pattern, the amount of the monomer having a photopolymerizable unsaturated bond is It is preferably 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.
Further, when a polyimine precursor or the like is used as the negative form of the (A) resin, in particular, in order to improve the viscosity and the sensitivity of the photosensitive resin composition when stored in a state containing a solvent solution, the stability of the photosensitive resin composition is improved. The thermal polymerization inhibitor can be optionally formulated. As the thermal polymerization inhibitor, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, morphine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2 -naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxyl Amine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like.
The blending amount in the case where the thermal polymerization inhibitor is blended in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the (A) resin.
On the other hand, in the photosensitive resin composition of the present invention, when a polycarbazole precursor or the like is used as the positive type of the (A) resin, a dye previously used as an additive of the photosensitive resin composition may be added as needed. A surfactant, a thermal acid generator, a dissolution promoter, a bonding aid for improving adhesion to a substrate, and the like.
<dye, surfactant, adhesion aid>
When the above additives are more specifically described, examples of the dye include methyl violet, crystal violet, and malachite green. In addition, examples of the surfactant include nonionic surfactants such as polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.) and MEGAFAC (for example). A fluorine-based surfactant such as a product name, manufactured by Dainippon Ink & Chemical Industry Co., Ltd. or a Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.) An organic oxoxane surfactant such as Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the adhesion aid include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl novolac, epoxy decane, epoxy polymer, and the like. Various decane coupling agents.
The blending amount of the dye and the surfactant is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the (A) resin.
Further, the thermal acid generator can be arbitrarily formulated from the viewpoint of exhibiting good thermal properties and mechanical properties of the cured product even when the curing temperature is lowered.
It is preferred to formulate a thermal acid generator from the viewpoint of exhibiting a good thermal property and mechanical properties of the cured product even when the curing temperature is lowered.
Examples of the thermal acid generator include a salt formed of a strong acid and a base such as a phosphonium salt having a function of generating an acid by heat, or a quinone sulfinate.
Examples of the onium salt include a diarylsulfonium salt such as an aryldiazonium salt or a diphenylsulfonium salt; and a di(alkylaryl)phosphonium salt such as a di(t-butylphenyl)phosphonium salt; a trialkylsulfonium salt such as a methyl phosphonium salt; a dialkyl monoarylsulfonium salt such as a dimethylphenylsulfonium salt; a diarylmonoalkylsulfonium salt such as a diphenylmethylsulfonium salt; and a triarylsulfonium salt; Salt and so on.
Among these, preferred are di(t-butylphenyl)phosphonium p-toluenesulfonate, bis(t-butylphenyl)phosphonium triflate, and trifluoromethanesulfonic acid. Methyl phosphonium salt, dimethylphenyl phosphonium salt of trifluoromethanesulfonic acid, diphenylmethyl phosphonium salt of trifluoromethanesulfonic acid, di(tert-butylphenyl) phosphonium salt of nonafluorobutanesulfonic acid And diphenyl sulfonium salt of camphorsulfonic acid, diphenyl phosphonium salt of ethanesulfonic acid, dimethylphenyl phosphonium salt of benzenesulfonic acid, diphenylmethyl phosphonium salt of toluenesulfonic acid, and the like.
Further, as the salt formed of a strong acid and a base, in addition to the above-mentioned phosphonium salt, a salt formed of a strong acid and a base such as a pyridinium salt may be used. Examples of the strong acid include arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acid such as camphorsulfonic acid, trifluoromethanesulfonic acid or nonafluorobutanesulfonic acid, and methanesulfonic acid. An alkylsulfonic acid such as ethanesulfonic acid or butanesulfonic acid. The base may, for example, be an alkylpyridine such as pyridine or 2,4,6-trimethylpyridine, an N-alkylpyridine such as 2-chloro-N-methylpyridine or a halogenated-N-alkylpyridine. Wait.
As the sulfhydrazine sulfonate, for example, naphthyl imine sulfonate or phthalimide sulfonate can be used, and it is not limited as long as it is a compound which generates an acid under heat.
The blending amount in the case of using a thermal acid generator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1 to 5 parts by mass, per 100 parts by mass of the (A) resin. .
In the case of a positive photosensitive resin composition, a dissolution promoter may be used in order to promote removal of a resin which is not useful after light exposure. Preferred are, for example, compounds having a hydroxyl group or a carboxyl group. Examples of the compound having a hydroxyl group include a ballast agent for the above naphthoquinone diazide compound, and a linear chain such as p-cumylphenol, bisphenols, resorcinol, and MtrisPC or MtetraPC. Non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenolic substituents of diphenylmethane, and 3,3-di 1 to 5 phenol substituents of phenylpropane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and 5-northene-2,3-dicarboxylic anhydride The compound obtained by reacting the ear with 1:2 is obtained by reacting bis-(3-amino-4-hydroxyphenyl)fluorene with 1,2-cyclohexyldicarboxylic anhydride at a molar ratio of 1:2. a compound, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-northene-2,3-dicarboxylimine, and the like. Examples of the compound having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactate, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, and 4-hydroxy-3-methoxy group. Mandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, 2-phenyl lactic acid, α-methoxyphenylacetic acid, O-acetyl sulphonic acid, Ikon Acid, etc.
The amount of the preparation in the case of using the dissolution promoter is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the (A) resin.
(state B)
In another aspect of the embodiment, (B) a sulfur-containing compound may be used instead of the above (B) cyclic compound having a carbonyl group. More specifically,
Provided is a photosensitive resin composition comprising
(A) selected from the group consisting of polyaminic acid, polyglycolate, polyamidate, polyhydroxy guanamine, polyamine amide, polyamine, polyamidimide, polyimine, poly a benzoxazole, and at least one resin selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass,
(B) sulfur-containing compound: 0.01 to 10 parts by mass based on 100 parts by mass of the above (A) resin, and
(C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin.
In this aspect, the (A) resin is preferably selected from the group consisting of the polyimine precursor containing the above formula (1), the polyamine containing the above formula (4), and the above formula (5). The polycarbazole precursor, at least one of the group consisting of the polyimine of the above formula (6), and a group consisting of a novolac, a polyhydroxystyrene, and a phenol resin containing the above formula (7).
Further, it is preferable that the photosensitive resin composition contains a phenol resin having a repeating unit represented by the above formula (7), and X in the above formula (7) is selected from the group consisting of the valence represented by the above formula (9) And a divalent organic group in the group consisting of the divalent group represented by the above formula (10).
By formulating a sulfur-containing compound in the photosensitive resin composition, a photosensitive resin composition capable of forming a cured film in which voids at the interface with the Cu layer after the high-temperature storage test are suppressed can be obtained.
(B) The sulfur-containing compound is an organic compound having sulfur, preferably sulfur and nitrogen, and sulfur is preferably contained in the form of an atom forming a ring structure or a thiocarbonyl group.
As the compound which can be used as the (B) sulfur-containing compound, sulfur is contained in the form of one of the atoms forming the 5-membered ring structure, and examples thereof include thiazole, 2-aminothiazole, and 2-(4-thiazolyl)benzene. Imidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione And benzothiazole, 2-aminobenzothiazole, etc., and the sulfur is contained in the form of an atom forming one of the 6-membered ring structures, and examples thereof include thiophenone and N-methylmorphothiquinone. The form of the carbonyl group contains sulfur, and examples thereof include: rhodamine, N-allyl rhodamine, diethyl thiourea, dibutyl thiourea, dicyclohexyl thiourea, diphenyl thiourea, 2- Thiourea, 4-thiouracil, 2,4-dimercaptopyrimidine, 2-9-oxothiopurine 2-mercapto-4(3H)-quinazolinone or the like. Among these, it is preferred to use a compound having a thiourea structure.
The blending amount of the (B) sulfur-containing compound is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the (A) resin. From the viewpoint of migration resistance, it is preferably 0.01 parts by mass or more, and from the viewpoint of solubility, it is preferably less than 10 parts by mass.
Sulfur-containing compounds, especially thioureas, can be coordinated to copper by a sulfur atom. Thereby, the state of the copper surface is changed, and copper migration is inhibited in the high temperature storage test.
(state C)
In another aspect of the embodiment, (B) at least one compound selected from the group consisting of the following general formulae (B-1), (B-2), and (B-3) may be used instead of the above (B). a cyclic compound of a carbonyl group. More specifically,
Provided is a photosensitive resin composition comprising
(A) selected from the group consisting of polyaminic acid, polyglycolate, polyamidate, polyhydroxy guanamine, polyamine amide, polyamine, polyamidimide, polyimine, poly a benzoxazole, and at least one resin selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass,
(B) selected from
The following general formula (B-1):
[化88]

{式,R _Q1 An organic group having 1 to 10 carbon atoms formed by a carbon atom, a hydrogen atom, a nitrogen atom or an oxygen atom,
The following general formula (B-2):
[化89]

{式,R _Q2 , R _Q3 And an organic group selected from a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and ll represents an integer selected from 1 to 10, and
The following general formula (B-3):
[化90]

{式,R _Q4 , R _Q5 Respectively, an organic group selected from a hydroxyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, X _S a hydrocarbon group having a carbon number of from 1 to 10, wherein m and nn represent at least one compound selected from the group consisting of an integer of from 1 to 10, in an amount of from 0.01 to 10 parts by mass based on 100 parts by mass of the above (A) resin, and
(C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin.
In this aspect, the (A) resin is preferably selected from the group consisting of the polyimine precursor containing the above formula (1), the polyamine containing the above formula (4), and the above formula (5). The polycarbazole precursor, at least one of the group consisting of the polyimine of the above formula (6), and a group consisting of a novolac, a polyhydroxystyrene, and a phenol resin containing the above formula (7).
Further, it is preferable that the photosensitive resin composition contains a phenol resin having a repeating unit represented by the above formula (7), and X in the above formula (7) is selected from the group consisting of the valence represented by the above formula (9) And a divalent organic group in the group consisting of the divalent group represented by the above formula (10).
(B) a compound represented by the formula (B-1), (B-2) and (B-3), preferably a compound represented by (B-1) by a nitrogen atom or an oxygen atom and copper The surface interacts and changes the surface state of the copper. Therefore, copper migration is inhibited during the high temperature storage test.
(B-1) is an organic compound formed of a carbon atom, a hydrogen atom, a nitrogen atom or an oxygen atom having a ureido group, and examples thereof include methyl urea, ethyl urea, butyl urea, and phenyl group. Urea, hydroxyethyl urea, beta-urea, allantoin, citrulline, etc. and mixtures thereof.
(B-2) is a polycondensate of ethylene glycol or a terminal etherified body thereof, and examples thereof include diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutylate. Ether, triethylene glycol, triethylene glycol monoethyl ether, triethylene glycol diethyl ether, tetraethylene glycol, tetraethylene glycol dimethyl ether, and the like, and mixtures thereof.
Further, (B-3) is an alkoxy polyethylene oxide ester or an alkoxyethyl ester of a dicarboxylic acid, and examples thereof include bis(2-methoxyethyl) adipate and Bis(2-butoxyethyl) dicarboxylate, bis(2-ethoxyethyl) sebacate, and the like, and mixtures thereof.
The (B) is selected from at least one of the compounds of the formulae (B-1), (B-2) and (B-3), and the compound represented by the formula (B-1) can be preferably used. .
The blending amount of (B) at least one compound selected from the group consisting of the general formulae (B-1), (B-2) and (B-3) is preferably 0.01 to 10 with respect to 100 parts by mass of the (A) resin. The mass part is more preferably 0.05 to 2 parts by mass. From the viewpoint of the migration resistance, it is preferably 0.01 parts by mass or more, and more preferably 10 parts by mass or less from the viewpoint of solubility.
(state D)
In another aspect of the present embodiment, (B) an aromatic amine compound, that is, an aniline derivative represented by the following formula (I), or a triazole represented by the following formula (II), can be used. At least one of the group consisting of the derivative and the triazole derivative represented by the following formula (III) is substituted for the above (B) cyclic compound having a carbonyl group. More specifically,
Provided is a photosensitive resin composition comprising
(A) selected from the group consisting of polyaminic acid, polyglycolate, polyamidate, polyhydroxyguanamine, polyamine amide, polyamine, polyamidimide, polyimine, and At least one resin of the group consisting of polybenzoxazole: 100 parts by mass,
(B) an aromatic amine compound, that is, the following formula (I):
[化91]

{Ra1 to Ra5, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group, and Ra6 to Ra7 may be the same. Further, it may be a hydrogen atom or a saturated hydrocarbon group having an alkyl number of 1 or more and 5 or less, an unsaturated hydrocarbon group, or an aromatic group.
The aniline derivative represented by the formula or the following formula (II):
[化92]

{Ra8 to Ra10, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group}
The represented triazole derivative or the following formula (III):
[化93]

{R11 to R13, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group}
At least one of the triazole derivatives represented: 0.01 to 15 parts by mass based on 100 parts by mass of the above (A) resin, and
(C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin.
In this aspect, the (A) resin is preferably selected from the group consisting of the polyimine precursor containing the above formula (1), the polyamine containing the above formula (4), and the above formula (5). At least one of a polycarbazole precursor and a group consisting of the polyimine of the above formula (6).
In the aspect of using the (B) aromatic amine compound, as the photosensitive resin, polyglycine, polyamidate, polyamidate, polyhydroxyguanamine, polyamine amide, polyfluorene can be used. An amine, a polyamidimide, a polyimine, and a polybenzoxazole. Among them, in terms of heat resistance and mechanical properties of the resin after heat treatment, it is preferred to use polyglycolic acid or polybenzazole. Amine esters, polyamidates, polyamines, polyhydroxyguanamines, polyimine resins, preferably polyimine precursors, polyimine resins.
By using the (B) aromatic amine compound, it is possible to suppress the occurrence of voids at the interface between the re-wiring Cu layer and the resin layer after the high-temperature storage test. The reason for this has not been determined, and it is considered that the reaction of the active Cu is blocked by the coordination of the elemental electron pair of the aromatic amine compound with the Cu element on the surface of the Cu layer, thereby suppressing the generation of voids.
As the (B) aromatic amine compound, the following general formula (I) can be preferably used:
[化94]

{Ra1 to Ra5, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group, and Ra6 to Ra7 may be the same. The aniline derivative represented by a saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic group having a hydrogen atom or an integer of 1 or more and 5 or less may be used.
As an example of a compound which is suitably used among the aniline derivatives represented by the formula (I), N-phenylbenzylamine, salicylide, naphthol AS, 2-acetamidoxime, Paclitaxel, N-allyl aniline, N-methylaniline, N-ethylaniline, porphyrin, N-n-butylaniline, 2-anilinoethanol, 4-methoxyacetanilide, Ethyl acetanilide, 1,2,3,4-tetrahydroquinoline, tert-butylphenyl carbamic acid, tert-butyl (3-hydroxyphenyl)carbamate, oxalic anilide, N,N'-diphenylethane-1,2-diamine and the like. Among them, N-phenylbenzylamine ((B)-1), N,N'-diphenylethane-1,2-diamine ((B)-2), amide formic acid can be preferably used. Ternyl butyl phenyl ester ((B)-3), (3-hydroxyphenyl) carbamic acid tert-butyl ester ((B)-4).
[化95]

[化96]

[化97]

[化98]

As the (B) triazole derivative, the following general formula (II) can be preferably used:
[化99]

{Ra8 to Ra10, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group}
The represented triazole derivative or the following formula (III):
[化100]

{Ra11 to Ra13, respectively, may be the same or different, and are a hydrogen atom or a hydroxyl group, or a saturated hydrocarbon group having an alkyl number of 1 or more and 15 or less, an unsaturated hydrocarbon group, an aromatic group or an amidino group}
The triazole derivative represented.
As a specific compound example of the triazole derivative represented by the above formula (II), benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 5-methyl group can be preferably used. -1H-benzotriazole, 1H-1,2,3-triazole, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (ADEKA Co., Ltd. Manufacture, Adekastab CDA-1), 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2- Phenol (made by ADEKA Co., Ltd., Adekastab LA-29), 2-(2'-hydroxy-3',5'-di-third aminophenyl)benzotriazole, 2-(2'-hydroxyl -5'-methylphenyl)benzotriazole. Among them, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide ((B)-5), 2-(2H-benzo[d] can be especially preferably used. ][1,2,3]Triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol ((B)-6).
[化101]

[化102]

As a specific compound example of the triazole derivative represented by the above formula (III), (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol can be preferably used. , trimethoxazole, 1,2,4-1H-triazole, triapenthenol, bitertanol, 4-(1H-1,2,4-triazol-1-yl)benzaldehyde , 4-(1H-1,2,4-triazol-1-yl)benzoic acid, 3-(1H-1,2,4-triazol-1-ylmethyl)benzoic acid, 4-[(1H -1,2,4-triazol-1-ylmethyl)phenyl]methanol, 3-(1H-1,2,4-triazol-1-yl)benzaldehyde, 3-(1H-1,2 , 4-triazol-1-ylmethyl)benzaldehyde, 3-(1H-1,2,4-triazol-1-yl)benzoic acid, 2-(1H-1,2,4-triazole- 1-Base) Aniline. Among them, (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol ((B)-7)) can be especially preferably used.
[化103]

(B) The aromatic amine compound is preferably a secondary amine which is an amine atom constituting the aniline derivative or the triazole derivative in terms of the coordination ability with the Cu element.
The content of the (B) aromatic amine compound is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 1 to 8 parts by mass, per 100 parts by mass of the resin (A). If the content is more than the above range, the storage stability is lowered, which is not preferable, and if the content is less than the above range, voids are likely to occur between the copper surface and the copper surface.
<Method of Manufacturing Hardened Emboss Pattern and Semiconductor Device>
Moreover, the present invention provides a method for producing a cured embossed pattern, comprising: (1) a step of forming a resin layer on the substrate by applying the photosensitive resin composition of the present invention on the substrate; (2) a step of exposing the resin layer; (3) developing the exposed resin layer to form a embossed pattern; and (4) forming a hardened embossed pattern by heat-treating the embossed pattern . The typical aspects of each step are explained below.
(1) a step of forming a resin layer on the substrate by coating a photosensitive resin composition on the substrate
In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and if necessary, dried to form a resin layer. As the coating method, a method previously applied for coating a photosensitive resin composition, for example, a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, or the like can be used. A method of applying the coating, a method of spraying by a spray coater, and the like.
The coating film containing the photosensitive resin composition can be dried as needed. As the drying method, air drying, heating drying by an oven or a hot plate, vacuum drying, or the like can be employed. Specifically, in the case of air drying or heat drying, drying can be carried out at 20 ° C to 140 ° C for 1 minute to 1 hour. The resin layer can be formed on the substrate by the above method.
(2) Step of exposing the resin layer
In this step, using an exposure device such as a contact exposure machine, a mirror projection exposure machine, a stepper, or the like, the photomask or the reticle is interposed, or directly by an ultraviolet light source or the like. The formed resin layer is exposed.
Thereafter, in order to improve the light sensitivity and the like, post-exposure baking (PEB) and/or pre-development baking under the conditions of any combination of temperature and time may be carried out as needed. The range of the baking conditions is preferably 40 to 120 ° C and time: 10 seconds to 240 seconds, but is not limited to this range as long as the characteristics of the photosensitive resin composition of the present invention are not impaired.
(3) Step of developing the exposed resin layer to form an embossed pattern
In this step, the exposed portion or the unexposed portion of the photosensitive resin layer after the exposure is developed and removed. When a negative photosensitive resin composition is used (for example, when a polyimide precursor or polyamine is used as the (A) resin), the unexposed portion is developed and removed, and a positive photosensitive resin is used. In the case of the composition (for example, when a polycarbazole precursor or a soluble polyimine is used as the (A) resin), the exposed portion is developed and removed. As the developing method, any method can be selected from a conventionally known developing method of a resist, for example, a rotary spray method, a liquid coating method, a dipping method accompanied by ultrasonic treatment, or the like. Further, after development, in order to adjust the shape of the embossed pattern, etc., post-development baking under the conditions of any combination of temperature and time may be carried out as needed.
The developer to be used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. For example, in the case of a photosensitive resin composition which is insoluble in an aqueous alkaline solution, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethyl group is preferred. Ethylamine, cyclopentanone, cyclohexanone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, etc., as a poor solvent, preferably toluene, xylene, methanol, ethanol, isopropanol Ethyl lactate, propylene glycol methyl ether acetate, water, and the like. In the case where a good solvent is used in combination with a poor solvent, it is preferred to adjust the ratio of the poor solvent to the good solvent in accordance with the solubility of the polymer in the photosensitive resin composition. Further, two or more kinds of solvents, for example, a plurality of solvents may be used in combination.
On the other hand, in the case of a photosensitive resin composition dissolved in an aqueous alkaline solution, the developing solution used for development dissolves the alkaline aqueous solution soluble polymer, typically alkaline dissolved in a basic compound. Aqueous solution. The basic compound dissolved in the developer may be any of an inorganic basic compound or an organic basic compound.
Examples of the inorganic basic compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium niobate, sodium citrate, and potassium citrate. Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.
Further, examples of the organic basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, and monoethylamine. , diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.
Further, a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, and a dissolution inhibitor of the resin may be added to the alkaline aqueous solution as needed. The embossed pattern can be formed by the above method.
(4) Step of forming a hardened embossed pattern by heat-treating the embossed pattern
In this step, the embossed pattern obtained by the above development is heated to be converted into a hardened embossed pattern. As a method of heat-hardening, various methods, such as a heating plate, an oven, and a temperature-increasing oven which can set a temperature control program, can be selected. The heating can be carried out, for example, at 180 ° C to 400 ° C for 30 minutes to 5 hours. As the ambient gas during heat curing, air may be used, and an inert gas such as nitrogen or argon may be used.
<semiconductor device>
The present invention also provides a semiconductor device comprising the hardened embossed pattern obtained by the above-described method for producing a cured embossed pattern of the present invention. The present invention also provides a semiconductor device comprising a substrate as a semiconductor element and a cured embossed pattern of a resin formed on the substrate by the method of manufacturing the cured embossed pattern. Further, the present invention is also applicable to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and a method of manufacturing the above-described hardened embossed 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 protective film formed by the above-described method for producing a cured embossed pattern. A protective film or the like of a semiconductor device having a bump structure is produced in combination with a known method of manufacturing a semiconductor device.
The photosensitive resin composition of the present invention can be applied to a semiconductor device in addition to the above, and can also be used for interlayer insulation of a multilayer circuit, a protective coating for a flexible copper plate, a solder resist film, and a liquid crystal alignment film.
Further, the above aspects A to M are separately described, but the present invention also includes combinations of the various aspects.
[Examples]
Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.
(1) Weight average molecular weight
The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the brand name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene is selected from the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko Co., Ltd. The solvent was N-methyl-2-pyrrolidone, and the detector was sold under the trade name "Shodex RI-930" manufactured by Showa Denko Co., Ltd.
(2) Fabrication of hardened embossed pattern on Cu
Sputtering 200 nm thick Ti on a 6-inch wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Co., Ltd.) , 400 nm thick Cu. Then, using a Coater Developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.), the photosensitive resin composition prepared by the following method was spin-coated on the wafer and dried to form a photosensitive resin composition. A film thickness of 6 to 10 μm. Using a photomask with a test pattern, a parallel light mask was used to align the exposure machine (PLA-501FA type, manufactured by Canon), and the coating film was irradiated at 300 mJ/cm. ² Energy. Then, in the case of a negative type, cyclopentanone was used as a developing solution, and in the case of a positive type, 2.38% TMAH (tetramethylammonium hydroxide, tetramethylammonium hydroxide) was used as a developing solution, and a coating developing device (D-Spin 60A) was used. The coating film was spray-developed, and was washed with propylene glycol methyl ether acetate in the case of a negative type, and rinsed with pure water in the case of a positive type, thereby obtaining an embossing on Cu. pattern.
Using a temperature-programming type curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.), the wafer on which the embossed pattern was formed on Cu was heat-treated for 2 hours under the nitrogen atmosphere at the temperatures described in the examples. Thereby, a hardened relief pattern comprising a resin having a thickness of about 6 to 7 μm is obtained on Cu.
(3) High temperature storage test of hardened relief pattern on Cu and subsequent evaluation
The wafer on which the hardened relief pattern was formed on Cu was heated in air at 150 ° C for 168 hours using a temperature-programming type curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.). Then, using a plasma surface treatment apparatus (EXAM type, manufactured by Shenkang Seiki Co., Ltd.), all the resin layers on Cu were removed by plasma etching. The plasma etching conditions are as follows.
Output: 133 W
Gas type, flow rate: O ₂ :40 ml/min+CF ₄ :1 ml/min
Gas pressure: 50 Pa
Mode: hard mode
Etching time: 1800 seconds
The surface of the Cu which was completely removed by the resin layer was observed by FE-SEM (Field Emission Scanning Electron Microscope) (S-4800, manufactured by Hitachi High-Technologies Co., Ltd.), and an image analysis software (A image) was used. Jun, manufactured by Asahi Kasei Co., Ltd., calculates the ratio of the area occupied by the void on the surface of the Cu layer.
(4) Evaluation of varnish preservation stability
The photosensitive resin compositions obtained in the examples and the comparative examples were allowed to stand in an environment of 23° C. and 50% Rh for 3 weeks, and the change in viscosity was observed.
The viscosity was measured using a TV-25 type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the viscosity at 23 ° C was measured.
○: The viscosity change rate (described below) of the composition after standing was within 10%.
×: The viscosity change rate of the composition after standing was more than 10%.
Viscosity change rate (%) = {(initial viscosity) - (after leaving the viscosity) absolute value} × 100 / (initial viscosity)
Example A
<Production Example A1> ((A) Synthesis of Polymer A as Polyimine Precursor)
In a separable flask with a volume of 2 L, put 5,4'-oxydiphthalic dianhydride (ODPA) 155.1 g, add 2-hydroxyethyl methacrylate (HEMA) 131.2 g and γ-butane 400 ml of the ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
Then, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring, followed by stirring. The obtained 4,4'-diaminodiphenyl ether (DADPE) 93.0 g was suspended in γ-butyrolactone 350 ml over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction liquid was added to 3 L of ethanol to form a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.
In addition, the weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: 2 Shodex KD-806M series
Mobile phase: 0.1 mol/L LiBr/NMP (N-methylpyrrolidone, N-methylpyrrolidone)
Flow rate: 1 ml/min.
<Production Example A2> ((A) Synthesis of Polymer B as a Polyimine Precursor)
Using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of the 4,4'-oxydiphthalic dianhydride (ODPA) 155.1 g of Production Example A1, except The reaction was carried out in the same manner as in the method described in Production Example A1 except that the polymer B was obtained. The molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.
<Production Example A3> ((A) Synthesis of Polymer C as Polyimine Precursor)
Using 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g instead of the 4,4'-diaminodiphenyl ether (DADPE) 93.0 g of Production Example A1, Other than this, the reaction was carried out in the same manner as in the above-described Production Example A1 to obtain a polymer C. The molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.
<Production Example A4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound end-capped body AIPA-MO)
5-Aminoisophthalic acid (hereinafter abbreviated as AIPA) 543.5 g and N-methyl-2-pyrrolidone 1700 g were placed in a separable flask having a volume of 5 L, and the mixture was stirred and heated by a water bath. 50 ° C. The solution was prepared by dropwise addition of 512.0 g (3.3 mol) of 2-methylpropenyloxyethyl isocyanate to gamma-butyrolactone 500 g by using a dropping funnel, and stirring at 50 ° C for about 2 hours. .
The reaction was completed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC) (5-aminoisophthalic acid disappeared), and then the reaction solution was poured into 15 L of ion-exchanged water and stirred. After standing, the crystallized precipitate of the reaction product is formed, and then filtered and separated, and after appropriate washing with water, vacuum drying at 40 ° C for 48 hours, thereby obtaining an amine group and an isocyanate from 5-aminoisophthalic acid. AIPA-MO obtained by the isocyanate action of 2-methylpropenyloxyethyl ester. The low molecular weight GPC of the obtained AIPA-MO is about 100% pure.
(Synthesis of Polymer D)
The obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), GBL (butyrolactone, γ-butyrolactone) 400 g were mixed in a separable flask of 2 L, and mixed. Cool to 5 ° C in an ice bath. Under ice cooling, the dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) was dissolved and diluted in GBL 125 g over a period of about 20 minutes, and then it was added dropwise over 20 minutes. 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in NMP 168 g, maintained in ice bath for 3 hours and not reached 5 ° C, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
A mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in NMP 650 g. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer E). The molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.
<Production Example A5> ((A) Synthesis of Polymer E as Polycarbazole Precursor)
2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1 g, N,N-dimethylacetamide (DMAc) 640.9 g in a separable flask of 3 L The pyridine 63.3 g was mixed and stirred at room temperature (25 ° C) to prepare a homogeneous solution. A solution obtained by dissolving 118.0 g of 4,4'-diphenylether dimethyl hydrazine chloride (DMDG) 354 g was added dropwise thereto using a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 °C. The time required for the dropping was 40 minutes, and the temperature of the reaction liquid was at most 30 °C.
Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture, and the mixture was stirred at room temperature for 15 hours to give a total of 99% of the polymer chain. The terminal group is terminated by a carboxycyclohexylamine group. The reaction rate at this time can be easily calculated by tracking the residual amount of the 1,2-cyclohexyldicarboxylic anhydride charged by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dried, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) as measured by the method.
After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is put into ion-exchanged water. The precipitated polymer was separated by filtration, washed with water and dried in vacuo to obtain a purified polybenzoxazole precursor (Polymer E).
<Production Example A6> ((A) Synthesis of Polymer F as Polyimine)
A glass-separable four-necked flask equipped with a Teflon (registered trademark) anchor type agitator was equipped with a cooling tube attached to a Dean-Stark separator. The flask was immersed in an oil bath while stirring with nitrogen gas.
2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-di-side oxytetrahydrogen) -3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60 g of toluene, and stirred at 100 rpm for 4 hours at room temperature, and then added 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was stirred while stirring at a bath temperature of 50 ° C for 10 hours at 100 rpm. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred at 100 rpm for 2 hours. The toluene and water distilled in the reaction were removed. After the imidization reaction, the reaction was returned to room temperature.
Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polyimine (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) as measured by the method.
<Production Example A7> ((A) Synthesis of Polymer G as a Phenolic Resin)
Methyl 3,5-dihydroxybenzoate 128.3 g (0.76 mol), 4,4'-bis(methoxymethyl) in a separable flask with a volume of 0.5 L in a Dean-Stark apparatus Biphenyl (hereinafter also referred to as "BMMB") 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), diethylene glycol dimethyl ether 140 g mixed at 70 ° C, and the solid matter Dissolved.
The mixed solution was heated to 140 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred directly at 140 ° C for 2 hours.
Then, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was additionally added thereto and stirred. The reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a 3,5-dihydroxy group in a yield of 70%. Copolymer of methyl benzoate/BMMB (Polymer G). The weight average molecular weight of the polymer G obtained by standard polystyrene conversion by the GPC method was 21,000.
<Production Example A8> ((A) Synthesis of Polymer H as a Phenolic Resin)
A 1.0 L volume separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, after which resorcinol 81.3 g (0.738 mol) and BMMB 84.8 g (0.35 mol) were placed in the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C to dissolve the solid matter.
The mixed solution was heated to 120 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred at 120 ° C for 3 hours.
Then, 2,6-bis(hydroxymethyl)-p-cresol 24.9 g (0.150 mol) and PGME 249 g were mixed and stirred in another container to uniformly dissolve, and the obtained solution was used for the dropping funnel for a period of time. The mixture was added dropwise to the separable flask over 1 hour, and the mixture was further stirred for 2 hours.
After completion of the reaction, the same treatment as in Production Example A7 was carried out, and a copolymer (polymer H) containing resorcin/BMMB/2,6-bis(hydroxymethyl)p-cresol was obtained in a yield of 77%. The weight average molecular weight of the polymer H obtained by standard polystyrene conversion by the GPC method was 9,900.
<Example A1>
Using the polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer A 50 g and B 50 g (corresponding to (A) resin) and xanthine (corresponding to (B) a cyclic compound having a carbonyl group) as a polyimide precursor are 0.2 g, 1-phenyl- 1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1) (corresponding to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g of ester, 1.5 g of N-[3-(triethoxydecyl)propyl]phthalic acid, and dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 80 A mixed solvent of g and ethyl lactate 20 g. A negative photosensitive resin composition was prepared by further adding a small amount of the above mixed solvent to adjust the viscosity of the obtained solution to about 35 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%.
<Example A2>
In the above-mentioned Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that the amount of the scutellaria was changed to 0.05 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.4%.
<Example A3>
In the above-mentioned Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that the amount of the xanthine added was changed to 5 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%.
<Example A4>
In the above-mentioned Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that 8-aza-xanthine was used instead of xanthine as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.1%.
<Example A5>
In the above Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that uric acid was used instead of xanthine as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%.
<Example A6>
In the above Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that dioxetane was used instead of xanthine as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example A7>
In the above Example A1, a negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that barbituric acid was used instead of xanthine as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 7.3%.
<Example A8>
A negative photosensitive resin composition solution was prepared in the same manner as in the above Example A1, and the composition was cured at 350 ° C by the above method to form a hardened relief pattern on the Cu layer, and after performing a high temperature storage test, The ratio of the area occupied by the voids on the surface of the Cu layer was evaluated, and a result of 4.5% was obtained.
<Example A9>
In the above Example A1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene fluorenyl)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, in addition to the examples A negative photosensitive resin composition solution was prepared in the same manner as in A1.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.1%.
<Example A10>
In the above Example A1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene hydrazide)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, and further changed the solvent into γ-butane A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 except that 85 g of the ester and 15 g of dimethylhydrazine were used.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%.
<Example A11>
In the above Example A1, a negative photosensitive property was prepared in the same manner as in Example A1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer C 100 g as the resin (A). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%.
<Example A12>
In the above Example A1, a negative photosensitive property was prepared in the same manner as in Example A1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer D 100 g as the resin (A). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.0%.
<Example A13>
Using the polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer E 100 g (corresponding to (A) resin) as a polycarbazole precursor and the following formula (96):
[化104]

A photosensitive diazonium compound represented by 77% of a phenolic hydroxyl group via naphthoquinonediazide-4-sulfonate (manufactured by Toyo Seisakusho Co., Ltd., equivalent to (C) sensitizer) (C1) 20 g, yellow嘌呤 (corresponding to (B) a cyclic compound having a carbonyl group) 0.2 g, 3-tributoxycarbonylaminopropyltriethoxydecane 6 g, and dissolved in γ-butyrolactone (as a solvent) 100 g. The positive photosensitive resin composition was prepared by further adding a small amount of γ-butyrolactone to adjust the viscosity of the obtained solution to about 20 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example A14>
In the above Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13 except that the polymer E 100 g was changed to the polymer F 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%.
<Example A15>
In the above Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13 except that the polymer E 100 g was changed to the polymer G 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.3%.
<Example A16>
In the above Example A13, a positive photosensitive resin composition solution was prepared in the same manner as in Example A13 except that the polymer E 100 g was changed to the polymer H 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.2%.
<Comparative Example A1>
In the same manner as in Example A1, a negative photosensitive resin composition was prepared in the same manner as in Example A1 except that 0.2 g of benzotriazole was added instead of 0.2 g of xanthine, and the same procedure as in Example A1 was carried out. Evaluation. Since the compound of the present invention (B) was not contained, the evaluation result was 15.2%.
<Comparative Example A2>
In the composition of Example A1, a negative photosensitive resin composition was prepared in the same manner as in Example A1 except that xanthine was not added, and the same evaluation as in Example A1 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 14.3%.
<Comparative Example A3>
In the composition of Example A10, a negative photosensitive resin composition was prepared in the same manner as in Example A10 except that xanthine was not added, and the same evaluation as in Example A10 was carried out. Since the compound of the present invention (B) was not contained, the evaluation result was 15.7%.
<Comparative Example A4>
In the composition of Example A11, a negative photosensitive resin composition was prepared in the same manner as in Example A11 except that xanthine was not added, and the same evaluation as in Example A11 was carried out. Since the compound of the present invention (B) was not contained, the evaluation result was 14.9%.
The results of the above Examples A1 to 16 and Comparative Examples A1 to 4 are collectively shown in Table 1.
Example B
<Production Example B1> ((A) Synthesis of Polymer A as Polyimine Precursor)
In a separable flask with a volume of 2 L, put 5,4'-oxydiphthalic dianhydride (ODPA) 155.1 g, add 2-hydroxyethyl methacrylate (HEMA) 131.2 g and γ-butane 400 ml of the ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
Then, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring, followed by stirring. The obtained 4,4'-diaminodiphenyl ether (DADPE) 93.0 g was suspended in γ-butyrolactone 350 ml over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction liquid was added to 3 L of ethanol to form a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.
In addition, the weight average molecular weight of the resin obtained in each Production Example B was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: 2 Shodex KD-806M series
Mobile phase: 0.1 mol/L LiBr/NMP
Flow rate: 1 ml/min.
<Production Example B2> ((A) Synthesis of Polymer B as a Polyimine Precursor)
Using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example B1, except The reaction was carried out in the same manner as in the method described in Production Example B1 except that the polymer B was obtained. The molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.
<Production Example B3> ((A) Synthesis of Polymer C as Polyimine Precursor)
Using 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g instead of the 4,4'-diaminodiphenyl ether (DADPE) of Production Example B1, 93.0 g, Other than this, the reaction was carried out in the same manner as in the above-described Production Example B1 to obtain a polymer C. The molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.
<Production Example B4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound end-capped body AIPA-MO)
5-Aminoisophthalic acid (hereinafter abbreviated as AIPA) 543.5 g and N-methyl-2-pyrrolidone 1700 g were placed in a separable flask having a volume of 5 L, and the mixture was stirred and heated by a water bath. 50 ° C. The solution was prepared by dropwise addition of 512.0 g (3.3 mol) of 2-methylpropenyloxyethyl isocyanate to gamma-butyrolactone 500 g by using a dropping funnel, and stirring at 50 ° C for about 2 hours. .
The reaction was completed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC) (5-aminoisophthalic acid disappeared), and then the reaction solution was poured into 15 L of ion-exchanged water and stirred. After standing, the crystallized precipitate of the reaction product is formed, and then filtered and separated, and after appropriate washing with water, vacuum drying at 40 ° C for 48 hours, thereby obtaining an amine group and an isocyanate from 5-aminoisophthalic acid. AIPA-MO obtained by the isocyanate action of 2-methylpropenyloxyethyl ester. The low molecular weight GPC of the obtained AIPA-MO is about 100% pure.
(Synthesis of Polymer D)
The obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), GBL 400 g were placed in a separable flask having a volume of 2 L, and mixed, and cooled to 5 ° C by an ice bath. Under ice cooling, the dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) was dissolved and diluted in GBL 125 g over a period of about 20 minutes, and then it was added dropwise over 20 minutes. 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in NMP 168 g, maintained in ice bath for 3 hours and not reached 5 ° C, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
A mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in NMP 650 g. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer E). The molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.
<Production Example B5> ((A) Synthesis of Polymer E as Polycarbazole Precursor)
2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1 g, N,N-dimethylacetamide (DMAc) 640.9 g in a separable flask of 3 L The pyridine 63.3 g was mixed and stirred at room temperature (25 ° C) to prepare a homogeneous solution. A solution obtained by dissolving 118.0 g of 4,4'-diphenylether dimethyl hydrazine chloride (DMDG) 354 g was added dropwise thereto using a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 °C. The time required for the dropping was 40 minutes, and the temperature of the reaction liquid was at most 30 °C.
Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture, and the mixture was stirred at room temperature for 15 hours to give a total of 99% of the polymer chain. The terminal group is terminated by a carboxycyclohexylamine group. The reaction rate at this time can be easily calculated by tracking the residual amount of the 1,2-cyclohexyldicarboxylic anhydride charged by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dried, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) as measured by the method.
After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is put into ion-exchanged water. The precipitated polymer was separated by filtration, washed with water and dried in vacuo to obtain a purified polybenzoxazole precursor (Polymer E).
<Production Example B6> ((A) Synthesis of Polymer F as Polyimine)
A glass-separable four-necked flask equipped with a Teflon (registered trademark) anchor type agitator was equipped with a cooling tube attached to a Dean-Stark separator. The flask was immersed in an oil bath while stirring with nitrogen gas.
2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-di-side oxytetrahydrogen) -3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60 g of toluene, and stirred at 100 rpm for 4 hours at room temperature, and then added 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was stirred while stirring at a bath temperature of 50 ° C for 10 hours at 100 rpm. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred at 100 rpm for 2 hours. The toluene and water distilled in the reaction were removed. After the imidization reaction, the reaction was returned to room temperature.
Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polyimine (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) as measured by the method.
<Production Example B7> ((A) Synthesis of Polymer G as a Phenolic Resin)
Methyl 3,5-dihydroxybenzoate 128.3 g (0.76 mol), 4,4'-bis(methoxymethyl) in a separable flask with a volume of 0.5 L in a Dean-Stark apparatus Biphenyl (hereinafter also referred to as "BMMB") 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), diethylene glycol dimethyl ether 140 g mixed at 70 ° C, and the solid matter Dissolved.
The mixed solution was heated to 140 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred directly at 140 ° C for 2 hours.
Then, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was additionally added thereto and stirred. The reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a 3,5-dihydroxy group in a yield of 70%. Copolymer of methyl benzoate/BMMB (Polymer G). The weight average molecular weight of the polymer G obtained by standard polystyrene conversion by the GPC method was 21,000.
<Production Example B8> ((A) Synthesis of Polymer H as a Phenolic Resin)
A 1.0 L volume separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, after which resorcinol 81.3 g (0.738 mol) and BMMB 84.8 g (0.35 mol) were placed in the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C to dissolve the solid matter.
The mixed solution was heated to 120 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred at 120 ° C for 3 hours.
Then, 2,6-bis(hydroxymethyl)-p-cresol 24.9 g (0.150 mol) and PGME 249 g were mixed and stirred in another container to uniformly dissolve, and the obtained solution was used for the dropping funnel for a period of time. The mixture was added dropwise to the separable flask over 1 hour, and the mixture was further stirred for 2 hours.
After completion of the reaction, the same treatment as in Production Example B7 was carried out, and a copolymer (polymer H) containing resorcin/BMMB/2,6-bis(hydroxymethyl)p-cresol was obtained in a yield of 77%. The weight average molecular weight of the polymer H obtained by standard polystyrene conversion by the GPC method was 9,900.
<Example B1>
Using the polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A 50 g and B 50 g (corresponding to (A) resin) and dicyclohexyl thiourea (corresponding to (B) sulfur-containing compound) 0.5 g, 1-phenyl- as a polyimide precursor 1,2-propanedione-2-(O-ethoxycarbonyl)-hydrazine (denoted as "PDO" in Table 2) (corresponding to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g of ester, 1.5 g of N-[3-(triethoxydecyl)propyl]phthalic acid, and dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 80 A mixed solvent of g and ethyl lactate 20 g. A negative photosensitive resin composition was prepared by further adding a small amount of the above mixed solvent to adjust the viscosity of the obtained solution to about 35 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example B2>
In the above Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that the amount of the dicyclohexylthiourea added was changed to 0.1 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.9%.
<Example B3>
In the above Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that the amount of the dicyclohexylthiourea added was changed to 4 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%.
<Example B4>
In the above Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that benzothiazole was used instead of dicyclohexylthiourea as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 7.3%.
<Example B5>
In the above Example B1, a negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that the component (B) was used instead of dicyclohexylthiourea.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 7.2%.
<Example B6>
In the above Example B1, as the component (B), 2-9-oxythiolane was used. A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that instead of dicyclohexylthiourea.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 7.3%.
<Example B7>
A negative photosensitive resin composition solution was prepared in the same manner as in the above Example B1, and a hardened relief pattern was formed on the Cu layer by curing at 350 ° C by the above method, and after performing a high temperature storage test, The ratio of the area occupied by the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%.
<Example B8>
In the above Example B1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene fluorenyl)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, in addition to the examples A negative photosensitive resin composition solution was prepared in the same manner as in B1.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%.
<Example B9>
In the above Example B1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene hydrazide)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, and further changed the solvent into γ-butane A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 except that 85 g of the ester and 15 g of dimethylhydrazine were used.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.6%.
<Example B10>
In the above Example B1, a negative photosensitive property was prepared in the same manner as in Example B1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer C 100 g as the resin (A). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%.
<Example B11>
In the above Example B1, a negative photosensitive property was prepared in the same manner as in Example B1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer D 100 g as the resin (A). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.3%.
<Example B12>
Using the polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer E 100 g (corresponding to (A) resin) as a polycarbazole precursor and the following formula (96):
[化105]

Photosensitive diazonium compound (manufactured by Toyo Synka Co., Ltd., equivalent to (C) sensitizer) (C1) 15 g, two, represented by 77% of the phenolic hydroxyl group via naphthoquinonediazide-4-sulfonate Cyclohexyl thiourea (corresponding to (B) sulfur-containing compound) 0.5 g, 3-tert-butoxycarbonylaminopropyltriethoxy decane 6 g, dissolved in γ-butyrolactone (as solvent) 100 g. The positive photosensitive resin composition was prepared by further adding a small amount of γ-butyrolactone to adjust the viscosity of the obtained solution to about 20 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%.
<Example B13>
In the above Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E 100 g was changed to the polymer F 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example B14>
In the above Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E 100 g was changed to the polymer G 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.7%.
<Example B15>
In the above Example B12, a positive photosensitive resin composition solution was prepared in the same manner as in Example B12 except that the polymer E 100 g was changed to the polymer H 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.6%.
<Comparative Example B1>
A negative photosensitive resin composition was prepared in the same manner as in Example B1 except that the dicyclohexylthiourea was not added, and the same evaluation as in Example B1 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 14.3%.
<Comparative Example B2>
A negative photosensitive resin composition was prepared in the same manner as in Example B11 except that the dicyclohexylthiourea was not added, and the same evaluation as in Example B11 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 15.5%.
<Comparative Example B3>
A positive photosensitive resin composition was prepared in the same manner as in Example B12 except that the dicyclohexylthiourea was not added, and the same evaluation as in Example B12 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 14.6%.
The results of the examples B1 to 15 and the comparative examples B1 to 3 are collectively shown in Table 2.
Example C
<Production Example C1> ((A) Synthesis of Polymer A as a Polyimine Precursor)
In a separable flask with a volume of 2 L, put 5,4'-oxydiphthalic dianhydride (ODPA) 155.1 g, add 2-hydroxyethyl methacrylate (HEMA) 131.2 g and γ-butane 400 ml of the ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
Then, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring, followed by stirring. The obtained 4,4'-diaminodiphenyl ether (DADPE) 93.0 g was suspended in γ-butyrolactone 350 ml over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction liquid was added to 3 L of ethanol to form a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.
In addition, the weight average molecular weight of the resin obtained in each Production Example C was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: 2 Shodex KD-806M series
Mobile phase: 0.1 mol/L LiBr/NMP
Flow rate: 1 ml/min.
<Production Example C2> ((A) Synthesis of Polymer B as a Polyimine Precursor)
Using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example C1, except The reaction was carried out in the same manner as in the method described in the above Production Example C1 to obtain a polymer B. The molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.
<Production Example C3> ((A) Synthesis of Polymer C as Polyimine Precursor)
Using 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g instead of the 4,4'-diaminodiphenyl ether (DADPE) 93.0 g of Production Example C1, Otherwise, the reaction was carried out in the same manner as in the method described in the above Production Example C1 to obtain a polymer C. The molecular weight of the polymer C was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.
<Production Example C4> ((A) Synthesis of Polymer D as Polyamide)
(Synthesis of phthalic acid compound end-capped body AIPA-MO)
5-Aminoisophthalic acid (hereinafter abbreviated as AIPA) 543.5 g and N-methyl-2-pyrrolidone 1700 g were placed in a separable flask having a volume of 5 L, and the mixture was stirred and heated by a water bath. 50 ° C. The solution was prepared by dropwise addition of 512.0 g (3.3 mol) of 2-methylpropenyloxyethyl isocyanate to gamma-butyrolactone 500 g by using a dropping funnel, and stirring at 50 ° C for about 2 hours. .
The reaction was completed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC) (5-aminoisophthalic acid disappeared), and then the reaction solution was poured into 15 L of ion-exchanged water and stirred. After standing, the crystallized precipitate of the reaction product is formed, and then filtered and separated, and after appropriate washing with water, vacuum drying at 40 ° C for 48 hours, thereby obtaining an amine group and an isocyanate from 5-aminoisophthalic acid. AIPA-MO obtained by the isocyanate action of 2-methylpropenyloxyethyl ester. The low molecular weight GPC of the obtained AIPA-MO is about 100% pure.
(Synthesis of Polymer D)
The obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), GBL 400 g were placed in a separable flask having a volume of 2 L, and mixed, and cooled to 5 ° C by an ice bath. Under ice cooling, the dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) was dissolved and diluted in GBL 125 g over a period of about 20 minutes, and then it was added dropwise over 20 minutes. 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in NMP 168 g, maintained in ice bath for 3 hours and not reached 5 ° C, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
A mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in NMP 650 g. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer E). The molecular weight of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.
<Production Example C5> ((A) Synthesis of Polymer E as Polycarbazole Precursor)
2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1 g, N,N-dimethylacetamide (DMAc) 640.9 g in a separable flask of 3 L The pyridine 63.3 g was mixed and stirred at room temperature (25 ° C) to prepare a homogeneous solution. A solution obtained by dissolving 118.0 g of 4,4'-diphenylether dimethyl hydrazine chloride (DMDG) 354 g was added dropwise thereto using a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 °C. The time required for the dropping was 40 minutes, and the temperature of the reaction liquid was at most 30 °C.
Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture, and the mixture was stirred at room temperature for 15 hours to give a total of 99% of the polymer chain. The terminal group is terminated by a carboxycyclohexylamine group. The reaction rate at this time can be easily calculated by tracking the residual amount of the 1,2-cyclohexyldicarboxylic anhydride charged by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dried, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) as measured by the method.
After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is put into ion-exchanged water. The precipitated polymer was separated by filtration, washed with water and dried in vacuo to obtain a purified polybenzoxazole precursor (Polymer E).
<Production Example C6> ((A) Synthesis of Polymer F as Polyimine)
A glass-separable four-necked flask equipped with a Teflon (registered trademark) anchor type agitator was equipped with a cooling tube attached to a Dean-Stark separator. The flask was immersed in an oil bath while stirring with nitrogen gas.
2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-di-side oxytetrahydrogen) -3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60 g of toluene, and stirred at 100 rpm for 4 hours at room temperature, and then added 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was stirred while stirring at a bath temperature of 50 ° C for 10 hours at 100 rpm. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred at 100 rpm for 2 hours. The toluene and water distilled in the reaction were removed. After the imidization reaction, the reaction was returned to room temperature.
Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polyimine (polymer F) having a weight average molecular weight of 23,000 (in terms of polystyrene) as measured by the method.
<Production Example C7> ((A) Synthesis of Polymer G as a Phenolic Resin)
Methyl 3,5-dihydroxybenzoate 128.3 g (0.76 mol), 4,4'-bis(methoxymethyl) in a separable flask with a volume of 0.5 L in a Dean-Stark apparatus Biphenyl (hereinafter also referred to as "BMMB") 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), diethylene glycol dimethyl ether 140 g mixed at 70 ° C, and the solid matter Dissolved.
The mixed solution was heated to 140 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred directly at 140 ° C for 2 hours.
Then, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was additionally added thereto and stirred. The reaction diluent was added dropwise to 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a 3,5-dihydroxy group in a yield of 70%. Copolymer of methyl benzoate/BMMB (Polymer G). The weight average molecular weight of the polymer G obtained by standard polystyrene conversion by the GPC method was 21,000.
<Production Example C8> ((A) Synthesis of Polymer H as a Phenolic Resin)
A 1.0 L volume separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, after which resorcinol 81.3 g (0.738 mol) and BMMB 84.8 g (0.35 mol) were placed in the separable flask. ), 3.81 g (0.02 mol) of p-toluenesulfonic acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C to dissolve the solid matter.
The mixed solution was heated to 120 ° C by an oil bath, and it was confirmed that methanol was formed from the reaction liquid. The reaction solution was stirred at 120 ° C for 3 hours.
Then, 2,6-bis(hydroxymethyl)-p-cresol 24.9 g (0.150 mol) and PGME 249 g were mixed and stirred in another container to uniformly dissolve, and the obtained solution was used for the dropping funnel for a period of time. The mixture was added dropwise to the separable flask over 1 hour, and the mixture was further stirred for 2 hours.
After completion of the reaction, the same treatment as in Production Example C7 was carried out, and a copolymer (polymer H) containing resorcin/BMMB/2,6-bis(hydroxymethyl)p-cresol was obtained in a yield of 77%. The weight average molecular weight of the polymer H obtained by standard polystyrene conversion by the GPC method was 9,900.
<Example C1>
Using the polymers A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A 50 g and B 50 g (corresponding to (A) resin) and butyl urea (corresponding to (B-1) compound) 1 g, 1-phenyl-1, as a polyimide precursor. 2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 3) (corresponding to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxydecyl)propyl]phthalic acid 1.5 g is dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 80 g and A mixed solvent of 20 g of ethyl lactate. A negative photosensitive resin composition was prepared by further adding a small amount of the above mixed solvent to adjust the viscosity of the obtained solution to about 35 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example C2>
In the above-mentioned Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that the amount of the butyl urea added was changed to 0.1 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.8%.
<Example C3>
In the above-mentioned Example C1, a negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that the amount of the butyl urea added was changed to 5 g as the component (B).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%.
<Example C4>
In the above Example C1, negative photosensitiveness was prepared in the same manner as in Example C1 except that tetraethylene glycol (corresponding to (B-2) compound) was used as the component (B) instead of butyl urea. Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.2%.
<Example C5>
In the above Example C1, as the component (B), bis(2-methoxyethyl) adipate (corresponding to the compound of (B-3)) was used instead of butyl urea, and other examples were carried out. A negative photosensitive resin composition solution was prepared in the same manner as in Example C1.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.3%.
<Example C6>
A negative photosensitive resin composition solution was prepared in the same manner as in the above Example C1, and a hardened relief pattern was formed on the Cu layer by curing at 350 ° C by the above method, and after performing a high temperature storage test, The ratio of the area occupied by the voids on the surface of the Cu layer was evaluated, and a result of 4.7% was obtained.
<Example C7>
In the above Example C1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene fluorenyl)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, in addition to the examples A negative photosensitive resin composition solution was prepared in the same manner as in C1.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%.
<Example C8>
In the above Example C1, as the (A) resin, the polymer A 50 g and the polymer B 50 g were changed to the polymer A 100 g, and as the component (C), the PDO 4 g was changed to 1,2-octane. Diketone-1-{4-(phenylthio)-2-(O-benzylidene hydrazide)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, and further changed the solvent into γ-butane A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 except that 85 g of the ester and 15 g of dimethylhydrazine were used.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example C9>
In the above Example C1, a negative photosensitive property was prepared in the same manner as in Example C1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer C 100 g as the resin (A). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.7%.
<Example C10>
In the above Example C1, a negative photosensitive property was prepared in the same manner as in Example C1 except that the polymer A 50 g and the polymer B 50 g were changed to the polymer D 100 g as the (A) resin. Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%.
<Example C11>
Using the polymer E, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer E 100 g (corresponding to (A) resin) as a polycarbazole precursor and the following formula (96):
[化106]

The photosensitive diazonium compound (manufactured by Toyo Seisakusho Co., Ltd., equivalent to (C) sensitizer) (C1) 15 g, butyl, represented by 77% of the phenolic hydroxyl group by naphthoquinone diazide-4-sulfonate The base urea (corresponding to the (B-1) compound) 1 g, 3-tributoxycarbonylaminopropyltriethoxydecane 6 g was dissolved in 100 g of γ-butyrolactone (as a solvent). The positive photosensitive resin composition was prepared by further adding a small amount of γ-butyrolactone to adjust the viscosity of the obtained solution to about 20 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.6%.
<Example C12>
In the above-mentioned Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that the polymer E 100 g was changed to the polymer F 100 g as the resin (A).
To the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.9%.
<Example C13>
In the above-mentioned Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C11 except that the polymer E 100 g was changed to the polymer G 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.5%.
<Example C14>
In the above-mentioned Example C11, a positive photosensitive resin composition solution was prepared in the same manner as in Example C13 except that the polymer E 100 g was changed to the polymer H 100 g as the resin (A).
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 220 ° C, and after the high-temperature storage test, the area ratio of the void on the surface of the Cu layer was evaluated to obtain a result of 5.4%.
<Comparative Example C1>
A negative photosensitive resin composition was prepared in the same manner as in Example C1 except that butyl urea was not added, and the same evaluation as in Example C1 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 14.3%.
<Comparative Example C2>
A positive photosensitive resin composition was prepared in the same manner as in Example C12 except that the butyl urea was not added, and the same evaluation as in Example C12 was carried out. Since the compound (B) of the present invention was not contained, the evaluation result was 15.5%.
<Comparative Example C3>
A positive photosensitive resin composition was prepared in the same manner as in Example C13 except that the butyl urea was not added, and the same evaluation as in Example C11 was carried out. Since the compound of the present invention (B) was not contained, the evaluation result was 15.7%.
Example D
<Production Example D1> ((A) Synthesis of Polymer (A)-1 as Polyimine Precursor)
In a separable flask with a volume of 2 L, put 5,4'-oxydiphthalic dianhydride (ODPA) 155.1 g, add 2-hydroxyethyl methacrylate (HEMA) 131.2 g and γ-butane 400 ml of the ester was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the exotherm caused by the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.
Then, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring, followed by stirring. The obtained 4,4'-diaminodiphenyl ether (DADPE) 93.0 g was suspended in γ-butyrolactone 350 ml over 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction liquid was added to 3 L of ethanol to form a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer (A)-1). The molecular weight of the polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.
In addition, the weight average molecular weight of the resin obtained in each Production Example D was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: 2 Shodex KD-806M series
Mobile phase: 0.1 mol/L LiBr/NMP
Flow rate: 1 ml/min.
<Production Example D2> ((A) Synthesis of Polymer (A)-2 as Polyimine Precursor)
Using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of the 4,4'-oxydiphthalic dianhydride (ODPA) 155.1 g of Production Example D1, except The reaction was carried out in the same manner as in the method described in the above Production Example D1 to obtain the polymer (A)-2. The molecular weight of the polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000.
<Production Example D3> ((A) Synthesis of Polymer (A)-3 as Polyimine Precursor)
Using 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) 147.8 g instead of the 4,4'-diaminodiphenyl ether (DADPE) 93.0 g of Preparation Example D1, Other than this, the reaction was carried out in the same manner as in the above-described Production Example D1 to obtain a polymer (A)-3. The molecular weight of the polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000.
<Production Example D4> ((A) Synthesis of Polymer (A)-4 as Polyamide)
(Synthesis of phthalic acid compound end-capped body AIPA-MO)
5-Aminoisophthalic acid (hereinafter abbreviated as AIPA) 543.5 g and N-methyl-2-pyrrolidone 1700 g were placed in a separable flask having a volume of 5 L, and the mixture was stirred and heated by a water bath. 50 ° C. The solution was prepared by dropwise addition of 512.0 g (3.3 mol) of 2-methylpropenyloxyethyl isocyanate to gamma-butyrolactone 500 g by using a dropping funnel, and stirring at 50 ° C for about 2 hours. .
The reaction was completed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC) (5-aminoisophthalic acid disappeared), and then the reaction solution was poured into 15 L of ion-exchanged water and stirred. After standing, the crystallized precipitate of the reaction product is formed, and then filtered and separated, and after appropriate washing with water, vacuum drying at 40 ° C for 48 hours, thereby obtaining an amine group and an isocyanate from 5-aminoisophthalic acid. AIPA-MO obtained by the isocyanate action of 2-methylpropenyloxyethyl ester. The low molecular weight GPC of the obtained AIPA-MO is about 100% pure.
(Synthesis of Polymer (A)-4)
The obtained AIPA-MO 100.89 g (0.3 mol), pyridine 71.2 g (0.9 mol), GBL 400 g were placed in a separable flask having a volume of 2 L, and mixed, and cooled to 5 ° C by an ice bath. Under ice cooling, the dicyclohexylcarbodiimide (DCC) 125.0 g (0.606 mol) was dissolved and diluted in GBL 125 g over a period of about 20 minutes, and then it was added dropwise over 20 minutes. 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB} 103.16 g (0.28 mol) dissolved in NMP 168 g, maintained in ice bath for 3 hours and not reached 5 ° C, and then The ice bath was removed and stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
A mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in NMP 650 g. The obtained crude polymer solution was added dropwise to 5 L of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (polymer (A)-4). The molecular weight of the polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 34,700.
<Production Example D5> ((A) Synthesis of Polymer (A)-5 as Polycarbazole Precursor)
2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 183.1 g, N,N-dimethylacetamide (DMAc) 640.9 g in a separable flask of 3 L The pyridine 63.3 g was mixed and stirred at room temperature (25 ° C) to prepare a homogeneous solution. A solution obtained by dissolving 118.0 g of 4,4'-diphenylether dimethyl hydrazine chloride (DMDG) 354 g was added dropwise thereto using a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 °C. The time required for the dropping was 40 minutes, and the temperature of the reaction liquid was at most 30 °C.
Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture, and the mixture was stirred at room temperature for 15 hours to give a total of 99% of the polymer chain. The terminal group is terminated by a carboxycyclohexylamine group. The reaction rate at this time can be easily calculated by tracking the residual amount of the 1,2-cyclohexyldicarboxylic anhydride charged by high performance liquid chromatography (HPLC). Thereafter, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dried, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (in terms of polystyrene) as measured by the method.
After re-dissolving the crude polybenzoxazole precursor obtained above in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin, and the solution thus obtained is put into ion-exchanged water. The precipitated polymer was separated by filtration, washed with water and dried in vacuo, whereby a purified polybenzoxazole precursor (polymer (A)-5) was obtained.
<Production Example D6> ((A) Synthesis of Polymer (A)-6 as Polyimine)
A glass-separable four-necked flask equipped with a Teflon (registered trademark) anchor type agitator was equipped with a cooling tube attached to a Dean-Stark separator. The flask was immersed in an oil bath while stirring with nitrogen gas.
2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Clariant Japan Co., Ltd.) (hereinafter referred to as BAP) 72.28 g (280 mmol), 5-(2,5-di-side oxytetrahydrogen) -3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70.29 g (266 mmol), γ-butyrolactone 254.6 g, 60 g of toluene, and stirred at 100 rpm for 4 hours at room temperature, and then added 4.6 g (28 mmol) of 5-northene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was stirred while stirring at a bath temperature of 50 ° C for 10 hours at 100 rpm. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred at 100 rpm for 2 hours. The toluene and water distilled in the reaction were removed. After the imidization reaction, the reaction was returned to room temperature.
Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and vacuum dried to obtain a gel permeation chromatography (GPC). A crude polyimine (polymer (A)-6) having a weight average molecular weight of 23,000 (in terms of polystyrene) as measured by the method.
<Example D1>
Using the polymers (A)-1 and (A)-2, a negative photosensitive resin composition was prepared by the following method, and the photosensitive resin composition was evaluated. Polymer (A)-1 50 g and (A)-2 50 g (corresponding to (A) resin) and N-phenylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyimide precursor Equivalent to (B)-1) 3 g, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (denoted as "PDO" in Table 4) (equivalent to (C) sensitizer) 4 g, tetraethylene glycol dimethacrylate 8 g, N-[3-(triethoxydecyl)propyl] phthalic acid 1.5 g together dissolved in A mixed solvent of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. A negative photosensitive resin composition was prepared by further adding a small amount of the above mixed solvent to adjust the viscosity of the obtained solution to about 35 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.5%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D2>
In the above Example D1, the component (B) was changed to N,N'-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and the same as Example D1. A negative photosensitive resin composition solution was prepared in the same manner.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.2%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D3>
In the above Example D1, negative photosensitive property was prepared in the same manner as in Example D1 except that the component (B) was changed to t-butylphenyl carbamic acid ester (manufactured by Tokyo Chemical Industry Co., Ltd.). Resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.1%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D4>
In the above-mentioned Example D1, the component (B) was changed to (3-hydroxyphenyl) carbamic acid tert-butyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), and the same manner as in Example D1 was carried out. A negative photosensitive resin composition solution was prepared.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D5>
In the above Example D1, the component (B) was changed to 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (manufactured by ADEKA Co., Ltd., Adekastab CDA-1) A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except for the above.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.8%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D6>
In the above Example D1, the component (B) was changed to 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethyl). A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that pentan-2-yl)phenol (manufactured by ADEKA Co., Ltd., Adekastab LA-29) was used.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.2%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D7>
In the above Example D1, the component (B) was changed to (4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except the above.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.1%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D8>
In the above Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of the component (B)-1 was changed to 1 g.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 8.5%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D9>
In the above Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of the component (B)-1 was changed to 6 g.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D10>
In the above Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the amount of the component (B)-1 was changed to 10 g.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 230 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.0%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D11>
In the above Example D1, a negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the curing temperature was changed from 230 ° C to 350 ° C.
For the composition, a hardened relief pattern was formed on the Cu layer, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.1%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D12>
In the above Example D1, as the (A) resin, the polymer (A) - 1 50 g and the polymer (A) - 2 50 g were changed into the polymer (A) - 1 100 g, and the (C) component was self-generated. PDO becomes 1,2-octanedione-1-{4-(phenylthio)-2-(O-benzylidene fluorenyl)} (Irgacure OXE01 (manufactured by BASF Corporation, trade name)) 2.5 g, A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except the above.
For the composition, a hardened relief pattern was formed on the Cu layer, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.8%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D13>
In the above Example D12, a negative photosensitive resin composition solution was prepared in the same manner as in Example D12 except that the solvent was changed to γ-butyrolactone 85 g and dimethyl hydrazine 15 g.
For the composition, a hardened relief pattern was formed on the Cu layer, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 5.4%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D14>
In the above Example D1, as the (A) resin, the polymer (A) - 1 50 g and the polymer (A) - 2 50 g were changed into the polymer (A) - 3 100 g, and the curing temperature was from 230 ° C. A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 except that the temperature was changed to 350 °C.
With respect to the composition, a hardened relief pattern was formed on the Cu layer, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 7.2%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D15>
In the above Example D1, as the (A) resin, the polymer (A) - 1 50 g and the polymer (A) - 2 50 g were changed to the polymer (A) - 4 100 g, by A negative photosensitive resin composition solution was prepared in the same manner as in Example D1.
For the composition, a hardened relief pattern was formed on the Cu layer, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 4.9%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D16>
Using the polymer (A)-5, a positive photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. The polymer (A) as a polycarbazole precursor is -5 100 g (corresponding to (A) resin) and the following formula (96):
[107]

The photosensitive diazonium compound (manufactured by Toyo Seisakusho Co., Ltd., equivalent to (C) component) (C1) 15 g of the phenolic hydroxyl group represented by 77% of the phenolic hydroxyl group is dissolved in γ - Butyrolactone (as solvent) 100 g. The positive photosensitive resin composition was prepared by further adding a small amount of γ-butyrolactone to adjust the viscosity of the obtained solution to about 20 poise.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 350 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.9%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Example D17>
In the above Example D16, a positive type was prepared in the same manner as in Example D12 except that the polymer (A)-5 100 g was changed to the polymer (A)-6 100 g as the (A) resin. A photosensitive resin composition solution.
With respect to the composition, a hardened relief pattern was formed on the Cu layer by the above method at 250 ° C, and after the high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated to obtain a result of 6.0%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Comparative Example D1>
In the composition of Example D1, a negative photosensitive resin composition was prepared in the same manner as in Example D1 except that the component (B)-1 was not added, and the same evaluation as in Example D1 was carried out. Since the component (B) of the present invention was not contained, the evaluation result was 15.2%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Comparative Example D2>
In the composition of Example D15, a negative photosensitive resin composition was prepared in the same manner as in Example D15 except that the component (B)-1 was not added, and the same evaluation as in Example D15 was carried out. Since the component (B) of the present invention was not contained, the evaluation result was 14.3%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Comparative Example D3>
In the composition of Example D13, a negative photosensitive resin composition was prepared in the same manner as in Example D13 except that the component (B)-1 was not added, and the same evaluation as in Example D13 was carried out. Since the component (B) of the present invention was not contained, the evaluation result was 15.7%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Comparative Example D4>
A positive photosensitive resin composition was prepared in the same manner as in Example D17 except that the component (B)-1 was not added, and the same evaluation as in Example D17 was carried out. Since the component (B) of the present invention was not contained, the evaluation result was 16.3%. Further, the viscosity change rate after the storage stability test of the obtained varnish was within 10%.
<Comparative Example D5>
In the same manner as in Example D1, a negative photosensitive resin composition was prepared in the same manner as in Example D1 except that the amount of the component (B)-1 was changed to 25 g, and the same procedure as in Example D1 was carried out. The same evaluation. The evaluation result was 7.2%. Further, the viscosity change rate after the storage stability test of the obtained varnish was 10% or more.
The results of the above Examples D1 to 17 and Comparative Examples D1 to 5 are collectively shown in Table 4.
[Table 1]
Table 1


[Table 2]
Table 2

[table 3]
table 3

[Table 4]
Table 4



[Industrial availability]
The photosensitive resin composition of the present invention is preferably used in the field of photosensitive materials useful for the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (7)

A photosensitive resin composition comprising: (A) selected from the group consisting of polyaminic acid, polyglycolate, polyamidate, polyhydroxy guanamine, polyamine amide, polyamine, polyamidimide, polyimine, poly a benzoxazole, and at least one resin selected from the group consisting of novolak, polyhydroxystyrene, and phenol resin: 100 parts by mass; (B) sulfur-containing compound: 0.01 to 10 parts by mass based on 100 parts by mass of the above (A) resin, and (C) Photosensitive agent: 1 to 50 parts by mass based on 100 parts by mass of the above (A) resin. The photosensitive resin composition of claim 1, wherein the (A) resin is selected from the group consisting of a polyamidene precursor containing the following general formula (1), a polyamine containing the following general formula (4), and a polycarbazole precursor of the following formula (5), a polyimine comprising the following formula (6), a novolac, a polyhydroxystyrene, and a phenol resin comprising the following formula (7); At least one of the group, wherein the following general formula (1) is [Chemical 1] In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom and a carbon number of 1 to 30 is saturated. An aliphatic group, an aromatic group, or the following formula (2): [Chemical 2] (wherein, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10), or a carbon number of 1 or a saturated aliphatic group of ～4 or the following general formula (3): [Chemical 3] (In the formula, R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₂ is an integer of 2 to 10) Polyacetamide precursor, polyglycolate or polyamidate, the following general formula (4) has [Chemical 4] In the formula, X ₂ is an organic group having a carbon number of 6 to 15 and Y ₂ is an organic group having a carbon number of 6 to 35, and may be the same structure or have a plurality of structures, and R ₉ is at least a polyamine having a structure of a radical polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n ₂ is an integer represented by 1 to 1000, and the following formula (5) has [ 5] In the formula, Y ₃ is a tetravalent organic group having a carbon atom, and Y ₄ , X ₃ and X ₄ are each independently a divalent organic group having two or more carbon atoms, and n ₃ is an integer of from 1 to 1000. , n ₄ is an integer of 0 to _{500., n 3 / (n 3 +} n 4)> 0.5, and comprises X ₃ and Y ₃ of n ₃ dihydroxy two Amides unit and comprising X n ₄ and Y ₄ of ₄ The arrangement of the diammonium unit is a polyhydroxyguanamine as a polycarbazole precursor of the structure represented by any of the formulas, and the following general formula (6) has [Chemical 6] Wherein X ₅ is an organic group having a valence of 4 to 14 and Y ₅ is an organic group having a valence of 2 to 12, and R ₁₀ and R ₁₁ each independently represent at least one member selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group or a thiol group. The organic group of the group in the group, n ₅ is an integer of from 3 to 200, and m ₃ and m ₄ represent a polyimine of the structure represented by an integer of from 0 to 10, and the following general formula (7) is [ 7] In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, 1 ≦(a+b)≦4, and R ₁₂ represents an organic group selected from a carbon number of 1 to 20, a halogen atom, and a nitro group. And a monovalent substituent in the group consisting of cyano groups. When b is 2 or 3, the plurality of R ₁₂ may be the same or different from each other, and X represents a carbon number selected from the group which may have an unsaturated bond. An aliphatic group having a valence of ～10, an alicyclic group having a carbon number of 3 to 20, and a general formula (8): [Chemical 8] (wherein, p is an integer of from 1 to 10), and a two-valent organic group in the group consisting of a divalent alkoxy group and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms The phenol resin represented by the base. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition contains a phenol resin having a repeating unit represented by the above formula (7), and X in the above formula (7) is selected from the group consisting of General formula (9): [Chemical 9] In the formula, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or a carbon in which one or both of hydrogen atoms are partially substituted with a fluorine atom. In the case of an aliphatic group having a value of 1 to 10, n ₆ is an integer of 0 to 4, and when n ₆ is an integer of 1 to 4, R ₁₇ is a halogen atom, a hydroxyl group, or a carbon number of 1 to 12 The organic group of the valence, at least one of R ₁₇ is a hydroxyl group, and when n ₆ is an integer of 2 to 4, the plurality of R ₁₇ may be the same or different from each other; (10): [10] In the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represent a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or a carbon in which one or all of a hydrogen atom is partially substituted with a fluorine atom. An aliphatic group having a valence of from 1 to 10, W being a single bond, an aliphatic group selected from the group consisting of an aliphatic group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, and a carbon number of 3 to 20 which may be substituted by a fluorine atom. Base, the following general formula (8): [Chemical 11] (wherein, p is an integer of 1 to 10), the divalent alkoxy group represented by the formula, and the following formula (11): The organic group of two valences in the group consisting of the base of two valences represented by the base of two valences in the group consisting of the two valence groups. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (B) sulfur-containing compound is a thiourea derivative. A method of manufacturing a hardened relief pattern, comprising: (1) a step of forming a photosensitive resin layer on the substrate by coating the photosensitive resin composition according to any one of claims 1 to 4 on a substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; (4) A step of forming a hardened embossed pattern by heat-treating the embossed pattern. The method of claim 5, wherein the substrate is formed of copper or a copper alloy. A semiconductor device comprising a hardened relief pattern obtained by the manufacturing method of claim 5 or 6.