JPWO2017170032A1 - Photosensitive film - Google Patents

Abstract

Provided is a photosensitive film which can obtain a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, that is, laminate properties. (A1) One or more types selected from alkali-soluble resins having a structural unit represented by general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof A photosensitive film containing an alkali-soluble resin containing, (B) a photoacid generator, and (C) a thermal crosslinking agent. In general formula (1), R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents an integer of 0 to 4, b represents an integer in the range of 1 to 3, and R2 represents hydrogen. Any one of an atom, a methyl group, an ethyl group, and a propyl group.)

Description

  The present invention relates to a photosensitive film. More specifically, the present invention relates to a photosensitive film suitable for a surface protective film on the surface of a semiconductor element, an interlayer insulating film, and an insulating layer of an organic electroluminescent element.

  Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, and are therefore used for surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like. In recent years, with the miniaturization of semiconductor elements, surface protection films, interlayer insulating films, and the like are required to have a resolution of several μm level. Therefore, in such applications, a positive photosensitive polyimide resin composition and a positive photosensitive polybenzoxazole resin composition that can be finely processed are often used.

  In a general semiconductor device manufacturing process, a semiconductor element is formed on a substrate, a photosensitive layer is formed on a passivation film typified by Si or SiN, and then heated and dried using a hot plate or the like. A pattern is formed through development. After the pattern is formed, heat treatment is performed at a high temperature, and the insulating layer is formed by curing.

  Conventionally, a circular substrate has been used for forming a semiconductor element, but in recent years, a rectangular substrate has been used as the size of the substrate increases.

  As a method for forming a photosensitive layer on a substrate, there are a method of applying a resin composition by a spin coating method and a method of laminating a photosensitive film by applying heat to the substrate. When an insulating layer is formed on a large square substrate, a method of laminating using a photosensitive film is generally used in order to increase the film thickness uniformity after the formation.

  The positive photosensitive polyimide used for the resin composition or photosensitive film is based on polyimide (for example, Patent Document 1), based on polyhydroxystyrene (for example, Patent Document 2), and polyimide and polyhydroxy. A mixture of styrene (for example, Patent Document 3) is known.

  In addition, a technique using a phenol resin as a photosensitive film (for example, Patent Document 4) and a technique using a polyimide having a low glass transition point (for example, Patent Document 5) have been proposed.

JP 2014-71374 A Japanese Patent Laid-Open No. 2006-154779 JP 2014-137523 A Japanese Patent Laid-Open No. 2015-19006 International Publication No. 2011/059089

  As described above, when an insulating layer is formed on a square substrate, a method of laminating using a photosensitive film is generally used in order to increase the film thickness uniformity after the formation. The photosensitive film is required to have mechanical properties such as high extensibility and heat resistance in the cured film. In addition to having good pattern processability (high sensitivity), it also has good adhesion to the substrate. Properties, that is, laminate properties are required.

  However, the film using the polyimide resin composition disclosed in Patent Documents 1 to 3 lacks flexibility, and cracks occur when laminating the film by applying heat to the substrate. The laminating property was not sufficient. Further, Patent Document 4 discloses a technique of using a phenol resin for the purpose of enhancing fluidity, but has a problem that the heat resistance of the cured film is low. Patent Document 5 discloses a technique using a polyimide having a low softening point, but has a problem that high heat resistance cannot be obtained.

  Therefore, the present invention provides a photosensitive film that can obtain a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, that is, laminate properties.

In order to solve the above problems, the photosensitive film of the present invention has the following constitution. That is, 1 selected from (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. A photosensitive film containing an alkali-soluble resin containing at least one kind, (B) a photoacid generator, and (C) a thermal crosslinking agent.

(In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, (Methyl group, ethyl group, or propyl group.)

  According to the present invention, a photosensitive film having good pattern processability (high sensitivity) and having good adhesion to a substrate, that is, laminating properties can be obtained. Moreover, according to the photosensitive film of the present invention, a cured film having high elongation and high heat resistance can be obtained.

It is an example of the schematic sectional drawing of the semiconductor device using the photosensitive film of this invention. It is an example of sectional drawing of the coil part of the inductor apparatus using the photosensitive film of this invention. It is an example of sectional drawing of the hollow part of the elastic wave apparatus using the photosensitive film of this invention. It is an example of sectional drawing of the semiconductor device which uses the photosensitive film of this invention and has a level | step difference in a board | substrate.

  The present invention is selected from (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. A photosensitive film containing an alkali-soluble resin containing one or more of the above, (B) a photoacid generator, and (C) a thermal crosslinking agent. Hereinafter, they may be abbreviated as (A1) resin, (A2) resin, (B) component, and (C) component, respectively.

The photosensitive film of this invention contains alkali-soluble resin which has a structural unit represented by said (A1) general formula (1). R ¹ in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer in the range of 1 to 3, R ² represents a hydrogen atom, methyl Represents any of a group, an ethyl group, and a propyl group. (A1) The sensitivity of a photosensitive film can be improved by containing resin.

  Examples of the structural unit represented by the general formula (1) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol. By polymerizing aromatic vinyl compounds having a phenolic hydroxyl group and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, singly or in a known manner. It can be obtained by subjecting a part of the obtained polymer to an addition reaction of an alkoxy group using a known method (for example, a method described in Japanese Patent No. 5659259).

  As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and / or m-hydroxystyrene is preferably used, and styrene is preferably used as the aromatic vinyl compound.

  (A1) The alkali-soluble resin having the structural unit represented by the general formula (1) further improves the sensitivity and adjusts the solubility in an alkali developer, so that the general formula (2) And at least one of the structural units represented by the general formula (3). Furthermore, from the viewpoint of solubility in an alkali developer, the structural unit of the general formula (3) is preferably 50 mol% or less.

(In general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents an integer in the range of 1 to 5)

(In general formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
The introduction rate of alkoxyalkyl (CH ₂ OR ² ) groups in the (A1) resin is preferably an introduction rate of 10 mol% or more per 1 mol of hydroxystyrene from the viewpoint of heat resistance after curing, and is 20 mol% or more. More preferably. From the viewpoint of improving the resolution, it is preferably 70 mol% or less, and more preferably 50 mol% or less.

  The polystyrene-converted weight average molecular weight (Mw) of the (A1) resin is preferably 3,000 or more from the viewpoint of forming an unexposed portion pattern without eluting it. Moreover, 60,000 or less is preferable from a viewpoint of maintaining the alkali solubility which can reduce the residue of an exposure part, and 25,000 or less are more preferable.

  The polystyrene-converted weight average molecular weight (Mw) is a value calculated using GPC (gel permeation chromatography) measurement based on polystyrene.

  The photosensitive film of the present invention contains an alkali-soluble resin containing at least one selected from (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof.

  The (A2) resin may contain two or more of any one of polyimide, polybenzoxazole, polyamideimide, their precursors, and copolymers thereof, or a copolymer having two or more of these repeating units. A polymer may be included. The (A2) resin preferably has a substituent that reacts with the alkoxyalkyl group of the (A1) resin. The alkoxyalkyl group (A1) particularly refers to an alkoxymethyl group. (A2) The structure of the resin is not particularly limited as long as it has a substituent that reacts with an alkoxyalkyl group, but a group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group at the main chain or terminal. It is preferable to have one or more.

  (A1) Since the alkoxyalkyl group of the resin and (A2) resin react at the time of thermosetting, heat resistance and mechanical properties can be sufficiently maintained, (A1) good pattern processability of the resin, (A2) Both high heat resistance and mechanical properties of the resin can be achieved. The content of (A2) resin is preferably 5 parts by mass or more and more preferably 10 parts by mass or more from the viewpoint of pattern processability with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Moreover, 90 mass parts or less are preferable from a viewpoint of heat resistance and a mechanical characteristic, and 70 mass parts or less are more preferable.

  The (A2) resin preferably has at least one of the structural units represented by the general formulas (4) and (5).

(In General Formula (4), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R ⁶ represents a divalent organic group having 20 to 100 carbon atoms. N ₁ represents 10 to 100. An integer in the range of 1,000.)

(In the general formula (5), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R ⁶ represents a divalent organic group having 20 to 100 carbon atoms. R ⁷ represents hydrogen or carbon. An organic group having a number of 1 to 20. n ₂ represents an integer within a range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 2.
In general formulas (4) and (5), R ⁵ represents a C 4-40 divalent or tetravalent organic group having a monocyclic or condensed polycyclic alicyclic structure. In R ⁵ , the monocyclic or condensed polycyclic alicyclic structure preferably contains one or more organic groups selected from the following general formulas (6) to (9).

(In the general formulas (6) to (9), R ^{8 to} R ⁵³ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms. In the organic group, a hydrogen atom contained in the organic group may be substituted with a halogen atom.)
In the general formulas (4) and (5), R ⁵ is an organic group derived from an acid dianhydride used as a raw material for the resin.

  Specific examples of the acid dianhydride containing a C 4-40 divalent organic group having a monocyclic or condensed polycyclic alicyclic structure used in the present invention include 1, 2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, Examples include compounds such as 3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

In the general formulas (4) and (5), pyromellitic acid, 3, 3 is preferable as a preferable structure of a C 4-40 divalent organic group having 1 to 4 aromatic rings in R ⁵ . ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4 '-Benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3- Dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) Methane, bis (2 3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6 , 7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, etc. And a structure in which 1 to 4 carbon atoms are substituted with 1 to 20 alkyl groups, fluoroalkyl groups, alkoxyl groups, ester groups, nitro groups, cyano groups, fluorine atoms, and chlorine atoms.

Alicyclic structure monocyclic or fused polycyclic at R ⁵ is improved general formula (4) and (5) when the the R ⁵ 100 mol% of, high elongation of the laminate against the substrate of the film If it is 10 mol% or more from the viewpoint to make it, it is more preferable if it is 30 mol% or more. From the viewpoint of obtaining an appropriate dissolution rate in the developer, it is preferably 80 mol% or less, more preferably 60 mol% or less.

For example, R ⁵ has 70 mol% of a monocyclic or condensed polycyclic alicyclic structure with respect to 100 mol% of the total amount of repeating units in the general formulas (4) and (5), and has an aromatic ring 4 When 30 mol% of a valent organic group is contained, it is calculated that the monocyclic or condensed polycyclic alicyclic structure is 70 mol%. At this time, when R ⁵ has two or more monocyclic or condensed polycyclic alicyclic structures, it is calculated as 70 mol%.

Further, R ⁶ in the general formulas (4) and (5) preferably has an organic group having a polyether structure represented by the following general formula (10).

(In the formula, R ^{54 to} R ⁵⁷ each independently represents an alkylene group having 1 to 6 carbon atoms. R ^{58 to} R ⁶⁵ each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. The structure represented in parentheses of repeating unit x is different from the structure represented in parentheses of repeating unit y, and the structure represented in parentheses of repeating unit z is different from the structure represented in parentheses of repeating unit y. X, y and z each independently represents an integer of 0 to 35.) In addition, R ⁶ in the general formulas (4) and (5) is derived from a diamine used as a raw material for the resin. Organic group.

Specific examples of the diamine containing an organic group having a polyether structure used in the present invention include “Jeffamine” (registered trademark) HK-511, ED-600, ED-900, ED-2003, and EDR-148. , EDR-176, D-200, D-400, D-2000, D-4000, “Elastamine” (registered trademark) RP-409, RP-2009, RT-1000, HT-1100, HE-1000, HT- An aliphatic diamine such as 1700 (trade name, manufactured by HUNTSMAN Co., Ltd.) can be used. By having a polyether structure, hydrophilicity and meltability at high temperatures are imparted, so that the laminate property to the substrate is improved, and flexibility is imparted, so that the elongation is improved and the elastic modulus is lowered. This is preferable because warpage of the wafer is suppressed. These characteristics are effective in multilayers and thick films. In the polyether structure represented by the general formula (10), when R ⁶ in the general formulas (4) and (5) is 100 mol%, the resin has flexibility, low stress, This is preferable because the laminate property to the substrate can be obtained. Moreover, if it is 80 mol% or less, it is preferable at the point that the suitable melt | dissolution rate with respect to a developing solution is obtained. It is more preferable to contain 20 mol%-50 mol%.

For example, R ⁶ has 70 mol% of an organic group derived from a diamine containing an organic group having a polyether structure with respect to 100 mol% of the total amount of repeating units in the general formulas (4) and (5), and an aromatic ring It is calculated that there are 70 mol% of organic groups derived from a diamine containing an organic group having a polyether structure when 30 mol% of a divalent organic group having an organic group is present. At this time, when R ⁶ has an organic group derived from a diamine containing an organic group having two or more polyether structures, it is calculated as 70 mol%.

Further, as R ⁵ in the general formulas (4) and (5), by further containing an organic group having a fluorine atom, water repellency is imparted to the resin, and permeation from the surface of the film is suppressed during alkali development. This is preferable. By suppressing the penetration from the surface of the film, it is possible to obtain a resin film having a high residual film ratio in which there is no development residue in the tack or processing pattern of the unexposed area. These characteristics are important in realizing thick film processing. When the total amount of R ⁵ is 100 mol%, the organic group having a fluorine atom can prevent the penetration of the interface if it is 20 mol% or more, and if it is 90 mol% or less, an appropriate dissolution rate in the developer. Is preferable, and it is more preferable to contain 40 mol%-60 mol%.

  Specific examples of the compound having a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, and amides. An aromatic acid dianhydride such as an acid dianhydride having a group can be mentioned. (A2) The resin is preferably a resin including a structure derived from these compounds.

  By using the acid dianhydride having an alicyclic structure having 4 to 40 carbon atoms, a diamine having a polyether structure having 20 to 100 carbon atoms, and a compound having a fluorine atom in the above range, high elongation is achieved. A high-sensitivity photosensitive film having a high residual film ratio free from tack and development residue at the time of development can be obtained while being moderate and low stress.

  These characteristics are particularly useful in a rewiring application of a semiconductor device used as an interlayer insulation film between metal wirings and used in a noise filter of an inductor device. Moreover, the photosensitive film of this invention may contain the structure derived from other acid dianhydrides and diamine in addition to the above-mentioned acid dianhydride and diamine in the range which does not reduce the above-mentioned characteristic.

  Specific examples of other dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Bis (2,3-dicarbox Phenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as dianhydrides, or compounds in which the hydrogen atoms of these compounds are substituted with alkyl groups or halogen atoms, or 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] octo-7-e -2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride, 3 , 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride such as alicyclic, semi-alicyclic tetracarboxylic dianhydride or alkyl of the hydrogen atom of these compounds And a compound substituted with a group or a halogen atom, and an acid dianhydride having an amide group. These can be used in combination with two or more acid dianhydrides containing an alicyclic structure having 4 to 40 carbon atoms.

  Specific examples of other diamines include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino-4-hydroxyphenyl) propane. Bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) Hydroxyl group-containing diamines such as fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, thiol group-containing diamines such as dimercaptophenylenediamine, 3,4′-diaminodiphenyl ether, 4,4 ′ -Diaminodiphenyl ether, 3,4'- Aminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4 -Bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3- Aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4 , 4'-Diaminobiphenyl, 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'- Aromatic diamines such as diaminobiphenyl, compounds in which some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, cyclohexyl diamine, methylene bis cyclohexyl amine And alicyclic diamines. These diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, you may use combining these 2 or more types of diamine components.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds of these aromatic rings substituted with an alkyl group or a halogen atom, and the like diamines having an amide group as preferred. These are used alone or in combination of two or more.

Further, an aliphatic group having a siloxane structure may be introduced as long as the heat resistance is not lowered, and the adhesion to the substrate can be improved. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p- aminophenyl) octamethyl pentasiloxane such general formula (4) and ^{R 6} in (5) 100 mol% 1-15 mol% copolymerized with respect to this.

  In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.

Moreover, it is preferable that (A2) resin has a phenolic hydroxyl group component. In the general formulas (4) and (5), it is preferable that at least one of R ⁵ and R ⁶ is an organic group having a phenolic hydroxyl group. Due to the presence of phenolic hydroxyl group, moderate solubility in alkaline developer is obtained, and it interacts with the photosensitizer to suppress solubility in the unexposed areas, thus improving the remaining film ratio and increasing sensitivity. Become. In addition, the phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, and thus is preferable in that high mechanical properties and chemical resistance can be obtained.

  Specifically, as the compound having a phenolic hydroxyl group, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, and Aromatic acid dianhydrides such as acid dianhydrides having an amide group, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3- Amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3 -Amino-4-hydroxyphenyl) fluorene-containing diamines such as fluorene, and these Some of the hydrogen atoms of the aromatic ring include an alkyl group and a fluoroalkyl group having 1 to 10 carbon atoms, compounds substituted with a halogen atom, and the like. (A2) The resin is preferably a resin including a structure derived from these compounds.

In the general formulas (4) and (5), n ₁ and n ₂ represent the degree of polymerization. When the molecular weight per unit of the general formulas (4) and (5) is M, and the weight average molecular weight of the alkali-soluble resin is Mw, the degree of polymerization n can be obtained by the formula n = Mw / M. The weight average molecular weight of the alkali-soluble resin is determined by GPC (gel permeation chromatography) as described in Examples. n ₁ and n ₂ can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method or the like. When the molecular weight of the repeating unit is M and the weight average molecular weight of the polymer is Mw, n = Mw / M. The number of repetitions n in the present invention refers to a value calculated using the simplest GPC (gel permeation chromatography) measurement in terms of polystyrene.

  (A2) The weight average molecular weight of the resin is preferably in the range of 3,000 to 80,000, more preferably in the range of 8,000 to 50,000, in terms of polystyrene by gel permeation chromatography. preferable. If it is this range, a thick film can be formed easily.

  In addition, (A2) resin may have its terminal blocked with a terminal blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid. By sealing the terminal of the resin with a terminal sealing agent having a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group or allyl group, the dissolution rate of the resin in an alkaline aqueous solution can be easily within a preferred range. Can be adjusted. The terminal blocking agent is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on the total amine component of the resin.

  Specific examples of end capping agents include monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, 3,5-diethynylaniline, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynyl. Monocarboxylic acids such as benzoic acid and 3,5-diethynylbenzoic acid, acid anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride, and the carboxyl group of the monocarboxylic acid was acid chlorided Compounds obtained by acid chloride of one carboxyl group of dicarboxylic acids such as compounds and maleic acid, active ester compounds obtained by reacting monoacid chloride compounds with N-hydroxy-5-norbornene-2,3-dicarboximide, etc. In addition to an end-capping agent having an unsaturated bond of 5-amino-8-hydroxyquinoline, 1-hydride Roxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2- Aminobenzenesulfonic acid, 3-aminobenzenesulfone Acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-amino Monoamines such as thiophenol, phthalic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercap Monocarboxylic acids such as -5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, and monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1 , 5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,6-dicarboxynaphthalene monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as acid chloride is converted, Examples thereof include end capping agents having no unsaturated bond such as an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole. Moreover, it can use as terminal blocker which has an unsaturated bond by substituting the hydrogen bond of the terminal blocker which does not have these unsaturated bonds with a vinyl group.

The resin having at least one of the structural units represented by the general formulas (4) and (5) can be produced according to known methods for producing polyimides and polyimide precursors. For example, (I) a method of reacting a tetracarboxylic dianhydride having an R ⁵ group, a diamine compound having an R ⁶ group, and a monoamino compound as a terminal blocking agent under low temperature conditions, (II) an R ⁵ group A diester obtained by having a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine compound having an R ⁶ group, a monoamino compound as a terminal blocking agent and a condensing agent, (III) R ⁵ group A diester is obtained by using tetracarboxylic dianhydride and alcohol, and then the remaining two carboxyl groups are acid chlorideed to react with a diamine compound having an R ⁶ group and a monoamino compound as a terminal blocking agent. be able to.

  The resin polymerized by the above method is preferably put into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved. Moreover, after imidating the polyimide precursor and ring-closing polyimide, after obtaining said polyimide precursor, it can synthesize | combine using the method of making a well-known imidation reaction.

Hereinafter, an example of a method for producing a polyimide precursor will be described as a preferred example of (I). First, a diamine compound having an R ⁶ group is dissolved in a polymerization solvent. To this solution, a tetracarboxylic dianhydride having an R ⁵ group, which is substantially equimolar with the diamine compound, is gradually added. Using a mechanical stirrer, the mixture is stirred at -20 to 100 ° C, preferably 10 to 50 ° C for 0.5 to 100 hours, more preferably 2 to 24 hours. When using terminal blocker, after adding tetracarboxylic dianhydride, after stirring at -20-100 degreeC, Preferably 10-50 degreeC for 0.1-24 hours, terminal blocker is gradually used. You may add and you may make it react at once.

  The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic dianhydrides and diamines which are raw material monomers. For example, N, N-dimethylformamide, N, N-dimethylacetamide, amides of N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl- Examples include 2-imidazolidinone, sulfolane, dimethyl sulfoxide, and the like.

  If the polymerization solvent is 100 parts by mass or more with respect to 100 parts by mass in total of the tetracarboxylic dianhydride, the diamine compound, and the monoamino compound that is the terminal blocking agent used in the polymerization reaction, the reaction is performed without precipitation of raw materials and resins. If it is 1900 mass parts or less, since reaction advances rapidly, it is preferable and 150-950 mass parts is more preferable.

  Next, the photosensitive film of the present invention will be described. The photosensitive film of this invention has photosensitivity by containing the (B) photo-acid generator. That is, (B) the photoacid generator has a characteristic that an acid is generated when irradiated with light, and the solubility of the light irradiated portion in an alkaline aqueous solution is increased. (B) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like. Among these, (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof. A quinonediazide compound is preferably used in that it exhibits an excellent dissolution inhibiting effect when used in combination with an alkali-soluble resin containing one or more selected types.

  The quinonediazide compound has a quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, a quinonediazide sulfonic acid bonded to a polyamino compound, and a quinonediazide sulfonic acid bonded to the polyhydroxypolyamino compound with an ester bond or sulfonamide bond. And those in which a sulfonic acid of quinonediazide is ester-bonded and sulfonamide-bonded to a polyhydroxypolyamino compound.

  Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When the substitution with quinonediazide is 50 mol% or more, the solubility in an alkali developer is not excessively high, a contrast with an unexposed portion is obtained, and a desired pattern can be obtained. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive film that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. Such compounds may be used alone or in combination of two or more. Further, by using two kinds of photoacid generators, the ratio of the dissolution rate between the exposed and unexposed areas can be increased, and as a result, a highly sensitive photosensitive film can be obtained.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.) and the like, but are not limited thereto.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfhydrides.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.

  In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used as a mixture.

  The molecular weight of the quinonediazide compound of the present invention is preferably in the range of 300 to 3,000. When the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, the adhesiveness is lowered, etc. Problems can arise.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators (B) used in the present invention, those that moderately stabilize the acid component generated by exposure are preferably sulfonium salts, phosphonium salts, or diazonium salts. Since the photosensitive film of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus and the like remain, and it is necessary to consider the color tone of the film, and among these, a sulfonium salt is preferably used. . Particularly preferred is a triarylsulfonium salt, which can suppress changes in the color tone of the film.

  (B) Content of a photo-acid generator becomes like this. Preferably it is 0.01-50 mass parts with respect to 100 mass parts of total amounts of (A1) resin and (A2) resin. Among these, the quinonediazide compound has a preferable range of 3-40 mass parts. In addition, the compound selected from sulfonium salts, phosphonium salts, and diazonium salts is preferably in the range of 0.05 to 40 parts by mass, and more preferably in the range of 0.1 to 30 parts by mass. (B) By making content of a photo-acid generator into this range, high sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  The photosensitive film of the present invention contains (C) a thermal crosslinking agent. (C) As the thermal crosslinking agent, a compound having an alkoxymethyl group is preferable, and a compound represented by the general formula (11) is particularly preferable.

(In the general formula (11), R ⁶⁶ represents a 1 to 10 valent organic group. The plurality of R ⁶⁷ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms. Represents an integer of 5. s represents an integer of 1 to 10.)
The alkoxymethyl group causes a thermal crosslinking reaction at 160 ° C. or higher. Therefore, a cross-linking reaction occurs in the step of thermosetting the photosensitive film, and a good pattern shape can be obtained.

  The number of alkoxymethyl groups is preferably 2 or more in order to improve the crosslink density, and more preferably 4 or more in order to improve chemical resistance. Moreover, in order to reduce the dimensional variation of the pattern after thermosetting, it is preferable to have (C) at least one compound having 6 or more alkoxymethyl groups as a thermal crosslinking agent.

  The compound represented by the general formula (11) functions as a thermoplastic agent at a temperature lower than 160 ° C. that causes a thermal crosslinking reaction. Lamination is preferably performed at a temperature of 150 ° C. or lower. At this time, the photosensitive layer is heated and melted, and the contact area with the substrate is increased. Therefore, it is presumed that the adhesion between the two is improved.

  Specific examples of the (C) thermal crosslinking agent include the following compounds, but are not limited thereto. Moreover, you may contain 2 or more types of these.

  (C) The content of the thermal crosslinking agent is to improve the crosslinking density, chemical resistance, and adhesion to the substrate in the resulting cured film, so that the total amount of (A1) resin and (A2) resin is 100 parts by mass. The amount is preferably 1 part by mass or more, and more preferably 5 parts by mass or more. Moreover, in order to improve a mechanical characteristic, it is preferable that it is 70 mass parts or less, and it is more preferable that it is 50 mass parts or less.

  (C) The weight average molecular weight (Mw) of the thermal crosslinking agent is preferably 100 or more and more preferably 300 or more in order to improve the mechanical properties of the cured film after heat treatment. Moreover, in order to improve laminating property, it is preferable that it is 2,500 or less, and it is more preferable that it is 2,000 or less.

  The photosensitive film of the present invention preferably contains a thermal crosslinking agent having a structural unit represented by the following general formula (12). By containing the cross-linking agent, it is possible to further improve the elongation while maintaining heat resistance and laminating properties.

(In General Formula (12), R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom or a methyl group. R ⁶⁸ is a divalent organic group having an alkylene group having 2 or more carbon atoms, and is linear. R ⁶⁸ may be an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, or a carbonyl group. , Allyl group, vinyl group, heterocyclic group, and combinations thereof, and may further have a substituent.)
Since the thermal crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, it is possible to improve the elongation while having heat resistance and laminating properties. Examples of the crosslinking group include, but are not limited to, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group. Among these, an epoxy group is preferred because it can react with the phenolic hydroxyl group of (A1) resin and (A2) resin to improve the heat resistance of the cured film and can react without dehydration. .

  Examples of the compound represented by the general formula (12) include, but are not limited to, the following structures.

(In the formula, n is an integer of 1 to 5, and m is 1 to 20.)
Among the above structures, n is preferably 1 to 2, and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

  Moreover, the addition amount of the compound represented by the general formula (12) is preferably 2 to 35 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the total amount of the (A1) resin and the (A2) resin. preferable. When the addition amount is 2 parts by mass or more, the effect of improving the elongation is sufficiently obtained, and when the addition amount is 35 parts by mass or less, the sensitivity reduction of the photosensitive film before curing can be suppressed.

  The photosensitive film of this invention may contain the (D) acrylate compound as needed. In the present invention, the (D) acrylate compound refers to a compound having an acryloyl group or a methacryloyl group. (D) The acrylate compound includes a monofunctional acrylate and a polyfunctional acrylate. The monofunctional acrylate refers to a compound having at least one of acryloyl group and methacryloyl group. For example, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, etc. can be mentioned. In addition, the polyfunctional acrylate compound refers to a compound having at least one of acryloyl group and methacryloyl group.

  The photosensitive film of the present invention is heat-treated after pattern processing. When used as a positive-type photosensitive film, the acrylate compound reacts with the heat-polymerized or alkali-soluble resin between the acrylate compounds and crosslinks to improve the elongation of the cured film. When used as a negative photosensitive resin film, the acrylates are photopolymerized by exposure during pattern processing, thereby forming a network structure with the alkali-soluble resin.

  In the case of a monofunctional acrylate compound, curing of the film by the crosslinking reaction does not proceed sufficiently, and the effect of improving the elongation is low, so that it is preferably a polyfunctional acrylate.

  (D) As a preferable example of an acrylate compound, NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT, A-9300, ATM-4E, ATM-35E, ATM-4P, AD-TMP, AD-TMP-L, A-DPH etc. are mentioned. In addition, Kyoeisha Chemical Co., Ltd. light ester series P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, G -101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP, etc. are mentioned. Moreover, Kyoeisha Chemical Co., Ltd. "Light acrylate" (trademark) series 3EG-A, 4EG-A, 9EG-A, 14EG-A, TMGA-250, NP-A, MPD-A, 1.6HX-A , BEPG-A, 1.9ND-A, MOD-A, DCP-A, BP-4EA, BP-4PA, BA-134, BP-10EA, HPP-A, TMP-A, TMP-3EO-A, TMP -6EO-3A, PE-3A, PE-4A, DPE-6A and the like. Moreover, Kyoeisha Chemical Co., Ltd. epoxy ester series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M, 3000A etc. are mentioned. In addition, "Aronix" (registered trademark) series M-203, M-208, M-210, M-211B, M-215, M-220, M-225, M-240, M- manufactured by Toa Gosei Co., Ltd. 243, M-245, M-260, M-270, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-350, M-360, M-402, M-408, M-450 etc. are mentioned. In addition, “KAYARAD” (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604 manufactured by Nippon Kayaku Co., Ltd. , R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), RP-1040, and the like. Also, “Blemmer” (registered trademark) series GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE-1000, manufactured by NOF Corporation. ADE-200, ADE-400, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDBE-200, PDBE-250, PDBE-450, PDBE-1300, ADBE-200, ADBE- 250, ADBE-450 and the like. Further, MBAA manufactured by MRC Unitech Co., Ltd. can be mentioned. You may contain 2 or more types of these compounds.

  Among the (D) acrylate compounds, acrylate compounds having a molecular weight of 100 or more and 2,000 or less are preferable. A cured film having a high elongation can be obtained when the molecular weight is 100 or more, and a resin composition having moderate alkali solubility and high compatibility with an alkali-soluble resin can be obtained when the molecular weight is 2,000 or less. Can do.

  Moreover, in this invention, in addition to (A2) resin, you may contain other alkali-soluble resin in the range which does not impair the heat resistance of the cured film obtained by heat processing. Specifically, acrylic polymers copolymerized with acrylic acid, siloxane resins, novolak resins, resole resins, polyhydroxystyrene resins and other phenol resins, and cross-link groups such as methylol groups, alkoxymethyl groups and epoxy groups. Examples thereof include introduced resins and copolymers thereof. Such a resin is soluble in an aqueous alkali solution such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the heat-resistant resin film.

  As another alkali-soluble resin, a phenol resin is preferable from the viewpoint of sensitivity. A phenol resin is obtained by polycondensing phenols and aldehydes by a known method. You may contain combining the resin which has 2 or more types of phenolic hydroxyl groups.

  Preferred examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like. In particular, phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol or 2,3,5-trimethylphenol are preferable. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkaline developer, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, the resin having a phenolic hydroxyl group preferably includes an m-cresol residue, or a cresol novolak resin containing an m-cresol residue and a p-cresol residue. At this time, the molar ratio of m-cresol residue to p-cresol residue in the cresol novolak resin (m-cresol residue / p-cresol residue, m / p) is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.

  Preferred examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde and the like. Of these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination. The amount of the aldehyde used is preferably 0.6 mol or more, more preferably 0.7 mol or more, per 1 mol of phenols. Moreover, 3 mol or less is preferable and 1.5 mol or less is more preferable.

In the polycondensation reaction between phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like. The usage-amount of these acidic catalysts is 1 * 10 < ^-5 > ^-5 * 10 < ^-1 > mol normally with respect to 1 mol of phenols. In the polycondensation reaction, water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of the reaction medium used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.

  The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials, but is usually 10 to 200 ° C. As a polycondensation reaction method, phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate. After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium, etc. present in the system, the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. The resin having a phenolic hydroxyl group is removed.

  In the present invention, the polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the phenol resin is preferably 1,000 or more, and more preferably 2,000 or more. Moreover, 20,000 or less is preferable and 10,000 or less is more preferable. If it is this range, it will be excellent in the workability | operativity and sensitivity at the time of apply | coating the positive photosensitive resin composition of this invention to a base material.

  The content of the other alkali-soluble resin is preferably 1 part by mass or more and more preferably 5 parts by mass or more from the viewpoint of sensitivity with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. From the viewpoint of mechanical properties and heat resistance, it is preferably 70 parts by mass or less, and more preferably 50 parts by mass or less.

  Of the resins contained in the photosensitive film of the present invention, the resin containing the structure represented by the general formulas (4) and (5) is preferably 30% by mass or more.

Moreover, you may contain the compound which has (E) phenolic hydroxyl group in the range which does not make the shrinkage | contraction rate after hardening as needed for the purpose of improving the sensitivity of a photosensitive film.
(E) Compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP -EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP , TrisP-PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis2 6X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Preferred (E) compounds having a phenolic hydroxyl group are Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisCP- IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, etc. .

  Particularly preferred (E) compounds having a phenolic hydroxyl group are Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F. It is. (E) By containing a compound having a phenolic hydroxyl group, it is hardly soluble in an alkali developer before exposure, but is easily dissolved in an alkali developer at the time of exposure. Can be obtained. (E) The content of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Is within the range.

  The photosensitive film of the present invention may contain (F) a solvent. (F) Solvents include polar aprotic solvents such as γ-butyrolactone, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and dialkylenes such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether. Glycol dialkyl ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ketones such as N, N-dimethylformamide, N, N-dimethylacetamide, acetates such as 3-methoxybutyl acetate and ethylene glycol monoethyl ether acetate , Esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, It can be used aromatic hydrocarbons such as xylene and the like alone or in combination. (F) 0.0001 mass part or more is preferable with respect to 100 mass parts of total amounts of (A1) resin and (A2) resin, and, as for content of a solvent, 50 mass parts or less are preferable.

  The photosensitive film of the present invention can contain (G) a silane compound and can be used as an adhesion aid for improving the adhesion to the base substrate. (G) Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenyl. Aminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryl Roxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and the structure shown below It can be mentioned that the silane compound is not limited thereto. Two or more of these may be contained.

  The content of (G) silane compound is preferably 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total amount of (A1) resin and (A2) resin. Within this range, a sufficient effect as an adhesion aid can be obtained while maintaining the heat resistance of the positive photosensitive film.

  Also, for the purpose of improving the wettability between the photosensitive film and the substrate, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, tetrahydrofuran, dioxane, etc. The ethers may be included. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

The photosensitive film of the present invention preferably contains (H) a compound represented by the following general formula (13) (hereinafter referred to as component (H)). By containing the component (H), the adhesion between the laminated film and the metal material, particularly copper, is remarkably improved. This is due to the fact that the S and N atoms of the compound represented by the general formula (13) interact with the metal surface, and further have a three-dimensional structure that easily interacts with the metal surface. To do. By these effects, it is possible to obtain a cured resin film that imparts photosensitivity to the resin composition and has excellent adhesion to a metal material even in a composition having an additive. In the general formula (13), R ^{71 to} R ^{73 each} represents an O atom, an S atom, or an N atom, and at least one of R ^{71 to} R ⁷³ represents an S atom. l represents 0 or 1, R ⁷¹ represents an oxygen atom or a sulfur atom when l is 0, and represents a nitrogen atom when l is 1. m and n represent 1 or 2. R ^{74 to} R ⁷⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ^{74 to} R ⁷⁶ include a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl. A group, a heterocyclic group, a combination thereof, and the like, and may further have a substituent.

  Moreover, the addition amount of (H) component has preferable 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A1) resin and (A2) resin. When the addition amount is 0.1 parts by mass or more, the effect of improving the adhesion after lamination to the metal material can be sufficiently obtained, and when the addition amount is 10 parts by mass or less, the photosensitive film used in the present invention can be obtained. The positive type is preferable because it can suppress a decrease in sensitivity of the photosensitive film due to the interaction with the photosensitive agent.

In the compound represented by the general formula (13) used in the present invention, R ^{71 to} R ^{73 each} represents an O atom, an S atom, or an N atom, and at least one of R ^{71 to} R ⁷³ is S An atom is preferred. In general, when a compound containing an N atom is added, the sensitivity may be impaired due to the interaction between the photosensitizer and the N atom-containing compound. The effect of improving the adhesion can be obtained without lowering. Moreover, it is more preferable to have a trialkoxymethyl group from the viewpoint of adhesion after lamination to a substrate other than metal such as silicon.

  Examples of the compound represented by the general formula (13) include the following, but are not limited to the following structures.

  The manufacturing method of the photosensitive film of this invention is illustrated. For example, (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), and (A2) a polyimide, polybenzoxazole, polyamideimide having a substituent that reacts with the (A1) alkali-soluble resin, An alkali-soluble resin having at least one selected from their precursors and their copolymers, (B) a photoacid generator, (C) a thermal crosslinking agent, (F) a solvent, and other components as necessary. Examples thereof include a method of stirring and dissolving in a glass flask or stainless steel container with a mechanical stirrer, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring deaerator. The viscosity of the composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinker, (F) solvent, etc. is preferably 200 to 10,000 mPa · s. Moreover, you may filter with the filter of 0.1 micrometer-5 micrometers pore size in order to remove a foreign material.

  The photosensitive film of the present invention preferably has a support film. A composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent, etc. is applied onto a support film and then dried to support it. A photosensitive film having a photosensitive layer on the film can be obtained.

  The support film is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. The bonding surface between the support film and the photosensitive film may be subjected to a surface treatment such as silicone, a silane coupling agent, an aluminum chelating agent, or polyurea in order to improve adhesion and peelability. The thickness of the support film is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

  Moreover, in order to protect the surface, the photosensitive film of this invention may have a protective film on a film | membrane. Thereby, the photosensitive film surface can be protected from contaminants such as dust and dust in the atmosphere.

  Examples of the protective film include polyolefin films and polyester films. The protective film preferably has a small adhesive force with the photosensitive film.

  As a method for forming a photosensitive layer by applying a composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent, etc. to a support film, Examples thereof include spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater and the like. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but it is usually preferable that the film thickness of the photosensitive layer obtained after drying is 0.5 μm or more and 100 μm or less. Moreover, it is more preferable that they are 3 micrometers or more and 40 micrometers or less.

  An oven, a hot plate, infrared rays, or the like can be used for drying. The drying temperature and the drying time may be in a range where the solvent can be volatilized, and it is preferable to appropriately set a range in which the resin film material for a semiconductor is in an uncured or semi-cured state. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps combining these temperatures, for example, you may heat-process at 50 degreeC, 60 degreeC, and 70 degreeC for 1 minute each.

  Next, a method for manufacturing a semiconductor device using a photosensitive film will be described. When the photosensitive film has a protective film, it is first peeled off. A photosensitive film and a board | substrate are made to oppose, and it bonds together by thermocompression bonding, transfers a photosensitive film to a board | substrate, and laminates. Next, the support film is peeled off to obtain a photosensitive coating. The thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like. The temperature for thermocompression bonding and lamination is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of adhesion to the substrate and embedding. In order to prevent the photosensitive film from being cured at the time of thermocompression bonding and the resolution of pattern formation in the exposure / development process from being deteriorated, the temperature of thermocompression bonding is preferably 150 ° C. or less, and preferably 120 ° C. or less. More preferred. Moreover, you may carry out under reduced pressure in order to remove a bubble at the time of thermocompression bonding.

  Moreover, after laminating the photosensitive film on the substrate, the support film is peeled off from the photosensitive film in a temperature range of 0 ° C. or higher and 100 ° C. or lower.

  Examples of the substrate to be used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and substrates on which circuit constituent materials are arranged.

  Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit materials include conductors containing metals such as gold, silver and copper, resistors containing inorganic oxides, low dielectrics containing glass materials, resins, etc., resins and high dielectric constants Examples thereof include high dielectric materials containing inorganic particles and insulators containing glass-based materials.

  Next, the photosensitive film formed by the above method is irradiated with actinic radiation through a mask having a desired pattern and exposed. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. . In the photosensitive film, when the support film is a material transparent to these light beams, the exposure may be performed after peeling the support film from the photosensitive film, or the exposure may be performed without peeling. . When exposure is performed without peeling, the support film is peeled after exposure and before development.

  In order to form a pattern, after exposure, an unexposed portion is removed using a developer. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good.

  Development can be performed by spraying the developer on the surface with the photosensitive coating, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. it can. The development conditions such as the development time and the temperature of the development step developer may be any conditions that allow the unexposed areas to be removed. In order to process fine patterns and remove residues between patterns, unexposed areas It is preferable to perform further development after the removal.

  After the development, rinsing with water may be performed. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment. When the resolution of the pattern at the time of development is improved and the allowable range of development conditions is increased, a step of performing a baking process before development can be incorporated. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-120 degreeC is especially more preferable. The time is preferably 5 seconds to several hours.

  After forming the pattern, a cured film is obtained by applying a temperature of 120 ° C. to 400 ° C. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 250 ° C. over 2 hours can be mentioned. At this time, the heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 180 ° C. or higher and 250 ° C. or lower.

  The thickness of the cured film is preferably 0.5 μm or more and more preferably 2 μm or more in order to improve insulation. Further, from the viewpoint of reducing the warpage of the substrate due to residual stress, 100 μm is preferable, and 40 μm or less is more preferable.

  The cured film obtained by curing the photosensitive film of the present invention is suitably used for applications such as a semiconductor passivation film, a semiconductor protective film, an interlayer insulating film of a multilayer wiring for high-density mounting, and an insulating layer of an organic electroluminescent element. Moreover, the cured film which hardened | cured the photosensitive film of this invention can be used for a semiconductor device in the state in which the relief pattern layer of this cured film was formed.

  Moreover, after arrange | positioning a cured film on a board | substrate with a film thickness of 2-40 micrometers as above-mentioned, and arrange | positioning a copper wiring on it, the cured film is further made into a film thickness of 2-40 micrometers as an insulating film between copper wiring. A semiconductor device can also be manufactured.

  An example of a suitable structure of a semiconductor device in which a cured film obtained by curing the photosensitive film of the present invention is disposed is shown in FIG. A passivation film 2 is formed on the semiconductor element 1. The photosensitive film according to the present invention is laminated on the passivation film 2 by thermocompression bonding, heat-dried using a hot plate or the like, and a pattern of the photosensitive film is formed through exposure and development. After the pattern formation of the photosensitive film, a high temperature treatment process by curing is performed to form the cured film 3. Metal wiring is formed on the cured film 3 by a technique such as sputtering, vapor deposition, electroless plating, or electrolytic plating. Further, in order to protect the metal wiring, the photosensitive film according to the present invention is laminated by thermocompression bonding, heat-dried using a hot plate or the like, and a pattern is formed through exposure and development. After the pattern formation of the photosensitive film, a high-temperature treatment process by curing is performed to form the cured film 5. By forming the cured film by the above method, a highly flat semiconductor device having high adhesion between the cured films and high adhesion between the cured film and the metal wiring can be provided.

  Next, an application example to the coil component of the inductor device in which the cured film obtained by curing the photosensitive film of the present invention is disposed will be described with reference to the drawings. FIG. 2 is a cross-sectional view of a coil component having the cured film of the present invention. As shown in FIG. 2, an insulating film 7 is formed on the substrate 6, and a cured film 8 is formed thereon as a pattern. As the substrate 6, ferrite or the like is used. The photosensitive film of the present invention may be used for either the cured film 7 or the cured film 8. A metal film 9 (Cr, Ti, etc.) is formed in the opening of this pattern, and a metal wiring 10 (Ag, Cu, etc.) is formed thereon by plating. The metal wiring 10 (Ag, Cu, etc.) is formed on the spiral. A function as a coil can be provided by repeating the steps 7 to 10 a plurality of times and laminating them. Finally, the metal wiring 10 (Ag, Cu, etc.) is connected to the electrode 12 by the metal wiring 11 (Ag, Cu, etc.) and sealed with the sealing resin 13.

  Next, an application example of an electronic component or a semiconductor device having a hollow portion in which a cured film obtained by curing the photosensitive film of the present invention is disposed will be described with reference to the drawings. FIG. 3 is an example of a cross-sectional view of a hollow portion of an elastic wave device using the photosensitive film of the present invention. As shown in FIG. 3, an IDT (Inter Digital Transducer) electrode 15 composed of a pair of comb-shaped electrodes each having a plurality of electrode fingers interleaved with each other is bonded to the substrate 14 and bonding for electrical conduction. A pad 16 is formed. Here, examples of the substrate 14 include lithium niobate, potassium niobate, lithium tantalate, crystal, langasite, ZnO, PZT, and lithium borate. Examples of the material of the electrode 15 and the bonding pad include metals such as Al, Pt, Cu, Au, Ti, Ni, Cr, W, Pd, Co, and Mn. Furthermore, a relief pattern layer of a cured film of the photosensitive resin composition is formed as a support material 18 on the piezoelectric substrate 14 in order to secure the hollow portion 17. Examples of the photosensitive resin composition include polyimide resins, epoxy resins, acrylic resins, and phenol resins. The covering material 19 is provided on the substrate 15 via the support material 17 so as to cover the electrode 15. Here, although the photosensitive film of the present invention is used for the covering material 19, it may be used for the support material 17. The thickness of the covering material 19 is, for example, 20 μm. The protection member 20 is provided so as to cover the substrate 14, the support material 18, and the covering material 19. For example, the thickness of the protective member 20 on the covering material 19 is, for example, 30 μm. The protective member is an insulating material, and examples thereof include epoxy resin, benzocyclobutene resin, silicon resin, SOG (Spin On Glass), and the like. Via conductors 21 may be provided inside the support member 17 and the covering member 19 so as to penetrate in the thickness direction. Solder bumps 22 are connected and formed on the via conductors 21.

  Next, an application example of the photosensitive film of the present invention to a semiconductor device composed of a substrate having a step will be described with reference to the drawings. FIG. 4 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a cured film of the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). The silicon wafer 23 on which the Al pad 24 and the passivation film 25 are formed is diced and cut into chips, and then sealed with a resin 26. When the sealing is performed, heat treatment is performed, and the contraction of the resin 26 causes a (T-1) step between the chip 23 and the resin 26. At this time, the (T-1) step formed by the (S-1) upper step on the surface of the chip 23 and the (S-2) lower step on the surface of the resin 26 is 2 to 40 μm. A cured film 27 is formed as a pattern of the photosensitive film of the present invention over each of (S-1) the upper stage and (S-2) the lower stage, and (S-1) is disposed on the upper stage. The (T-2) step difference between the cured film and the cured film disposed on the (S-2) lower step is 5 μm or less.

  Further, a metal (Cr, Ti, etc.) film 28 and a metal wiring 29 are formed. Thereafter, the barrier metal 31 and the solder bump 32 are formed in the opening of the insulating film 30 formed on the sealing resin outside the chip. The fan-out WLP is provided with an extended portion using a sealing resin such as epoxy resin around the semiconductor chip, rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package that secures the necessary number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more materials such as a semiconductor chip provided with metal wiring and a sealing resin, and wiring is formed on the interlayer insulating film. In addition to this, in a semiconductor package of a type in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this aspect, an interlayer insulating film is formed on a base material made of two or more materials, and wiring is formed on the interlayer insulating film. When the cured film obtained by curing the photosensitive film of the present invention is disposed on a substrate made of two or more kinds of materials, the level difference on the substrate can be reduced and the flatness of the cured film can be maintained. Therefore, it is suitably used as an interlayer insulating film provided on a substrate made of two or more materials.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited by these. Evaluation of the esterification rate of the synthesized quinonediazide compound and evaluation of the photosensitive film were performed by the following methods.

<Measuring method of film thickness>
A Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and development was measured at a refractive index of 1.629 based on polyimide.

<Measurement of imidation ratio of polyimide>
(A2) The imidization rate of the alkali-soluble resin was such that an N-methylpyrrolidone (hereinafter, NMP) solution having a solid content concentration of polyimide resin of 50% by mass was applied onto a 6-inch silicon wafer by spin coating, and then 120 Baking was performed for 3 minutes with a hot plate at ℃ (Dai Nippon Screen Manufacturing Co., Ltd. SKW-636) to prepare a pre-baked film having a thickness of 10 μm ± 1 μm. This film was divided in half, and one side was placed in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), raised to a curing temperature of 350 ° C. over 30 minutes, and heat-treated at 350 ° C. for 60 minutes. Then, it annealed until the inside of oven became 50 degrees C or less, and obtained the cured film. About the obtained cured film (A) and the film (B) before curing, an infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). The peak intensity in the vicinity of 1377 cm ⁻¹ due to the CN stretching vibration of the imide ring was determined, and the value of “peak intensity of the film (B) before curing / peak intensity of the cured film (A)” was defined as the imidization ratio.

<Evaluation of laminating properties>
The protective film of the photosensitive film produced by each Example and comparative example which are mentioned later was peeled. The release surface was then laminated on a silicon wafer or a copper substrate. As the copper substrate, a substrate (copper plating substrate) having a metal material layer formed by sputtering titanium and copper on a silicon wafer to a thickness of 100 nm and then forming a copper plating film with a thickness of 2 μm by electrolytic plating was used. Lamination was performed using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M) under the conditions of a stage temperature of 80 ° C., a roll temperature of 80 ° C., a degree of vacuum of 150 Pa, a sticking speed of 5 mm / sec, and a sticking pressure of 0.2 MPa. After lamination, the photosensitive coating was cut in a grid pattern in the center of the film on the substrate using a cutter guide so that 100 squares were formed at intervals of 2 mm × 2 mm. After the cellophane tape was applied to the grid-like portion, it was pulled and peeled off at an angle of 90 ° with respect to the substrate. The number of the photosensitive coatings that were peeled out of the 100 when it was peeled off was counted. When the number of peeling is small, it indicates that the adhesiveness is high, and when it is large, it indicates that the adhesiveness is low. It is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less. The evaluation of the laminating property was performed on a silicon wafer, and the condition 1 was performed on a copper substrate.

<Evaluation of pattern processability (high sensitivity)>
The protective film of the photosensitive film produced in each Example and Comparative Example was peeled off, and the peeled surface was placed on an 8-inch silicon wafer using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M) at a stage temperature of 80. Lamination was performed under the conditions of ° C., roll temperature 120 ° C., degree of vacuum 150 Pa, sticking speed 5 mm / sec, sticking pressure 0.2 Mpa. Subsequently, it baked for 3 minutes with a 120 degreeC hotplate (ACT-8 use), and produced the 10-micrometer-thick prebaked film | membrane. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an i-line stepper (NIKON NSR i9). After exposure, development is performed with a 2.38 mass% tetramethylammonium (TMAH) aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, followed by rinsing with pure water, and development with an isolated space of 5 μm. Membrane A was obtained.

In the development film A, the exposure amount (hereinafter referred to as the minimum exposure amount Eth) at which the exposed portion of the isolated space of 5 μm was not completely eluted after exposure and development was defined as sensitivity. If Eth is 400 mJ / cm ² or less, it can be determined that the sensitivity is high. 300 mJ / cm ² and more preferably less, more preferably 250 mJ / cm ² or less.

<Evaluation of high elongation>
The protective film of the photosensitive film produced in each Example and Comparative Example was peeled off, and the stage temperature was 80 ° C. and the roll temperature was 120 ° C. on a silicon wafer using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M). The film was laminated so that the film thickness T1 was 11 μm under the conditions of a vacuum degree of 150 Pa, a sticking speed of 5 mm / second, and a sticking pressure of 0.2 Mpa. After pre-baking the laminated substrate at 120 ° C. for 3 minutes on a hot plate, an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) was used and an oxygen concentration of 20 ppm or less under a nitrogen stream was 3.5 per minute. The temperature was raised to 220 ° C. at a rate of temperature rise, and heat treatment was performed at 220 ° C. for 1 hour. Peeling was performed with a 46% by mass hydrofluoric acid aqueous solution to obtain a cured film (heat-resistant resin film). The cured film obtained by this method was cut out with a single blade so as to be 7 × 1 cm, and this was pulled at 50 mm / min with a Tensilon universal testing machine (RTM-100, manufactured by Orientec Corp.). A value obtained by dividing the amount of elongation at this time by the sample length was obtained. This measurement was performed on 10 samples, and the maximum value was defined as the elongation. The elongation is preferably 10% or more, more preferably 20% or more, and even more preferably 40% or more.

<5% weight loss temperature measurement (evaluation of heat resistance)>
A cured film obtained by the same method as in the above <evaluation of high extensibility> was subjected to a rate of 10 ° C./min in a nitrogen stream at 80 mL / min using a thermogravimetry measuring instrument (TGA50 manufactured by Shimadzu Corporation). The temperature was raised and measured. The 5% weight loss temperature is preferably 260 ° C or higher, more preferably 300 ° C or higher, and further preferably 340 ° C or higher.

Abbreviations and names of the compounds used in the examples and comparative examples are as follows.
PMDA-HH: 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride TDA-100: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride CBDA: cyclobutane tetracarboxylic dianhydride 6FDA: 4,4′-hexafluoroisopropylidene diphthalic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride SiDA: 1,1 , 3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane BAHF: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane DAE: 4,4′-diaminodiphenyl ether NMP: N-methyl-2-pyrrolidone ED-600: Jeffamine ED-600 (trade name, HUNTSM N (Ltd.))
MAP: metaaminophenol NA: 5-norbornene-2,3-dicarboxylic anhydride KBM-403: 3-glycidoxypropyltrimethoxysilane (silane compound (a)).

  The (C) thermal crosslinking agent and (H) compound used in each Example and Comparative Example are shown below.

Synthesis Example 1 Synthesis of quinonediazide compound (a) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.10 mol), 13.43 g (0.05 mol) of 4-naphthoquinonediazide sulfonyl chloride was dissolved in 50 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise while confirming that the inside of the system was not 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (a) represented by the following formula.

Synthesis Example 2 Synthesis of polyhydroxystyrene resin (a0-1) 500 ml of tetrahydrofuran and 0.01 mol of sec-butyllithium as an initiator were added to a mixed solution of pt-butoxystyrene and styrene at a molar ratio of 3: 1. A total of 20 g was added in a proportion and polymerized with stirring for 3 hours. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. Furthermore, after dissolving in 400 ml of acetone, adding a small amount of concentrated hydrochloric acid at 60 ° C. and stirring for 7 hours, the mixture is poured into water, the polymer is precipitated, pt-butoxystyrene is deprotected and converted to hydroxystyrene, and washed. When dried, a purified copolymer of p-hydroxystyrene and styrene (hereinafter (a0-1)) was obtained. Moreover, the weight average molecular weight (Mw) was 3500 (GPC polystyrene conversion) by the analysis by GPC, and dispersion degree was (Mw / Mn) 2.80.

Synthesis Example 3 Synthesis of polyhydroxystyrene resin (a0-2) The same procedure was performed except that mt-butoxystyrene was used instead of pt-butoxystyrene of Synthesis Example 2. The obtained copolymer of m-hydroxystyrene and styrene (hereinafter referred to as (a0-2)) has a weight average molecular weight (Mw) of 5000 (in terms of GPC polystyrene) and a dispersity of (Mw / Mn) 3 by GPC analysis. .20.

Synthesis Example 4 Synthesis of polyhydroxystyrene resin (a0-3) The same procedure was performed except that styrene of Synthesis Example 2 was not added. The obtained p-hydroxystyrene resin (hereinafter (a0-3)) had a weight average molecular weight (Mw) of 3000 (converted to GPC polystyrene) and a dispersity of (Mw / Mn) of 1.60 according to analysis by GPC. .

Synthesis Example 5 Synthesis of Alkali-Soluble Resin (a1-1) Polyhydroxystyrene resin (a0-1) was dissolved in a solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of a 36-38 mass% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. The white solid formed in the solution after standing was washed with 100 mL of water. This white solid was vacuum-dried at 50 ° C. for 48 hours.

Next, the white solid thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rohman Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Then, GBL500mL was added, methanol was removed with the rotary evaporator, and it was set as the GBL solution. This was analyzed by ¹³ C-NMR (manufactured by JEOL Ltd., GX-270), and an alkali-soluble resin (hereinafter (a1-1)), which is a partially hydroxylated polyhydroxystyrene resin, was obtained. It was confirmed. As a result of analysis by GPC, the weight average molecular weight (Mw) was 8000 (in terms of GPC polystyrene), and the alkoxylated hydroxystyrene had an introduction rate of 35 mol% per mol of hydroxystyrene.

Synthesis Example 6 Synthesis of Alkali-Soluble Resin (a1-2) Synthesis was performed in the same production method except that (a0-2) was used instead of (a0-1) in Synthesis Example 5. The obtained alkali-soluble resin (hereinafter referred to as (a1-2)), which is an alkoxylated polyhydroxystyrene resin, has a weight average molecular weight (Mw) of 7500 (in terms of GPC polystyrene) as analyzed by GPC, and the introduction rate of alkoxy groups. Was 55 mol% per mol of hydroxystyrene.

Synthesis Example 7 Synthesis of Alkali-Soluble Resin (a1-3) Synthesis was performed in the same production method except that (a0-3) was used instead of (a0-1) in Synthesis Example 5. The obtained alkali-soluble resin (hereinafter referred to as (a1-3)), which is an alkoxylated polyhydroxystyrene resin, has a weight average molecular weight (Mw) of 3500 (in terms of GPC polystyrene) as analyzed by GPC, and the introduction rate of alkoxy groups. Was 69 mol% per mol of hydroxystyrene.

Synthesis Example 8 Synthesis of Novolak Resin (e) Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of 37% by mass aqueous formaldehyde solution ( 0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were immersed in an oil bath, and the polycondensation reaction was performed for 4 hours while refluxing the reaction solution. went. Thereafter, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 40 to 67 hPa, volatile components are removed, the dissolved resin is cooled to room temperature, and alkali-soluble. A novolac resin (e) polymer solid was obtained. It was confirmed by GPC analysis that the weight average molecular weight (Mw) was 3,500. Γ-butyrolactone (GBL) was added to the resulting novolak resin (e) to obtain a novolak resin (e) solution having a solid content concentration of 43% by mass.

Synthesis Example 9 Synthesis of Ring-Closed Polyimide Resin (A) Under a dry nitrogen stream, 4.48 g (0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED-600 6.00g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, The mixture was reacted at 60 ° C. for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (A).

Synthesis Example 10 Synthesis of Ring-Closed Polyimide Resin (B) PMDA-HH 1.12 g (0.005 mol), 6FDA 11.11 g (0.025 mol), ODPA 4.65 g (0.015 mol) NMP 100 g in a dry nitrogen stream Dissolved in. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.00g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (B).

Synthesis Example 11 Synthesis of Ring-Closed Polyimide Resin (C) Under a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.00g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (C).

Synthesis Example 12 Synthesis of Ring-Closed Polyimide Resin (D) Under a dry nitrogen stream, 0.98 g (0.005 mol) of CBDA, 11.11 g (0.025 mol) of 6FDA and 4.65 g (0.015 mol) of ODPA were dissolved in 100 g of NMP. I let you. BAHF11.90g (0.033mol), DAE0.50g (0.003mol), ED600 7.50g (0.013mol), SiDA0.62g (0.003mol) were added with NMP20g here, 60 degreeC After stirring at 180 ° C. for 4 hours, 1.64 g (0.010 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride is added together with 10 g of NMP as a terminal blocking agent, The reaction was carried out at 1 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (D).

Synthesis Example 13 Synthesis of Ring-Closed Polyimide Resin (E) CBDA 0.98 g (0.005 mol), 6FDA 11.11 g (0.025 mol), TDA-100 4.50 g (0.015 mol) under a dry nitrogen stream. Dissolved in 100 g of NMP. BAHF11.90g (0.033mol), DAE0.50g (0.003mol), ED600 7.50g (0.013mol), SiDA0.62g (0.003mol) were added with NMP20g here, 60 degreeC After stirring at 180 ° C. for 4 hours, 1.64 g (0.010 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride is added together with 10 g of NMP as a terminal blocking agent, The reaction was carried out at 1 ° C. for 1 hour. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (E).

Synthesis Example 14 Synthesis of already-closed polyimide resin (F) PMDA-HH (0.009 g, 0.045 mol) was dissolved in NMP (100 g) under a dry nitrogen stream. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Further, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP and reacted at 60 ° C. for 1 hour, and then at 180 ° C. for 4 hours. Stir. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed ring polyimide resin (F).

Synthesis Example 15 Synthesis of already-closed polyimide resin (G) Under a dry nitrogen stream, 8.82 g (0.045 mol) of CBDA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Further, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE and 0.62 g (0.003 mol) of SiDA were added together with 20 g of NMP and reacted at 60 ° C. for 1 hour, and then at 180 ° C. for 4 hours. Stir. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (G).

Synthesis Example 16 Synthesis of already-closed polyimide resin (H) 13.96 g (0.045 mol) of ODPA was dissolved in 100 g of NMP under a dry nitrogen stream. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.0g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (H).

Synthesis example 17 Synthesis | combination of already-closed polyimide resin (I) Under dry nitrogen stream, 6.01 g (0.020 mol) of TDA-100 and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.0g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (I).

Synthesis Example 18 Synthesis of already-closed polyimide resin (J) In a dry nitrogen stream, 19.99 g (0.045 mol) of 6FDA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Furthermore, BAHF11.90g (0.033mol), DAE1.00g (0.005mol), ED600 6.0g (0.010mol), SiDA0.62g (0.003mol) were added with NMP20g, and at 60 degreeC. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (J).

Synthesis Example 19 Synthesis of Polybenzoxazole Precursor (K) In a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was adjusted. Cooled to -15 ° C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by mass of methanol to precipitate a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble polybenzoxazole precursor (K).

Synthesis Example 20 Synthesis of Polyimide Precursor Resin (L) Under a dry nitrogen stream, 4,4′-diaminophenyl ether (hereinafter referred to as DAE) 7.51 g (0.038 mol), SiDA 1.86 g (0.007 mol), 1.09 g (0.010 mol) of 3-aminophenol was dissolved in 100 g of NMP. To this, 13.96 g (0.045 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 9.25 g (0.08 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes and reacted at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Further, after washing twice with 2 L of water, it was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide resin (K).

Synthesis Example 21 Synthesis of polyimide resin (M) Under a dry nitrogen stream, 8.11 g (0.04 mol) of DAE and 1.09 g (0.010 mol) of 3-aminophenol were dissolved in 100 g of NMP. To this, 13.96 g (0.045 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, the mixture was stirred at 180 ° C. for 5 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a polyimide resin (M).

Synthesis Example 22 Synthesis of Ring-Closed Polyimide Resin (N) Under a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Further, BAHF 10.07 g (0.028 mol), DAE 1.00 g (0.005 mol), ED600 10.50 g (0.018 mol), SiDA 0.62 g (0.003 mol) were added together with NMP 20 g at 60 ° C. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (N).

Synthesis example 23 Synthesis | combination of already-closed polyimide resin (O) CBDA 3.92g (0.020mol) and 6FDA 11.11g (0.025mol) were dissolved in NMP100g under dry nitrogen stream. To this was added 1.09 g (0.010 mol) of 3-aminophenol together with 20 g of NMP. Further, BAHF 7.33 g (0.020 mol), DAE 1.00 g (0.005 mol), ED600 15.00 g (0.025 mol), SiDA 0.62 g (0.003 mol) were added together with NMP 20 g at 60 ° C. The reaction was carried out for 1 hour and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried for 72 hours in a vacuum dryer at 50 ° C. to obtain a powder of a closed ring polyimide resin (O).

Synthesis Example 24 Synthesis of Novolak Resin (f) M-cresol 108.0 g, methanol 108.0 g, and sodium hydroxide 40.0 g were charged in a nitrogen-substituted three-necked flask 1000 ml, heated to 67 ° C. with stirring, The reflux reaction was performed for 30 minutes. Thereafter, the reaction solution was cooled to 40 ° C., charged with 65.2 g of 92% by mass paraformaldehyde, heated again to 67 ° C., and then refluxed for 5 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C. or less, and 140.0 g of 30% by mass sulfuric acid was added dropwise over 30 minutes so that the reaction solution did not become 35 ° C. or more. The pH of the obtained reaction liquid was 4.9. Further, 540.0 g of ion-exchanged water was added to the reaction solution, stirred for 20 minutes and allowed to stand for 20 minutes, and then the separated aqueous layer was removed. After removing the aqueous layer, 108.0 g of dioxane was added, and residual water was removed to less than 3% by mass at 40 ° C. and a pressure of 0.08 MPa. Methanol 432.0g and 96 mass% sulfuric acid 2.0g were added to the reaction liquid. The pH of the obtained reaction liquid was 0.8. The temperature of the reaction solution was raised to 60 ° C., and an alkoxylation reaction was performed at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution is cooled to 30 ° C. or lower, and a 10% by mass aqueous sodium hydroxide solution is added over 30 minutes until the pH of the reaction solution reaches 9.0 so that the temperature of the reaction solution does not exceed 35 ° C. It was dripped. Methyl isobutyl ketone (MIBK) 216.0 g and ion-exchanged water 324.0 g as a separation solvent for washing were added to the reaction solution, stirred at 30 ° C. for 20 minutes, allowed to stand for 20 minutes, and the separated aqueous layer was removed. Further, 324.0 g of ion-exchanged water was added, and the washing operation was repeated with ion-exchanged water until the electric conductivity of the removed water became 100 μScm or less. After completion of washing, 300 g of γ-butyrolactone was added, and ion-exchanged water and MIBK were distilled off at 70 ° C. and a pressure of 0.08 MPa to obtain a novolak resin solution (f) having a solid content of 50% by mass.

  The obtained novolak resin solution (f) had a weight average molecular weight (Mw) of 7000 (in terms of GPA polystyrene) and a dispersity (Mw / Mn) of 7.5 according to analysis by GPC. The number of moles of alkoxyalkyl group per mole of phenol skeleton by 13C NMR was 57 mol%, and the alkoxylation rate was 100 mol%.

Example 1
6. 10.5 g of an alkali-soluble resin (a1-1), 10.5 g of the resin (A) obtained in Synthesis Example 9, 3.0 g of the quinonediazide compound (a) obtained in Synthesis Example 1, and a crosslinking agent MX-270 2 g of KBM-403 1.0 g was added to 25 g of GBL to obtain varnish A of a positive photosensitive resin composition.

  The obtained varnish was applied onto a PET film having a thickness of 38 μm using a comma roll coater, dried at 80 ° C. for 8 minutes, and then laminated with a PP film having a thickness of 10 μm as a protective film. A characteristic film was obtained. The film thickness of the photosensitive film was adjusted to 10 μm.

  Using the obtained photosensitive film, each evaluation of the laminate property to a silicon substrate, high extensibility, 5% weight loss temperature (heat resistance), and pattern processability was performed.

Examples 2-33, Comparative Examples 1-8
The addition amounts of (A1) alkali-soluble resin, (A2) alkali-soluble resin, other additives, (B) photoacid generator and (C) cross-linking agent are as shown in Table 1, Table 2-1, and Table 2-2. A varnish was prepared in the same manner as in Example 1 except that the varnish was changed. Using the obtained photosensitive film, each evaluation of the laminate property to a silicon substrate, high extensibility, 5% weight loss temperature (heat resistance), and pattern processability was performed.

  Table 1 shows the molar ratio of the components of (A2) alkali-soluble resin.

  The evaluation results are shown in Table 3-1 and Table 3-2.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Passivation film 3 Cured film 4 Metal wiring 5 Cured film 6 Substrate 7 Cured film 8 Cured film 9 Metal film 10 Metal wiring 11 Metal wiring 12 Electrode 13 Sealing resin 14 Substrate 15 IDT electrode 16 Bonding pad 17 Hollow part 18 Support material 19 Cover material 20 Protective member 21 Via conductor 22 Solder bump 23 Silicon wafer 24 Al pad 25 Passivation film 26 Resin 27 Cured film 28 Metal film 29 Metal wiring 30 Insulating film 31 Barrier metal 32 Solder bump

Claims (20)

(A1) an alkali-soluble resin having a structural unit represented by the general formula (1),
(A2) an alkali-soluble resin containing one or more selected from polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof,
A photosensitive film containing (B) a photoacid generator and (C) a thermal crosslinking agent.
(In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, (Methyl group, ethyl group, or propyl group.) The photosensitive film of Claim 1 whose weight average molecular weight (Mw) of said (A1) alkali-soluble resin exists in the range of 3,000-60,000. The photosensitive film according to claim 1 or 2, wherein the (A1) alkali-soluble resin further has at least one of the structural units represented by the general formula (2) and the general formula (3).
(In general formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents an integer in the range of 1 to 5)
(In general formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The photosensitive film in any one of Claims 1-3 whose weight average molecular weights (Mw) of the said (C) thermal crosslinking agent are 100-2,500. The photosensitive film according to claim 1, wherein the (A2) alkali-soluble resin has one or more substituents selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. The photosensitive film according to claim 1, wherein the (A2) alkali-soluble resin has at least one of the structural units represented by the general formulas (4) and (5).
(In General Formula (4), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R ⁶ represents a divalent organic group having 20 to 100 carbon atoms. N ₁ represents 10 to 100. An integer in the range of 1,000.)
(In the general formula (5), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R ⁶ represents a divalent organic group having 20 to 100 carbon atoms. R ⁷ represents hydrogen or carbon. And represents an organic group having a number of 1 to 20. n ₂ represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 2. R ⁶ in the general formulas (4) and (5) has an organic group having a polyether structure and 20 to 100 carbon atoms in a total amount of 100 mol% of the repeating units in the general formulas (4) and (5). The photosensitive film of Claim 6 containing 10-80 mol% with respect to. The photosensitive film of Claim 7 whose organic group which has the said polyether structure and is C20-100 is an organic group represented by General formula (10).
(In the formula, R ^{54 to} R ⁵⁷ each independently represents an alkylene group having 1 to 6 carbon atoms. R ^{58 to} R ⁶⁵ each independently represents hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. The structure represented in the parentheses of the repeating unit x is different from the structure represented in the parentheses of the repeating unit y, and the structure represented in the parentheses of the repeating unit z is different from the structure represented in the parentheses of the repeating unit y. (X, y and z each independently represents an integer of 0 to 35). R ⁵ in the general formulas (4) and (5) is an organic group having an alicyclic structure and having 4 to 40 carbon atoms in a total amount of 100 mol% of the repeating units in the general formulas (4) and (5). The photosensitive film in any one of Claims 6-8 containing 10-80 mol% with respect to. Furthermore, the photosensitive film in any one of Claims 1-9 containing the compound represented by (H) general formula (13).
(In the general formula ^{(13), R} 71 ~R ⁷³ is, O atom or S atom, one of the N ^atoms, .l 0 or 1 indicating the least one S atom of R 71 ^{to R 73} R ⁷¹ represents an oxygen atom or a sulfur atom when l is 0, and represents a nitrogen atom when l is 1. m and n represent 1 or 2. R ^{74 to} R ⁷⁶ each represents Independently, it represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.) Furthermore, the said (C) thermal crosslinking agent contains the thermal crosslinking agent which has a structural unit represented by General formula (12), The photosensitive film in any one of Claims 1-10.
(In General Formula (12), R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom or a methyl group. R ⁶⁸ is a divalent organic group having an alkylene group having 2 or more carbon atoms, and is linear. , Any of branched, and annular may be used.) The photosensitive film in any one of Claims 1-11 which has a photosensitive layer whose film thickness is 3-45 micrometers. The photosensitive film of Claim 12 which has a protective film on the said photosensitive layer, and has a support film under the said photosensitive layer. A cured film obtained by curing the photosensitive film according to claim 1. The interlayer insulation film or semiconductor protective film in which the cured film of Claim 14 was arrange | positioned. The electronic component or semiconductor device which has the relief pattern layer of the cured film of Claim 14. The cured film according to claim 14 is provided on a substrate with a film thickness of 2 to 40 μm, copper wiring is provided thereon, and the cured film according to claim 14 is further provided as an insulating film between the copper wirings. An electronic component or semiconductor device having a thickness of 2 to 40 μm. A relief pattern layer of a cured film of the photosensitive resin composition as a support material is provided on the substrate, and further, the cured film according to claim 14 is provided on the support material as a coating material, and the relief pattern of the support material is provided. An electronic component or a semiconductor device, wherein the covering material is disposed in an opening of the layer and has a hollow portion surrounded by the support material, the covering material, and the substrate. (T-1) The step is 2 to 40 μm, (S-1) has an upper step and (S-2) a lower step on the substrate,
The cured film of Claim 14 is arrange | positioned on each of the said (S-1) upper stage part and (S-2) lower stage part,
The cured film according to claim 14 disposed on the (S-1) upper stage part and the cured film according to claim 14 disposed on the (S-2) lower stage part (T -2) The step is 5 μm or less.
Electronic components or semiconductor devices. It is a method of manufacturing a semiconductor device using the photosensitive film of Claims 1-13, Comprising: A photosensitive film is formed by thermocompression-bonding the said photosensitive film on the board | substrate at the temperature of 40-150 degreeC. The manufacturing method of an electronic component or a semiconductor device including the process, the process of exposing the said photosensitive film through an exposure mask, and the process of removing the exposed part of the said photosensitive film with an alkali developing solution, and developing.