TW201802597A - Photosensitive film - Google Patents

Abstract

Provided is a photosensitive film which is able to provide a cured film having high heat resistance, and which has a good pattern processing ability (high sensitivity) and simultaneously exhibits good adhesion to a substrate, i.e., good laminating properties. This photosensitive film contains: an alkali-soluble resin (A1) having the structural unit represented by general formula (1); an alkali-soluble resin (A2) that comprises at least one member selected from among polyimides, polybenzooxazoles, polyamide imides, precursors thereof, and copolymers thereof; a photoacid generator (B); and a thermal crosslinking agent (C). (In general formula (1), R1 represents a hydrogen atom or an alkyl group having 1-5 carbon atoms; a represents an integer of 0-4, and b represents an integer of 1-3; and R2 represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group.).

Description

Photosensitive film

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

唑所代表的樹脂，因為具有優異的耐熱性、電絕緣性，所以使用於半導體元件之表面保護膜、層間絕緣膜、有機場效發光元件之絕緣層等。近年來，伴隨半導體元件之細微化，在表面保護膜或層間絕緣膜等也需要數μm等級的解析度。因此，在如前述的用途中，大多使用可細微加工的正型感光性聚醯亞胺樹脂組成物或正型感光性聚苯并

唑樹脂組成物。 Polyimide or polybenzo

The resin represented by azole has excellent heat resistance and electrical insulation properties, so it is used for surface protection films, interlayer insulation films, and insulation layers for organic light-emitting elements in semiconductor devices. In recent years, with the miniaturization of semiconductor devices, resolutions on the order of several μm are also required for surface protective films, interlayer insulating films, and the like. Therefore, in the applications as described above, a finely-processable positive photosensitive polyfluorene imine resin composition or a positive photosensitive polybenzo is often used.

Azole resin composition.

In a general manufacturing process of a semiconductor device, a semiconductor element is formed on a substrate, a photosensitive layer is formed on the passivation film represented by Si or SiN, and then heated and dried using a hot plate or the like, and a pattern is formed by exposure and development. After the pattern is formed, a high-temperature heat treatment is performed to form an insulating layer by hardening.

Conventionally, a circular substrate has been used for the formation of a semiconductor element. However, in recent years, with the increase in the size of the substrate, a rectangular substrate has been used.

As a method of forming a photosensitive layer on a substrate, there is a method of applying a resin composition by a spin coating method, or a method of applying heat to a substrate and pressure-bonding and laminating a photosensitive film. When forming an insulating layer on a large square substrate, in order to improve the uniformity of the film thickness after formation, a method of laminating a photosensitive thin film is generally used.

As the positive photosensitive polyimide used for a resin composition or a photosensitive film, a polyimide is used as a substrate (for example, Patent Document 1), and a polyhydroxystyrene is used as a substrate (for example, patent Document 2), and those in which polyfluorene imine and polyhydroxystyrene are mixed (for example, Patent Document 3).

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

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 2014-71374

Patent Document 2 Japanese Patent Laid-Open No. 2006-154779

Patent Document 3 Japanese Patent Application Publication No. 2014-137523

Patent Document 4 Japanese Patent Laid-Open No. 2015-19006

Patent Document 5 International Publication No. 2011/059089

As described above, when forming an insulating layer on a square substrate, in order to improve the uniformity of the film thickness after the formation, a photosensitive film is generally used. Layer approach. On the photosensitive film, in addition to the mechanical properties such as high stretchability and heat resistance that can be imparted to the cured film, in addition to having good pattern processability (high sensitivity), it is also necessary to have good adhesion to the substrate. Sexuality, that is, laminarity.

However, as disclosed in Patent Documents 1 to 3, the film of a resin composition using polyimide has insufficient flexibility. When heat is applied to a substrate and the film is laminated by pressure bonding, cracks may be generated. insufficient. Further, Patent Document 4 discloses a technique using a phenol resin for the purpose of improving fluidity, but there is a problem that the heat resistance of the cured film is low. In addition, Patent Document 5 discloses a technique using polyimide having a low softening point, but there is a problem that high heat resistance cannot be obtained.

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

唑、聚醯胺醯亞胺、此等之前驅物、及此等之共聚物之1種以上的鹼可溶性樹脂、(B)光酸產生劑、以及(C)熱交聯劑。 In order to solve the above-mentioned problems, the photosensitive film of the present invention has the following configuration. That is, it is a photosensitive film containing (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), and (A2) containing a resin selected from the group consisting of polyimide and polybenzo

One or more kinds of alkali-soluble resins such as azole, polyamidoimine, these precursors, and copolymers thereof, (B) a photoacid generator, and (C) a thermal crosslinking agent.

(In the 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 in the range of 1 to 3; R ² represents a hydrogen atom, a methyl group, or an ethyl group; Either radical or propyl.)

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

1‧‧‧semiconductor element

2‧‧‧ passivation film

3‧‧‧hardened film

4‧‧‧ metal wiring

5‧‧‧hardened film

6‧‧‧ substrate

7‧‧‧hardened film

8‧‧‧hardened film

9‧‧‧ metal film

10‧‧‧ Metal wiring

11‧‧‧Metal wiring

12‧‧‧ electrode

13‧‧‧sealing resin

14‧‧‧ substrate

15‧‧‧IDT electrode

16‧‧‧Joint pad

17‧‧‧ Hollow

18‧‧‧ support material

19‧‧‧ Covering material

20‧‧‧Protective member

21‧‧‧Interlayer conductor

22‧‧‧Solder bump

23‧‧‧ silicon wafer

24‧‧‧Al pad

25‧‧‧ passivation film

26‧‧‧Resin

27‧‧‧hardened film

28‧‧‧metal film

29‧‧‧Metal wiring

30‧‧‧ insulating film

31‧‧‧metal barrier

32‧‧‧solder bump

FIG. 1 is an example of a schematic cross-sectional view of a semiconductor device using the photosensitive film of the present invention.

FIG. 2 is an example of a cross-sectional view of a coil portion of an inductor device using the photosensitive film of the present invention.

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.

4 is an example of a cross-sectional view of a semiconductor device having a step on a substrate using the photosensitive film of the present invention.

Implementation of the invention

唑、聚醯胺醯亞胺、此等之前驅物、及此等之共聚物之1種以上的鹼可溶性樹脂、(B)光酸產生劑、以及(C)熱交聯劑。以下有時各別省略為(A1)樹脂、(A2)樹脂、(B)成分、(C)成分。 The present invention is a photosensitive film containing the alkali-soluble resin (A1) having a structural unit represented by the general formula (1), and (A2) containing a resin selected from the group consisting of polyimide and polybenzo

One or more kinds of alkali-soluble resins such as azole, polyamidoimine, these precursors, and copolymers thereof, (B) a photoacid generator, and (C) a thermal crosslinking agent. Hereinafter, it may be omitted separately as (A1) resin, (A2) resin, (B) component, and (C) component.

The photosensitive film of this invention contains the alkali-soluble resin (A1) which has the structural unit represented by General formula (1). In the 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 in the range of 1 to 3, and R ² represents a hydrogen atom, a methyl group, or an ethyl group. Or propyl. By containing (A1) resin, the sensitivity of a photosensitive film can be improved.

The structural unit represented by the aforementioned general formula (1) is, for example, a combination of p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, Aromatic vinyl compounds having phenolic hydroxyl groups such as o-isopropenylphenol, and aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene A part of the polymer obtained by polymerization alone or two or more of them by a known method, and obtained by subjecting an alkoxy group to an addition reaction 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 can be suitably used, and as the aromatic vinyl compound, styrene can be suitably used.

The alkali-soluble resin (A1) having a structural unit represented by the general formula (1) is more preferably a compound having the general formula (2) from the viewpoint of further improving sensitivity and adjusting the solubility in an alkali developer. ) 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 the 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 the general formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

The introduction rate of the alkoxyalkane (CH ₂ OR ² ) group of the aforementioned (A1) resin is, from the viewpoint of heat resistance after curing, preferably an introduction rate of 10 mol% or more per mol of hydroxystyrene. , More preferably 20 mol% or more. From the viewpoint of improving the resolution, it is preferably 70 mol% or less, and more preferably 50 mol% or less.

The polystyrene equivalent weight average molecular weight (Mw) of the (A1) resin is preferably 3,000 or more from the viewpoint that the pattern of the unexposed portion is not dissolved out and formed. From the viewpoint of maintaining the alkali solubility of the residue in the exposed portion, it is preferably 60,000 or less, and more preferably 25,000 or less.

The polystyrene-equivalent weight average molecular weight (Mw) refers to a value calculated by measurement using polystyrene-equivalent GPC (colloidal permeation chromatography).

唑、聚醯胺醯亞胺、此等之前驅物、及此等之共聚物之1種以上的鹼可溶性樹脂。 The photosensitive film of the present invention contains (A2)

One or more kinds of alkali-soluble resins such as azole, polyamidoimine, these precursors, and copolymers of these.

唑、聚醯胺醯亞胺、此等之前驅物、及此等之共聚物中之任一者，也可包含具有該等之2種以上的重複單元之共聚物。又，(A2)樹脂，較佳為具有與前述(A1)樹脂的烷氧烷基反應之取代基。(A1)的烷氧烷基特別是指烷氧甲基。(A2)樹脂的結構，只要具有對烷氧烷基反應的取代基，則沒有特別限定，較佳為在主鏈或末端具有一個以上之選自羧基、酚性羥基、磺酸基、及硫醇基的基。 The (A2) resin may contain two or more kinds of polyimide and polybenzo

Any one of azole, polyamidine, imine, these precursors, and these copolymers may include a copolymer having two or more of these repeating units. The (A2) resin preferably has a substituent that reacts with the alkoxyalkyl group of the (A1) resin. The alkoxyalkyl group of (A1) particularly means 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, and preferably has one or more members selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a sulfur group in the main chain or terminal. Alcohol-based group.

The (A1) resin's alkoxyalkyl group reacts with the (A2) resin during thermal curing, so it can fully maintain heat resistance and mechanical properties, so it can have both the good pattern processability of the (A1) resin and (A2) ) The resin has high heat resistance and mechanical properties. 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. From the viewpoint of heat resistance and mechanical properties, it is preferably 90 parts by mass or less, and more preferably 70 parts by mass or less.

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

(In the general formula (4), R ⁵ represents a 2- to 4-valent organic group having 4 to 40 carbon atoms. R ⁶ represents a divalent organic group having 20 to 100 carbon atoms. N ₁ represents an integer in the range of 10 to 100,000. )

(In the general formula (5), R ⁵ represents a 2- to 4-valent 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 an organic group having 1 to 20 carbon atoms Base. N ₂ represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 2.)

In the general formulae (4) and (5), R ⁵ represents a 2- to 4-valent organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure. In R ⁵ , as the monocyclic or condensed polycyclic alicyclic structure, it is preferable to contain one or more organic groups selected from the following general formulae (6) to (9).

(In the general formulae (6) to (9), R ⁸ to R ⁵³ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 3 carbon atoms. A monovalent organic group having 1 to 3 carbon atoms, which The hydrogen atom contained in the organic group may be substituted with a halogen atom.)

R ⁵ in the general formulae (4) and (5) is an organic group derived from an acid dianhydride used as a raw material of a resin.

As the acid dianhydride containing a 2- to 4-valent organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure used in the present invention, specific examples include 1,2, 3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl- Compounds of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

In the general formulae (4) and (5), as R ⁵ , a preferable structure of a 2- to 4-valent organic group having 4 to 40 carbon atoms having 1 to 4 aromatic rings is exemplified by benzene homogenate. Tetraacid, 3,3 ', 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-dicarboxybenzene 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) fluorene, Bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid Acid, 3,4,9,10-fluorenetetracarboxylic acid and other aromatic tetracarboxylic acids to remove the structure of the carboxyl group, or a part of these hydrogen atoms, using an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, Structures in which 1 to 4 alkoxy groups, ester groups, nitro groups, cyano groups, fluorine atoms, and chlorine atoms are substituted.

R ⁵ of a monocyclic or condensed polycyclic alicyclic structure based upon the formula (4) and (5) the R ⁵ as 100 mole%, from a high degree of elongation, enhancing film with respect to the substrate From the standpoint of lamination, 10 mol% is more preferable, and 30 mol% or more is more preferable. From the viewpoint of obtaining an appropriate dissolution rate with respect to the developer, it is preferably 80 mol% or less, and more preferably 60 mol% or less.

For example, R ⁵ contains 70 mol% of a monocyclic or condensed polycyclic alicyclic structure with respect to 100 mol% of the total repeating units of the general formulae (4) and (5), and contains an aromatic ring When the molar amount of the tetravalent organic group is 30 mol%, the monocyclic or condensed polycyclic alicyclic structure is calculated as 70 mol%. In this case, when R ⁵ has two or more types of monocyclic or condensed polycyclic alicyclic structures, it is calculated as 70 mol%.

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

(In the formula, R ⁵⁴ to R ⁵⁷ each independently represent an alkylene group having 1 to 6 carbon atoms. R ⁵⁸ to R ⁶⁵ each independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms. However, repeating The structure shown in the brackets of the unit x is different from the structure shown in the brackets of the repeating unit y. The structure shown in the brackets of the repeating unit z is different from the structure shown in the brackets of the repeating unit y. X, y and z each independently represent an integer of 0 to 35.) Moreover, R ⁶ in the general formulae (4) and (5) is an organic group derived from a diamine used as a raw material of a resin.

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, 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 -1700 (above the trade name, manufactured by HUNTSMAN) and other aliphatic diamines. By having a polyether structure, it imparts hydrophilicity and meltability at high temperature, so it can improve the lamination of the substrate and give flexibility, so it can improve the elongation, and the elastic coefficient can be reduced to suppress the warpage of the wafer. It is better. These characteristics are effective characteristics in a multilayer or a thick film. When the polyether structure represented by the general formula (10) is 100 mol% when R ^{6 of the} general formulae (4) and (5) is set, if it is 10 mol% or more, flexibility and low resin properties are obtained. Stressability and lamination to a substrate are preferred. From the viewpoint of obtaining an appropriate dissolution rate with respect to the developing solution, it is preferably 80 mol% or less. More preferably, it contains 20 mol% to 50 mol%.

For example, R ⁶ contains 70 mol% of an organic group derived from a diamine containing an organic group having a polyether structure, and contains 100 mol% of the total repeating units of the general formulae (4) and (5). When the molar amount of the divalent organic group of the aromatic ring is 30 mol%, the organic group derived from a diamine containing an organic group having a polyether structure is calculated as 70 mol%. In this case, when R ⁶ has two or more organic groups derived from a diamine containing an organic group having a polyether structure, it is calculated as 70 mol%.

In addition, by further containing an organic group having a fluorine atom as R ^{5 of the} general formulae (4) and (5), it is possible to impart water repellency to the resin and to suppress permeation from the surface of the film during alkali development, so it is preferable. . By suppressing the permeation from the surface of the film, a resin film with a high residual film rate can be obtained, which is free from the tackiness of the unexposed portion or without the development residue in the processed pattern. These characteristics are premised on the realization of thick film processing, and are important characteristics. For an organic group having a fluorine atom, when the total amount of R ⁵ is set to 100 mol%, if it is 20 mol% or more, the effect of preventing permeation at the interface can be obtained, and the appropriate dissolution rate with respect to the developing solution can be obtained. From a viewpoint, if it is 90 mol% or less, it is more preferable, and it is more preferable to contain 40 mol% to 60 mol%.

Specific examples of the compound having a fluorine atom include a compound in which 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or an aromatic ring thereof is substituted with an alkyl group or a halogen atom. Compounds, and aromatic acid dianhydrides such as acid dianhydrides having amidino groups. (A2) The resin is preferably a resin containing a structure derived from these compounds.

By using the aforementioned 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, one can be obtained The high-sensitivity photosensitive film has high elongation and low stress, and has a high residual film rate without stickiness or development residue during development.

These characteristics are particularly useful as an interlayer insulating film between metal wirings, and is used for rewiring of a semiconductor device regardless of how many layers are laminated, or for use as a noise filter for an inductor device. In addition, the photosensitive film of the present invention is in a range that does not degrade the characteristics, In addition to the above-mentioned acid dianhydride and diamine, it may contain a structure derived from another acid dianhydride and diamine.

Specific examples of the other acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'- Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ' , 3,3'-benzophenone tetracarboxylic 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-dicarboxyphenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-pyridinetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3 , 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. or compounds in which the hydrogen atom of the compound is substituted with an alkyl group or a halogen atom, or a compound such as 5- ( 2,5-Dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride , Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetracarboxylic acid Furan tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride Alicyclic, semialicyclic tetracarboxylic dianhydride or a compound in which a hydrogen atom is substituted with an alkyl group or a halogen atom, and an acid dianhydride having an amidino group. These can be used in combination with two or more kinds of 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) fluorene, and bis (3-amine 4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3- Hydroxyl-containing diamines such as amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3-sulfonic acid -4,4'-diaminodiphenyl ether, sulfonic acid-containing diamines, dimercaptophenylenediamine, thiol group-containing diamines, 3,4'-diamine diphenyl ether, 4, 4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylhydrazone, 4,4 ' -Diaminodiphenylhydrazone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, Petroleum ether, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) fluorene, bis (3-amine Phenylphenoxyphenyl) fluorene, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl) ether, 1,4-bis (4-amino (Phenoxy) 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'- (Trifluoromethyl) -4,4'-diaminobiphenyl and other aromatic diamines, or a portion of the hydrogen atom of the aromatic ring is an alkyl or fluoroalkyl group having 1 to 10 carbon atoms , Substituted compounds such as halogen atoms, alicyclic diamines such as cyclohexanediamine, methylenebiscyclohexylamine, and the like. These diamines can be used directly or in the form of a corresponding diisocyanate compound or trimethylsilanized diamine. Moreover, you may use combining these two or more types of diamine components.

Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylhydrazone, and 4,4'- Diaminodiphenylphosphonium, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) fluorene, bis (3 -Aminophenoxyphenyl) fluorene, 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] hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane or aromatics thereof Compounds in which the ring is substituted with an alkyl group or a halogen atom, and diamines having an amidino group are preferred. These can be used individually or in combination of 2 or more types.

In addition, an aliphatic group having a siloxane structure can be introduced within a range that does not reduce heat resistance, and adhesion to a substrate can be improved. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane, bis (p-aminophenyl) octamethylpentasiloxane, and the like. (4) and (5) R ⁶ 100 mole%, copolymerization of 1 to 15 mole%, etc.

For applications requiring heat resistance, the use of an aromatic diamine is preferably 50 mol% or more of the total diamine.

The (A2) resin preferably has a phenolic hydroxyl component. In the general formulae (4) and (5), at least one of R ⁵ and R ⁶ is preferably an organic group having a phenolic hydroxyl group. Due to the presence of the phenolic hydroxyl group, it is possible to obtain appropriate solubility in an alkali developer, and to interact with a photosensitizer to suppress solubility in an unexposed portion. Therefore, it is possible to improve the residual film rate and increase sensitivity. Moreover, since a phenolic hydroxyl group also contributes to a reaction with a crosslinking agent, it is also preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

Specific examples of the compound having a phenolic hydroxyl group include substitution of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or an aromatic ring thereof with an alkyl group or a halogen atom. Compounds, aromatic acid dianhydrides such as acid dianhydrides having amidino groups, or bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl ) 碸, 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, or a part of the hydrogen atoms of the aromatic rings are substituted with 1 to 10 carbon or fluoroalkyl groups, halogen atoms, etc. Compounds. (A2) The resin is preferably a resin containing a structure derived from these compounds.

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

(A2) The weight average molecular weight of the resin, in terms of polystyrene conversion using colloidal permeation chromatography, is preferably in the range of 3,000 to 80,000, and more preferably in the range of 8,000 to 50,000. Within this range, a thick film can be easily formed.

In addition, the (A2) resin may be terminated with a blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid. The end of the resin is blocked with a blocking agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, and the alkali water relative to the resin can be blocked. The dissolution rate of the solution can be easily adjusted to a better range. The capping agent is preferably 0.1 to 60 mol%, more preferably 5 to 50 mol%, relative to the total amine component of the resin.

Specific examples of the capping agent include monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, 3,5-diethynylaniline, 3-ethynylbenzoic acid, and 4-ethynylbenzoic acid. , Monocarboxylic acids such as 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. Compounds that are chlorinated by carboxyl groups of carboxylic acids or compounds that are chlorinated by carboxyl groups of dicarboxylic acids such as maleic acid. Monochloro compounds and N-hydroxy-5-norbornene-2,3 -In addition to the terminal blocking agent having an unsaturated bond, such as an active ester compound obtained by the reaction of dicarboxyphosphonium imine, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 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 -Amine water Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2- Monoamines, 3-aminophenols, 4-aminophenols, 2-aminothiophenols, 3-aminothiophenols, 4-aminothiophenols and other monoamines, phthalic anhydride, cyclohexane Acid anhydrides such as dicarboxylic anhydride, 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-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxy Monocarboxylic acids such as benzenesulfonic acid Compounds, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxyl Dicarboxylic acids such as naphthalene, and only one carboxyl group is subjected to fluorinated monofluorinated chlorine compounds, and active ester compounds obtained by the reaction of monofluorinated chlorine compounds with N-hydroxybenzotriazole are not provided with unsaturated bonds.端 剂。 Terminal agent. In addition, by replacing the hydrogen bond of the capping agent having no unsaturated bond with a vinyl group, the capping agent having an unsaturated bond can be used.

The resin having at least one of the structural units represented by the general formulae (4) and (5) can be produced according to a known method for producing polyimide and a polyimide precursor. Examples include (I) a method in which a tetracarboxylic dianhydride having an R ⁵ group is reacted with a diamine compound having an R ⁶ group, a monoamine compound as a blocking agent, and (II) ) Using a tetracarboxylic dianhydride having an R ⁵ group and an alcohol to obtain a diester, and then reacting a diamine compound having an R ⁶ group and a monoamine compound as a blocking agent in the presence of a condensing agent Method, (III) using a tetracarboxylic dianhydride having an R ⁵ group and an alcohol to obtain a diester, and then chlorinating the remaining 2 carboxyphosphonium groups with a diamine compound having an R ⁶ group as a capping agent A method for reacting a monoamine compound.

The resin polymerized by the method described above is preferably charged into a large amount of water or a mixed solution of methanol / water, etc., precipitated, filtered and dried, and separated. This precipitation operation removes unreacted monomers, oligomer components such as dimers and trimers, and improves the film characteristics after heat curing. Further, the fluorene imidization of the polyfluorene imide precursor and the ring-closed polyfluorene imine can be synthesized by a known fluorene imine reaction method after obtaining the polyfluorene imine precursor.

Hereinafter, as a preferred example of (I), an example of a method for producing a polyimide precursor will be described. 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 having a molar amount substantially equal to that of a diamine compound was gradually added. Using a mechanical stirrer, stir at -20 to 100 ° C, preferably 10 to 50 ° C, for 0.5 to 100 hours, more preferably for 2 to 24 hours. When using a capping agent, after adding tetracarboxylic dianhydride, at -20 to 100 ° C, preferably 10 to 50 ° C, after stirring for 0.1 to 24 hours, the capping agent can be gradually added, or it can be added at one time. reaction.

The polymerization solvent is not particularly limited as long as it can dissolve tetracarboxylic dianhydrides and diamines as raw material monomers. Examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone amines, γ-butyrolactone, γ- Cyclolactones such as valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate, propylene carbonate, Diols such as triethylene glycol, phenols such as m-cresol, p-cresol, acetophenone, 1,3-dimethyl-2-imidazolinone, cyclobutane, dimethylarsine, and the like.

The polymerization solvent is 100 mass parts with respect to the total of the tetracarboxylic dianhydride, diamine compound, and monoamine compound used as a capping agent for the superposition reaction, and if it is 100 mass parts or more, it can be performed without precipitating raw materials or resin If the reaction is 1900 parts by mass or less, the reaction can proceed quickly, and therefore, it is more preferable, and it is more preferably 150 to 950 parts by mass.

唑、聚醯胺醯亞胺、此等之前驅物、及此等之共聚物之1種以上的鹼可溶性樹脂合併使用，可展現優異的溶解抑止效果之觀點來看，可適當使用醌二疊氮化合物。 Next, the photosensitive film of this invention is demonstrated. The photosensitive film of the present invention is photosensitive by containing a (B) photoacid generator. That is, the (B) photoacid generator has a characteristic that an acid is generated by light irradiation, and the solubility of the light irradiated part with respect to the alkaline aqueous solution is increased. Examples of the (B) photoacid generator include quinonediazide compounds, sulfonium salts, sulfonium salts, diazonium salts, and sulfonium salts. Among them, by combining with an alkali-soluble resin selected from (A1) having a structural unit represented by the general formula (1), (A2) polyfluorene imine, and polybenzo

One or more alkali-soluble resins such as azole, polyamidoimine, these precursors, and these copolymers are used in combination, and from the viewpoint of exhibiting excellent dissolution-inhibiting effects, quinone diester can be suitably used. Nitrogen compounds.

Examples of the quinonediazide compound include those in which a polyhydroxy compound and a quinonediazide sulfonic acid are bonded by an ester, and those in which a polyamine compound and a quinonediazide sulfonic acid are bonded by a sulfonamide. Polyhydroxy polyamine compound and quinonediazide sulfonic acid are ester-bonded or sulfonamide bond, and polyhydroxypolyamine compound and quinonediazide sulfonic acid are ester-bonded and sulfonamide bond End those who wait.

All of the functional groups of the polyhydroxy compound or the polyamine compound may not be substituted with quinone diazide, but preferably more than 50 mol% of the total functional groups are substituted with quinone diazide. When the substitution of the quinonediazide is 50 mol% or more, the solubility with respect to the alkali developing solution does not become too high, a comparison with the unexposed portion can be obtained, and a desired pattern can be obtained. By using the quinonediazide compound as described above, a positive-type photosensitive film that is sensitive to i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) as a general ultraviolet mercury lamp can be obtained. The aforementioned compounds may be used alone or in combination of two or more. In addition, by using two kinds of photoacid generators, it is possible to obtain a larger ratio of the dissolution rate of the exposed portion and the unexposed portion. As a result, a highly sensitive photosensitive film can be obtained.

Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP-IPZ , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Ginseng-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 (the above are the trade names, 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 (The above are the trade names, Asahi has Machinery Industry Co., Ltd.), 2,6-Dimethoxymethyl-4-tertiary butylphenol, 2,6-Dimethoxymethyl-p-cresol, 2,6-Diethoxymethyl -p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.) System) and so on, but it is not limited to these.

Examples of the polyamine compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, and the like are not limited thereto.

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

In the present invention, as the quinonediazide, any of 5-naphthoquinonediazidesulfonyl group and 4-naphthoquinonediazidesulfonyl group can be used. The 4-naphthoquinonediazide sulfonate compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. 5-naphthoquinonediazide sulfonate compound, which absorbs and extends up to the g-ray region of a mercury lamp, and is suitable for g-ray exposure.

In the present invention, a 4-naphthoquinonediazide sulfonate compound and a 5-naphthoquinonediazide sulfonate compound are preferably selected according to the wavelength of exposure. In addition, naphthoquinonediazidesulfonyl compound and 4-naphthoquinonediazidesulfonyl group combined with 5-naphthoquinonediazidesulfonyl group can be obtained in the same molecule. -Naphthoquinonediazide sulfonate compound and 5-naphthoquinonediazide sulfonate compound.

The molecular weight of the quinonediazide compound of the present invention is preferably in the range of 300 to 3,000. If the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound cannot be sufficiently thermally decomposed in the subsequent heat treatment, and thus the resulting film has reduced heat resistance, mechanical properties, and adhesiveness. Possibility of problems.

The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. Examples thereof include a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine. Examples of the method for synthesizing the phenol compound include a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

Among the (B) photoacid generators used in the present invention, a sulfonium salt, a sulfonium salt, or a diazonium salt is preferred as the acid component to be appropriately stabilized by exposure. Since the photosensitive film of the present invention is used as a permanent film, residual phosphorus and the like are inferior to the environment, and it also needs to be considered. The color tone of the film, therefore, it is preferable to use sulfonium salt among these. A particularly preferred one is a triarylsulfonium salt, which can suppress a change in color tone of the film.

The content of the (B) photoacid generator is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the total amount of the (A1) resin and (A2) resin. Among them, the quinonediazide compound is preferably in a range of 3 to 40 parts by mass. The compound selected from the sulfonium salt, sulfonium salt, and diazonium salt is preferably in the range of 0.05 to 40 parts by mass, more preferably in the range of 0.1 to 30 parts by mass. When the content of the (B) photoacid generator falls within this range, high sensitivity can be achieved. Furthermore, if necessary, a sensitizer may be contained.

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

(In the general formula (11), R ⁶⁶ represents a 1 to 10 valent organic group. A plurality of R ⁶⁷ may be the same or different, and each represents an alkyl group having 1 to 4 carbon atoms. R represents an integer of 1 to 5). s represents an integer from 1 to 10.)

The alkoxymethyl system generates a thermal crosslinking reaction at a temperature of 160 ° C or higher. Therefore, in the step of thermally curing the photosensitive film, a crosslinking reaction occurs, and a good pattern shape can be obtained.

The number of alkoxymethyl groups is preferably two or more in order to increase the crosslinking density, and more preferably four or more in order to improve the chemical resistance. Further, in order to reduce the size unevenness of the pattern after heat curing, as the (C) thermal crosslinking agent, a compound having at least one type having 6 or more alkoxymethyl groups is preferred.

The compound represented by the general formula (11) functions as a thermoplastic agent at a temperature of less than 160 ° C in which a thermal crosslinking reaction occurs. The lamination can be performed at a temperature of 150 ° C. or lower. At this time, the photosensitive layer is heated and melted to increase the contact area with the substrate. Therefore, it is estimated that the adhesion between the two can be improved.

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

(C) The content of the thermal crosslinking agent, in order to improve the cross-linking density, chemical resistance, and adhesion to the substrate of the obtained cured film, 100 masses relative to the total amount of (A1) resin and (A2) resin Serving, preferably 1 quality The amount is not less than 5 parts by mass, and more preferably not less than 5 parts by mass. In order to improve the mechanical properties, it is preferably 70 parts by mass or less, and more preferably 50 parts by mass 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 the heat treatment. In order to improve the build-up property, it is preferably 2,500 or less, and more preferably 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 including the aforementioned crosslinking agent, it is possible to maintain the heat resistance and the build-up property while further improving the elongation.

(In the 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 may be linear or branched. And cyclic groups. Examples of R ⁶⁸ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, (Carbonyl, allyl, vinyl, heterocyclyl, combinations of these, etc., may further have a substituent.)

The thermal cross-linking agent itself has a soft alkylene group and a rigid aromatic group, so it has heat resistance and lamination, and can improve elongation. Examples of the crosslinking group include an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group, but are not limited thereto. Among these, an epoxy group is preferable from the viewpoint that the phenolic hydroxyl group of the (A1) resin and the (A2) resin can react to improve the heat resistance of the cured film and that the reaction can proceed without dehydration.

The compound represented by the general formula (12) is exemplified by the following, but is not limited to the following structure.

(Where n is an integer from 1 to 5, and m is from 1 to 20.)

Among the above structures, from the viewpoint of both heat resistance and elongation, n is preferably 1 to 2, and m is preferably 3 to 7.

The 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 based on 100 parts by mass of the total amount of the (A1) resin and (A2) resin. . When the addition amount is 2 parts by mass or more, the effect of improving the elongation can be sufficiently obtained, and when it is 35 parts by mass or less, the decrease in the sensitivity of the photosensitive film before curing can be suppressed.

The photosensitive film of this invention may contain (D) an acrylate compound as needed. In the present invention, (D) an acrylate compound means a compound having an acrylfluorenyl group or a methacrylfluorenyl group. (D) Acrylate compounds include monofunctional acrylates and polyfunctional acrylates. The monofunctional acrylate refers to a compound having at least one of a propylene fluorenyl group and a methacryl fluorenyl group. Examples include acrylate, methacrylate, acrylamide, and methacrylamide. The polyfunctional acrylate compound refers to a compound having at least one of two or more acrylfluorenyl groups and methacrylfluorenyl groups.

The photosensitive film of this invention is heat-processed after pattern processing. When used as a positive-type photosensitive film, at this time, the acrylate compound is thermally polymerized between the acrylate compounds or reacted with an alkali-soluble resin and crosslinked to increase the elongation of the cured film. When used as a negative-type photosensitive resin film, acrylates are photopolymerized with each other by exposure during pattern processing, thereby forming a grid structure with an alkali-soluble resin.

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

Preferable examples of the (D) acrylate compound include NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, manufactured by Shin Nakamura Chemical Industry Co., Ltd. BPE-100, 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. Examples include LIGHT ESTER series P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, 1.10DC, manufactured by Kyoeisha Chemical Co., Ltd. G-101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM, TMP, etc. Examples include "LIGHT ACRYLATE" (registered 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, etc. In addition, EPOXY ESTER series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M, 3000A and the like manufactured by Kyoeisha Chemical Co., Ltd. are mentioned. In addition, "ARONIX" (registered trademark) series M-203, M-208, M-210, M-211B, M-215, M-220, M-225, and M-240 made by Toa Synthesis , M-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. Examples include "KAYARAD" (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), RP-1040, etc. Examples include "Blenmer" (registered trademark) series GMR-H, GAM, PDE-50, PDE-100, PDE-150, PDE-200, PDE-400, PDE-600, PDE -1000, 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, etc. In addition, examples include MBC Unitec (shares) MBAA and the like. It may contain two or more of these compounds.

Among the (D) acrylate compounds, acrylate compounds having a molecular weight of 100 to 2,000 are preferred. Since the molecular weight is 100 or more, a cured film having a high elongation can be obtained, and since it is 2,000 or less, a resin composition having suitable alkali solubility and high compatibility with an alkali-soluble resin can be obtained.

In the present invention, in addition to the (A2) resin, other alkali-soluble resins may be contained within a range that does not impair the heat resistance of the cured film obtained by the heat treatment. Specific examples include acrylic polymers copolymerized with acrylic acid, siloxane resins, or phenol resins such as novolac resins, soluble phenol resins, polyhydroxystyrene resins, or the introduction of methylol, Resin of cross-linking group such as alkoxymethyl group or epoxy group, co-polymer thereof and the like. The aforementioned resin is a base dissolved in tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. Water solution. By containing these alkali-soluble resins, heat resistance can be maintained Adhesiveness or excellent sensitivity of the resin film can also impart properties to each alkali-soluble resin.

As another alkali-soluble resin, a phenol resin is preferable from a viewpoint of sensitivity. A phenol resin can be obtained by polycondensing a phenol and an aldehyde by a well-known method. A resin having two or more phenolic hydroxyl groups may be included in combination.

Preferable examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, and 3,4-diphenol. Cresol, 3,5-xylenol, 2,3,5-tricresol, 3,4,5-tricresol, etc. Particularly preferred are phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, or 2,3 , 5-Tricresol. These phenols may be used in combination of two or more kinds. From the viewpoint of solubility in an alkali developing solution, m-cresol is preferred, and a combination of m-cresol and p-cresol is more preferred. That is, as the resin having a phenolic hydroxyl group, a cresol novolak resin containing an m-cresol residue or an m-cresol residue and a p-cresol residue is preferable. At this time, the molar ratio of m-cresol residue to p-cresol residue (m-cresol residue / p-cresol residue, m / p) in the cresol novolac resin is preferably 1.8 or more. If it is this range, it will show appropriate solubility with respect to an alkali developing solution, and favorable sensitivity will be obtained. More preferably, it is 4 or more.

In addition, as preferable examples of the aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and salaldehyde are mentioned. Among these, formaldehyde is particularly preferred. These aldehydes may be used in combination of two or more kinds. The amount of the aldehydes used is preferably 0.6 mol or more, more preferably 0.7 mol or more, relative to 1 mol of the phenols. It is preferably 3 mol or less, and more preferably 1.5 mol or less.

烷等之環狀醚類。作為親油性溶媒，可舉出甲基乙酮、甲基異丁酮、2-庚酮等之酮類。該等之反應媒體的使用量，通常係相對於反應原料每100質量份而為20~1,000質量份。 The reaction of polycondensation of phenols and aldehydes usually uses an acidic catalyst. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and p-toluenesulfonic acid. The usage amount of these acidic catalysts is usually 1 × 10 ^-5 to 5 × 10 ^-1 mol relative to 1 mol of phenols. In the polycondensation reaction, water is generally used as the reaction medium, but when it becomes an inhomogeneous system since the initial stage of the reaction, a hydrophilic solvent or a lipophilic solvent can be used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; tetrahydrofuran,

Cyclic ethers such as alkanes. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw materials.

The reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw materials, and is usually 10 to 200 ° C. As a reaction method for polycondensation, a method of adding phenols, aldehydes, acidic catalysts and the like at one time to perform a reaction, or simultaneous addition of phenols and aldehydes in the presence of an acidic catalyst to the reaction can be suitably adopted. Methods etc. After the completion of the polycondensation reaction, in order to remove unreacted raw materials, acid catalysts, reaction media, and the like existing in the system, generally, the reaction temperature is raised to 130 to 230 ° C, and the volatile portion is removed under reduced pressure, and the Resin of phenolic hydroxyl group.

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. It is preferably 20,000 or less, and more preferably 10,000 or less. Within this range, both the workability and sensitivity when applying the positive photosensitive resin composition of the present invention to a substrate are excellent.

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 the (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.

The resin contained in the photosensitive film of the present invention contains a resin having a structure represented by the general formulae (4) and (5), and is preferably 30% by mass or more.

Moreover, in order to improve the sensitivity of a photosensitive film, you may contain (E) the compound which has a phenolic hydroxyl group as needed, in the range which does not reduce the shrinkage rate after hardening.

(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 (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, Bis26X-OCHP, BisOCHP-OC , Bis236T-OCHP, Methylene Ginseng-FR-CR, BisRS-26X, BisRS-OCHP, (the above are the trade names, 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 (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.).

Preferred (E) compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP-IPZ , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Ginseng-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC- F and so on.

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. By containing a compound having a phenolic hydroxyl group (E), a photosensitive film can be obtained, which is difficult to dissolve in the alkali developer before exposure and easily dissolves in the alkali developer during exposure, so the film thickness caused by development is reduced. Less, and can be developed in a short time. (E) The content of the compound having a phenolic hydroxyl group is preferably within a range of 1 to 50 parts by mass, and more preferably within a range of 3 to 40 parts by mass, relative to 100 parts by mass of the total amount of the (A1) resin and (A2) resin. .

烷、丙二醇單甲醚等之醚類、二丙二醇二甲醚、二乙二醇二甲醚、二乙二醇乙基甲醚等之二烷二醇二烷醚類、丙酮、甲基乙酮、二異丁酮、二丙酮醇、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等之酮類、乙酸3-甲氧基丁酯、乙二醇單乙醚乙酸酯等之乙酸酯類、乙酸乙酯、丙二醇單甲醚乙酸酯、乳酸乙酯等之酯類、甲苯、二甲苯等之芳香族烴類等單獨、或混合而使用。(F)溶劑的含量，相對於(A1)樹脂與(A2)樹脂的總量100質 量份，較佳為0.0001質量份以上，較佳為50質量份以下。 The photosensitive film of this invention may contain (F) solvent. As the (F) solvent, polar aprotic solvents such as γ-butyrolactone, tetrahydrofuran,

Ethers such as alkane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and other dialkyl glycol dialkyl ethers, acetone, methyl ethyl ketone , Ketones such as diisobutanone, diacetone alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxybutyl acetate, ethylene glycol monoethyl ether Acetic esters such as acetate, ethyl acetate, esters such as propylene glycol monomethyl ether acetate, ethyl lactate, and aromatic hydrocarbons such as toluene and xylene are used alone or in combination. The content of the (F) solvent is preferably 0.0001 parts by mass or more, and more preferably 50 parts by mass or less with respect to 100 parts by mass of the total amount of the (A1) resin and (A2) resin.

The photosensitive film of the present invention can contain a (G) silane compound and can be used as a bonding aid to improve the adhesion to the underlying substrate. Specific examples of the (G) silane compound include N-phenylamineethyltrimethoxysilane, N-phenylamineethyltriethoxysilane, N-phenylaminepropyltrimethoxysilane, and N-benzene Aminopropylpropyl triethoxysilane, N-phenylaminobutyl trimethoxysilane, N-phenylaminobutyl triethoxysilane, ethylene trimethoxysilane, ethylene triethoxysilane, ethylene trichlorosilane, ethylene ginseng (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methyl Acrylic fluorenyloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or a silane compound having a structure shown below is not limited thereto. It may contain two or more of these.

The content of the (G) silane compound is preferably from 0.01 to 15 parts by mass based on 100 parts by mass of the total amount of the (A1) resin and (A2) resin. Within this range, a sufficient effect can be obtained as a bonding aid while maintaining the heat resistance of the positive-type photosensitive film.

烷等之醚類。又，也可含有二氧化矽、二氧化鈦等之無機粒子、或聚醯亞胺的粉末等。 In addition, for the purpose of improving the wettability of the photosensitive film and the substrate, it may contain esters such as ethyl lactate or propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, and methyl isobutyl ketone. Ketones, Tetrahydrofuran, Di

Ethers such as alkanes. In addition, it may contain inorganic particles such as silicon dioxide and titanium dioxide, or powders of polyimide.

The photosensitive film of the present invention preferably contains (H) a compound represented by the following general formula (13) (hereinafter referred to as (H) component). By containing the (H) component, the adhesion between the laminated film and the metal material can be significantly improved, especially the adhesion with copper. This is because the S atom or N atom from the compound represented by the general formula (13) interacts with the metal surface and has a three-dimensional structure that easily interacts with the metal surface. According to these effects, a resin composition is provided with a photosensitivity, and in a composition having an additive, a resin cured film having excellent adhesion to a metal material can be obtained. In the general formula (13), R ⁷¹ to R ⁷³ represent any one of an O atom, an S atom, and 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 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. Examples of R ⁷⁴ to R ⁷⁶ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. Groups, vinyl groups, heterocyclic groups, combinations thereof, and the like, and may further have a substituent.

The addition amount of the (H) component is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the (A1) resin and (A2) resin. When the addition amount is 0.1 parts by mass or more, the effect of improving the adhesion to the metal material after lamination can be sufficiently obtained, and when it is 10 parts by mass or less, the photosensitive film used in the present invention is a positive type In this case, it is preferable to reduce the 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 preferably represent any one of an O atom, an S atom, and an N atom, and at least one of R ⁷¹ to R ⁷³ is S atom. 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 compound containing an N atom. However, by containing an S atom, the interaction effect can be ensured without affecting The sensitivity is reduced, and the effect of improving adhesion can be obtained. Moreover, it is more preferable that it has a trialkoxymethyl group from the point of the adhesiveness with respect to the laminated | stacked board | substrate other than metal, such as silicon.

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

唑、聚醯胺醯亞胺、此等之前驅物及此等之共聚物之1種以上的鹼可溶性樹 脂、(B)光酸產生劑、(C)熱交聯劑、(F)溶劑、及視需要將其它的成分，放入玻璃製的燒瓶或不鏽鋼製的容器，藉由機械式攪拌器等攪拌溶解的方法、以超音波溶解的方法、以行星式攪拌脫泡裝置進行攪拌溶解的方法等。包含(A1)樹脂、(A2)樹脂、(B)光酸產生劑、(C)熱交聯劑、(F)溶劑等之組成物的黏度，較佳為200~10,000mPa‧s。又，為了除去異物，亦可以0.1μm~5μm之孔洞大小的過濾器進行過濾。 The manufacturing method of the photosensitive film of this invention is illustrated. Examples thereof include (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) a substituent having a substituent that reacts with the above-mentioned (A1) alkali-soluble resin, and a member selected from the group consisting of polyimide, Polybenzo

One or more alkali-soluble resins such as azole, polyamidoimine, these precursors, and these copolymers, (B) photoacid generator, (C) thermal cross-linking agent, (F) solvent, And if necessary, put other components into a glass flask or stainless steel container, stir and dissolve by a mechanical stirrer, etc., dissolve by ultrasonic, dissolve by a planetary agitation defoaming device, and dissolve. Method, etc. The viscosity of a composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal cross-linking agent, (F) solvent and the like is preferably 200 to 10,000 mPa · s. In addition, in order to remove foreign matter, filtration may be performed with a filter having a pore size of 0.1 μm to 5 μm.

The photosensitive film of the present invention preferably has a supporting film. A composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal cross-linking agent, (F) solvent, etc. is coated on a support film, and then, by drying this, A photosensitive film having a photosensitive layer on a supporting film can be obtained.

The supporting film is not particularly limited, and various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. In order to improve the adhesion and peelability of the bonding surface between the support film and the photosensitive film, surface treatments such as silicone, silane coupling agent, aluminum chelating agent, and polyurea may be performed. 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.

The photosensitive film of the present invention may have a protective film on the film in order to protect the surface. Thereby, the surface of the photosensitive film can be protected from contamination such as garbage or dust in the atmosphere.

Examples of the protective film include polyolefin films and polyester films. The protective film is preferably one having a small adhesion to the photosensitive film.

As a method for applying a composition containing (A1) resin, (A2) resin, (B) photoacid generator, (C) thermal crosslinking agent, (F) solvent and the like to a support film to form a photosensitive layer, Use of spray coating, roll coating, screen printing, blade coating machines, die coating machines, roll coating machines, meniscus coating machines, rod coating machines, roll coating machines, notch wheel coating machines, gravure coating machines, screen printing Coating machine, slot die coating machine, etc. The thickness of the coating film varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but the film thickness of the photosensitive layer usually obtained after drying is preferably 0.5 μm or more and 100 μm or less. It is more preferably 3 μm or more and 40 μm or less.

For drying, use oven, hot plate, infrared, etc. The drying temperature and the drying time may be in a range in which 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 unhardened or semi-hardened state. Specifically, it is preferably performed in a range of 40 ° C to 120 ° C for 1 minute to several tens of minutes. Further, these temperatures may be combined to increase the temperature stepwise. For example, heat treatment may be performed at 50 ° C, 60 ° C, and 70 ° C for 1 minute, respectively.

Next, a method for manufacturing a semiconductor device using a photosensitive film will be described. When the photosensitive film has a protective film, this is peeled first. The photosensitive film and the substrate were opposed to each other, and were bonded by heating and pressure bonding, and the photosensitive film was transferred to the substrate and laminated. Next, the support film was peeled to obtain a photosensitive film. The thermocompression bonding can be performed by a hot pressing process, a thermal lamination process, a thermal vacuum lamination process, or the like. The temperature at which the thermocompression bonding and lamination are performed is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher, from the viewpoints of adhesion to the substrate and embedding property. In addition, in order to prevent the photosensitive film from hardening during thermal compression bonding, The resolution of the pattern formation in the shadowing step is deteriorated, and the temperature of the thermal compression bonding is preferably 150 ° C or lower, and more preferably 120 ° C or lower. In addition, the purpose of removing bubbles during thermocompression bonding may be performed under reduced pressure.

After laminating the photosensitive film on the substrate, the support film from the photosensitive film is peeled off at a temperature range of 0 ° C to 100 ° C.

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 components constituting circuits on such substrates. Such.

Examples of organic circuit boards include glass substrates, copper-clad laminates such as glass cloth, epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwovens, epoxy copper-clad laminates, and polyethers. Soft substrates such as imide resin substrates, polyether ketone resin substrates, polyfluorene-based resin substrates, and other heat-resistant and thermoplastic substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic-based circuit substrate include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal-based substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials include conductors containing metals such as gold, silver, and copper, resistors containing inorganic oxides, low dielectric materials containing glass-based materials, resins, and resins or high dielectric materials. High-dielectric materials such as permittivity inorganic particles, and insulators containing glass-based materials.

Then, on the photosensitive film formed by the above method, actinic rays are irradiated through a mask having a desired pattern, and exposed. As actinic rays used in exposure, there are ultraviolet rays and visible rays. Light rays, electron beams, X-rays and the like, but in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp are preferably used. In a photosensitive film, when the supporting film is a transparent material with respect to such light, the supporting film may be exposed after being peeled from the photosensitive film, or may be exposed without being peeled. When exposure is performed without peeling, the support film is peeled after the exposure and before the development process.

After the pattern is formed, the unexposed portions are removed using a developing solution. As the developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, and dimethyl are preferred. Aqueous solutions of basic compounds such as amines, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethylmethacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. Furthermore, depending on the case, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylene may be contained alone in these alkaline aqueous solutions. Polar solvents such as gadolinium, γ-butyrolactone, methacrylamide, alcohols such as methanol, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone, Cyclohexanone, isobutyl ketone, methyl isobutyl ketone, and other ketones or a combination of several kinds.

The development can be performed by spraying the above-mentioned developing solution on the surface having a photosensitive film, dipping in the developing solution, applying ultrasonic waves while immersing, or spraying the developing solution while rotating the substrate. The conditions at the time of development called the development time or the temperature of the developer in the development step may be conditions for removing unexposed portions. In order to process fine patterns and remove residues between the patterns, it is preferable to remove unexposed portions. For further development.

After development, it may be rinsed with water. Here, an alcohol such as ethanol or isopropanol, an ester such as ethyl lactate, propylene glycol monomethyl ether acetate, or the like may be added to water to perform a rinse treatment. When the resolution of the pattern during development is improved, and the acceptable range of the development conditions is increased, a step of baking treatment may also be included before the development. The temperature is preferably in the range of 50 to 180 ° C, and particularly preferably in the range of 60 to 120 ° C. The time is preferably 5 seconds to several hours.

After the pattern is formed, a temperature of 120 ° C to 400 ° C is applied to obtain a cured film. The heat treatment may be performed at a temperature stepwise or continuously at a certain temperature range for 5 minutes to 5 hours. As an example, heat treatment was performed at 130 ° C and 200 ° C for 30 minutes, respectively. Alternatively, a method such as linearly increasing the temperature from room temperature to 250 ° C over 2 hours can be mentioned. In this case, the heating temperature is preferably a temperature of 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 the insulation. Moreover, from a viewpoint of reducing the curvature of the board | substrate by a residual stress, it is preferable that it is 100 micrometers, and it is more preferable that it is 40 micrometers or less.

The cured film for curing the photosensitive film of the present invention can be suitably used in applications such as semiconductor passivation films, semiconductor protective films, interlayer insulating films for multilayer wiring for high-density mounting, and insulating layers for organic light-emitting devices. The cured film of the photosensitive film of the present invention can be used in a semiconductor device in a state where a relief pattern layer of the cured film is formed.

In addition, as described above, a cured film may be arranged on the substrate with a film thickness of 2 to 40 μm, and copper wirings may be disposed thereon, and then a cured film may be formed with a film thickness of 2 to 40 μm as insulation between the copper wirings. Film to produce a semiconductor device.

An example of a suitable structure of a semiconductor device provided with a cured film for curing the photosensitive film of the present invention is shown in FIG. 1 below. A passivation film 2 is formed on the semiconductor element 1. The photosensitive film of the present invention is laminated on the passivation film 2 by heating and pressure bonding, and is heated and dried using a hot plate or the like, and then exposed and developed to form a pattern of the photosensitive film. After the pattern of the photosensitive film is formed, a curing high-temperature process is performed to form a cured film 3. Metal wiring is formed on the cured film 3 by a method such as sputtering, vapor deposition, electroless plating, and electroplating. In addition, in order to protect the metal wiring, the photosensitive film of the present invention is laminated by heating and pressure bonding, and is heated and dried using a hot plate or the like, and patterned by exposure and development. After the pattern of the photosensitive film is formed, a curing high-temperature process is performed to form a cured film 5. By forming the cured film by the above-mentioned method, it is possible to provide a semiconductor device having high flatness with high adhesion between the cured films and high adhesion between the cured film and the metal wiring.

Next, an application example of a coil component for an inductor device in which a cured film that hardens 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 a 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, fat iron or the like is used. Any of the cured film 7 and the cured film 8 may be used for the photosensitive film of the present invention. A metal film 9 (Cr, Ti, etc.) is formed in the opening of this pattern, and Metal wiring 10 (Ag, Cu, etc.) is formed thereon by electroplating. The metal wiring 10 (Ag, Cu, etc.) is formed on a spiral. By repeating the steps from 7 to 10 multiple times, and being laminated, it can have the function of a coil. Finally, the metal wiring 10 (Ag, Cu, etc.) is connected to the electrode 12 via the metal wiring 11 (Ag, Cu, etc.), and sealed with a sealing resin 13.

Next, an application example of an electronic component or a semiconductor device having a hollow portion in which a cured film for curing the photosensitive film of the present invention is disposed will be described with reference to the drawings. 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 栉 -type electrode having a pair of a plurality of electrode fingers inserted into each other and a bonding pad 16 for obtaining electrical conduction are formed on the substrate 14. Here, the substrate 14 includes, for example, lithium niobate, potassium niobate, lithium tantalate, crystal, Langasite, ZnO, PZT, lithium 4-borate, and the like. 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. In order to secure the hollow portion 17 of the piezoelectric substrate 14, a relief pattern layer of a cured film of a photosensitive resin composition is formed as the support material 18. Examples of the photosensitive resin composition include polyimide resins, epoxy resins, acrylic resins, and phenol resins. The covering material 19 covers the electrodes 15 and is provided on the substrate 15 via the support material 17. Here, as the covering material 19, the photosensitive film of the present invention can be used, and it can also be used for the supporting material 17. The thickness of the covering material 19 is, for example, 20 μm. The protective member 20 is provided so as to cover the substrate 14, the supporting material 18, and the covering material 19. For example, the thickness of the protective member 20 on the coating material 19 is, for example, 30 μm. The protective member is an insulating material, for example For example, epoxy resin, benzocyclobutene resin, silicon resin, SOG (Spin On Grass) and the like. The support material 17 and the covering material 19 may be penetrated in the thickness direction to provide an interlayer conductor 21. Solder bumps 22 are connected to the interlayer conductor 21.

Hereinafter, an application example of a semiconductor device including a substrate having a step difference using the photosensitive film of the present invention will be described using 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 is 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, cut into the entire wafer, and sealed with a resin 26. A heat treatment is performed during sealing, and a shrinkage of the resin 26 causes a (T-1) step difference between the wafer 23 and the resin 26. At this time, the (T-1) step difference between the (S-1) upper step portion on the surface of the wafer 23 and the (S-2) lower step portion on the surface of the resin 26 is 2 to 40 μm. The hardened film 27 is formed on the upper part of (S-1) and the lower part of (S-2) as a pattern using the photosensitive film of the present invention, and the hardened film disposed on the upper part of (S-1) and The (T-2) step difference of the hardened film arrange | positioned in the said (S-2) lower step part becomes 5 micrometers or less.

Further, a metal (Cr, Ti, etc.) film 28 and a metal wiring 29 can be formed. Thereafter, a metal barrier layer 31 and a solder bump 32 are formed in the opening portion of the insulating film 30 formed on the sealing resin outside the wafer. Fan-Out WLP uses a sealing resin such as epoxy resin on the periphery of the semiconductor wafer, and provides an expansion part. The electrodes on the semiconductor wafer are connected to the expansion part and rewiring is performed. Solder balls are also mounted on the expansion part. And ensure the required number of terminals in the semiconductor package. In Fan-Out WLP, the edge formed across the main surface of the semiconductor wafer and the main surface of the sealing resin Boundaries are provided for wiring. That is, an interlayer insulating film is formed on a base material including a semiconductor wafer that implements metal wiring and two or more materials of a sealing resin, and wiring is formed on the interlayer insulating film. In addition to the foregoing, a semiconductor wafer-type semiconductor package is embedded in a recess formed in a glass epoxy substrate, and wiring is provided across a boundary line between the main surface of the semiconductor wafer and the main surface of the printed substrate. In this aspect, an interlayer insulating film is also formed on a substrate including 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 including two or more materials, the step difference on the substrate can be reduced and the flatness of the cured film can be maintained. Therefore, it can be suitably used as An interlayer insulating film provided on a substrate of two or more materials.

[Example]

Examples and comparative examples are given below to illustrate the present invention, but the present invention is not limited to these. The evaluation of the esterification rate of the synthesized quinonediazide compound and the evaluation of the photosensitive film were performed by the following methods.

<Method for measuring film thickness>

Lambda Ace STM-602 (manufactured by Dainippon Screen Co., Ltd.) was used. The film after prebaking and development was measured using polyimide as a reference and the refractive index was 1.629.

<Determination of hydrazone imidization rate of polyfluorene>

(A2) The rate of fluorene imidization of the alkali-soluble resin is a 6-inch silicon wafer, and a 50% by mass solid N-methylpyrrolidone (NMP) solution of the polyfluorene resin is The coating was performed by a spin coating method, followed by baking at 120 ° C. for 3 minutes on a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.) to prepare a pre-baked film having a thickness of 10 μm ± 1 μm. This film was divided into two halves, and one of the halves was put into an oxidation-free oven (INH-21CD manufactured by Koyo Thermo Systems), and the temperature was raised to a hardening temperature of 350 ° C. for 30 minutes, and heat treatment was performed at 350 ° C. for 60 minutes. After that, it was slowly cooled until the inside of the oven became 50 ° C or lower to obtain a cured film. About the obtained cured film (A) and the film (B) before hardening, the infrared absorption spectrum was measured using the Fourier transform infrared spectrophotometer FT-720 (made by Horiba). Calculate the peak intensity around 1377 cm ^-1 caused by the CN stretching vibration of the fluorene imine ring, and take the value of "the peak intensity of the film (B) before curing / the peak intensity of the cured film (A)" as the fluorene Amination rate.

<Evaluation of stackability>

The protective film of the photosensitive film produced by each Example and a comparative example mentioned later was peeled. Next, the peeled surface is laminated on a silicon wafer or a copper substrate. As the copper substrate, a substrate (copper-plated substrate) having a metal material layer having a thickness of 2 μm formed by copper plating by electroplating was used on a silicon wafer by sputtering titanium and copper at 100 nm. The lamination was carried out using a lamination device (manufactured by Takatori Co., Ltd., VTM-200M) under the conditions of a stage temperature of 80 ° C, a roll temperature of 80 ° C, a vacuum of 150 Pa, an adhesion speed of 5 mm / sec, and an adhesion pressure of 0.2 Mpa. After lamination, using a cutting guide in the center of the film on the substrate, a dent is formed on the photosensitive film in a checkerboard pattern at intervals of 2 mm × 2 mm so that it can become 100 squares. After the cellophane tape was pasted on the checkerboard-shaped portion, it was stretched toward the substrate at an angle of 90 ° and peeled off. At the time of peeling, the number of peeled photosensitive films was counted out of 100 pieces. When the number of peelings is small, the adhesiveness is high, and when it is large, the adhesiveness is low. Compare It is preferably 50 or less, more preferably 20 or less, and particularly preferably 10 or less. Condition 1 was evaluated for lamination performance on a silicon wafer, and condition 2 was evaluated for a copper substrate.

<Evaluation of pattern processability (high sensitivity)>

The protective film of the photosensitive film prepared in each of the Examples and Comparative Examples was peeled off, and the peeled surface was laminated on an 8-inch silicon wafer using a lamination device (manufactured by Takatori Co., Ltd., VTM-200M) at a platform temperature of 80 ° C, Lamination was performed under the conditions of a roll temperature of 120 ° C, a vacuum of 150 Pa, an adhesion speed of 5 mm / sec, and an adhesion pressure of 0.2 MPa. Then, it baked on the hot plate (using ACT-8) of 120 degreeC for 3 minutes, and prepared the pre-baking film with a thickness of 10 micrometers. This film was exposed using an i-ray stepper (NIKON NSR i9) with an exposure amount of 0 to 1000 mJ / cm ² at 10 mJ / cm ² steps. After exposure, it was developed with a 2.38 mass% tetramethylammonium (TMAH) aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D) for 90 seconds, and then rinsed with pure water to obtain a development having a 5 μm isolation space. Film A.

With the development film A, after exposure and development, the exposure amount (referred to as the minimum exposure amount Eth) that does not completely dissolve in the exposed portion of the 5 μm isolation space is taken as the sensitivity. When Eth is 400 mJ / cm ² or less, it can be judged as high sensitivity. It is more preferably 300 mJ / cm ² or less, and particularly preferably 250 mJ / cm ² or less.

<Evaluation of High Extensibility>

The protective film of the photosensitive film produced in each of the Examples and Comparative Examples was peeled off. On a silicon wafer, a lamination device (manufactured by Takatori Co., Ltd., VTM-200M) was used. The platform temperature was 80 ° C, the roll temperature was 120 ° C, and the vacuum was applied. 150Pa, sticking speed 5mm / s, sticking pressure 0.2Mpa The layers were laminated so as to have a film thickness T1 = 11 μm. The laminated substrate was pre-baked on a hot plate at 120 ° C for 3 minutes, and then an oxidation-free oven CLH-21CD-S (manufactured by Koyo Thermo Systems) was used under a nitrogen flow at an oxygen concentration of 20 ppm or less, and 3.5 was used per minute The temperature rising rate of the temperature was increased to 220 ° C, and a heat treatment was performed at 220 ° C for 1 hour. It peeled with 46 mass% hydrofluoric acid aqueous solution, and obtained the cured film (heat-resistant resin film). It was cut out with a sheet-like blade so that the cured film obtained by this method became 7 × 1 cm, and the cutout was stretched at 50 mm / min using a Tensilon universal testing machine (RTM-100 manufactured by Orientec Corporation). Calculate the amount of extension at this time by the sample length. This measurement was performed on 10 samples, and the maximum value was used as the elongation. The elongation is preferably 10% or more, more preferably 20% or more, and particularly preferably 40% or more.

<5% weight reduction temperature measurement (evaluation of heat resistance)>

The cured film obtained by the same method as the above <Evaluation of High Extensibility> was heated at a rate of 10 ° C / min under a nitrogen flow of 80 mL / min using a thermal weight reduction measuring machine (TGA50 manufactured by Shimadzu Corporation) and Perform the measurement. The 5% weight reduction temperature is preferably 260 ° C or higher, more preferably 300 ° C or higher, and particularly preferably 340 ° C or higher.

The 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: Cyclobutanetetracarboxylic 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, HUNTSMAN (stock) system)

MAP: m-aminophenol

NA: 5-norbornene-2,3-dicarboxylic anhydride

KBM-403: 3-glycidoxypropyltrimethoxysilane (silane compound (a)).

(C) The thermal crosslinking agent and (H) compound used by each Example and a comparative example are shown below.

Synthesis Example 1 Synthesis of quinonediazide compound (a)

烷50g，並成為室溫。在此，使系統內不會成為35℃以上而一邊確認一邊滴加與1,4-二

烷50g混合的三乙胺15.18g。滴加後，在30℃攪拌2小時。過濾三乙胺鹽，將濾液投入於水。之後，將析出的沉澱以過濾收集。將此沉澱以真空乾燥機進行乾燥，得到下述式所示的醌二疊氮化合物(a)。 Under a dry nitrogen stream, 21.22 g (0.05 mole) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g (0.10 mole) of 5-naphthoquinonediazidesulfonium chloride, 4-naphthalene 13.43 g (0.05 mol) of quinonediazidesulfonium chloride dissolved in 1,4-bis

50 g of alkane and became room temperature. Here, the inside of the system does not become 35 ° C or higher, and the dropwise addition and 1,4-two are checked while confirming.

50g of hexane was mixed with 15.18g of triethylamine. After the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. After that, the 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)

To a mixed solution of 500 ml of tetrahydrofuran and 0.01 mol of secondary butyl lithium as a starter, add a total of 20 g of p-tertiary butoxystyrene and styrene in a molar ratio of 3: 1, while stirring Polymerization was carried out for 3 hours. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, the reaction mixture was poured into methanol in order to purify the polymer, and when the precipitated polymer was dried, a white polymer was obtained. It was further dissolved in 400 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C. and stirred for 7 hours, then poured into water to precipitate the polymer, and p-tertiary butoxystyrene was deprotected to be converted into hydroxystyrene, and When washing and drying, purified p-hydroxystyrene and styrene are obtained. Copolymer (hereinafter (a0-1)). In addition, according to analysis by GPC, the weight average molecular weight (Mw) was 3500 (GPC polystyrene conversion), and the degree of dispersion was (Mw / Mn) 2.80.

Synthesis example 3 Synthesis of polyhydroxystyrene resin (a0-2)

The procedure was performed in the same manner except that m-tertiary butoxystyrene was used instead of p-tertiary butoxystyrene in Synthesis Example 2. The obtained copolymer of m-hydroxystyrene and styrene (hereinafter (a0-2)) was analyzed by GPC, and the weight average molecular weight (Mw) was 5000 (GPC polystyrene conversion), and the degree of dispersion was (Mw / Mn) 3.20.

Synthesis Example 4 Synthesis of Polyhydroxystyrene Resin (a0-3)

The procedure was performed in the same manner except that the styrene of Synthesis Example 2 was not added. The obtained p-hydroxystyrene resin (hereinafter (a0-3)) was analyzed by GPC, and the weight average molecular weight (Mw) was 3000 (GPC polystyrene conversion), and the degree of dispersion was (Mw / Mn) 1.60.

Synthesis Example 5 Synthesis of Alkali-Soluble Resin (a1-1)

Polyhydroxystyrene resin (a0-1) was dissolved in a solution in which 80 g (2.0 mol) of sodium hydroxide was dissolved in 800 g of pure water. After completely dissolving, 686 g of a 36 to 38% by mass aqueous formaldehyde solution was added dropwise at 20 to 25 ° C. for 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. To this was added 98 g of sulfuric acid and 552 g of water to neutralize, and left in this state for 2 days. The white solid produced 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 obtained as described above 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 anion-type ion exchange resin (manufactured by Rohm and Haas, Amberlyst IRA96SB) was added, followed by stirring for 1 hour, and the ion exchange resin was removed by filtration. After that, 500 mL of GBL was added, and methanol was removed on a rotary evaporator to obtain a GBL solution. This solution was analyzed by ¹³ C-NMR (manufactured by Japan Electronics Co., Ltd., GX-270), and it was confirmed that an alkali-soluble resin (hereinafter (a1-1)) of a polyhydroxystyrene resin partially alkoxylated was obtained. According to the analysis by GPC, the weight average molecular weight (Mw) was 8000 (GPC polystyrene conversion), and the alkoxylated hydroxystyrene-based hydroxystyrene had an introduction rate of 35 mol% per mol.

Synthesis Example 6 Synthesis of Alkali Soluble Resin (a1-2)

(A0-2) was used instead of (a0-1) in Synthesis Example 5 described above, and synthesis was performed in the same production method. The obtained alkali-soluble resin of the alkoxylated polyhydroxystyrene resin (hereinafter (a1-2)) was analyzed by GPC, and the weight average molecular weight (Mw) was 7500 (GPC polystyrene conversion), and the alkoxy group was introduced. Rate, 55 mol% per mol of hydroxystyrene.

Synthesis Example 7 Synthesis of Alkali-Soluble Resin (a1-3)

(A0-3) was used instead of (a0-1) in Synthesis Example 5 described above, and synthesis was performed in the same production method. The obtained alkali-soluble resin of the alkoxylated polyhydroxystyrene resin (hereinafter (a1-3)) was analyzed by GPC, and the weight average molecular weight (Mw) was 3500 (GPC polystyrene conversion). Rate, 69 mol% per mol of hydroxystyrene.

Synthesis Example 8 Synthesis of Novolac 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, and a 37% by mass aqueous formaldehyde solution were added. After 75.5 g (0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone, the polymer was immersed in an oil bath, and a polycondensation reaction was performed while refluxing the reaction solution for 4 hours. After that, the temperature of the oil bath was raised for 3 hours. Thereafter, the pressure in the flask was reduced to 40 to 67 hPa, the volatile matter was removed, and the dissolved resin was cooled to room temperature to obtain an alkali-soluble novolac resin (e). Polymer solid. Analysis by GPC confirmed that the weight average molecular weight (Mw) was 3,500. Γ-butyrolactone (GBL) was added to the obtained novolak resin (e) to obtain a novolak resin (e) solution having a solid content concentration of 43% by mass.

Synthesis Example 9 Synthesis of a closed ring polyfluorene imine resin (A)

PMDA-HH 4.48 g (0.020 mol) and 6FDA11.11 g (0.025 mol) were dissolved in 100 g of NMP under a stream of dry nitrogen. Here, 1.09 g (0.010 mole) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 moles), DAE1.00g (0.005 moles), ED-600 6.00g (0.010 moles), SiDA0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C. 1 Then, it stirred at 180 degreeC for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (A).

Synthesis Example 10 Synthesis of Closed Ring Polyimide Resin (B)

PMDA-HH 1.12 g (0.005 mol), 6FDA11.11 g (0.025 mol), and ODPA 4.65 g (0.015 mol) were dissolved in 100 g of NMP under a stream of dry nitrogen. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 Mo Ear), DAE 1.00g (0.005 moles), ED600 6.00g (0.010 moles), SiDA 0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, and then stirred at 180 ° C for 4 hours . After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (B).

Synthesis Example 11 Synthesis of Closed Ring Polyimide Resin (C)

Under dry nitrogen flow, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 moles), DAE1.00g (0.005 moles), ED600 6.00g (0.010 moles), SiDA0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, Then, it stirred at 180 degreeC for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (C).

Synthesis Example 12 Synthesis of Closed Ring Polyimide Resin (D)

In a dry nitrogen stream, 0.98 g (0.005 mole) of CBDA, 11.11 g (0.025 mole) of 6FDA, and 4.65 g (0.015 mole) of ODPA were dissolved in 100 g of NMP. Here, BAHF11.90g (0.033 moles), DAE0.50g (0.003 moles), ED600 7.50g (0.013 moles), SiDA0.62g (0.003 moles) and NMP20g are added simultaneously, and the reaction is performed at 60 ° C. 1 Hours, then, after stirring at 180 ° C for 4 hours, 1.64 g (0.010 moles) of 5-norbornene-2,3-dicarboxylic anhydride as a capping agent and 10 g of NMP were added at the same time, and the reaction was performed at 60 ° C for 1 hour. After the stirring was completed, 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 in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of a closed polyimide resin (D).

Synthesis Example 13 Synthesis of Closed Ring Polyimide Resin (E)

Under a stream of dry nitrogen, 0.98 g (0.005 mol) of CBDA, 11.11 g (0.025 mol) of 6FDA, and 4.50 g (0.015 mol) of TDA-100 were dissolved in 100 g of NMP. Here, BAHF11.90g (0.033 moles), DAE0.50g (0.003 moles), ED600 7.50g (0.013 moles), SiDA0.62g (0.003 moles) and NMP20g are added simultaneously, and the reaction is performed at 60 ° C. 1 Hours, followed by stirring at 180 ° C for 4 hours, then 1.64 g (0.010 mol) of 5-norbornene-2,3-dicarboxylic anhydride as a capping agent was added simultaneously with 10 g of NMP, and the reaction was performed at 60 ° C for 1 hour. . After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (E).

Synthesis Example 14 Synthesis of Closed Ring Polyimide Resin (F)

Under a stream of dry nitrogen, 10.09 g (0.045 moles) of PMDA-HH was dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. Then, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE, 0.62 g (0.003 mol) of SiDA were added simultaneously with 20 g of NMP, and the reaction was performed at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. The 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 a powder of a closed polyimide resin (F).

Synthesis Example 15 Synthesis of Closed Ring Polyimide Resin (G)

Under a stream of dry nitrogen, 8.82 g (0.045 mol) of CBDA was dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. Then, 15.57 g (0.043 mol) of BAHF, 1.00 g (0.005 mol) of DAE, 0.62 g (0.003 mol) of SiDA were added simultaneously with 20 g of NMP, and the reaction was performed at 60 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. The 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 a powder of a closed polyimide resin (G).

Synthesis Example 16 Synthesis of Closed Ring Polyimide Resin (H)

Under a stream of dry nitrogen, 13.96 g (0.045 mol) of ODPA was dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 moles), DAE1.00g (0.005 moles), ED600 6.0g (0.010 moles), SiDA0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, Then, it stirred at 180 degreeC for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (H).

Synthesis Example 17 Synthesis of Closed Polyimide Resin (I)

Under a stream of dry nitrogen, 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. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 moles), DAE1.00g (0.005 moles), ED600 6.0g (0.010 mol), SiDA 0.62g (0.003 mol) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, and then stirred at 180 ° C for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (I).

Synthesis Example 18 Synthesis of Closed Ring Polyimide Resin (J)

19.99 g (0.045 mol) of 6FDA was dissolved in 100 g of NMP under a stream of dry nitrogen. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF11.90g (0.033 moles), DAE1.00g (0.005 moles), ED600 6.0g (0.010 moles), SiDA0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, Then, it stirred at 180 degreeC for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C. for 72 hours to obtain a powder of a closed polyimide resin (J).

Synthesis Example 19 Polybenzo

Synthesis of azole precursor (K)

唑前驅物(K)。 Under a stream of dry nitrogen, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of epoxypropyl methyl ether, and the temperature of the solution was cooled down to -15 ° C. Here, a solution obtained by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Pesticide Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After the dropwise addition was completed, stirring was continued at -15 ° C for 6 hours. After the reaction was completed, the solution was poured into 3 L of water containing 10% by mass of methanol to precipitate a white precipitate. The precipitate was filtered and collected, washed three times with water, and then dried in a vacuum dryer at 50 ° C for 72 hours to obtain an alkali-soluble polybenzo

Azole precursor (K).

Synthesis Example 20 Synthesis of Polyimide Precursor Resin (L)

Under a dry nitrogen stream, 7.51 g (0.038 moles) of 4,4'-diaminophenyl ether (hereafter DAE), 1.86 g (0.007 moles) of SiDA, and 1.09 g (0.010 moles) of 3-aminophenol In NMP100g. Here, 13.96 g (0.045 mol) of ODPA was added simultaneously with 20 g of NMP, and the reaction was performed at 20 ° C for 1 hour, and then, the reaction was performed at 50 ° C for 4 hours. Thereafter, a solution of 9.25 g (0.08 mol) of N, N-dimethylformamide dimethyl acetal diluted with 5 g of NMP was added dropwise over 10 minutes, and the reaction was performed at 50 ° C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. After further washing twice with 2 L of water, it was dried in 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 stream of dry nitrogen, 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. Here, 13.96 g (0.045 mol) of ODPA was added simultaneously with 20 g of NMP, and the reaction was performed at 20 ° C for 1 hour, and then, the reaction was performed at 50 ° C for 4 hours. And then stirred at 180 ° C for 5 hours. After the stirring was completed, 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 in a vacuum dryer at 80 ° C. for 20 hours to obtain a polyfluoreneimide resin (M).

Synthesis Example 22 Synthesis of Closed Ring Polyimide Resin (N)

Under dry nitrogen flow, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF10.07g (0.028 moles), DAE1.00g (0.005 moles), ED600 10.50 g (0.018 mol), SiDA 0.62 g (0.003 mol) and NMP20 g were added simultaneously, and the reaction was carried out at 60 ° C. for 1 hour, followed by stirring at 180 ° C. for 4 hours. After the stirring was completed, 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 in a vacuum dryer at 50 ° C for 72 hours to obtain a powder of a closed polyimide resin (N).

Synthesis Example 23 Synthesis of Closed Polyimide Resin (O)

Under dry nitrogen flow, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. Here, 1.09 g (0.010 mol) of 3-aminophenol was added simultaneously with 20 g of NMP. And BAHF 7.33g (0.020 moles), DAE 1.00g (0.005 moles), ED600 15.00g (0.025 moles), SiDA 0.62g (0.003 moles) and NMP20g were added simultaneously, and the reaction was performed at 60 ° C for 1 hour, Then, it stirred at 180 degreeC for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. The 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 a powder of a closed polyimide resin (O).

Synthesis Example 24 Synthesis of Novolac Resin (f)

烷108.0g，在40℃、壓力0.08Mpa下將殘留水分除去直到小於3質量%。在反應液加入甲醇432.0g、96質量%硫酸2.0g。得到的反應液之pH為0.8。將反應液升溫直到60℃，在60℃進行烷氧化反應3小時。反應結束後，將反應液冷卻直到30℃以下，並使反應液不會成為35℃以上而花費30分鐘滴加10質量%氫氧化鈉水溶液，直到反應液的pH成為9.0。在反應液加入作為清洗用分離溶劑之甲基異丁酮(MIBK)216.0g、離子交換水324.0g，在30℃攪拌20分鐘，且靜置20分鐘，將分離的水層除去。並且加入離子交換水324.0g，以離子交換水重複清洗操作，直到除去水的導電度成為100μScm以下。清洗結束後，加入γ-丁內酯300g，在70℃、壓力0.08Mpa下進行離子交換水及MIBK之蒸餾去除，得到固體含量50質量%的酚醛清漆樹脂溶液(f)。 In 1000 ml of a three-neck flask substituted with nitrogen, 108.0 g of m-cresol, 108.0 g of methanol, and 40.0 g of sodium hydroxide were added, and the temperature was raised to 67 ° C. while stirring, and then a reflux reaction was performed for 30 minutes. Then, the reaction liquid was cooled down to 40 ° C, 92.5% by mass of paraformaldehyde (65.2 g) was added, and the temperature was raised again to 67 ° C, and then refluxed for 5 hours. After the completion of the reaction, the reaction solution was cooled to 30 ° C. or lower, 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 higher. The pH of the obtained reaction solution was 4.9. Further, 540.0 g of ion-exchanged water was added to the reaction solution, and after stirring for 20 minutes and standing for 20 minutes, the separated aqueous layer was removed. After removing the water layer, add two

108.0 g of alkane was removed at 40 ° C. under a pressure of 0.08 MPa to less than 3% by mass. 432.0 g of methanol and 2.0 g of 96% by mass sulfuric acid were added to the reaction solution. The pH of the obtained reaction solution was 0.8. The reaction solution was heated up to 60 ° C, and an alkoxylation reaction was performed at 60 ° C for 3 hours. After completion of the reaction, the reaction solution was cooled to 30 ° C. or lower, and the reaction solution was added dropwise to a 10% by mass sodium hydroxide aqueous solution for 30 minutes without causing the reaction solution to become 35 ° C. or higher until the pH of the reaction solution reached 9.0. 216.0 g of methyl isobutyl ketone (MIBK) and 324.0 g of ion-exchanged water were added to the reaction solution as a separation solvent for washing, and the mixture was stirred at 30 ° C. for 20 minutes and left to stand for 20 minutes to remove the separated aqueous layer. 324.0 g of ion-exchanged water was added, and the washing operation was repeated with ion-exchanged water until the conductivity of the removed water became 100 μScm or less. After the washing was completed, 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 novolac resin solution (f) having a solid content of 50% by mass.

According to the analysis by GPC, the obtained novolak resin solution (f) had a weight average molecular weight (Mw) of 7000 (GPA polystyrene conversion) and a dispersion degree (Mw / Mn) of 7.5. The mole number per 1 mole of alkoxyalkyl group by 13CNMR was 57 mole%, and the alkoxylation rate was 100 mole%.

Example 1

10.5 g of alkali-soluble resin (a1-1), 10.5 g of resin (A) obtained in Synthesis Example 9, and quinone diazide compound obtained in Synthesis Example 1 (a) 3.0 g, 7.2 g of cross-linking agent MX-270, and 1.0 g of KBM-403 were added to 25 g of GBL to obtain varnish A of a positive photosensitive resin composition.

The obtained varnish was applied to a PET film having a thickness of 38 μm using a notched wheel coater, and dried at 80 ° C. for 8 minutes, and then a PP film having a thickness of 10 μm was laminated as a protective film to obtain a photosensitive film. The thickness of the photosensitive thin film was adjusted to 10 μm.

Using the obtained photosensitive film, various evaluations of lamination properties, high extensibility, 5% weight reduction temperature (heat resistance), and pattern processability of the silicon substrate were performed.

Examples 2 to 33, Comparative Examples 1 to 8

Add the amount of (A1) alkali-soluble resin, (A2) alkali-soluble resin, other additives, (B) photoacid generator and (C) crosslinking agent, as shown in Table 1, Table 2-1, and Table 2- 2 except that the varnish was produced in the same manner as in Example 1 except that it was changed. Using the obtained photosensitive film, each evaluation of the lamination property, high extensibility, 5% weight reduction temperature (heat resistance), and pattern processability of the silicon substrate was performed.

The molar ratios of the components of the (A2) alkali-soluble resin are shown in Table 1.

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

1‧‧‧semiconductor element

2‧‧‧ passivation film

3‧‧‧hardened film

4‧‧‧ metal wiring

5‧‧‧hardened film

Claims (20)

A photosensitive film containing (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), and (A2) containing a resin selected from the group consisting of polyimide and polybenzo

One or more alkali-soluble resins, (B) a photoacid generator, and (C) a thermal crosslinking agent;

(In the 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 in the range of 1 to 3; R ² represents a hydrogen atom, a methyl group, or an ethyl group; Or propyl). The photosensitive film according to claim 1, wherein the weight average molecular weight (Mw) of the (A1) alkali-soluble resin is in a range of 3,000 to 60,000. The photosensitive film according to claim 1 or 2, wherein the (A1) alkali-soluble resin further has at least any one of the structural units represented by the general formula (2) and the general formula (3);

(In the 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 the general formula (3), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The photosensitive film according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of the (C) thermal crosslinking agent is 100 to 2,500. The photosensitive film according to any one of claims 1 to 4, 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 any one of claims 1 to 5, wherein the (A2) alkali-soluble resin has at least any one of the structural units represented by the general formulae (4) and (5);

(In the general formula (4), R ⁵ represents a 2- to 4-valent organic group having 4 to 40 carbon atoms; R ⁶ represents a divalent organic group having 20 to 100 carbon atoms; n ₁ represents an integer in the range of 10 to 100,000)

(In the general formula (5), R ⁵ represents a 2- to 4-valent 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 an organic group having 1 to 20 carbon atoms. Base; n ₂ represents an integer in the range of 10 to 100,000, and p and q represent integers satisfying 0 ≦ p + q ≦ 2). For example, the photosensitive film of claim 6, wherein R ⁶ of the general formulae (4) and (5) is 100 mol% with respect to the total amount of repeating units of the general formulae (4) and (5), and contains 10 to 80 mol. Ear% has an organic group with a polyether structure and 20 to 100 carbon atoms. The photosensitive film according to claim 7, wherein the organic group having a polyether structure and having a carbon number of 20 to 100 is an organic group represented by the general formula (10);

(In the formula, R ⁵⁴ to R ⁵⁷ each independently represent an alkylene group having 1 to 6 carbon atoms; R ⁵⁸ to R ⁶⁵ each independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms; however, repeating The structure shown in the brackets of the unit x is different from the structure shown in the brackets of the repeating unit y; the structure shown in the brackets of the repeating unit z is different from the structure shown in the brackets of the repeating unit y; x, y and z each independently represent an integer from 0 to 35). The photosensitive film according to any one of claims 6 to 8, wherein R ⁵ of the general formulae (4) and (5) is 100 mol% relative to the total amount of repeating units of the general formulae (4) and (5) It contains 10 to 80 mole% of organic groups having an alicyclic structure and having 4 to 40 carbon atoms. The photosensitive film according to any one of claims 1 to 9, further comprising a compound represented by (H) a general formula (13);

(In the general formula (13), R ⁷¹ to R ⁷³ represent any one of an O atom, an S atom, and an N atom, and at least one of R ⁷¹ to R ⁷³ represents an S atom; l represents 0 or 1, and R ⁷¹ When l is 0, it represents an oxygen atom or a sulfur atom, and when l is 1, it represents a nitrogen atom; 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) . The photosensitive film according to any one of claims 1 to 10, wherein the (C) thermal crosslinking agent further comprises a thermal crosslinking agent having a structural unit represented by the general formula (12);

(In the 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 may be linear or branched. , And any of the rings). The photosensitive film according to any one of claims 1 to 11, which has a photosensitive layer having a film thickness of 3 to 45 μm. The photosensitive film according to claim 12, which has a protective film on the photosensitive layer and a supporting film under the photosensitive layer. A cured film which hardens the photosensitive film according to any one of claims 1 to 13. An interlayer insulating film or a semiconductor protective film is provided with a hardened film as claimed in claim 14. An electronic component or semiconductor device having a relief pattern layer having a cured film as claimed in claim 14. An electronic component or semiconductor device, which is a hardened film having a film thickness of 2 to 40 μm on the substrate as requested in item 14, and a wiring on copper thereon, and a film thickness of 2 to 40 μm as requested in item 14 The cured film serves as an insulating film between copper wirings. An electronic component or a semiconductor device having a relief pattern layer of a cured film of a photosensitive resin composition on a substrate as a supporting material, and a covering material having a cured film as claimed in claim 14 as a covering material The covering material is arranged at the opening portion of the relief pattern layer of the supporting material, and has a hollow portion surrounded by the supporting material, the covering material, and the substrate. An electronic component or a semiconductor device, which has a (T-1) upper step portion (S-1) and a (S-2) lower step portion having a (T-1) step difference of 2 to 40 μm, and each is located in the (S-1) The upper section and the lower section (S-2) are provided with a hardened film such as the item 14 in the upper section, and the hardened film as described in the request 14 is provided in the upper section (S-1). The (T-2) step difference of the hardened film as set forth in claim 14 on the lower section is 5 μm or less. A method for manufacturing an electronic part or a semiconductor device, which is a method for manufacturing a semiconductor device using the photosensitive film according to any one of claims 1 to 13, and includes the following steps: the photosensitive film is placed on a substrate at 40 to 150 A step of forming a photosensitive film by heating and pressure bonding at a temperature of ℃, a step of exposing the photosensitive film through an exposure mask, and removing the exposed portion of the photosensitive film with an alkali developing solution to perform development step.