KR20180130099A - Photosensitive film - Google Patents

Abstract

[일반식(1) 중, R¹은 수소 원자 또는 탄소수 1∼5의 알킬기를 나타내고, a는 0∼4, b는 1∼3의 범위 내의 정수를 나타내며, R²는 수소 원자, 메틸기, 에틸기, 프로필기 중 어느 하나임]The present invention provides a photosensitive film which can obtain a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, that is, laminate property.
(A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) at least one compound selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof An alkali-soluble resin, (B) a photoacid generator, and (C) a heat-crosslinking agent.

Wherein R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, a methyl group, an ethyl group , Or a propyl group]

Description

Photosensitive film

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

Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulating properties and are therefore used for a surface protective film of a semiconductor device, an interlayer insulating film, an insulating layer of an organic electroluminescent device, and the like. In recent years, with the miniaturization of semiconductor devices, a resolution of several μm is required for a surface protective film, an interlayer insulating film, and the like. Therefore, in such applications, a positive working photosensitive polyimide resin composition and a positive working photosensitive polybenzoxazole resin composition that can be finely processed are widely used.

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

Conventionally, a circular substrate has been used for forming a semiconductor device, but recently, it has become possible to use a square type substrate as the substrate becomes larger.

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

Examples of the positive photosensitive polyimide used in the resin composition and the photosensitive film include those based on polyimide (for example, Patent Document 1), those based on polyhydroxystyrene (for example, Patent Document 2) and And polyimide and polyhydroxystyrene are mixed (for example, Patent Document 3).

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

Japanese Patent Application Laid-Open No. 2014-71374 Japanese Patent Application Laid-Open No. 2006-154779 Japanese Patent Application Laid-Open No. 2014-137523 Japanese Patent Application Laid-Open No. 2015-19006 International publication 2011/059089

As described above, when an insulating layer is formed on a rectangular substrate, a method of laminating using a photosensitive film is generally used in order to increase film thickness uniformity after formation. The photosensitive film is required to have mechanical properties such as high elongation and high heat resistance in a cured film and has good pattern processability (high sensitivity). In addition to having good pattern workability (high sensitivity) , I.e., lamination is required.

However, a film using a resin composition made of a polyimide as disclosed in Patent Documents 1 to 3 has insufficient flexibility, cracks may occur when the film is laminated by applying heat to the substrate, and the like , The lamination property was not sufficient. Patent Document 4 discloses a technique of using a phenol resin for the purpose of increasing fluidity, but there is a problem that the heat resistance of the film after curing is low. Patent Document 5 discloses a technique of using polyimide having a low softening point, but there is a problem that high heat resistance can not be obtained.

Accordingly, the present invention provides a photosensitive film which can obtain a cured film having high heat resistance, has good pattern processability (high sensitivity), and has good adhesion to a substrate, i.e., laminate property.

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

Wherein R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, a methyl group, an ethyl group , Or a propyl group]

According to the present invention, it is possible to obtain a photosensitive film having good pattern processability (high sensitivity) and having good adhesion to a substrate, i.e., laminate property. Further, according to the photosensitive film of the present invention, it is possible to obtain a cured film having high degree of curability and high heat resistance.

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

The present invention relates to (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) one kind selected from polyimide, polybenzoxazole, polyamideimide, a precursor thereof and a copolymer thereof (B) a photoacid generator, and (C) a heat crosslinking agent. Hereinafter, the resin (A1), the resin (A2), the component (B) and the component (C) may be omitted.

The photosensitive film of the present invention comprises an alkali-soluble resin having the structural unit represented by the general formula (1) of the above-mentioned (A1). R ¹ in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, An ethyl group, or a propyl group. By containing the resin (A1), the sensitivity of the photosensitive film can be improved.

The structural unit represented by the general formula (1) is, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m- An aromatic vinyl compound having a phenolic hydroxyl group such as propenylphenol and an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc., Can be obtained by subjecting a part of the polymer to an addition reaction with an alkoxy group using a known method (for example, the method described in Japanese Patent No. 5659259).

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

The alkali-soluble resin (A1) having the structural unit represented by the general formula (1) is preferably an alkali-soluble resin represented by the general formula (2) and the general formula (3) from the viewpoints of further improving the sensitivity and adjusting the solubility in an alkali developer. Or a structural unit represented by the following formula (1). In terms of solubility in an alkali developing solution, 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 within a 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 alkoxyalkyl (CH ₂ OR ² ) group in the resin (A1) is preferably 10 mol% or more, more preferably 20 mol% or more, per mol of hydroxystyrene from the viewpoint of heat resistance after curing. From the viewpoint of improving the resolution, it is preferably 70 mol% or less, more preferably 50 mol% or less.

The polystyrene reduced weight average molecular weight (Mw) of the resin (A1) is preferably 3,000 or more from the viewpoint of forming the pattern of the unexposed portion without eluting. Further, from the viewpoint of maintaining the alkali solubility capable of reducing the residue of the exposed portion, it is preferably 60,000 or less, more preferably 25,000 or less.

The polystyrene reduced weight average molecular weight (Mw) is a value calculated by GPC (gel permeation chromatography) measurement in terms of polystyrene.

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

The resin (A2) may contain two or more kinds of polyimide, polybenzoxazole, polyamideimide, a precursor thereof and a copolymer thereof, and may include a copolymer having two or more repeating units do. It is preferable that the resin (A2) has a substituent which reacts with the alkoxyalkyl group of the resin (A1). The alkoxyalkyl group in the general formula (A1) means, in particular, an alkoxymethyl group. The structure of the resin (A2) is not particularly limited as long as it has a substituent reactive with an alkoxyalkyl group, and it is preferable that the resin has at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group at the main chain or terminal.

(A1) the alkoxyalkyl group of the resin (A1) and the resin (A2) react at the time of thermosetting to sufficiently maintain the heat resistance and the mechanical properties, And mechanical characteristics can be compatible with each other. The content of the resin (A2) 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 the resin (A1) and the resin (A2). From the viewpoints of heat resistance and mechanical properties, the amount is preferably 90 parts by mass or less, more preferably 70 parts by mass or less.

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

[In the general formula (4), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms, R ⁶ represents a divalent organic group having 20 to 100 carbon atoms, and n ₁ represents an integer within a range of 10 to 100,000. ]

[Wherein R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms, R ⁶ represents a divalent organic group having 20 to 100 carbon atoms, and R ⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms N ₂ represents an integer within the range of 10 to 100,000, and p and q represent integers satisfying 0? P + q? 2.

In the general formulas (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. As the monocyclic or condensed polycyclic alicyclic structure in R ⁵ , those containing at least one organic group selected from the following general formulas (6) to (9) are preferable.

[In the formulas (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, and the monovalent organic group having 1 to 3 carbon atoms, A hydrogen atom contained in the organic group may be substituted with a halogen atom]

In the general formulas (4) and (5), R ⁵ represents an organic group derived from an acid anhydride used as a raw material for a resin.

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

Preferred structures of organic groups having 2 to 4 carbon atoms of 4 to 40 carbon atoms and having 1 to 4 aromatic rings in R ⁵ in the general formulas (4) and (5) include pyromellitic acid, 3,3 '4,4'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3 ' Benzophenone tetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane), bis (3,3-dicarboxyphenyl) Dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis Aromatic tetra-carboxylic acids such as 6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinedetracarboxylic acid and 3,4,9,10- To carboxylic acid Or a structure in which a part of hydrogen atoms thereof is substituted with 1 to 4 substituents selected from an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom and a chlorine atom Structure and the like.

The monocyclic or condensed polycyclic alicyclic structure represented by R ⁵ is preferably an alicyclic structure represented by the general formula (4) and the formula (5) in the case where R ⁵ is 100 mol% It is preferably 10 mol% or more, more preferably 30 mol% or more. It is preferably 80 mol% or less and more preferably 60 mol% or less from the viewpoint of obtaining an appropriate dissolution rate for the developer.

For example, when R ⁵ represents 70 mol% of the monocyclic or condensed polycyclic alicyclic structure and 4 mol% of the aromatic ring has an aromatic ring for 100 mol% of the total amount of the repeating units in the general formulas (4) and (5) When the organic group is 30 mol%, the monocyclic or condensed polycyclic alicyclic structure is calculated to be 70 mol%. In this case, when R ⁵ has two or more monocyclic or condensed polycyclic alicyclic structures, it is calculated as 70 mol%.

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

Wherein R ⁵⁴ to R ⁵⁷ each independently represent an alkylene group having 1 to 6 carbon atoms and R ⁵⁸ to R ⁶⁵ each independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, the structures displayed in the parentheses of x and y are different from each other, and the structures displayed in the parentheses of the repeat unit z and the structures shown in the parentheses of the repeat unit y are different from each other, and x and y , and z each independently represent an integer of 0 to 35). In the general formulas (4) and (5), R ⁶ is an organic group derived from a diamine used as a raw material for a resin.

Examples of the diamine having an organic group having a polyether structure used in the present invention include "Jefamine" (registered trademark) HK-511, ED-600, ED-900, ED-2003, EDR- RP-409, RP-2009, RT-1000, HT-1100, HE-1000, HT-1700, D-200, D-400, D-2000, D-4000 And aliphatic diamines such as [trade name, manufactured by HUNTSMAN CO., LTD.]. By having a polyether structure, hydrophilicity and melting property at a high temperature are imparted, laminate property to a substrate is improved, flexibility is imparted, elongation is improved, and elasticity is lowered to suppress warpage of the wafer . These properties are effective in multilayer or thick films. When the polyether structure represented by the general formula (10) is 10 mol% or more when R ⁶ in the general formula (4) and the general formula (5) is 100 mol%, the polyether structure represented by the general formula (10) In order to obtain laminate properties. When the amount is 80 mol% or less, an appropriate dissolution rate for the developer is preferably obtained. And more preferably 20 mol% to 50 mol%.

For example, with respect to 100 mol% of the total amount of the repeating units in the general formula (4) and the general formula (5), R ⁶ has 70 mol% of an organic group derived from a diamine containing an organic group having a polyether structure, It is calculated that when the divalent organic group having an aromatic ring is contained in an amount of 30 mol%, an organic group derived from a diamine containing an organic group having a polyether structure is 70 mol%. In this case, when R ⁶ is an organic group derived from a diamine containing an organic group having at least two polyether structures, it is calculated as 70 mol%.

Further, it is preferable that R ⁵ in the general formulas (4) and (5) further contain an organic group having a fluorine atom because water repellency is imparted to the resin and permeation from the surface of the film during alkali development can be suppressed . By suppressing the penetration from the surface of the film, it is possible to obtain a resin film having a high residual film ratio and free of development residue in the tact or pattern of the unexposed portion. These characteristics are important characteristics for realizing thick film processing. When the total amount of R ⁵ is 100 mol%, the organic group having a fluorine atom has an anti-seizing effect at the interface if it is 20 mol% or more, and preferably 90 mol% or less when the total amount of R ⁵ is 100 mol% , And more preferably 40 mol% to 60 mol%.

Specific examples of the fluorine atom-containing compound include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with alkyl or halogen atoms, and acid anhydrides having an amide group Aromatic dianhydrides and the like. The resin (A2) is preferably a resin containing a structure derived from these compounds.

By using the above-mentioned 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 within the above-mentioned range, At the time of development, a photosensitivity film having a high acceptance rate and no sensitivity residue is obtained.

These characteristics are particularly useful in the rewiring of a semiconductor device which is used as an interlayer insulating film between metal wirings and also in several layers, the use of a noise filter of an inductor device, and the like. The photosensitive film of the present invention may contain a structure in which the aforementioned acid dianhydride, diamine, and other acid dianhydrides and diamines are derived from the above-mentioned range without deteriorating the above-mentioned properties.

Specific examples of other acid dianhydrides 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'-benzophenonetetracar Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane 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-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3 , 4,9,10-perylene tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3 ', 4,4'- Aromatic tetracarboxylic dianhydrides such as benzyltetracarboxylic dianhydride, and compounds obtained by substituting hydrogen atoms of these compounds with alkyl groups or halogen atoms, 5- (2,5-dioxotetrahydrofuryl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct- , 6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornanacetic acid dianhydride, 3,4-dicarboxy- Cyclic, ring-cyclic tetracarboxylic dianhydrides such as 1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, or acid anhydrides having an amide group with compounds in which the hydrogen atom of the compound is substituted with an alkyl group or a halogen atom And the like. These acids can be used in combination of two or more kinds of anhydrides 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- Propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino- Sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, diamine-containing diamines such as dimercaptophenylenediamine, 3-hydroxyphenylenediamine, , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diamino Diphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy ) Benzene, benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene Diamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4 ' Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3' - tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) Aromatic diamines such as 4,4'-diaminobiphenyl, compounds obtained by substituting a part of the hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, a cyclohexyldiamine, a methylenebiscyclo And alicyclic diamines such as hexylamine. These diamines can be used as such or as the corresponding diisocyanate compound, trimethylsilylated diamine. These two or more diamine components may be used in combination.

Of these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4 (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfone, bis ) Biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, Bis (4-aminophenoxy) phenyl] propane, 2,2-bis (3-amino-4- Hydroxyphenyl) hexafluoropropane, diamines having an amide group, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, and the like. These may be used alone or in combination of two or more.

Further, an aliphatic group having a siloxane structure may be introduced within a range not lowering the heat resistance, and adhesion with the substrate can be improved. Specifically, bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane as the diamine component are reacted with R ⁶ in the general formula (4) And 1 to 15 mol% of the copolymer in terms of mol%.

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

The resin (A2) preferably has a phenolic hydroxyl group component. In the general formulas (4) and (5), it is preferable that at least one of R ⁵ and R ⁶ is an organic group having a phenolic hydroxyl group. By the presence of the phenolic hydroxyl group, appropriate solubility in an alkaline developer can be obtained. Further, since the solubility of the unexposed portion is inhibited by interacting with the photosensitizer, the residual film ratio and the sensitivity can be improved. The phenolic hydroxyl group also contributes to the reaction with the cross-linking agent, so that it is preferable from the viewpoint of obtaining high mechanical properties and chemical resistance.

Specific examples of the compound having a phenolic hydroxyl group include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride or a compound in which an aromatic ring thereof is substituted with an alkyl group or a halogen atom, and an acid having an amide group (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, bis ) Propane, bis (3-amino-4-hydroxyphenyl) methylene, bis 4-hydroxyphenyl) fluorene, and compounds obtained by substituting a part of hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. The resin (A2) is preferably a resin containing a structure derived from these compounds.

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

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

The resin (A2) may be end-capped with an end-capping agent such as monoamine, acid anhydride, acid chloride or monocarboxylic acid. The dissolution rate of the resin in the aqueous alkali solution can be easily adjusted to a desired range by sealing the terminal of the resin with a terminal 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. The terminal endblock is preferably used in an amount of 0.1 to 60 mol%, more preferably 5 to 50 mol%, based on the total amine component of the resin.

Specific examples of the terminal endblocker include monoamines such as 3-aminophenylacetylene, 4-aminophenylacetylene, and 3,5-diethynylaniline, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, , 3,5-diethynylbenzoic acid and the like, acid anhydrides such as maleic anhydride and 5-norbornene-2,3-dicarboxylic anhydride, compounds obtained by acidifying the carboxyl group of the monocarboxylic acid, An acid ester compound obtained by the reaction of a monoacid chloride compound with N-hydroxy-5-norbornene-2,3-dicarboxyimide or the like, or a compound obtained by acid chloridation of a carboxyl group of a dicarboxylic acid such as an acid Amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1 - hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaph Amino-naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, Carboxy-5-aminophthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid Aminophenol, 3-aminophenol, 4-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, Monoamines such as aminophenol, 2-aminothiophenol, 3-aminothiophenol and 4-aminothiophenol, acid anhydrides such as phthalic anhydride, cyclohexanedicarboxylic anhydride and 3-hydroxyphthalic anhydride, , 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7- Carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto- Naphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like, monoacid chloride compounds in which their carboxyl groups are acid chloridated, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxy naphthalene , A monoacid chloride compound in which only one carboxyl group of a dicarboxylic acid such as 1,6-dicarboxy naphthalene, 1,7-dicarboxy naphthalene, and 2,6-dicarboxy naphthalene is acid chloridated, a mono acid chloride compound And end-capping agents having no unsaturated bonds such as active ester compounds obtained by the reaction of N-hydroxybenzotriazole. Further, by substituting the hydrogen bond of the terminal endblock having no unsaturated bond with a vinyl group, it can be used as a terminal endblock having an unsaturated bond.

The resin having at least any one of the structural units represented by the general formula (4) and the general formula (5) can be produced in accordance with a known method for producing a polyimide and a polyimide precursor. For example, (I) tetracarboxylic acid having a tetracarboxylic dianhydride and diamine compounds, endcapping agent mono-amino compound having a group R ⁶ having a group R ^5, to react under low temperature conditions, (II) R ⁵ group dianhydride A method in which a diester is obtained by water and an alcohol, and thereafter the reaction is carried out in the presence of a diamine compound having R ⁶ group, a monoamino compound as a terminal endblocker and a condensing agent, (III) a method of reacting a tetracarboxylic dianhydride having R ⁵ group with an alcohol And then reacting the remaining two carboxyl groups with an acid chloride to react with a diamine compound having an R ⁶ group and a monoamino compound as a terminal endblocker.

The resin superimposed by the above method is preferably injected into a large amount of water or a mixture of methanol and water, precipitated, separated by filtration, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimer are removed, and the film characteristics after heat curing are improved. The polyimide precursor is allowed to undergo imidization and the ring-closed polyimide can be synthesized by a known imidization reaction method after obtaining the polyimide precursor.

Hereinafter, as a preferred example of (I), an example of a method for producing a polyimide precursor will be described. First, the diamine compound having an R < ⁶ > group is dissolved in a polymerization solvent. To this solution, an equimolar amount of a tetracarboxylic dianhydride having an R ⁵ group is added gradually to the diamine compound. The mixture is stirred at -20 to 100 占 폚, preferably 10 to 50 占 폚, for 0.5 to 100 hours, more preferably 2 to 24 hours using a mechanical stirrer. In the case of using an end-capping agent, the terminal end-capping agent may be added slowly after adding tetracarboxylic dianhydride and stirring at -20 to 100 占 폚, preferably 10 to 50 占 폚 for 0.1 to 24 hours, The reaction may be carried out at once.

The polymerization solvent is not particularly limited as long as it is capable of dissolving tetracarboxylic dianhydrides and diamines as raw material monomers. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, amides of N-methyl-2-pyrrolidone,? -Butyrolactone,? -Valerolactone, , cyclic esters such as? -caprolactone,? -caprolactone and? -methyl-? -butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, m- Cresol and the like, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like.

When the polymerization solvent is 100 parts by mass or more based on the total 100 parts by mass of the tetracarboxylic dianhydride, the diamine compound, and the monoamino compound used as the endcapping agent, the reaction can be carried out without precipitation of the starting material and the resin, If it is below the boiling point, the reaction proceeds quickly, and more preferably 150 to 950 parts by weight.

Next, the photosensitive film of the present invention will be described. The photosensitive film of the present invention has photosensitivity by containing (B) a photoacid generator. That is, the photoacid generator (B) is characterized in that an acid is generated by light irradiation and the solubility of the light irradiation portion in an aqueous alkali solution is increased. (B) photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, (A1) an alkali-soluble resin having a structural unit represented by the general formula (1), (A2) a polyimide, a polybenzoxazole, a polyamideimide, a precursor thereof, and a copolymer thereof Quinone diazide compounds are preferably used because they exhibit an excellent dissolution inhibiting effect by being used in combination with an alkali-soluble resin containing at least one kind of an alkali-soluble resin.

The quinone diazide compound may be a compound in which a sulfonic acid of quinone diazide is ester-bonded to a polyhydroxy compound, a sulfonic acid-bonded quinonediazide sulfonic acid in a polyamino compound, a sulfonic acid ester of quinone diazide in a polyhydroxypolyamino compound A bond or a sulfonamide bond, a sulfonic acid bond of a quinonediazide to a polyhydroxypolyamino compound, and a sulfonamide bond.

Although not all functional groups of these polyhydroxy compounds and polyamino compounds need to be substituted with quinone diazides, it is preferable that at least 50 mol% of the entire functional groups are substituted with quinone diazides. When the substitution by the quinone diazide is 50 mol% or more, the solubility in an alkali developing solution is not excessively high, and contrast with the unexposed portion can be obtained, and a desired pattern can be obtained. By using such a quinone diazide compound, it is possible to obtain a positive type photosensitive film which is exposed to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of ordinary mercury vapor. These compounds may be used alone or in combination of two or more. Further, by using two kinds of photoacid generators, the dissolution rate of the exposed portion and the unexposed portion can be largely compared, and as a result, a photosensitive film with high sensitivity can be obtained.

Bisp-PZ, BisP-IPZ, BisOCP, BisP-ZZ, BisP-PZ, BisP-PZ, BisP-PZ, BisP- DML-PCP, DML-PC, DML-PCP, DIP-DIP, bisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris- PML, TML-BP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BISOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML- (Trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA and HML- BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, , Manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxy Methyl-p-cresol, naphthol, tetrahydroxybenzophenone, glycine methyl ester, bisphenol A, Nol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo K.K.), and the like, but are not limited thereto.

The polyamino compound may be 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'- Phenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like, but are not limited thereto.

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

In the present invention, quinone diazide is preferably a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidesulfonyl ester compound is absorbed to the g line region of a mercury lamp and is suitable for g-line exposure.

In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinonediazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, and 4-naphthoquinone diazide sulfonic acid A sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be mixed and used.

The molecular weight of the quinone diazide compound of the present invention is preferably in the range of 300 to 3,000. If the molecular weight of the quinone diazide compound is larger than 5,000, the quinone diazide compound is not sufficiently pyrolyzed in the subsequent heat treatment, so that the heat resistance of the resulting film is deteriorated, mechanical properties are lowered, and adhesiveness is lowered .

The quinone diazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, 5-naphthoquinone diazide sulfonyl chloride and a phenol compound are reacted in the presence of triethylamine. A method for synthesizing a phenol compound includes a method in which an? - (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

Among the photoacid generators (B) used in the present invention, the sulfonium salt, phosphonium salt or diazonium salt is preferably used for appropriately stabilizing the acid component generated by exposure. Since the photosensitive film of the present invention is used as a permanent film, it is not preferable in terms of environment that phosphorus and the like remain, and the color tone of the film also needs to be taken into consideration. Among them, a sulfonium salt is preferably used. Particularly preferred is a triarylsulfonium salt, and it is possible to suppress the change in color tone of the film.

The content of the photoacid generator (B) is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2). The amount of the quinone diazide compound is preferably in the range of 3 to 40 parts by mass. The total amount of the compound selected from sulfonium salts, phosphonium salts and diazonium salts is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass. By setting the content of the photoacid generator (B) within the above range, high sensitivity can be achieved. A sensitizer, and the like may be added as needed.

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

Wherein R ⁶⁶ represents an organic group of 1 to 10 carbon atoms, plural R ^{67 s} may be the same or different and each represents an alkyl group of 1 to 4 carbon atoms, r represents an integer of 1 to 5, , s represents an integer of 1 to 10]

The alkoxymethyl group causes a thermal crosslinking reaction at 160 ° C or higher. Therefore, in the step of thermosetting the photosensitive film, a cross-linking reaction is generated and a favorable pattern shape can be obtained.

The number of alkoxymethyl groups is preferably two or more since the crosslinking density is improved, and more preferably four or more because the chemical resistance is improved. In order to reduce the dimensional irregularity of the pattern after heat curing, it is preferable that (C) at least one compound having 6 or more alkoxymethyl groups as a thermal crosslinking agent is contained.

The compound represented by the general formula (11) functions as a thermal plasticizer at a temperature lower than 160 占 폚 at which a thermal crosslinking reaction is caused. The lamination is preferably performed at a temperature of 150 DEG C or less, but at this time, the photosensitive layer is heated and melted to increase the contact area with the substrate, so that it is estimated that the adhesion between the two layers is improved.

Specific examples of the (C) thermal cross-linking agent include, but are not limited to, the following compounds. Two or more of them may be contained.

(C) The content of the heat crosslinking agent is preferably 1 part by mass (parts by mass) relative to 100 parts by mass of the total amount of the resin (A1) and the resin (A2) in order to improve the crosslinking density, chemical resistance, And more preferably 5 parts by mass or more. Further, in order to improve the mechanical properties, it is preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

The weight average molecular weight (Mw) of the heat crosslinking agent (C) 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. Further, in order to improve the lamination property, it is preferably 2,500 or less, more preferably 2,000 or less.

The photosensitive film of the present invention preferably contains a heat crosslinking agent having a structural unit represented by the following general formula (12). By containing the crosslinking agent, the elongation can be further improved while maintaining the heat resistance and the lamination property.

In the general formula (12), R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom or a methyl group, and R ⁶⁸ represents a divalent organic group having an alkylene group having 2 or more carbon atoms, and may be any of linear, branched, And R ^{68 is a combination of} alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, arylether, carboxyl, carbonyl, allyl, Etc., and may further have a substituent]

Since the heat-crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, it is possible to improve the elongation while having heat resistance and lamination properties. Examples of the crosslinking group include, but are not limited to, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group. Among them, an epoxy group is preferable in that it can react with a phenolic hydroxyl group of the resin (A1) and the resin (A2) to improve the heat resistance of the cured film and react without dehydration.

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

(Wherein n is an integer of 1 to 5, and m is 1 to 20)

Among these structures, n is preferably 1 to 2 and m is preferably 3 to 7 in view of achieving both heat resistance and elongation improvement.

The addition amount of the compound represented by the general formula (12) is preferably 2 to 35 parts by mass, more preferably 5 to 25 parts by mass, per 100 parts by mass of the total amount of the resin (A1) and the resin (A2). When the addition amount is 2 parts by mass or more, the effect of improving the elongation is sufficiently obtained. When the addition amount is 35 parts by mass or less, sensitivity deterioration of the photosensitive film before curing can be suppressed. The photosensitive film of the present invention may optionally contain (D) an acrylate compound. In the present invention, the (D) acrylate compound means a compound having an acryloyl group or a methacryloyl group. (D) acrylate compounds include monofunctional acrylates and polyfunctional acrylates. Monofunctional acrylate refers to a compound having at least one of an acryloyl group and a methacryloyl group. Examples thereof include acrylic acid esters, methacrylic acid esters, acrylamide and methacrylamide. The polyfunctional acrylate compound means a compound having at least one of an acryloyl group and a methacryloyl group.

The photosensitive film of the present invention is subjected to heat treatment after patterning. When used as a positive photosensitive film, the degree of elongation of the cured film is improved by the acrylate compound reacting with the thermally polymerized or alkali-soluble resin and cross-linking at this time. When used as a negative type photosensitive resin film, acrylate is photopolymerized by exposure during pattern processing to form a mesh structure with an alkali-soluble resin.

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

Preferred examples of the (D) acrylate compound include NK ester series 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD (manufactured by Shin Nakamura Chemical Co., , NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, A- ATM-4E, ATM-4E, ATM-4P, A-BPE-4, 701A, TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT, A-9300, , AD-TMP, AD-TMP-L, and A-DPH. P-1M, P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6 (manufactured by Kyoeisha Chemical Co., HX, 1.9ND, 1.10DC, G-101P, G-201P, DCP-M, BP-2EM, BP-4EM, BP-6EM and TMP. A, 4EG-A, 9EG-A, 14EG-A, TMGA-250, NP-A, MPD-A, BP-10A, HPP-A, TMP-A, TMP-3EO-BPA-A, BEPG-A, A, TMP-6EO-3A, PE-3A, PE-4A and DPE-6A. Further, epoxy ester series 40EM, 70PA, 200PA, 80MFA, 3002M, 3002A, 3000M and 3000A manufactured by Kyoeisha Kagaku Co., Ltd. and the like can be given. Further, "Aronix" series M-203, M-208, M-210, M-211B, M-215, M-220, M- 225, M-240, M-243, M-245, M-260, M-270, M-305, M-309, M-310, M- M-350, M-360, M-402, M-408 and M-450. KAYARAD (registered trademark) series R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R (trade name) manufactured by Nippon Kayaku Co., TP-320, TPA-330, PET-30, T-1420 (T), RP-1040 . 100, PDE-150, PDE-200, PDE-400, PDE-600 (manufactured by NOF CORPORATION) , PDE-1000, ADE-200, ADE-400, PDP-400, ADP-200, ADP-400, PDT-650, ADT-250, PDBE-200, PDBE-250, PDBE- -200, ADBE-250, and ADBE-450. Further, MBAA manufactured by MRC Unitech Co., Ltd. and the like can be mentioned. Two or more of these compounds may be contained.

Among the acrylate compounds (D), acrylate compounds having a molecular weight of 100 or more and 2,000 or less are preferable. When the molecular weight is 100 or more, a cured film of high degree of curability can be obtained. When the molecular weight is 2,000 or less, a resin composition having suitable alkali solubility and high usability with an alkali-soluble resin can be obtained.

In addition to the resin (A2), other alkali-soluble resins may be contained in the present invention within the range not to impair the heat resistance of the cured film obtained by the heat treatment. Specific examples thereof include a resin obtained by introducing a crosslinking group such as a methylol group, an alkoxymethyl group or an epoxy group into an acrylic polymer copolymerized with acrylic acid, a siloxane resin, a novolak resin, a resor resin, a polyhydroxystyrene resin, , And their copolymeric polymers. Such a resin is dissolved in an aqueous solution of an alkali such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate and the like. By containing these alkali-soluble resins, the properties of each alkali-soluble resin can be imparted while maintaining the adhesiveness and excellent sensitivity of the heat-resistant resin coating.

As another alkali-soluble resin, a phenol resin is preferable from the viewpoint of sensitivity. The phenol resin is obtained by polycondensation of phenols and aldehydes by a known method. A resin having two or more phenolic hydroxyl groups may be contained in combination.

Preferable examples of the phenol include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4- , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, and the like. Particularly, it is preferable to use phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, Trimethylphenol is preferred. Two or more of these phenols may be used in combination. From the viewpoint of solubility in an alkali developing solution, m-cresol is preferable, and a combination of m-cresol and p-cresol is also preferable. That is, as the resin having a phenolic hydroxyl group, it is preferable to include an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue. At this time, the molar ratio (m-cresol residue / p-cresol residue, m / p) of the m-cresol residue to the p-cresol residue in the cresol novolak resin is preferably 1.8 or more. When the pH is in the above range, it exhibits suitable solubility in an alkaline developer and good sensitivity can be obtained. More preferably 4 or more.

Preferable examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde and the like. Of these, formalin is particularly preferable. These aldehydes may be used in combination of two or more. The amount of the aldehyde to be used is preferably 0.6 mol or more, more preferably 0.7 mol or more, per 1 mol of the phenol. It is preferably 3 mol or less, more preferably 1.5 mol or less.

For the polycondensation reaction of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, acetic acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and p-toluenesulfonic acid. The amount of these acidic catalysts to be used is usually 1 × 10 ^{-5 to} 5 × 10 ^-1 mol per 1 mol of the phenol. In the polycondensation reaction, water is usually used as a reaction medium, but when it becomes a heterogeneous system from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as a reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; And cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media to be used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.

The reaction temperature for the polycondensation can be suitably adjusted according to the reactivity of the raw material, but is usually from 10 to 200 캜. As a reaction method of the polycondensation, a method in which phenols, aldehydes, acidic catalysts, etc. are collectively injected and reacted, or a method in which phenols, aldehydes and the like are added together with the progress of the reaction in the presence of an acidic catalyst are suitably employed . After completion of the polycondensation reaction, in order to remove unreacted raw materials, acidic catalysts, reaction media, and the like existing in the system, the reaction temperature is raised to 130 to 230 캜, volatile components are removed under reduced pressure, Is recovered.

In the present invention, the weight average molecular weight (hereinafter referred to as " Mw ") of the phenolic resin in terms of polystyrene is preferably 1,000 or more, and more preferably 2,000 or more. It is preferably 20,000 or less, more preferably 10,000 or less. Within this range, the workability and sensitivity when the positive photosensitive resin composition of the present invention is applied to a substrate are excellent.

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

In the resin included in the photosensitive film of the present invention, the resin containing the structure represented by the general formula (4) and the general formula (5) is preferably 30 mass% or more.

Further, for the purpose of improving the sensitivity of the photosensitive film, a compound having a phenolic hydroxyl group (E) may be contained within a range not lowering the shrinkage ratio after curing, if necessary.

(E) The compound having a phenolic hydroxyl group is, for example, bis-Z, BisOC-Z, BisOP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP- BisPX-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis P- BisP-OCHP, Bis25-OCHP, Bis26-OCHP, BisOCHP-OC, BisP-OCHP, BisP-OCHP, BIR-PC, BIR-PTBP, BIR-PC (trade name, manufactured by Honshu Kagaku Kogyo K.K.), Bis- -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F and TEP-BIP-A (trade names, manufactured by Asahi Yuki Kai Kogyo K.K.).

The preferred compounds having a phenolic hydroxyl group (E) are Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP- , BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP and BIR-BIPC-F .

Especially preferred compounds having a phenolic hydroxyl group (E) are Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP and BIR-BIPC-F . (E) containing a compound having a phenolic hydroxyl group, it is possible to provide a photosensitive film which is low in film loss due to development and can be developed for a short time in order to dissolve easily in an alkaline developing solution while being hardly used in an alkali developer before exposure, Can be obtained. The content of the compound (E) having a phenolic hydroxyl group is preferably from 1 to 50 parts by mass, more preferably from 3 to 40 parts by mass, per 100 parts by mass of the total amount of the resin (A1) and the resin (A2) It is mine.

The photosensitive film of the present invention may contain (F) a solvent. Examples of the solvent (F) include polar aprotic solvents such as? -Butyrolactone, ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene Ketone such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N, N-dimethylformamide and N, N-dimethylacetamide, ketone such as 3 Methoxybutyl acetate and ethylene glycol monoethyl ether acetate; esters such as ethyl acetate, propyleneglycol monomethyl ether acetate and ethyl lactate; aromatic hydrocarbons such as toluene and xylene; . The content of the (F) solvent is preferably 0.0001 part by mass or more, more preferably 50 parts by mass or less based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2).

The photosensitive film of the present invention may contain a (G) silane compound and may be used as an adhesion promoter for improving adhesion to a base substrate. Specific examples of the (G) silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N- Vinyltriethoxysilane, vinyltris (? -Methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltris Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Include silane compounds having the structures shown below, but are not limited thereto. Two or more of these may be contained.

The content of the (G) silane compound is preferably 0.01 part by mass or more and 15 parts by mass or less based on 100 parts by mass of the total amount of the resin (A1) and the resin (A2). Within the above range, a sufficient effect can be obtained as an adhesive preparation while maintaining the heat resistance of the positive photosensitive film.

For the purpose of improving the wettability between the photosensitive film and the substrate, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, ketones such as tetrahydrofuran , And dioxane. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powders of polyimide may also be contained.

The photosensitive film of the present invention preferably contains (H) a compound represented by the following general formula (13) [hereinafter referred to as (H) component]. (H) component, the adhesiveness between the laminated film and the metal material, particularly copper, is remarkably improved. This is due to the fact that the S atom or N atom of the compound represented by the general formula (13) originates from interaction with the metal surface, and also has a three-dimensional structure which is easy to interact with the metal surface. By these effects, it is possible to obtain a resin cured film which is imparted with photosensitivity to the resin composition and excellent in adhesion to a metal material even in the composition (composition) having the additive. In the general formula (13), R ⁷¹ to R ^{73 each} represent an O atom, an S atom or an N atom, and at least one of R ⁷¹ to R ⁷³ represents an S atom. l represents 0 or 1, R ⁷¹ represents an oxygen atom or a sulfur atom when l is 0, and represents a nitrogen atom when l is 1. m and n represent 1 or 2. Each of R ⁷⁴ to R ⁷⁶ independently represents 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 alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, Or a combination thereof, and may further have a substituent.

The addition amount of the component (H) is preferably from 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the resin (A1) and the resin (A2). When the addition amount is 0.1 part by mass or more, the effect of improving the adhesion after lamination to the metal material can be sufficiently obtained. When the amount is 10 parts by mass or less, when the photosensitive film used in the present invention is a positive type, And the sensitivity of the photosensitive film due to the action can be suppressed.

In the compound represented by the general formula (13) used in the present invention, R ⁷¹ to R ⁷³ each 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 preferably an S atom . In general, when a compound containing an N atom is added, there is a possibility of impairing the sensitivity due to the interaction between the sensitizer and the N atom-containing compound, but since the interaction effect is appropriately maintained by containing the S atom, The effect of improving the adhesion can be obtained without lowering the adhesion. From the viewpoint of adhesion after lamination to a substrate other than a metal such as silicon, it is more preferable to have a trialkoxymethyl group.

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

A method for producing the photosensitive film of the present invention is illustrated. For example, (A1) an alkali-soluble resin having a structural unit represented by the general formula (1) and (A2) a polyimide, polybenzoxazole, polyamide having a substituent which reacts with the alkali- (B) a photoacid generator, (C) a thermal cross-linking agent, (F) a solvent and, if necessary, other components in a glass A container made of stainless steel or the like and subjected to stirring and melting by a mechanical stirrer or the like; a method of dissolving by ultrasonic waves; and a method of stirring and dissolving by a planetary stirring defoaming device. The viscosity of the composition including the resin (A1), the resin (A2), the photoacid generator (B), the heat crosslinking agent (C), the solvent (F) and the like is preferably 200 to 10,000 mPa · s. Further, filtration may be performed using a filter having a pore size of 0.1 mu m to 5 mu m to remove foreign matter.

The photosensitive film of the present invention preferably has a support film. A composition comprising (A1) a resin, (A2) a resin, (B) a photoacid generator, (C) a heat crosslinking agent, and (F) a solvent is applied onto a support film, A photosensitive film having a photosensitive layer can be obtained.

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

In order to protect the surface of the photosensitive film of the present invention, a protective film may be provided on the film. As a result, the surface of the photosensitive film can be protected from contaminants such as dust and dirt in the air.

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

Examples of a method of applying a composition containing a resin (A1), a resin (A2), a photoacid generator (B), a heat crosslinking agent (C), a solvent (F) and the like to a support film and forming a photosensitive layer include spray coating, roll A coating method, a screen printing method, a blade coater, a die coater, a calendar coater, a meniscus coater, a bar coater, a roll coater, a comma roll coater, a gravure coater, a screen coater and a slit die coater. The thickness of the coating film differs depending on the application method, the solid content concentration of the composition, the viscosity, and the like, but it is preferable that the thickness of the photosensitive layer obtained after drying is 0.5 mu m or more and 100 mu m or less. Further, it is more preferably not less than 3 mu m and not more than 40 mu m.

For drying, oven, hot plate, infrared ray and the like can be used. The drying temperature and the drying time are preferably within a range capable of volatilizing the solvent, and it is preferable to appropriately set the range in which the semiconductor resin film material is in an uncured or semi-cured state. Concretely, it is preferable to perform one minute to several tens of minutes in the range of 40 占 폚 to 120 占 폚. The temperature may be raised step by step by combining these temperatures. For example, heat treatment may be performed for 1 minute at 50 占 폚, 60 占 폚 and 70 占 폚.

Next, a method of manufacturing a semiconductor device using a photosensitive film will be described. If the photosensitive film has a protective film, it is peeled off first. The photosensitive film and the substrate are opposed to each other and bonded by heating and pressing, and the photosensitive film is transferred onto the substrate and laminated. Then, the support film is peeled off to obtain a photosensitive film. The hot pressing can be performed by hot pressing, thermal lamination, thermal vacuum laminating or the like. The temperature for hot pressing and laminating is preferably 40 占 폚 or higher and more preferably 50 占 폚 or higher in terms of adhesion to the substrate and filling property. Further, in order to prevent the photosensitive film from hardening at the time of hot pressing and to prevent the resolution of the pattern formation in the exposure and development process from becoming poor, the temperature of the heat press bonding is preferably 150 ° C or lower, more preferably 120 ° C or lower . Further, at the time of thermocompression bonding, it may be performed under reduced pressure for the purpose of removing bubbles.

Further, after the photosensitive film is laminated on the substrate, the peeling of the support film from the photosensitive film is performed in a temperature range of 0 ° C to 100 ° C.

The substrate to be used includes, but is not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and those in which circuit components are arranged on these substrates.

Examples of organic circuit boards include glass-based copper-clad laminates such as glass fabric and epoxy copper clad laminates, composite-laminated boards such as glass nonwoven fabric and epoxy copper clad laminate, polyetherimide resin substrates, polyether ketone resin substrates, poly A flexible substrate such as a heat resistant / thermoplastic substrate such as a sulphone resin substrate, a polyester copper film substrate, and a polyimide copper film substrate. Examples of the inorganic circuit substrate include ceramic substrates such as an alumina substrate, an aluminum nitride substrate and a silicon carbide substrate, and metal-based substrates such as an aluminum base substrate and an iron base substrate. Examples of the constituent material of the circuit include a conductor containing a metal such as gold, silver and copper, a resistor containing an inorganic oxide or the like, a low dielectric material containing a glass material, a resin or the like, An insulator containing a high-dielectric-constant material, a glass-based material, and the like.

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

In order to form a pattern, the unexposed portion is removed by using a developer after exposure. Examples of the developer include aqueous solutions of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol , Dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like are preferable. Further, in some cases, these alkaline aqueous solutions may be mixed with an aqueous solution of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Polar solvents such as methanol, ethanol and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone; Alone or in combination of several species.

The development can be carried out by spraying the above-mentioned developer onto any surface of the photosensitive film, by immersing it in a developing solution, by applying ultrasonic waves while immersing it, or by spraying the developing solution while rotating the substrate. The conditions at the time of development such as the development time, developing step and developing solution may be any conditions under which the unexposed portion is removed. In order to process a fine pattern and remove residues between the patterns, .

After development, rinse treatment may be performed with water. Also here, rinsing may be performed by adding an alcohol such as ethanol or isopropyl alcohol, or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate to water. In the case where the resolution of the pattern at the time of development is improved and the allowable range of the developing conditions is increased, a step of baking treatment before development may be added. The temperature is preferably in the range of 50 to 180 占 폚, more preferably in the range of 60 to 120 占 폚. The time is preferably 5 seconds to several hours.

After the pattern is formed, a cured film is obtained over a temperature range of 120 占 폚 to 400 占 폚. The heating treatment is carried out for 5 minutes to 5 hours by selecting a temperature, raising the temperature stepwise, or continuously raising the temperature by selecting a certain temperature range. As an example, heat treatment is performed at 130 캜 and 200 캜 for 30 minutes each. Alternatively, the temperature may be raised linearly from room temperature to 250 DEG C over 2 hours. In this case, the heating temperature is preferably 150 ° C or more and 300 ° C or less, more preferably 180 ° C or more and 250 ° C or less.

The film thickness of the cured film is preferably 0.5 탆 or more, and more preferably 2 탆 or more, in order to improve the insulating property. Further, from the viewpoint of reducing warping of the substrate due to the residual stress, 100 mu m is preferable, and 40 mu m or less is more preferable.

The cured film obtained by curing the photosensitive film of the present invention is suitably used for a passivation film of a semiconductor, a semiconductor protective film, an interlayer insulating film of a multilayer wiring for high density mounting, and an insulating layer of an organic electroluminescent device. Further, the cured film obtained by curing the photosensitive film of the present invention can be used for a semiconductor device in a state where a relief pattern layer of the cured film is formed.

Further, the cured film is placed on the substrate with a film thickness of 2 to 40 m as described above, and a copper wiring is disposed thereon. Thereafter, a cured film is further formed as an insulating film between the copper wiring with a thickness of 2 to 40 m, A semiconductor device may also be fabricated.

Fig. 1 shows an example of a structure in which a semiconductor device in which a cured film of a photosensitive film of the present invention is cured is well known. A passivation film (2) is formed on the semiconductor element (1). The photosensitive film according to the present invention is laminated on the passivation film 2 by hot pressing, heated and dried using a hot plate or the like, and a pattern of the photosensitive film is formed through exposure and development. After the pattern formation of the photosensitive film, a curing process is performed to form a cured film 3. Metal wiring is formed on the cured film 3 by sputtering, vapor deposition, electroless plating, electrolytic plating, or the like. Further, in order to protect the metal wiring, the photosensitive film according to the present invention is laminated by heat-pressing, heated and dried using a hot plate, and patterned through exposure and development. After the pattern formation of the photosensitive film, a curing process is performed to form a cured film 5. By forming the cured film by the above method, it is possible to provide a highly flat semiconductor device having high adhesion between the cured film and high adhesion of the cured film and the metal wiring.

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

Next, an application example of an electronic component or a semiconductor device having a hollow portion, in which a cured film of the photosensitive film of the present invention is cured, will be described with reference to the drawings. 3 is an example of a cross-sectional view of a hollow portion of an acoustic wave device using the photosensitive film of the present invention. 3, the substrate 14 is provided with an IDT (Inter Digital Transducer) electrode 15 constituted by a pair of interdigital electrodes each having a plurality of electrode fingers interposed therebetween, and a bonding pad (16) is formed. Here, the substrate 14 includes, for example, lithium niobate, potassium niobate, lithium tantalate, quartz, langasite, ZnO, PZT, lithium tetraborate 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. A relief pattern layer of the cured film of the photosensitive resin composition is formed as the supporting member 18 in the piezoelectric substrate 14 in order to secure the hollow portion 17. [ Examples of the photosensitive resin composition include a polyimide resin, an epoxy resin, an acrylic resin, and a phenol resin. The covering material 19 is provided on the substrate 15 through the supporting member 17 so as to cover the electrode 15. [ Here, the photosensitive film of the present invention is used for the covering material 19, but it may be used as the supporting material 17. The thickness of the covering material 19 is, for example, 20 占 퐉. The protection member 20 is provided so as to cover the substrate 14, the supporting member 18, and the covering member 19. [ For example, the thickness of the protective member 20 on the covering material 19 is, for example, 30 占 퐉. The protective member is an insulating material, and examples thereof include an epoxy resin, a benzocyclobutene resin, a silicone resin, and SOG (Spin On Grass). A via conductor 21 may be provided in the support member 17 and the cover member 19 so as to penetrate in the thickness direction. A solder bump 22 is connected and formed on the via conductor 21.

Next, an application example to a semiconductor device comprising a substrate having a step difference using the photosensitive film of the present invention will be described with reference to the drawings. 4 is an enlarged 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-outWLP). The silicon wafer 23 on which the Al pad 24 and the passivation film 25 are formed is diced and divided into chips and sealed with a resin 26. Then, (T-1) step is generated between the chip 23 and the resin 26 due to the shrinkage of the resin 26. As a result, At this time, the (T-1) level difference between the (S-1) upper end of the chip 23 and the (S-2) lower end of the resin 26 surface is 2 to 40 占 퐉. The cured film 27 is formed as a pattern of the photosensitive film of the present invention over the upper end of the (S-1) and the lower end of (S-2) (T-2) step of the cured film disposed on the lower end of the (S-2) is 5 占 퐉 or less.

Further, a metal (Cr, Ti, etc.) film 28 and a metal wiring 29 are formed. Thereafter, the barrier metal 31 and the solder bump 32 are formed in the opening of the insulating film 30 formed on the sealing resin other than the chip. In the fan-out WLP, an expanded portion is provided by using an encapsulating resin such as epoxy resin around the semiconductor chip, rewiring is performed from the electrode on the semiconductor chip to the extended portion, and a solder ball is mounted on the extended portion. . In the fan-out WLP, wirings are provided so as to extend across the boundary formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a substrate made of two or more kinds of materials, that is, a semiconductor chip on which metal wiring is performed and a sealing resin, and wirings are formed on the interlayer insulating film. In addition, in the semiconductor package of the type in which the semiconductor chip is embedded in the recess formed in the glass epoxy resin substrate, the wiring is provided across the boundary between the main surface of the semiconductor chip and the main surface of the printed board. Also in this embodiment, an interlayer insulating film is formed on a substrate made of two or more kinds of materials, and wirings are formed on the interlayer insulating film. When the cured film obtained by curing the photosensitive film of the present invention is disposed on a substrate made of two or more kinds of materials, it is possible to reduce the level difference on the substrate and maintain the flatness of the cured film, It is used as an interlayer insulating film to be installed.

<Examples>

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited thereto. The esterification rate of the synthesized quinone diazide compound and the evaluation of the photosensitive film were carried out by the following methods.

&Lt; Method of measuring film thickness &

Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and after development was measured with a refractive index of 1.629 on the basis of polyimide .

&Lt; Measurement of imidization rate of polyimide &

(A2) The imidization rate of the alkali-soluble resin was determined by applying a solution of N-methylpyrrolidone (hereinafter referred to as NMP) having a solid content concentration of polyimide resin of 50% by mass on a 6-inch silicon wafer by spin coating, Then, the substrate was baked for 3 minutes by a hot plate (SKW-636, manufactured by Dainippon Screen Seiko Chemical Industry Co., Ltd.) at 120 占 폚 to prepare a prebaked film having a thickness of 10 占 퐉 占 1 占 퐉. The membrane was divided in half and one side was charged into an inert oven (INH-21CD, manufactured by Koyo Thermo Systems Co., Ltd.) and heated to a curing temperature of 350 占 폚 for 30 minutes And heated at 350 DEG C for 60 minutes. Thereafter, the temperature in the oven was gradually cooled to 50 DEG C or lower to obtain a cured film. The infrared absorption spectrum of the obtained cured film (A) and the film (B) before curing was measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by HORIBA, Ltd.) The peak intensity near 1377 cm ^-1 due to CN stretching vibration was obtained and the value of the "peak intensity of the film (B) before curing / peak intensity of the cured film (A)" was regarded as the imidization rate.

&Lt; Evaluation of lamination property &

The protective film of the photosensitive film produced in each of the following Examples and Comparative Examples was peeled off. The release surface was then laminated on a silicon wafer or on a copper substrate. The copper substrate used was a substrate (copper-plated substrate) having 100 nm of titanium and copper sputtered on a silicon wafer, followed by electrolytic plating to form a copper plating film with a metal material layer having a thickness of 2 μm on the surface. The lamination was carried out under the conditions of a stage temperature of 80 占 폚, a roll temperature of 80 占 폚, a degree of vacuum of 150 pa, a sticking speed of 5 mm / sec, a sticking pressure 0.2 MPa. After the laminating, perforations were inserted into the photosensitive film in a lattice pattern of a checkerboard so that 100 squares were formed at intervals of 2 mm x 2 mm using a cutter guide at the center of the film on the substrate. A cellophane tape was stuck to the lattice-shaped portion of the checkerboard, and then pulled out in an angular direction of 90 DEG to the substrate to peel off. When peeling off, the number of photosensitive films peeled off from 100 pieces was counted. When the amount of peeling is small, the adhesion is high, and when it is large, the adhesion is low. More preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less. Condition 1 was performed on a silicon wafer to evaluate the lamination property, and Condition 2 was performed on a copper substrate.

&Lt; Evaluation of pattern processability (high sensitivity)

The protective film of the photosensitive film prepared in each of the examples and the comparative examples was peeled off and the peeled surface was peeled off on a 8-inch silicon wafer using a laminator (VTM-200M, manufactured by Takashima KK) Lt; 0 &gt; C, a roll temperature of 120 DEG C, a degree of vacuum of 150 pa, an attaching speed of 5 mm / sec, and a sticking pressure of 0.2 MPa. Subsequently, the substrate was baked for 3 minutes on a hot plate (using ACT-8) at 120 占 폚 to prepare a prebaked film having a thickness of 10 占 퐉. The film was exposed using an i-line stepper (NIKON NSR i9) at an exposure amount of 0 to 1000 mJ / cm 2 in 10 mJ / cm 2 steps. After the exposure, the resist film was developed for 90 seconds in an aqueous solution of 2.38% by mass of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Company, Inc., ELM-D), rinsed with pure water, A developing membrane A having an isolation space of 5 mu m was obtained.

After the exposure and development in the developing film A, the exposed area of the isolated space of 5 mu m was completely eluted and the amount of exposure (minimum exposure amount Eth) was determined as the sensitivity. If Eth is 400 mJ / cm &lt; 2 &gt; or less, high sensitivity can be determined. More preferably 300 mJ / cm 2 or less, and still more preferably 250 mJ / cm 2 or less.

<Assessment of high-visibility>

The protective film of the photosensitive film prepared in each of the examples and the comparative examples was peeled off and the laminate was peeled off from the protective film of the photosensitive film at a stage temperature of 80 占 폚 and a roll temperature of 120 占 폚 using a laminator (VTM-200M, manufactured by Takashima KK) , A degree of vacuum of 150 pa, a sticking speed of 5 mm / sec, and a sticking pressure of 0.2 Mpa. The laminated substrate was pre-baked at 120 DEG C for 3 minutes on a hot plate, and then was heat-treated at 400 DEG C for 3.5 minutes at an oxygen concentration of 20 ppm or less under nitrogen flow using an inert gas oven CLH-21CD-S (manufactured by Koyo Sakosystem Co.) Lt; 0 &gt; C, and then heat-treated at 220 DEG C for 1 hour. And peeled off with a 46 mass% hydrofluoric acid aqueous solution to obtain a cured film (heat resistant resin film). The cured film obtained by the above-mentioned method was cut into one blade so as to have a size of 7 x 1 cm and pulled at 50 mm / min by a Tensilon universal testing machine (RTM-100 manufactured by Orientech). The value obtained by dividing the elongation at this time by the sample length was obtained. The above measurement was performed on 10 samples, and the maximum value was defined as elongation. The elongation is preferably 10% or more, more preferably 20% or more, and even more preferably 40% or more.

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

The cured film obtained in the same manner as in < evaluation of high-knessiness > was measured under a condition of 80 mL / min in a nitrogen stream using a thermogravimetric analyzer (TGA50 manufactured by Shimadzu Corporation) / min. &lt; / RTI &gt; The 5% weight reduction temperature is preferably 260 占 폚 or higher, more preferably 300 占 폚 or higher, and even more preferably 340 占 폚 or higher.

The abbreviated symbols and the names of the compounds used in the respective Examples and Comparative Examples are as follows.

PMDA-HH: 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride

TDA-100: 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

CBDA: Cyclobutane tetracarboxylic dianhydride

6FDA: 4,4'-hexafluoroisopropylidene diphthalic acid 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, manufactured by HUNTSMAN Co., Ltd.)

MAP: Metaaminophenol

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

KBM-403: 3-glycidoxypropyltrimethoxysilane [silane compound (a)]

The (C) thermal crosslinking agent and the (H) compound used in each of the examples and comparative examples are shown below.

Synthesis Example 1 Synthesis of quinone diazide compound (a)

(0.05 mole) of TrisP-PA (trade name, manufactured by Honshu Kagaku Kogyo K.K.), 26.86 g (0.10 mole) of 5-naphthoquinonediazide sulfonyl chloride, 0.10 mole of 4-naphthoquinonediamine 13.43 g (0.05 mol) of zidosulfonyl chloride was dissolved in 1,4-dioxane (50 g) and the temperature was brought to room temperature. Then, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise while confirming that the temperature of the system did not exceed 35 占 폚. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. Thereafter, precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum drier to obtain a quinone diazide compound (a) represented by the following formula.

Synthesis Example 2 Synthesis of polyhydroxystyrene resin (a0-1)

To a mixed solution obtained by adding 500 ml of tetrahydrofuran and 0.01 mole of sec-butyllithium as an initiator, 20 g in total of p-t-butoxystyrene and styrene in a molar ratio of 3: 1 was added and polymerized while stirring for 3 hours. The termination of the polymerization was carried out by adding 0.1 mol of methanol to the reaction solution. Next, to purify the polymer, the reaction mixture was poured into methanol, and the precipitated polymer was dried to obtain a white polymer. Further, a small amount of concentrated hydrochloric acid was added at 60 占 폚 and stirred for 7 hours. Subsequently, the solution was poured into water to precipitate a polymer and deprotect pt-butoxystyrene to obtain hydroxystyrene After the conversion and washing and drying, a copolymer of purified p-hydroxystyrene and styrene [hereinafter referred to as (a0-1)] was obtained. The weight average molecular weight (Mw) was 3500 (in terms of GPC polystyrene) and the degree of dispersion (Mw / Mn) was 2.80 by GPC analysis.

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

Except that m-t-butoxystyrene was used in place of p-t-butoxystyrene of Synthesis Example 2. The obtained copolymer of m-hydroxystyrene and styrene (hereinafter referred to as (a0-2)) had a weight average molecular weight (Mw) of 5000 (in terms of GPC polystyrene) and a degree of dispersion of (Mw / Mn) of 3.20 .

Synthesis Example 4 Synthesis of polyhydroxystyrene resin (a0-3)

Except that the styrene of Synthesis Example 2 was not added. The obtained p-hydroxystyrene resin (hereinafter referred to as (a0-3)) had a weight average molecular weight (Mw) of 3000 (in terms of GPC polystyrene) and a degree of dispersion (Mw / Mn) of 1.60 by GPC analysis.

Synthesis Example 5 Synthesis of alkali-soluble resin (a1-1)

The polyhydroxystyrene resin (a0-1) was dissolved in a solution of 80 g (2.0 mol) of sodium hydroxide dissolved in 800 g of pure water. After completely dissolving, 686 g of 36 to 38 mass% of formalin aqueous solution was added dropwise at 20 to 25 캜 over 2 hours. Thereafter, the mixture was stirred at 20 to 25 캜 for 17 hours. To this, 98 g of sulfuric acid and 552 g of water were added, neutralization was carried out, and the mixture was allowed to stand for 2 days. After standing, the white solid formed in the solution was washed with 100 mL of water. The white solid was vacuum dried at 50 &lt; 0 &gt; C for 48 hours.

Then, the white solid thus obtained was dissolved in 300 mL of methanol, and 2 g of sulfuric acid was added thereto, followed by stirring at room temperature for 24 hours. To this solution was added 15 g of an anion type ion exchange resin (Amberlyst IRA96SB, manufactured by Rohmand Haas), stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of GBL was added, and the methanol was removed by a rotary evaporator to obtain a GBL solution. This was analyzed by ¹³ C-NMR (GX-270, manufactured by JEOL Ltd.) to obtain an alkali-soluble resin (hereinafter referred to as (a1-1)) which is an alkoxylated polyhydroxystyrene resin The weight average molecular weight (Mw) was 8,000 (in terms of GPC polystyrene) by the analysis by GPC, and the introduction rate of the alkoxylated hydroxystyrene was 35 mol% per 1 mol of hydroxystyrene.

Synthesis Example 6 Synthesis of alkali-soluble resin (a1-2)

Synthesis was carried out in the same manner as in Synthesis Example 5 except that (a0-2) was used instead of (a0-1). The resulting alkoxylated polyhydroxystyrene resin, alkali-soluble resin (hereinafter referred to as (a1-2)), had a weight average molecular weight (Mw) of 7500 (in terms of GPC polystyrene) and an introduction ratio of alkoxy groups And 55 mol% per 1 mol of styrene.

Synthesis Example 7 Synthesis of alkali-soluble resin (a1-3)

Synthesis was carried out in the same manner as in Synthesis Example 5 except that (a0-3) was used instead of (a0-1). The resulting alkoxylated polyhydroxystyrene resin, alkali-soluble resin (hereinafter referred to as (a1-3)), had a weight average molecular weight (Mw) of 3500 (in terms of GPC polystyrene) and an introduction ratio of alkoxy groups Was 69 mol% per 1 mol of styrene.

Synthesis Example 8 Synthesis of Novolak Resin (e)

(0.35 mole) of m-cresol, 37.8 g (0.35 mole) of p-cresol, 75.5 g of a 37 mass% formaldehyde aqueous solution (0.93 mole of formaldehyde), 0.63 g (0.005 mole) of oxalic acid dihydrate, 264 g of methyl isobutyl ketone was added, and the mixture was immersed in an oil bath and subjected to a polycondensation reaction for 4 hours while refluxing the reaction mixture. Thereafter, the temperature of the oil bath was raised over 3 hours, and thereafter the pressure in the flask was reduced to 40 to 67 hPa to remove volatile components, and the dissolved resin was cooled to room temperature to obtain an alkali soluble novolak resin (e) Of polymer solids. It was confirmed by GPC analysis that the weight average molecular weight (Mw) was 3,500. ? -Butyrolactone (GBL) was added to the obtained novolac resin (e) to obtain a novolac resin (e) solution having a solid content concentration of 43 mass%.

Synthesis Example 9 Synthesis of a cyclic polyimide resin (A)

(0.020 mol) of PMDA-HH and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP in a dry nitrogen gas stream. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of BAHF, 1.00 g (0.005 mole) of DAE, 6.00 g (0.010 mole) of ED-600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP, Followed by stirring at 180 ° C for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (A).

Synthesis Example 10 Synthesis of a cyclic polyimide resin (B)

1.12 g (0.005 mole) of PMDA-HH, 11.11 g (0.025 mole) of 6FDA and 4.65 g (0.015 mole) of ODPA were dissolved in 100 g of NMP in a dry nitrogen stream. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of BAHF, 1.00 g (0.005 mole) of DAE, 6.00 g (0.010 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 ° C for 1 hour, followed by 180 C &lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a cyclic polyimide resin (B).

Synthesis Example 11 Synthesis of a cyclic polyimide resin (C)

In a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of BAHF, 1.00 g (0.005 mole) of DAE, 6.00 g (0.010 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 ° C for 1 hour, followed by 180 C &lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a cyclic polyimide resin (C).

Synthesis Example 12 Synthesis of a cyclic polyimide resin (D)

(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 under a dry nitrogen flow. To this was added 11.90 g (0.033 mole) of BAHF, 0.50 g (0.003 mole) of DAE, 7.50 g (0.013 mole) of ED600 and 0.62 g (0.003 mole) of SiDA together with 20 g of NMP, reacted at 60 DEG C for 1 hour, (0.010 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added together with 10 g of NMP as a terminal endblock, and the mixture was reacted at 60 ° C for 1 hour. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (D).

Synthesis Example 13 Synthesis of a cyclic polyimide resin (E)

In a dry nitrogen stream, 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. To this was added 11.90 g (0.033 mole) of BAHF, 0.50 g (0.003 mole) of DAE, 7.50 g (0.013 mole) of ED600 and 0.62 g (0.003 mole) of SiDA together with 20 g of NMP, reacted at 60 DEG C for 1 hour, (0.010 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added together with 10 g of NMP as a terminal endblock, and the mixture was reacted at 60 ° C for 1 hour. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (E).

Synthesis Example 14 Synthesis of a cyclic polyimide resin (F)

Under a dry nitrogen gas stream, 10.09 g (0.045 mol) of PMDA-HH was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. 1.00 g (0.005 mole) of DAE and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP, followed by reaction at 60 ° C for 1 hour, followed by stirring at 180 ° C for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (F).

Synthesis Example 15 Synthesis of a cyclic polyimide resin (G)

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

Synthesis Example 16 Synthesis of a cyclic polyimide resin (H)

Under a dry nitrogen gas stream, 13.96 g (0.045 mol) of ODPA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of DAF, 6.0 g (0.010 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 占 폚 for 1 hour and then reacted at 180 占 폚 Lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (H).

Synthesis Example 17 Synthesis of cyclic polyimide resin (I)

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 in a dry nitrogen gas stream. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of DAF, 6.0 g (0.010 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 占 폚 for 1 hour and then reacted at 180 占 폚 Lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (I).

Synthesis Example 18 Synthesis of a cyclic polyimide resin (J)

In a dry nitrogen stream, 19.99 g (0.045 mol) of 6FDA was dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.033 mole) of DAF, 6.0 g (0.010 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 占 폚 for 1 hour and then reacted at 180 占 폚 Lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (J).

Synthesis Example 19 Synthesis of polybenzoxazole precursor (K)

In a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether and the solution was cooled to -15 캜. A solution obtained by dissolving 14.7 g (0.050 mol) of diphenyl ether dicarboxylic acid dichloride (Nihon Nohyaku Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise at a temperature of 0 ° C After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by mass of methanol to precipitate a white precipitate. , Washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain an alkali-soluble polybenzoxazole precursor (K).

Synthesis Example 20 Synthesis of polyimide precursor resin (L)

(0.038 mol) of 4,4'-diaminophenyl ether (hereinafter referred to as DAE), 1.86 g (0.007 mol) of SiDA and 1.09 g (0.010 mol) of 3-aminophenol were dissolved in 100 g of NMP under a dry nitrogen gas stream . 13.96 g (0.045 mol) of ODPA was added together with 20 g of NMP, followed by reaction at 20 ° C for 1 hour, followed by reaction at 50 ° C for 4 hours. Thereafter, a solution of 9.25 g (0.08 mol) of N, N-dimethylformamide dimethylacetal diluted with 5 g of NMP was added dropwise over 10 minutes, and the mixture was reacted at 50 ° C for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. After washing twice with 2 L of water, it was dried in a vacuum dryer at 80 캜 for 20 hours to obtain a polyimide resin (K).

Synthesis Example 21 Synthesis of polyimide resin (M)

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

Synthesis Example 22 Synthesis of cyclic polyimide resin (N)

In a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. (0.028 mole) of BAHF, 1.00 g (0.005 mole) of DAE, 10.50 g (0.018 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 DEG C for 1 hour, Lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 DEG C for 72 hours to obtain a powder of a ring-closing polyimide resin (N).

Synthesis Example 23 Synthesis of cyclic polyimide resin (O)

In a dry nitrogen stream, 3.92 g (0.020 mol) of CBDA and 11.11 g (0.025 mol) of 6FDA were dissolved in 100 g of NMP. To this was added 1.09 g (0.010 mole) of 3-aminophenol with 20 g of NMP. 1.00 g (0.005 mole) of DAE, 15.00 g (0.025 mole) of ED600 and 0.62 g (0.003 mole) of SiDA were added together with 20 g of NMP and reacted at 60 ° C for 1 hour, Lt; / RTI &gt; for 4 hours. After completion of the stirring, the solution was poured into 2 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 캜 for 72 hours to obtain a powder of a ring-closing polyimide resin (O).

Synthesis Example 24 Synthesis of novolac resin (f)

108.0 g of m-cresol, 108.0 g of methanol and 40.0 g of sodium hydroxide were placed in 1000 ml of a nitrogen-purged three-necked flask, and the mixture was heated to 67 DEG C with stirring, and refluxed for 30 minutes. Thereafter, the reaction solution was cooled to 40 캜, 65.2 g of 92% by mass paraformaldehyde was added, and the temperature was further raised to 67 캜, followed by reflux reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to 30 캜 or lower, and 140.0 g of 30 mass% sulfuric acid was added dropwise over 30 minutes in the same manner as the reaction solution did not exceed 35 캜. The pH of the obtained reaction solution was 4.9. 540.0 g of ion-exchanged water was further added to the reaction solution, stirred for 20 minutes and allowed to stand for 20 minutes, and then the separated aqueous layer was removed. After removal of the water layer, 108.0 g of dioxane was added, and the residual moisture was removed to less than 3% by mass at 40 캜 under a pressure of 0.08 MPa. 432.0 g of methanol and 2.0 g of 96 mass% sulfuric acid were added to the reaction solution. The pH of the obtained reaction solution was 0.8. The reaction solution was heated to 60 캜, and subjected to an alkoxylation reaction at 60 캜 for 3 hours. After completion of the reaction, the reaction solution was cooled to 30 DEG C or lower, and a 10 mass% aqueous sodium hydroxide solution was added dropwise over 30 minutes so that the temperature of the reaction solution did not exceed 35 DEG C until the pH of the reaction solution became 9.0 . 216.0 g of methyl isobutyl ketone (MIBK) as a washing solvent for separation and 324.0 g of ion-exchanged water were added to the reaction solution, and the mixture was stirred at 30 DEG C for 20 minutes and allowed to stand for 20 minutes to remove the separated aqueous layer. 324.0 g of ion-exchanged water was further added, and the washing operation was repeated with ion-exchanged water until the electrical conductivity of the removed water became 100 mu Scm or less. After the completion of the washing, 300 g of? -Butyrolactone was added and ion-exchanged water and MIBK were distilled off at 70 占 폚 and a pressure of 0.08 MPa to obtain a novolak resin solution (f) having a solid content of 50 mass%.

The resulting novolak resin solution (f) had a weight average molecular weight (Mw) of 7000 (in terms of GPA polystyrene) and a degree of dispersion (Mw / Mn) of 7.5 by GPC analysis. The number of moles of the alkoxyalkyl group per 1 mole of the phenol skeleton by 13CNMR was 57 mol% and the alkoxylation rate was 100 mol%.

&Lt; Example 1 >

10.5 g of the alkali-soluble resin (a1-1), 10.5 g of the resin (A) obtained in Synthesis Example 9, 3.0 g of the quinone diazide compound (a) obtained in Synthesis Example 1, 7.2 g of the crosslinking agent MX- Was added to 25 g of GBL to obtain a varnish (A) of a positive photosensitive resin composition.

The obtained varnish was coated on a PET film having a thickness of 38 占 퐉 using a comma roll coater and dried at 80 占 폚 for 8 minutes and then a PP film having a thickness of 10 占 퐉 was laminated as a protective film to obtain a photosensitive film. The film thickness of the photosensitive film was adjusted to be 10 mu m.

The resulting photosensitive film was evaluated for lamination property, high durability, 5% weight reduction temperature (heat resistance) and pattern workability on a silicon substrate.

&Lt; Examples 2 to 33, Comparative Examples 1 to 8 >

The amounts of the (A1) alkali-soluble resin, (A2) the alkali-soluble resin and other additives, (B) the photoacid generator and (C) the crosslinking agent were changed as shown in Tables 1, 2-1 and 2-2 A varnish was produced in the same manner as in Example 1 except for that. The obtained photosensitive film was used to evaluate the lamination property, the high shinability property, the 5% weight reduction temperature (heat resistance) and the pattern formability of the silicone substrate.

The molar ratio of the alkali-soluble resin component (A2) is shown in Table 1.

[Table 1]

[Table 2-1]

[Table 2-2]

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

[Table 3-1]

[Table 3-2]

1: Semiconductor device
2: Passivation film
3:
4: metal wiring
5:
6: substrate
7:
8:
9: metal film
10: metal wiring
11: metal wiring
12: Electrode
13: sealing resin
14: substrate
15: IDT electrode
16: bonding pad
17:
18: Support material
19: Cover material
20: Protection member
21: via conductor
22: solder bump
23: Silicon wafer
24: Al pad
25: Passivation film
26: Resin
27:
28: metal film
29: metal wiring
30: Insulating film
31: Barrier metal
32: Solder bump

Claims (20)

(A1) an alkali-soluble resin having a structural unit represented by the general formula (1)
(A2) an alkali-soluble resin comprising at least one selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof, and copolymers thereof;
(B) a photoacid generator, and
(C) Heat-crosslinking agent
: &Lt; / RTI &gt;

Wherein R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, a represents 0 to 4, b represents an integer within a range of 1 to 3, R ² represents a hydrogen atom, a methyl group, an ethyl group , Or a profile group]. The method according to claim 1,
Wherein the weight-average molecular weight (Mw) of the alkali-soluble resin (A1) is in the range of 3,000 to 60,000. 3. The method according to claim 1 or 2,
Wherein the alkali-soluble resin (A1) further comprises at least 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 within a 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]. 4. The method according to any one of claims 1 to 3,
Wherein the weight average molecular weight (Mw) of the heat crosslinking agent (C) is 100 to 2,500. 5. The method according to any one of claims 1 to 4,
Wherein the alkali-soluble resin (A2) has at least one substituent selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. 6. The method according to any one of claims 1 to 5,
The photosensitive film (A2) in which the alkali-soluble resin has at least any one of the structural units represented by the general formula (4) and the general formula (5)

[In the general formula (4), R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms, R ⁶ represents a divalent organic group having 20 to 100 carbon atoms, and n ₁ represents an integer within a range of 10 to 100,000. ]

[Wherein R ⁵ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms, R ⁶ represents a divalent organic group having 20 to 100 carbon atoms, and R ⁷ represents hydrogen or an organic group having 1 to 20 carbon atoms N ₂ represents an integer within a range of 10 to 100,000, and p and q represent integers satisfying 0? P + q? 2. The method according to claim 6,
Wherein R ^{6 in} the general formulas (4) and (5) is an organic group having a polyether structure and having 20 to 100 carbon atoms and a total amount of repeating units represented by formulas (4) and (5) %, Based on the total mass of the photosensitive film. 8. The method of claim 7,
The organic group having a polyether structure and having 20 to 100 carbon atoms is an organic group represented by the general formula (10)

(Wherein R ⁵⁴ to R ⁵⁷ each independently represent an alkylene group having 1 to 6 carbon atoms, and R ⁵⁸ to R ⁶⁵ each independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, the structures displayed in the parentheses of x and y are different from each other, and the structures displayed in the parentheses of the repeat unit z and the structures shown in the parentheses of the repeat unit y are different from each other, and x and y , z each independently represents an integer of 0 to 35). 9. The method according to any one of claims 6 to 8,
R ⁵ in the general formulas (4) and (5) represents an organic group having an alicyclic structure and having 4 to 40 carbon atoms and having a total amount of 100 mol% of the repeating units of the general formulas (4) and (5) Based on the total weight of the photosensitive film. 10. The method according to any one of claims 1 to 9,
(H) A photosensitive film further containing a compound represented by the general formula (13):

[Formula (13) of, R ⁷¹ ~R ⁷³ represents any one of O atom or a S atom, N atom, R ⁷¹ ~R ⁷³ at least one of which represents a S atom, l is 0 or 1, R ⁷¹ represents an oxygen atom or a sulfur atom when l is 0, a nitrogen atom when l is 1, m and n represent 1 or 2, and R ⁷⁴ to R ⁷⁶ each independently represent a hydrogen atom or An organic group having 1 to 20 carbon atoms]. 11. The method according to any one of claims 1 to 10,
The photosensitive film (C) further comprises a heat 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, and R ⁶⁸ represents a divalent organic group having an alkylene group having 2 or more carbon atoms, and may be any of linear, branched, One can be]. 12. The method according to any one of claims 1 to 11,
And a photosensitive layer having a film thickness of 3 to 45 mu m. 13. The method of claim 12,
A protective film on the photosensitive layer, and a supporting film below the photosensitive layer. A cured film obtained by curing the photosensitive film according to any one of claims 1 to 13. An interlayer insulating film or a semiconductor protective film in which the cured film according to claim 14 is disposed. An electronic component or a semiconductor device having a relief pattern layer of the cured film according to claim 14. A cured film according to claim 14, wherein the cured film has a thickness of 2 to 40 占 퐉 on a substrate, a copper wiring is formed thereon, and a cured film according to claim 14 is further formed to a thickness of 2 to 40 占 퐉, An electronic component or semiconductor device. The relief pattern layer of the cured film of the photosensitive resin composition is provided on the substrate as a support material and the cured film of claim 14 is formed on the support material as a cover material and the cover material is disposed in the opening of the relief pattern layer of the support material , And a hollow portion surrounded by the support material, the cover material, and the substrate. (S-1) upper end and (S-2) lower end with a step difference of (T-1)
The cured film according to claim 14 is disposed on each of the upper end portion of (S-1) and the lower end portion of (S-2)
Wherein the cured film according to claim 14 disposed on the upper end of the (S-1) and the cured film according to claim 14 disposed on the lower end of the (S-2)
An electronic component or semiconductor device. A method of manufacturing a semiconductor device using the photosensitive film according to any one of claims 1 to 13,
A step of forming a photosensitive film by heating and pressing the photosensitive film at a temperature of 40 to 150 캜 on a substrate,
Exposing the photosensitive film through an exposure mask, and
A step of removing the exposed portion of the photosensitive film with an alkaline developer to perform development
And a semiconductor device.

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