JP5895789B2 - Radiation sensitive resin composition, polyimide film, semiconductor element and organic EL element - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a polyimide film, a semiconductor element, and an organic EL element.

  In recent years, in the field of electronic devices such as display elements and semiconductor elements, a film made of an organic material (hereinafter simply referred to as “organic film”) that is formed from a radiation-sensitive resin composition and can be patterned by a photolithography method. ) Is actively used. For example, the organic film is an important component used for an insulating film, a protective film, a planarizing film, or the like of a display element or a semiconductor element.

  More specifically, the organic film is used as an insulating film in the field of an organic EL (Electro Luminescence) element using electroluminescence by an organic compound. The organic EL element is expected as a next-generation illumination technique in addition to a display element such as a display. In particular, an organic EL display element, which is a display element using an organic EL element, is self-luminous, does not require a backlight, and can display an image with a wide viewing angle and high-speed response. And it has low power consumption and has excellent characteristics such as thinness and light weight. Therefore, the organic EL display element has been actively developed in recent years.

An organic EL display element is generally manufactured by the following method. First, an anode (hole injection electrode) made of ITO (Indium Tin Oxide) or the like and a hole transport layer pattern are formed on a substrate. Next, in the passive organic EL display element, after forming an insulating film pattern and a cathode barrier rib pattern, the organic light emitting layer, the electron transport layer, and the cathode (electron injection electrode) are patterned by, for example, vapor deposition. In an active organic EL display element, after forming an ITO pattern and an insulating film pattern that also serves as a partition of the organic light emitting layer, the organic light emitting layer pattern is formed by a masking method, an ink jet method, or the like, and then an electron transport layer and A cathode (electron injection electrode) is formed. Here, the insulating film to be a partition wall is preferably formed using a resin that can be patterned by photolithography (see, for example, Patent Documents 1 and 2). As the organic light emitting layer, for example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ or BeBq ₃ can be used.

  In recent years, display elements have been required to have high definition, and studies have been made to increase the aperture ratio of organic EL display elements.

  For example, in an active organic EL display element, in addition to an insulating film forming a partition wall, an insulation having a flattening function as described in Patent Document 1 and Patent Document 2 can be realized so as to realize a higher aperture ratio. The introduction of membranes is being considered. The introduction of the insulating film in such an active organic EL display element is performed by the following method, for example. First, a thin film transistor (TFT), which is an active element, is formed for each of a plurality of pixels provided in a matrix on a substrate such as glass. A first insulating film that also serves as a planarizing film is formed on the TFT. Next, an anode pattern is formed thereon. The pattern formation at this time usually uses a wet etching method. Further, a hole transport layer pattern is formed thereon by a masking method. Then, the pattern of the 2nd insulating film used as the partition of an anode and an organic light emitting layer, and the pattern of an organic light emitting layer are formed by a masking method, an inkjet method, etc. Then, an electron carrying layer and a cathode are formed sequentially. At this time, in order to connect the anode and the TFT, it is necessary to form a through hole of about 1 μm to 15 μm in the first insulating film.

  Although the organic EL display element has the above structure and manufacturing method, the insulating film functioning as the partition of the organic light emitting layer and the planarizing film on the TFT uses a resin that is an organic material that can be easily patterned as desired. Is preferred. In that case, the resin constituting the insulating film is required to have various characteristics such as low hygroscopicity, high heat resistance, a small amount of gas generated by thermal decomposition, and excellent mechanical strength. Furthermore, in the formation of the insulating film, it is preferable that a liquid radiation-sensitive resin composition can be used so that simple film formation and simple patterning using, for example, a photolithography method are possible. From this point of view, in Patent Document 3, polyimide having excellent properties such as low hygroscopicity, high heat resistance, low gas generation amount due to thermal decomposition, and excellent mechanical strength is disclosed in Patent Document 3. A technique using a polyimide film made of is disclosed.

In addition, the use of organic films has been actively studied in the field of semiconductor elements that can be used in the structure of display elements.
For example, display elements such as liquid crystal display elements and organic EL display elements have recently been required to have higher performance, such as a large screen for providing a large-sized television and a flexible display using a flexible substrate. It has become. For this reason, high performance is also required for TFTs (Thin Film Transistors), which are semiconductor elements that constitute the main constituent elements of display elements.

  Conventionally, TFTs, which are semiconductor elements, have been frequently used in which amorphous silicon or polycrystalline silicon is used for a semiconductor layer. Recently, a TFT having a new structure that can be formed at a lower temperature, can be formed on a flexible substrate such as a resin substrate, and obtains a desired mobility has been studied. .

For example, Patent Document 4 discloses a TFT technology that uses a transparent oxide semiconductor for a semiconductor layer. In the TFT described in Patent Document 4, IGZO (indium gallium zinc oxide) is used for the semiconductor layer. Then, the TFT can be formed at a low temperature, and the TFT is formed on a resin substrate having poor heat resistance, so that a flexible active matrix liquid crystal display element can be provided.
However, a semiconductor using an oxide semiconductor for a semiconductor layer has a problem in light resistance.

JP 2011-107476 A JP 2010-237310 A JP 2009-9934 A JP 2006-165529 A

  More specifically, a semiconductor layer using an oxide semiconductor may have absorption in the ultraviolet wavelength region. For this reason, in semiconductor elements using the same, the resistance at the time of OFF decreases when light is irradiated from the outside, and a sufficient ON / OFF ratio may not be obtained when used as a switching element of a display element. . Therefore, when the semiconductor element is used for a display element, there is a problem that characteristics deteriorate due to the influence of light from the outside.

  The problem of deterioration of characteristics due to the influence of light is a problem even in a conventional semiconductor element using amorphous silicon or the like for a semiconductor layer, although there is a difference in lightness. Accordingly, there is a demand for a technique for improving light resistance in a semiconductor element, particularly in a semiconductor element used for a display element.

  Therefore, a technique for introducing a film having a function of protecting a semiconductor element into the semiconductor element as a constituent element has been studied. In that case, a liquid radiation-sensitive resin composition can be used for film formation so that simple film formation and high-precision patterning using, for example, a photolithography method are possible. preferable. That is, the film to be introduced is preferably an organic film, and the organic film is required to have low hygroscopicity and good properties such as heat resistance and mechanical strength.

  As described above, in the field of display elements and semiconductor elements, the introduction of organic films has been actively studied in order to improve the performance. Therefore, there is a need for a radiation-sensitive resin composition that can be formed with a simple film and that can be patterned with high accuracy by using, for example, a photolithography method. In addition, the film formed from the radiation-sensitive resin composition has low hygroscopicity, excellent heat resistance, a small amount of gas generation due to thermal decomposition, and excellent mechanical properties such as excellent mechanical strength. Therefore, it is required to have excellent reliability performance.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a radiation-sensitive resin composition that can be patterned and can form a film having excellent reliability such as heat resistance and mechanical strength.

  An object of the present invention is to provide a polyimide film that is formed from a radiation-sensitive resin composition and has both panning properties and reliability.

  An object of the present invention is to provide a semiconductor element formed from a radiation-sensitive resin composition and having a polyimide film having both panning properties and reliability.

  Moreover, it is providing the organic EL element comprised from the radiation sensitive resin composition and having the polyimide film which has both panning property and reliability.

The first aspect of the present invention is:
[A] It is related with the radiation sensitive resin composition characterized by including the polyimide precursor which has a structural unit shown by following formula (1), and [B] a photo-acid generator.

（式（１）中、Ａは４価の有機基を示し、Ｂは２価の有機基を示す。Ｘ^１およびＸ^２は、上記式（２）で示される基である。
式（２）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、炭素数１〜３０の炭化水素基、または炭素数１〜３０の炭化水素基が有する水素原子の一部をヒドロキシル基、ハロゲン原子若しくはシアノ基で置換した基である（但し、Ｒ^１およびＲ^２が共に水素原子である場合はない。）。Ｒ^３は、炭素数１〜３０のエーテル基、炭素数１〜３０の炭化水素基、または炭素数１〜３０の炭化水素基が有する水素原子の一部をヒドロキシル基、ハロゲン原子若しくはシアノ基で置換した基である。Ｒ^１とＲ^３とが連結して環を形成してもよい。）

(In formula (1), A represents a tetravalent organic group, B represents a divalent organic group, and X ¹ and X ² are groups represented by the above formula (2).
In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atoms that the hydrocarbon group having 1 to 30 carbon atoms has Group substituted with a group, a halogen atom or a cyano group (provided that R ¹ and R ² are not both hydrogen atoms). R ³ is a hydroxyl group, a halogen atom or a cyano group in which a part of hydrogen atoms of an ether group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms is substituted. A substituted group. R ¹ and R ³ may be linked to form a ring. )

  1st aspect of this invention WHEREIN: It is preferable that A of the said Formula (1) is a tetravalent organic group which has an alicyclic structure.

  In the first embodiment of the present invention, it is preferable to further contain a compound having a [C] cyclic ether group.

  1st aspect of this invention WHEREIN: It is preferable that A of the said Formula (1) is at least 1 type of structure chosen from following formula (A-1)-following formula (A-5).

（式（Ａ−１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３およびＲ^１４は、それぞれ独立に、水素、フッ素または炭素数１〜４の有機基を表す。）

(In formula (A-1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents hydrogen, fluorine or an organic group having 1 to 4 carbon atoms.)

  1st aspect of this invention WHEREIN: It is preferable that B of the said Formula (1) is at least 1 type of structure chosen from following formula (B-1)-following formula (B-10).

（式（Ｂ−１）〜式（Ｂ−８）中、Ｒ^５は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基または水酸基を表す。）

(In Formula (B-1) to Formula (B-8), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group.)

  In the first embodiment of the present invention, the [B] photoacid generator is preferably a compound containing an oxime sulfonate group represented by the following formula (3).

（式（３）中、Ｒ^６は、アルキル基、シクロアルキル基またはアリール基であり、これらの基の水素原子の一部または全部が置換基で置換されていてもよい。）

(In Formula (3), R ⁶ is an alkyl group, a cycloalkyl group, or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.)

  In the first embodiment of the present invention, it is preferable that a [D] base generator is further contained.

  A second aspect of the present invention relates to a polyimide film obtained by using the radiation-sensitive resin composition of the first aspect of the present invention.

  According to a third aspect of the present invention, there is provided a semiconductor device comprising the polyimide film according to the second aspect of the present invention.

  A 4th aspect of this invention is related with the organic EL element characterized by having the polyimide film of the 2nd aspect of this invention.

  In the fourth aspect of the present invention, the semiconductor element of the third aspect of the present invention is preferably included.

  According to the first aspect of the present invention, it is possible to obtain a radiation-sensitive resin composition that can be patterned and can form a film having excellent reliability performance.

  According to the 2nd aspect of this invention, the polyimide film which is formed from a radiation sensitive resin composition and has both panning property and reliability is obtained.

  According to the 3rd aspect of this invention, the semiconductor element comprised by having a polyimide film which is formed from a radiation sensitive resin composition and has both panning property and reliability is obtained.

  According to the 4th aspect of this invention, the organic EL element comprised from the radiation sensitive resin composition and having the polyimide film which has both panning property and reliability is obtained.

(A)-(d) is typical sectional drawing which shows each manufacturing process of the manufacturing method of the polyimide film of embodiment of this invention. It is sectional drawing which illustrates the structure of the semiconductor element of this embodiment typically. It is sectional drawing which illustrates typically the structure of the principal part of the organic EL display element of this embodiment.

Hereinafter, embodiments of the present invention will be described.
In the present invention, “radiation” irradiated upon exposure is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present embodiment is a radiation sensitive resin composition suitable for forming a film constituting an organic EL element or a film constituting a semiconductor element. The radiation sensitive resin composition of the present embodiment contains [A] a polyimide precursor and [B] a photoacid generator. Furthermore, the radiation sensitive resin composition of this embodiment can contain a compound having a [C] cyclic ether group and a [D] base generator.

And the radiation sensitive resin composition of this embodiment can be used for formation of the polyimide film of embodiment of this invention used suitably as an insulating film of an organic EL element, or an insulating film of a semiconductor element. The polyimide precursor includes a polyamic acid, and the polyamic acid includes those obtained by protecting the carboxyl group with a protective group.
Hereinafter, the detail of the component contained in the radiation sensitive resin composition of this embodiment is demonstrated.

[[A] polyimide precursor]
[A] The polyimide precursor contained in the radiation sensitive resin composition of the present embodiment is preferably a polyimide precursor having a structural unit represented by the following formula (1). By having the structure of the following formula (1), the coating film obtained from the radiation-sensitive resin composition of the present embodiment can be patterned by a photolithography method using a photoacid generator [B] as described later. It becomes possible.

In the above formula (1), A represents a tetravalent organic group, and B represents a divalent organic group. X ¹ and X ² are groups represented by the following formula (2).

In the above formula (2), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of hydrogen atoms possessed by a hydrocarbon group having 1 to 30 carbon atoms. A group substituted with a hydroxyl group, a halogen atom or a cyano group. (However, R ¹ and R ² are not both hydrogen atoms.) R ³ is an ether group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or carbonization having 1 to 30 carbon atoms. This is a group in which a part of hydrogen atoms of a hydrogen group is substituted with a hydroxyl group, a halogen atom or a cyano group. R ¹ and R ³ may be linked to form a ring.

In the above formula (2), the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ² is preferably a linear or branched alkyl group, cycloalkyl group or aryl group having 1 to 30 carbon atoms. And the alkyl chain may have an oxygen atom, a sulfur atom, or a nitrogen atom.

  Specific examples of the linear and branched alkyl groups described above include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n -Linear alkyl group such as -dodecyl group, n-tetradecyl group, n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group, etc. A branched alkyl group may be mentioned.

  The cycloalkyl group described above is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and may have an oxygen atom in the ring. Specific examples of the cycloalkyl group described above include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, and the like.

  The aryl group described above is preferably an aryl group having 6 to 14 carbon atoms, may be a single ring, may have a structure in which single rings are connected, or may be a condensed ring. Specific examples of the aryl group described above include a phenyl group and a naphthyl group.

In the above formula (2), part or all of the hydrogen atoms of the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ² may be substituted with a substituent. As such a substituent, for example, a halogen atom, a hydroxyl group, and a cyano group are preferable.

  In addition to the above-mentioned substituents, a nitro group, a carboxyl group, a carbonyl group, a cycloalkyl group (for this cycloalkyl group, the description of the cycloalkyl group can be preferably applied), and aryl. Group (the description of the aryl group can be suitably applied as the aryl group), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, and a propoxy group. , N-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc.), acyl group (preferably an acyl group having 2 to 20 carbon atoms, such as acetyl group, propionyl) Group, butyryl group, i-butyryl group, etc.), acyloxy group (preferably acyl having 2 to 10 carbon atoms) For example, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, For example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a haloalkyl group (a group in which some or all of the hydrogen atoms of the alkyl group or cycloalkyl group are substituted with a halogen atom, Perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, fluorocyclopropyl group, fluorocyclobutyl group, etc.). As for the cyclic structure in the aryl group, cycloalkyl group and the like, the above alkyl group may be mentioned as a further substituent.

The ether group having 1 to 30 carbon atoms represented by R ³ in the above formula (2) is a general term for a group in which a hydrocarbon group having 1 to 30 carbon atoms is bonded to oxygen, specifically, a methoxy group. , Ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, dodecyloxy group, phenoxy group, naphthoxy Group, benzyloxy group, cyclopentyloxy group, cyclohexyloxy group, vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group and the like.

The hydrocarbon group having 1 to 30 carbon atoms constituting the ether group, or a group in which a part of hydrogen atoms of the hydrocarbon group having 1 to 30 carbon atoms is substituted with a hydroxyl group, a halogen atom or a cyano group is R The explanations for ¹ and R ² can be applied.

In the above formula (2), as described above, R ¹ and R ³ may be linked to form a cyclic ether. Examples of such cyclic ethers include 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 2-dioxanyl group and the like. Some or all of the hydrogen atoms of the cyclic ether may be substituted with the above substituents.

  In the [A] polyimide precursor contained in the radiation sensitive resin composition of this embodiment, A in the structural unit represented by the above formula (1) is a tetravalent organic group having an alicyclic structure. It is preferable. [A] When the polyimide precursor has an alicyclic structure, visible light transmittance can be improved in the polyimide film of this embodiment formed using the radiation-sensitive resin composition of this embodiment. Specific examples of the hydrocarbon constituting the alicyclic structure include monocyclic structures, bicyclic structures, and tricyclic or higher alicyclic structures.

  In particular, the [A] polyimide precursor has at least one structure in which A in the structural unit represented by the above formula (1) is selected from, for example, the following formula (A-1) to the following formula (A-5). It is preferable that [A] The solubility in a solvent can be improved because the polyimide precursor has such an alicyclic structure.

In said formula (A-1), R < ¹¹ >, R <^12> , R <^13> and R < ¹⁴ > represent hydrogen, a fluorine, or a C1-C4 organic group each independently.

  [A] The polyimide precursor may contain a tetravalent organic group other than the tetravalent organic group having an alicyclic structure in A in the structural unit represented by the above formula (1). In that case, A in the above formula (1) can contain a tetravalent aromatic hydrocarbon group and / or a tetravalent chain hydrocarbon group. Specific examples of the tetravalent aromatic hydrocarbon group include a tetravalent group in which four hydrogens in the mother skeleton of the aromatic hydrocarbon are substituted.

  Examples of the chain hydrocarbon of the tetravalent chain hydrocarbon group include ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, n-dodecane, and the like. it can. These tetravalent chain hydrocarbon groups may contain an aromatic ring in at least a part of the structure.

  [A] The polyimide precursor has at least one structure in which B in the structural unit represented by the above formula (1) is selected from, for example, the following formula (B-1) to the following formula (B-10). It is preferable that By having such a structure, the [A] polyimide precursor has improved solubility in a solvent, and in the polyimide film of this embodiment formed using the radiation-sensitive resin composition of this embodiment, visible light The permeability can be improved.

In the formula (B-1) ~ the formula (B-8), ^{R 5} each independently represent a hydrogen atom, an alkyl group or a hydroxyl group having 1 to 6 carbon atoms.

  [A] The polyimide precursor is obtained by protecting the carboxyl group of the polyamic acid ester obtained by polymerization reaction of tetracarboxylic dianhydride and diamine by a group represented by the above formula (2) by a known method. be able to. For example, for a polyamic acid ester obtained by polymerization reaction of tetracarboxylic dianhydride and diamine, as shown in the following reaction formula, a vinyl ether derivative having a desired structure and a carboxyl group of the polyamic acid ester in the presence of an acid catalyst Can be synthesized by reacting.

In the above reaction scheme, R'corresponds to the structure except for ^{X 1} and ^{X 2} in the formula (1), ^{R 1} and ^{R 3} each correspond to ^{R 1} and ^{R 3} in the formula (1) , R ⁷ and R ⁸ correspond to R ² in the above formula (1) as —CH (R ⁷ ) (R ⁸ ).

  [A] In the polymerization reaction of tetracarboxylic dianhydride and diamine for forming a polyimide precursor, examples of the tetracarboxylic dianhydride include the following formulas (A-1-1) to (A The tetracarboxylic dianhydride shown in -5-1) can be used.

In said formula (A-1-1), R < ¹¹ >, R <^12> , R <^13> and R < ¹⁴ > are synonymous with the thing of said formula (A-1), Comprising: Each independently hydrogen, fluorine, or carbon number 1 Represents an organic group of ~ 4.

  By using the tetracarboxylic dianhydride represented by the above formula (A-1-1) to the above formula (A-5-1) as the tetracarboxylic dianhydride, the [A] polyimide precursor is A in the structural unit represented by the formula (1) may be at least one structure selected from the above formulas (A-1) to (A-5).

  Moreover, in the above-mentioned polymerization reaction, as the diamine, for example, a diamine represented by the following formula (B-1-1) to the following formula (B-10-1) can be used.

The formula (B-1-1) ~ the above formula (B-8-1), ^{R 5} is a same meaning as in the formula (B-1) ~ the formula (B-8), independently Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group.

  By using the diamine represented by the above formula (B-1-1) to the above formula (B-10-1) as the diamine, the [A] polyimide precursor is in the structural unit represented by the above formula (1). B may be at least one structure selected from the above formulas (B-1) to (B-10).

  [A] The polyimide precursor may include a structure other than the above formula (B-1) to the above formula (B-10) in B in the structural unit represented by the above formula (1). . In that case, in the formation reaction of [A] polyimide precursor, B can contain such a structure by using diamine of desired structures other than the diamine of the structure mentioned above.

  [A] Examples of the diamine that can be used for the formation reaction of the polyimide precursor include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4 ′. -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5- Diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4 ′ -Aminophenyl) -1,3,3-trimethylindane, 3,3'-diaminobenzophenone, 3,4'-diamy Benzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis ( 4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro- , 4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′ -(P-phenyleneisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane , 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, etc. Can be mentioned.

  [A] Examples of diamines that can be used in the polyimide precursor formation reaction include metaxylylenediamine, paraxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and heptamethylene. Diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, tetrahydrodi Cyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6.2.1.02,7] -undecylenedimethyl diamine, 4,4′-methylene bis (Si B hexylamine) aliphatic and alicyclic diamines, and the like.

  [A] Examples of the diamine that can be used for the polyimide precursor formation reaction include diaminoorganosiloxanes such as 1,3-bis (3-aminopropyl) -tetramethyldisiloxane.

  [A] The polymerization reaction between the tetracarboxylic dianhydride and the diamine for forming the polyimide precursor is carried out in accordance with a known method, with the tetracarboxylic dianhydride having the structure as described above and the diamine in a polymerization solvent. A method in which mixing is performed is preferable.

[A] In the polymerization reaction of tetracarboxylic dianhydride and diamine to obtain a polyimide precursor, the ratio of the tetracarboxylic dianhydride component and diamine used is tetra The ratio in which the acid anhydride group of the carboxylic dianhydride is 0.2 to 2 equivalents is preferable, and the ratio in which 0.3 to 1.2 equivalents is more preferable.
This polymerization reaction is preferably performed in a polymerization solvent, preferably at −20 ° C. to 150 ° C., more preferably at 0 ° C. to 100 ° C., preferably 0.1 hour to 120 hours, more preferably 0.5 hour to 48 hours. Done for hours.

As the polymerization solvent, a solvent capable of dissolving the raw materials and products in the synthesis of [A] polyimide precursor is selected.
Examples of the polymerization solvent include aprotic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

Specific examples of these polymerization solvents include the above-mentioned aprotic polar solvent media such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, Tetramethylurea, hexamethylphosphortriamide, etc .;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate;
Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl. Examples include ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and tetrahydrofuran.

Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;
Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, and diisopentyl ether.

  Among these polymerization solvents, one or more selected from the group consisting of an aprotic polar solvent and phenol and derivatives thereof (first group polymerization solvent), or one selected from the first group polymerization solvent It is preferable to use a mixture of the above and one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group polymerization solvent). In the latter case, the proportion of the second group polymerization solvent used is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total of the first group polymerization solvent and the second group polymerization solvent. Furthermore, it is preferable that it is 30 weight% or less.

  The amount (s) of the polymerization solvent used is such that the total amount (t) of tetracarboxylic dianhydride and diamine is 0.1% to 50% by weight with respect to the total amount (s + t) of the reaction solution. It is preferable that

  [A] About a polyimide precursor, the polystyrene conversion weight average molecular weight (henceforth "Mw") measured by gel permeation chromatography (GPC) becomes like this. Preferably it is about 2000-500000, More preferably, it is 3000- About 300,000. If Mw is less than 2000, sufficient mechanical properties tend not to be obtained in a polyimide film formed using the Mw. On the other hand, when Mw exceeds 500,000, the solubility of the photosensitive resin composition obtained using the [A] polyimide precursor in a solvent tends to be poor.

[[B] Photoacid generator]
[B] The photoacid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used as described above. The radiation-sensitive resin composition of the present embodiment includes a [B] photoacid generator, and thus exhibits positive radiation-sensitive characteristics, and can be used as a positive-type radiation-sensitive resin composition. it can. [B] The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, p-toluenesulfonic acid, camphorsulfonic acid, etc.) by irradiation with radiation. [B] The content of the photoacid generator in the radiation-sensitive resin composition is a form of a photoacid generator (hereinafter also referred to as “[B] photoacid generator”) which is a compound as described later. [A] It may be in the form of a photoacid generating group incorporated as part of a polyimide precursor or other polymer, or in both forms.

  Further, such a [B] photoacid generator is decomposed by heating at about 200 ° C. to generate an acid. The acid generated by such heat functions as an imidization catalyst that promotes the polyimide formation of the [A] polyimide precursor in the post-baking step. By promoting imidization, a polyimide film having a high imidization rate can be obtained. Since a polyimide film with a low imidization rate generates a large amount of gas due to thermal decomposition, when used as a polyimide film for organic EL, it causes a decrease in reliability.

  [B] Examples of the photoacid generator include oxime sulfonate compounds and sulfonimide compounds, among which oxime sulfonate compounds are preferred.

(Oxime sulfonate compound)
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (3) is preferable.

In the above formula (3), R ⁶ is an alkyl group, a cycloalkyl group or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the above formula (3), the alkyl group for R ⁶ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ⁶ includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group). Group) and the like. As the aryl group for R ^6, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁶ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate group represented by the above formula (3) is more preferably an oxime sulfonate compound represented by the following formula (3-1).

In the above formula (3-1), R ⁶ has the same meaning as the description of R ⁶ in the above formula (3). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, the plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Among these, as a catalyst capable of promoting imidization, a case where X is p-toluenesulfonic acid is particularly preferable.

  In the above formula (3-1), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the above formula (3-1), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Specific examples of the oxime sulfonate compound represented by the above formula (3) include, for example, compounds (3-1-i) represented by the following formulas (3-1-i) to (3-1-v), respectively. , Compound (3-1-ii), compound (3-1-iii), compound (3-1-iv), compound (3-1-v) and the like.

  These can be used alone or in combination of two or more, and [B] can also be used in combination with other photoacid generators as a photoacid generator. Compound (3-1-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], Compound (3-1-ii) [(5H-octylsulfonyl) Oxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (3-1-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) ) Acetonitrile], Compound (3-1-iv) [(5-p-Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] and Compound (3-1-v) [ (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile It may be commercially available.

(Sulfonimide compound)
[B] A sulfonimide compound preferable as a photoacid generator, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- ( 2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoro) Methylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfo Ruoxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxyl N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N -(4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N -(4-Fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2 .1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylpheny Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (phenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Xyl) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) C) Naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  In addition, onium salts such as diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, and tetrahydrothiophenium salt can also be used. Of these, diphenyliodonium salts and triphenylsulfonium salts are preferred.

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

  Among the above-described [B] photoacid generators, from the viewpoint of improving radiation sensitivity and solubility, an oxime sulfonate compound is preferable as described above, and contains an oxime sulfonate group represented by the above formula (3). The compound which performs is more preferable, and the oxime sulfonate compound represented by the said Formula (3-1) is further more preferable. Among them, [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (3-1-i), [(5H-octylsulfonyloxyimino), which are commercially available. -5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (3-1-ii), [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methyl Phenyl) acetonitrile] (3-1-iv), [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (3-1-iii), [(5-octylsulfonyl) Especially oxyimino)-(4-methoxyphenyl) acetonitrile] (3-1-v) Masui.

  [B] One photoacid generator may be used alone, or two or more photoacid generators may be mixed and used. As content of the [B] photo-acid generator in the radiation sensitive resin composition of this embodiment, Preferably it is 0.1 mass part-10 mass parts with respect to 100 mass parts of [A] polyimide precursors. Preferably they are 1 mass part-5 mass parts. [B] When the content of the photoacid generator is in the above range, the radiation sensitivity of the radiation-sensitive resin composition can be optimized.

[[C] Compound having cyclic ether group]
The radiation sensitive resin composition of this embodiment contains the above-mentioned [A] polyimide precursor and [B] photoacid generator, and further contains a compound having [C] a cyclic ether group. it can.

  [C] The cyclic ether group of the compound having a cyclic ether group is a group having a thermally reactive group such as an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), and [C As the compound having a cyclic ether group (hereinafter, also simply referred to as “[C] compound”), the following compounds may be mentioned.

  Examples of the [C] compound having one epoxy group or oxetanyl group in the molecule include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl. Glycidyl acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxy α-ethyl acrylate Heptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxy Methyl oxetane, phenyl glycidyl ether, γ-glycidoxyp Pills trimethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, .gamma.-glycidoxypropyl diethoxy silane, and the like.

As the [C] compound having two or more epoxy groups in the molecule, for example,
Bisphenol type diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil.

Commercially available [C] compounds having two or more epoxy groups in the molecule include, for example, Epicoat (registered trademark) 1001, 1002, 1003, 1004, 1007, and 1009 as bisphenol A type epoxy resins. , 1010, 828 (above, manufactured by Japan Epoxy Resin Co., Ltd.)
As bisphenol F type epoxy resin, Epicoat (registered trademark) 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolac type epoxy resin, Epicoat (registered trademark) 152, 154, 157S65 (above, Japan Epoxy Resin), EPPN (registered trademark) 201, 202 (above, Nippon Kayaku Co., Ltd.) and the like;
As cresol novolac type epoxy resins, EOCN (registered trademark) 102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 180S75 (manufactured by Japan Epoxy Resin), etc .;
As a polyphenol type epoxy resin, Epicoat (registered trademark) 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite (registered trademark) CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (manufactured by U.C.C.), Shodyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (manufactured by Dainippon Ink, Inc.), Epicoat (registered trademark) 871, 872 Japan Epoxy Resin Co., Ltd.), ED-5661, 5562 (above, made by Celanese Coating), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol (registered trademark) TMP (manufactured by NOF Corporation), and the like.

Examples of the [C] compound having two or more oxetanyl groups in the molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl). ) Methyl] ether (also known as bis (3-ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-[1,3- (2 -Methylenyl) propanediylbis (oxymethylene)] bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl -3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl- -Oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3 -Oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3) -Oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxeta) Rumethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanyl) Methyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl) -3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxe) Tanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl) -3-Oxetanylmethyl) ether and the like. A compound having two or more oxetane structures may be used alone or in combination of two or more to form a [C] compound.

  Of these compounds having two or more oxetane structures, di [1-ethyl- (3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like are preferable. .

  [C] A compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. As content of the [C] compound in the radiation sensitive resin composition of this embodiment, it is 1 to 100 weight part with respect to 100 weight part of [A] polyimide precursor. And it is preferable that it will be 1 to 50 weight part with respect to 100 weight part of [A] polyimide precursor, Furthermore, it is 1 to 25 weight part with respect to 100 weight part of [A] polyimide precursor. Is more preferable. [A] When the amount is less than 1 part by weight relative to 100 parts by weight of the polyimide precursor, the effect of improving the heat resistance and transparency of the cured film by the [C] compound cannot be sufficiently obtained. There is a possibility that sufficient sensitivity in the conductive resin composition cannot be obtained.

[[D] Base generator]
The radiation sensitive resin composition of the present embodiment contains the above-mentioned [A] polyimide precursor and [B] photoacid generator, or [A] polyimide precursor, [B] photoacid generator and [B]. C] contains a compound having a cyclic ether group, and [D] a base generator. The base generator refers to a compound that generates a base by heat treatment or light irradiation. [D] Examples of the base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like.

  [D] Examples of transition metal complexes that serve as base generators include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate Acid salts, hexamethylamine cobalt perchlorate, hexapropylamine cobalt perchlorate and the like.

  [D] Examples of orthonitrobenzyl carbamates that serve as base generators include [{(2-nitrobenzyl) oxy} carbonyl] methylamine, [{(2-nitrobenzyl) oxy} carbonyl] propylamine, [{ (2-nitrobenzyl) oxy} carbonyl] hexylamine, [{(2-nitrobenzyl) oxy} carbonyl] cyclohexylamine, [{(2-nitrobenzyl) oxy} carbonyl] aniline, [{(2-nitrobenzyl) Oxy} carbonyl] piperidine, bis [{(2-nitrobenzyl) oxy} carbonyl] hexamethylenediamine, bis [{(2-nitrobenzyl) oxy} carbonyl] phenylenediamine, bis [{(2-nitrobenzyl) oxy} Carbonyl] toluenediamine, bis [{(2-nitrate Benzyl) oxy} carbonyl] diaminodiphenylmethane, bis [{(2-nitrobenzyl) oxy} carbonyl] piperazine, [{(2,6-dinitrobenzyl) oxy} carbonyl] methylamine, [{(2,6-dinitrobenzyl ) Oxy} carbonyl] propylamine, [{(2,6-dinitrobenzyl) oxy} carbonyl] hexylamine, [{(2,6-dinitrobenzyl) oxy} carbonyl] cyclohexylamine, [{(2,6-dinitro Benzyl) oxy} carbonyl] aniline, [{(2,6-dinitrobenzyl) oxy} carbonyl] piperidine, bis [{(2,6-dinitrobenzyl) oxy} carbonyl] hexamethylenediamine, bis [{(2,6 -Dinitrobenzyl) oxy} carbonyl] phenyle Diamine, bis [{(2,6-dinitrobenzyl) oxy} carbonyl] toluenediamine, bis [{(2,6-dinitrobenzyl) oxy} carbonyl] diaminodiphenylmethane, bis [{(2,6-dinitrobenzyl) oxy } Carbonyl] piperazine and the like.

  [D] Examples of α, α-dimethyl-3,5-dimethoxybenzylcarbamate as a base generator include [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] methylamine, [{(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] propylamine, [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] hexylamine, [{(α , Α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] cyclohexylamine, [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] aniline, [{(α, α-dimethyl- 3,5-dimethoxybenzyl) oxy} carbonyl] piperidine, bis [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy } Carbonyl] hexamethylenediamine, bis [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] phenylenediamine, bis [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} Carbonyl] toluenediamine, bis [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] diaminodiphenylmethane, bis [{(α, α-dimethyl-3,5-dimethoxybenzyl) oxy} carbonyl] And piperazine.

  [D] Examples of acyloxyiminos serving as base generators include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoylacetophenone oxime, Examples thereof include poylbenzophenone oxime, adipoylacetone oxime, acroylacetophenone oxime, acroylbenzophenone oxime, acroylacetone oxime, and the like.

  [D] Other examples of the base generator are 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide.

  [D] A base generator may be used individually by 1 type, and 2 or more types may be mixed and used for it. As content of the [D] base generator in the radiation sensitive resin composition of this embodiment, Preferably it is 0.1 mass part-10 mass parts with respect to 100 mass parts of [A] polyimide precursors, More preferably. Is 1 part by mass to 5 parts by mass. [D] When the content of the base generator is within the above range, the hardness and transparency of the resulting polyimide film can be improved.

  The radiation-sensitive resin composition of the present embodiment includes an ultraviolet absorber, a surfactant, a storage stabilizer, and an adhesion assistant (silane coupling agent) as necessary, as long as the effects of the present invention are not impaired. ), And other optional components such as a heat resistance improver. Each of these optional components may be used alone or in combination of two or more.

[Preparation of radiation-sensitive resin composition]
The radiation-sensitive resin composition of the present embodiment includes [C] a compound having a cyclic ether group, [D] added in addition to the above [A] polyimide precursor and [B] photoacid generator, if necessary. Prepared by mixing base generator and other optional ingredients. And the radiation sensitive resin composition of this embodiment can be used as a positive type radiation sensitive resin composition. The radiation-sensitive resin composition of this embodiment is preferably prepared and used in a state where each component contained is dissolved or dispersed in an appropriate solvent. For example, in a solvent, the [A] component ([A] polyimide precursor), the [B] component ([B] photoacid generator), and the possible [C] component (having a [C] cyclic ether group Compound), [D] component ([D] base generator), and other arbitrary components are mixed in a predetermined ratio to prepare a radiation sensitive resin composition.

  As the solvent that can be used for the preparation of the radiation-sensitive resin composition of the present embodiment, as described above, a solvent that uniformly dissolves or disperses each component and does not react with each component is preferably used.

  As a solvent which can be used for preparation of the radiation sensitive resin composition of this embodiment, the polymerization solvent illustrated as what is used for the polymerization reaction for obtaining a [A] polyimide precursor can be mentioned. Moreover, the organic solvent believed to be a poor solvent of a polyamic acid and a polyimide conventionally can also be selected suitably, and can be used together.

  Preferred examples of such organic solvents include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl. -2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol -I-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, cyclohexanone, diacetone alcohol, Examples thereof include ethyl carbitol, ethoxyethyl propionate, butyl cellosolve acetate, carbitol acetate, and propylene carbonate. These can be used alone or in admixture of two or more.

  The solid content concentration of the radiation-sensitive resin composition of the present embodiment (the ratio of the total weight of the components excluding the solvent in the composition solution to the total weight of the composition solution) depends on the purpose of use, desired film thickness, etc. Although it can set arbitrarily according to it, Preferably it is 5 mass%-50 mass%, More preferably, it is 10 mass%-40 mass%, More preferably, it is 15 mass%-35 mass%. In practice, a solid content concentration is set in accordance with a desired film thickness value or the like in the above concentration range.

  The solution-like radiation-sensitive resin composition thus prepared is preferably used for forming the polyimide film of the present embodiment after being filtered using a Millipore filter having a pore size of about 0.5 μm.

<Manufacture of polyimide film>
Next, the polyimide film of this embodiment using the radiation sensitive resin composition of this embodiment mentioned above and its manufacturing method are described.
The polyimide film of the present embodiment is manufactured using the radiation-sensitive resin composition of the present embodiment, and is obtained as a low hygroscopic and highly reliable organic film patterned into a desired shape by a photolithography method. Can do. The manufacturing method of the polyimide of this embodiment can be comprised including the following processes as the main processes in the following order.

(1) A step of forming a coating film of the radiation-sensitive resin composition of the present embodiment on a substrate (hereinafter, simply referred to as “coating layer forming step”),
(2) A step of irradiating at least a part of the coating film formed in step (1) (hereinafter, simply referred to as “radiation irradiation step”),
(3) a step of developing the coating film irradiated with radiation in step (2) (hereinafter, simply referred to as “developing step”), and (4) a coating film developed in step (3). (Hereinafter, simply referred to as “heating step”).

  Drawing 1 (a)-(d) is a typical sectional view showing each manufacturing process of a manufacturing method of a polyimide film of an embodiment of the present invention.

The above-described step (1) coating film forming step corresponds to, for example, FIG. Step (2) The radiation irradiation step corresponds to, for example, FIG. Step (3) The developing step corresponds to, for example, FIG. Step (4) The heating step corresponds to, for example, FIG.
Hereinafter, the steps (1) to (4) will be described in more detail.

(1) Coating film forming step As shown in FIG. 1 (a), in the (1) coating film forming step, the radiation-sensitive resin composition of the present embodiment is applied onto the substrate 1, and preferably prebaked. By removing the solvent, a coating film 2 of the radiation sensitive resin composition is formed.
In the coating film 2 to be formed, as described above, [A] a polyimide precursor and a photoacid generator having a structural unit represented by the following formula (1) which is a component of the radiation-sensitive resin composition of the present embodiment. [B] Photoacid generators such as

In the above formula (1), A, B, X ¹ and X ² have the same meaning as described above.

  In this step, examples of the substrate 1 that can be used include a resin substrate and a glass substrate, and a silicon substrate such as a silicon wafer. An example of the substrate used for forming an organic EL display element or the like is a substrate on which a TFT, its wiring, or the like is formed.

  The application method of the radiation sensitive resin composition of the present embodiment is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method), a slit die coating method, a bar coating method, An appropriate method such as an inkjet method can be employed. Among these coating methods, the spin coating method and the slit die coating method are particularly preferable. The prebaking conditions vary depending on the type of each component, the use ratio, and the like, but for example, the heating temperature can be 60 ° C. to 120 ° C. and the heating time can be about 30 seconds to 15 minutes. The film thickness of the coating film to be formed can be 1 μm to 10 μm as a value after pre-baking.

(2) Radiation irradiation process As shown in FIG.1 (b), in the (2) radiation irradiation process, it exposes by irradiating a part of formed coating films 2 with the radiation 4. FIG. In this step, it is preferable to irradiate the radiation 4 through the mask 3 having a predetermined pattern shape so that the desired portion of the coating film 2 can be irradiated with the radiation 4. And the exposure part 5 of the desired shape is formed in the coating film 2. Examples of the radiation 4 used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

  Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable.

Energy of exposure intensity at the wavelength 365nm of the radiation emitted as a value measured by a luminometer (OAI model 356, Optical Associates Ltd. ^Inc.), can be ^{10J / m 2 ~10000J / m 2} , preferably it is ^{100J / m 2 ~3000J / m 2} , more preferably ^{500J / m 2 ~2000J / m 2} .

In the exposure part 5, an acid is generated by the action of the photoacid generator [B] such as a photoacid generator contained in the coating film 2, and the protective group in the [A] polyimide precursor of the above formula (1) is used. out there was X ¹ and X ^2, changes in the polyamic acid having a structural unit represented by the following formula (1-1).

(3) Development Step As shown in FIG. 1 (c), in the (3) development step, development is performed on the coating film 2 irradiated with the radiation 4 in the above (2) radiation irradiation step, and the radiation 4 The exposed portion 5 that is the irradiated portion of (2) is removed, and a coating film 2 ′ patterned into a desired shape can be formed.
That is, the polyamic acid having the structural unit of the above formula (1-1) having a free carboxyl group is generated in the exposed portion 5 and is more easily dissolved in the developer described later than the unexposed portion. . Therefore, it is possible to remove only the exposed portion 5 using a developer.

  Examples of the developer used in the development processing in this step include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. Also, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition of the present embodiment Can be used as a developer. As the organic solvent, those mentioned as the polymerization solvent for obtaining the above-mentioned [A] polyimide precursor can be used.

  Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. Although development time changes with compositions of a radiation sensitive resin composition, it can be made into 30 second-120 second, for example.

(4) Heating step As shown in FIG. 1 (d), in the (4) heating step, an appropriate heating device such as a hot plate or an oven is used to form the patterned coating film 2 ′ shown in FIG. 1 (c). Heat. By heating, the [A] polyimide precursor having the structural unit of the above formula (1) in the coating film 2 ′ is changed to a polyimide having a structural unit represented by the following formula (1-2). As a result, a patterned polyimide film 6 can be formed on the substrate 1.

  The heating temperature in this step is a temperature at which the [A] polyimide precursor changes to polyimide, for example, 120 ° C. to 250 ° C. The heating time varies depending on the type of the heating device. For example, when heat treatment is performed on a hot plate, it may be 5 minutes to 30 minutes, and when heat treatment is performed in an oven, it may be 30 minutes to 180 minutes. it can. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used. In this way, a polyimide film 6 having a desired pattern can be formed on the substrate 1.

  The polyimide film formed as described above exhibits good characteristics in terms of visible light transmittance, heat resistance, patterning properties, solvent resistance, and the like, and an insulating film that forms a partition of an organic EL element, an organic EL element It can be suitably used as an insulating film having a flattening function and an insulating film of a semiconductor element.

<Semiconductor element>
FIG. 2 is a cross-sectional view schematically illustrating the structure of the semiconductor element of this embodiment.

FIG. 2 shows an example in which the semiconductor element 11 of this embodiment is provided on one surface of the substrate 20.
The semiconductor element 11 includes a semiconductor layer 12 and an electrode provided on a first surface, which is the upper surface of the semiconductor layer 12 in FIG. The electrode comprises a first source-drain electrode 13 and a second source-drain electrode 14.

  The semiconductor element 11 has the polyimide film 15 of the present embodiment described above disposed between the semiconductor layer 12 and the first source-drain electrode 13 and the second source-drain electrode 14. The polyimide film 15 is patterned into a desired shape, and a through hole 16 is provided. The semiconductor element 11 includes an electrical connection between the first surface of the semiconductor layer 12 and the first source-drain electrode 13, and an electrical connection between the first surface of the semiconductor layer 12 and the second source-drain electrode 14. Each connection is made through a corresponding through hole 16.

  A semiconductor element 11 in FIG. 2 has a gate electrode 21 on a second surface of the semiconductor layer 12, which is a lower surface in FIG. 2, with a gate insulating film 22 interposed therebetween. That is, in the semiconductor element 11, the gate electrode 21 is disposed on the substrate 20, and the gate insulating film 22 is formed on the gate electrode 21. The semiconductor layer 12 has a first source-drain electrode 13 and a second source-drain electrode 14 that are disposed on the gate electrode 21 through the gate insulating film 22 and connected to the semiconductor layer 12. The semiconductor element 11 constitutes a bottom gate type semiconductor element.

  The semiconductor device according to the embodiment of the present invention is not limited to the bottom gate type shown in FIG. A gate electrode is provided on the first surface side, which is the upper surface of the semiconductor layer, via a gate insulating film, and a first source-drain electrode and a second source-drain electrode connected to the first surface are provided on the first surface. It is also possible to adopt a top gate type having the above.

  In the semiconductor element 11 shown in FIG. 2, the gate electrode 21 can be formed by forming a metal thin film on the substrate 20 by vapor deposition or sputtering, and performing patterning using an etching process. In addition, a metal oxide conductive film or an organic conductive film can be patterned and used.

  Examples of the material of the metal thin film constituting the gate electrode 21 include Al (aluminum), Mo (molybdenum), Cr (chromium), Ta (tantalum), Ti (titanium), Au (gold), and Ag (silver). And alloys such as Al-Nd (neodymium) and APC (Ag / Pd (palladium) / Cu (copper)) alloys. And as a metal thin film, it is also possible to use laminated films, such as a laminated film of Al and Mo.

Examples of the material of the metal oxide conductive film constituting the gate electrode 21 include metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Can be mentioned.
Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.
The thickness of the gate electrode 21 is preferably 10 nm to 1000 nm.

The gate insulating film 22 disposed so as to cover the gate electrode 21 can be formed by forming an oxide film or a nitride film by sputtering, CVD, vapor deposition, or the like. The gate insulating film 22 can be formed from, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. It can also be composed of an organic material such as a polymer material. The film thickness of the gate insulating film 22 is preferably 10 nm to 10 μm. In particular, when an inorganic material such as a metal oxide is used, 10 nm to 1000 nm is preferable, and when an organic material is used, 50 nm to 10 μm is preferable.

  The first source-drain electrode 13 and the second source-drain electrode 14 connected to the semiconductor layer 12 are made of a conductive film constituting the electrodes by a sputtering method, a CVD method, a vapor deposition method in addition to a printing method and a coating method. After forming using such a method, patterning using a photolithography method or the like can be performed. Examples of the constituent material of the first source-drain electrode 13 and the second source-drain electrode 14 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag, and Al—Nd and APC. Conductive metal oxides such as alloys, tin oxide, zinc oxide, indium oxide, ITO, IZO, AZO (aluminum doped zinc oxide), and GZO (gallium doped zinc oxide), polyaniline, polythiophene, polypyrrole, etc. Examples thereof include conductive organic compounds.

  The thickness of the first source-drain electrode 13 and the second source-drain electrode 14 is preferably 10 nm to 1000 nm.

  The semiconductor layer 12 of the semiconductor element 11 of the present embodiment is formed by using a Si (silicon) material such as a-Si (amorphous-silicon), p-Si (poly-silicon), or microcrystalline silicon, for example. can do.

  Moreover, the semiconductor layer 12 of the semiconductor element 11 of this embodiment can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 12 of the present embodiment include single crystal oxide, polycrystalline oxide, amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  As an amorphous oxide applicable to the semiconductor layer 12, an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn) can be given.

  Specific examples of amorphous oxides applicable to the semiconductor layer 12 include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn oxide (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga An oxide, a Sn—In—Zn oxide, and the like can be given. In the above case, the composition ratio of the constituent materials is not necessarily 1: 1, and a composition ratio that realizes desired characteristics can be selected.

For example, when the semiconductor layer 12 using an amorphous oxide is formed using IGZO or ZTO, a semiconductor layer is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method. Etc. are used for patterning by a resist process and an etching process. The thickness of the semiconductor layer 12 using an amorphous oxide is preferably 1 nm to 1000 nm.
By using the oxides exemplified above, the semiconductor layer 12 with high mobility can be formed at a low temperature, and the semiconductor element 11 of this embodiment including the semiconductor layer 12 can be provided.

As oxides particularly preferable for forming the semiconductor layer 12 of the semiconductor element 11 of this embodiment, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide ( ZIO).
By using these oxides, the semiconductor element 11 has the semiconductor layer 12 having excellent mobility formed at a lower temperature, and can exhibit a high ON / OFF ratio.

  In the semiconductor element 11 of this embodiment, the polyimide film 15 of this embodiment is disposed between the semiconductor layer 12 and the first source-drain electrode 13 and the second source-drain electrode 14. As described above, the polyimide film 15 of the present embodiment is an insulating film formed from the radiation-sensitive resin composition of the embodiment of the present invention including [A] a polyimide precursor and [B] a photoacid generator. It is.

  As described above, the polyimide film 15 is formed by applying the radiation-sensitive resin composition of the embodiment of the present invention on the substrate 20 on which the gate electrode 21, the gate insulating film 22, and the semiconductor layer 12 are formed. After necessary patterning such as formation of the holes 16, it is formed by heating. The formed polyimide film 15 can contain a [B] photoacid generator having an absorptivity to light such as ultraviolet rays, and in that case, excellent light shielding properties can be realized. In the present embodiment, the polyimide film 15 may further include an ultraviolet absorber.

  Therefore, the semiconductor element 11 of the present embodiment having the polyimide film 15 between the semiconductor layer 12 and the first source-drain electrode 13 and the second source-drain electrode 14 has a semiconductor effect due to the effect of the polyimide film 15. The light shielding of the layer 12 is possible. And the semiconductor element 11 of this embodiment can reduce the deterioration of the characteristic by the influence of light by the light shielding effect of the polyimide film 15.

  At this time, as an element configured using a semiconductor element, for example, there is a liquid crystal display element as described above. In the case of a liquid crystal display element, it is manufactured by sandwiching a liquid crystal between a semiconductor substrate having a TFT as a semiconductor element and a color filter substrate having a color filter. In general, a backlight unit is disposed on the semiconductor substrate side to enable image display with a high contrast ratio.

  Therefore, it is necessary for the semiconductor substrate side of the liquid crystal display element to easily transmit light from the backlight unit, particularly light in the visible region (transparency), and it is usually necessary to provide a light-shielding film. It is not preferable.

  However, the semiconductor element 11 of the present embodiment uses the polyimide film 15 containing a suitably selected [B] photoacid generator, so that visible light transmission (transparency) and light shielding required for a liquid crystal display element or the like are required. The balance of sex can be suitably controlled.

  As described above, in the semiconductor element 11 of this embodiment, the polyimide film 15 exhibits a specific effect and becomes a main constituent element.

<Organic EL device>
As an organic EL element according to an embodiment of the present invention, an example of an organic EL display element according to an embodiment of the present invention will be described with reference to the drawings.

  FIG. 3 is a cross-sectional view schematically illustrating the structure of the main part of the organic EL display element of this embodiment.

  The organic EL display element 101 of the present embodiment is an active matrix type organic EL display element having a plurality of pixels formed in a matrix. The organic EL display element 101 may be either a top emission type or a bottom emission type. The organic EL display element 101 includes a thin film transistor (hereinafter also referred to as “TFT”) 103 which is an active element in each pixel portion on the substrate 102.

  With respect to the substrate 102 of the organic EL display element 101, when the organic EL display element 101 is a bottom emission type, the substrate 102 is required to be transparent. Therefore, as an example of the material of the substrate 102, PET (polyethylene terephthalate) or Transparent resins such as PEN (polyethylene naphthalate) and PI (polyimide), and glass such as non-alkali glass are used. On the other hand, when the organic EL display element 101 is a top emission type, since the substrate 102 does not need to be transparent, an arbitrary insulator can be used as the material of the substrate 102. Similarly to the bottom emission type, a glass material such as alkali-free glass can be used.

  The TFT 103 is disposed on the substrate 102 via a gate electrode 104 that forms part of a scanning signal line (not shown), a gate insulating film 105 that covers the gate electrode 104, and a gate insulating film 105 on the gate electrode 104. A first source-drain electrode 107 connected to the semiconductor layer 106 by forming a part of a video signal line (not shown), and a second source-drain electrode 108 connected to the semiconductor layer 106. And is configured.

  The gate electrode 104 can be formed by forming a metal thin film on the substrate 102 by vapor deposition or sputtering, and performing patterning using an etching process. In addition, a metal oxide conductive film or an organic conductive film can be patterned and used.

  As a material of the metal thin film constituting the gate electrode 104, for example, Al (aluminum), Cu (copper), Mo (molybdenum), Cr (chromium), Ta (tantalum), Ti (titanium), Au (gold), Mention may be made of metals such as W (tungsten) and Ag (silver), alloys of these metals, and alloys such as Al-Nd and APC alloys (silver, palladium, copper alloys). And as a metal thin film, it is also possible to use the laminated film which consists of a layer of a different material, such as a laminated film of Al and Mo.

As a material of the metal oxide conductive film constituting the gate electrode 104, a metal oxide conductive film such as tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide) and indium zinc oxide (IZO) is used. Can be mentioned.
Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.
The thickness of the gate electrode 104 is preferably 10 nm to 1000 nm.

The gate insulating film 105 disposed so as to cover the gate electrode 104 can be formed by forming an oxide film or a nitride film by a sputtering method, a CVD method, an evaporation method, or the like. The gate insulating film 105 can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or in a stacked manner. It can also be composed of an organic material such as a polymer material. The film thickness of the gate insulating film 105 is preferably 10 nm to 10 μm. In particular, when an inorganic material such as a metal oxide is used, 10 nm to 1000 nm is preferable, and when an organic material is used, 50 nm to 10 μm is preferable.

For the first source-drain electrode 107 and the second source-drain electrode 108 connected to the semiconductor layer 106, a conductive film constituting the electrodes is formed by a sputtering method, a CVD method, a vapor deposition method in addition to a printing method or a coating method. After forming using such a method, patterning using a photolithography method or the like can be performed. Examples of the constituent material of the first source-drain electrode 107 and the second source-drain electrode 108 include metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, and alloys of these metals. And alloys such as Al-Nd and APC. Also, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide) and GZO (gallium doped zinc oxide), polyaniline, polythiophene and polypyro Examples thereof include conductive organic compounds such as As the conductive film constituting these electrodes, a laminated film made of layers of different materials such as a laminated film of Ti and Al can be used.
The thicknesses of the first source-drain electrode 107 and the second source-drain electrode 108 are preferably 10 nm to 1000 nm.

  The semiconductor layer 106 is made of, for example, Si (amorphous silicon) or p-Si (polysilicon) obtained by crystallization of a-Si by excimer laser or solid phase growth. It can be formed by using a (silicon) material.

  Further, the semiconductor layer 106 of the TFT 103 can be formed using an oxide. Examples of the oxide that can be used for the semiconductor layer 106 include single crystal oxides, polycrystalline oxides, amorphous oxides, and mixtures thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  As an amorphous oxide applicable to the semiconductor layer 106, an amorphous oxide including at least one element of In (indium), Zn (zinc), and Sn (tin) can be given.

  Specific examples of amorphous oxides applicable to the semiconductor layer 106 include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn oxide (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga An oxide, a Sn—In—Zn oxide, and the like can be given. In the above case, the composition ratio of the constituent materials is not necessarily 1: 1, and a composition ratio that realizes desired characteristics can be selected.

  For example, when the semiconductor layer 106 using an amorphous oxide is formed using IGZO or ZTO, a semiconductor layer is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method. Etc. are used for patterning by a resist process and an etching process. The thickness of the semiconductor layer 6 using an amorphous oxide is preferably 1 nm to 1000 nm.

In the case where the above-described oxide is used for the semiconductor layer 106 of the TFT 103, for example, 5 nm to 80 nm in a region where the first source-drain electrode 107 and the second source-drain electrode 108 are not formed on the upper surface of the semiconductor layer 106. It is preferable to provide a protective layer (not shown) made of SiO _{2 with} a thickness of. This protective layer is sometimes referred to as an etching stop layer or a stop layer.
By using the oxides exemplified above, the semiconductor layer 106 with high mobility can be formed at low temperature, and the TFT 103 with excellent performance can be provided.

As oxides particularly preferable for forming the semiconductor layer 106 of the semiconductor element 101 of this embodiment, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide ( ZIO).
By using these oxides, the TFT 103 has the semiconductor layer 106 having excellent mobility formed at a lower temperature, and can exhibit a high ON / OFF ratio.

An inorganic insulating film 119 can be provided over the TFT 103 so as to cover the TFT 103. The inorganic insulating film 119 can be formed using, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN alone or in a stacked manner. The inorganic insulating film 119 is provided to protect the semiconductor layer 106 and prevent it from being affected by humidity, for example. In the organic EL display element 101 of the present embodiment, the inorganic insulating film 119 may not be provided, and the polyimide film 110 that is the first insulating film may be disposed on the TFT 103.

  Next, in the organic EL display element 101, a polyimide film 110 as a first insulating film is disposed on the inorganic insulating film 119 so as to cover the TFT 103 on the substrate 102. The polyimide film 110 has a function of flattening unevenness caused by the TFT 103 formed on the substrate 102. The polyimide film 110 is an insulating film formed using the radiation-sensitive resin composition of the present embodiment described above, and is an organic insulating film. The polyimide film 110 preferably has an excellent function as a planarizing film, and is preferably formed thick from this viewpoint. For example, the polyimide film 110 can be formed with a thickness of 1 μm to 6 μm. The polyimide film 110 is formed according to the polyimide film manufacturing method described above.

  On the polyimide film 110 which is the first insulating film, an anode 111 forming a pixel electrode is disposed. The anode 111 is made of a conductive material. As the material of the anode 111, it is preferable to select a material having different characteristics depending on whether the organic EL display element 101 is a bottom emission type or a top emission type. In the case of the bottom emission type, since the anode 111 is required to be transparent, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, or the like is selected as the material of the anode 111. On the other hand, when the organic EL display element 101 is a top emission type, the anode 111 is required to have light reflectivity. As the material of the anode 111, APC alloy (silver, palladium, copper alloy) or ARA (silver, rubidium) is used. , Gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and chromium alloy), and the like are selected. The thickness of the anode 111 is preferably 100 nm to 500 nm.

  Since the anode 111 disposed on the polyimide film 110 which is the first insulating film is connected to the second source-drain electrode 108, a through hole 112 penetrating the polyimide film 110 is formed in the polyimide film 110. Yes. The through hole 112 is formed so as to penetrate the inorganic insulating film 119 under the polyimide film 110. The polyimide film 110 can be formed using the radiation sensitive resin composition of this embodiment mentioned above. Therefore, according to the above-described method for producing a polyimide film, the coating film of the radiation-sensitive resin composition is irradiated with radiation to form a polyimide film 110 having a through hole having a desired shape, and then this polyimide film 110 is used as a mask for inorganic insulation. By performing dry etching on the film 119, the through hole 112 can be completed. In the case where the inorganic insulating film 119 is not disposed on the TFT 103, the through hole formed in the polyimide film 110 constitutes the through hole 112. As a result, the anode 111 covers at least a part of the polyimide film 110 and is connected to the TFT 103 through the through hole 112 provided in the polyimide film 110 so as to penetrate the polyimide film 110. 108 can be connected.

  In the organic EL display element 101, a polyimide film 113 is formed on the anode 111 on the polyimide film 110, which is the first insulating film, as a second insulating film serving as a partition that defines the arrangement region of the organic light emitting layer 114. Is formed. The polyimide film 113 as the second insulating film can be manufactured by using the radiation-sensitive resin composition of the present embodiment described above and patterning the coating film according to the above-described method for manufacturing a polyimide film. Therefore, for example, it can have a lattice shape in plan view. In an area defined by the polyimide film 113, an organic light emitting layer 114 that emits electroluminescence is disposed. In the organic EL display element 101, the polyimide film 113 as the second insulating film serves as a barrier surrounding the periphery of the organic light emitting layer 114 and partitions each of a plurality of adjacent pixels.

  In the organic EL display element 101, the height of the polyimide film 113 as the second insulating film (the distance between the upper surface of the polyimide film 113 and the upper surface of the anode 111 in the arrangement region of the organic light emitting layer 114) is 0.1 μm to 2 μm is preferable, and 0.8 μm to 1.2 μm is more preferable. When the height of the polyimide film 113 is 2 μm or more, there is a possibility of colliding with the sealing substrate 120 above the polyimide film 113. Further, when the height of the polyimide film 113 is 0.1 μm or less, when an ink-like light-emitting material composition is applied to the region defined by the polyimide film 113 by an inkjet method, the light-emitting material composition There is a risk that an object leaks from the polyimide film 113.

  The polyimide film 113 of the organic EL display element 101 can be formed by using the radiation sensitive resin composition of the present embodiment described above and patterning the coating film according to the method of forming the insulating film described above. it can. The polyimide film 113 has a low wettability because it defines a region where an ink-like light-emitting material composition containing an organic light-emitting material is applied when an ink-like light-emitting material composition is applied by an inkjet method. Is preferred. When the wettability of the polyimide film 113 is controlled to be particularly low, the polyimide film 113 can be plasma-treated with fluorine gas, and the radiation-sensitive resin composition of this embodiment for forming the polyimide film 113 can be used. A liquid repellent may be included. Since the plasma treatment may adversely affect other components of the organic EL display element 101, the radiation sensitive resin composition of the present embodiment for forming the polyimide film 113 as the second insulating film contains a liquid repellent. It may be preferable to do this.

An organic light emitting layer 114 that emits light by applying an electric field is disposed in a region defined by the polyimide film 113 that is the second insulating film. The organic light emitting layer 114 is a layer containing an organic light emitting material that emits electroluminescence.
The organic light emitting material included in the organic light emitting layer 114 may be a low molecular organic light emitting material or a polymer organic light emitting material. For example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ or BeBq ₃ can be used. Moreover, when using the coating method of the organic luminescent material by the inkjet method, it is preferable that it is a polymeric organic luminescent material suitable for it. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly 3 -Hexylthiophene (Poly 3-hexyl thiophene (P3HT)) and its derivatives, polyfluorene (Poly fluorene (PF)), its derivatives, etc. can be selected and used.

  The organic light emitting layer 114 is disposed on the anode 111 in a region defined by the polyimide film 113 that is the second insulating film. The thickness of the organic light emitting layer 114 is preferably 50 nm to 100 nm. Here, the thickness of the organic light emitting layer 114 means the distance from the bottom surface of the organic light emitting layer 114 on the anode 111 to the top surface of the organic light emitting layer 114 on the anode 111.

  A hole injection layer and / or an intermediate layer may be disposed between the anode 111 and the organic light emitting layer 114. When the hole injection layer and the intermediate layer are disposed between the anode 111 and the organic light emitting layer 114, the hole injection layer is disposed on the anode 111, the intermediate layer is disposed on the hole injection layer, and An organic light emitting layer 114 is disposed on the intermediate layer. In addition, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode 111 to the organic light emitting layer 114.

  In the organic EL display element 101, a cathode 115 is formed so as to cover the organic light emitting layer 114 and a polyimide film 113 which is a second insulating film for pixel division. The cathode 115 is formed so as to cover a plurality of pixels in common, and serves as a common electrode of the organic EL display element 101.

The organic EL display element 101 of this embodiment has a cathode 115 on the organic light emitting layer 114, and the cathode 115 is made of a conductive member. The material used for forming the cathode 115 differs depending on whether the organic EL display element 101 is a bottom emission type or a top emission type. In the case of the top emission type, the cathode 115 is preferably an ITO electrode or an IZO electrode that constitutes a visible light transmissive electrode. On the other hand, when the organic EL display element 101 is a bottom emission type, the cathode 115 does not have to be visible light transmissive. In that case, the constituent material of the cathode 115 is not particularly limited as long as it is conductive. For example, Ba (barium), BaO (barium oxide), Al (aluminum), and an alloy containing Al can be selected. is there.
An electron injection layer made of, for example, Ba (barium), LiF (lithium fluoride), or the like may be disposed between the cathode 115 and the organic light emitting layer 114.

  A passivation film 116 can be provided on the cathode 115. The passivation film 116 can be formed using a metal nitride such as SiN or AlN (aluminum nitride) or the like alone or in a stacked manner. By the action of the passivation film 116, the intrusion of moisture and oxygen into the organic EL display element 101 can be suppressed.

  The main surface of the substrate 102 thus configured on which the organic light emitting layer 114 is disposed uses a sealing agent (not shown) applied in the vicinity of the outer peripheral edge, and the sealing substrate is interposed through the sealing layer 117. It is preferable to seal with 120. The sealing layer 117 can be a layer of an inert gas such as dried nitrogen gas or a layer of a filler material such as an adhesive. As the sealing substrate 120, a glass substrate such as non-alkali glass can be used.

  In the organic EL display element 101 of the present embodiment having the above structure, the polyimide film 110 that is the first insulating film and the polyimide film 113 that is the second insulating film, which are constituent elements, are made of polyimide with low hygroscopicity. And has a low water absorption structure. Therefore, it is possible to reduce a slight amount of moisture contained in the conventional insulating film forming material in the form of adsorbed water from gradually entering the organic light emitting layer 114, and to reduce deterioration of the organic light emitting layer 114 and inhibition of the light emitting state. Can do.

  Moreover, in the organic EL display element of the embodiment of the present invention, as another example, the semiconductor element of the embodiment of the present invention described above can be used for the TFT. By having such a configuration, in another example of the organic EL display element of the embodiment of the present invention, it is possible to achieve both excellent driving characteristics and reliability.

Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.
<Synthesis of polyimide precursor>
(Synthesis Example 1)
After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, diamine and tetracarboxylic dianhydride are added to the polymerization solvent so that the solid content concentration becomes 20% by mass with respect to a total of 80 g of the polymerization solvent. Added inside. At this time, the tetracarboxylic dianhydride added 90 mol part with respect to 100 mol part of the whole quantity of diamine. In this synthesis example, 2,2′-bis (4-aminophenyl) hexafluoropropane (BAF) was used as the diamine compound, dissolved therein, and then 2,3,4 as tetracarboxylic dianhydride. -Tricarboxycyclopentyl acetic acid dianhydride (TCA) was charged.

Thereafter, the mixture was reacted at 60 ° C. for 3 hours. As a result, about 100 g of a polyamic acid ester solution having a solid content concentration of 20% by mass and a solution viscosity of 100 mPa · s was obtained.
Next, 185 mol parts of ethyl vinyl ether and 0.1 mol parts of 10-camphorsulfonic acid were added to the obtained polyamic acid ester solution, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was neutralized with triethylamine, extracted with distilled water and ethyl acetate, and then the organic layer was concentrated to obtain a polyamic acid ester in which the carboxyl group was protected. This is designated as polyimide precursor (A-1).

(Synthesis Example 2)
After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, 2,2-bis (trifluoromethyl) benzidine was used instead of the diamine used in Synthesis Example 1, and used in Synthesis Example 1. Instead of tetracarboxylic dianhydride, 1,2,3,4, -cyclobutanetetracarboxylic dianhydride was used and reacted in the same manner as in Synthesis Example 1, whereby a solid content concentration of 20% by mass was obtained. About 100 g of a polyamic acid ester solution having a solution viscosity of 90 mPa · s was obtained.

  Next, 185 mol parts of dihydropyran and 0.1 mol parts of 10-camphorsulfonic acid were added to the obtained polyamic acid ester solution, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was neutralized with triethylamine, extracted with distilled water and ethyl acetate, and then the organic layer was concentrated to obtain a polyamic acid ester in which the carboxyl group was protected. This is designated as polyimide precursor (A-2).

(Synthesis Example 3)
After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used in place of the diamine used in Synthesis Example 1. And using 1,3-dimethyl-1,2,3,4, -cyclobutanetetracarboxylic dianhydride instead of the tetracarboxylic dianhydride used in Synthesis Example 1 in the same manner as in Synthesis Example 1. As a result, about 100 g of a polyamic acid ester solution having a solid content concentration of 20% by mass and a solution viscosity of 95 mPa · s was obtained.

  Next, 90 mol part of di-tert-butyl dicarbonate and 1 mol part of triethylamine were added to the obtained polyamic acid ester solution, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was neutralized with dilute hydrochloric acid, extracted with distilled water and ethyl acetate, and the organic layer was concentrated to obtain a polyamic acid in which the phenolic hydroxyl group was protected with a tert-butyl group.

  Next, 185 mol parts of dihydropyran and 0.1 mol part of 10-camphorsulfonic acid were added to the polyamic acid ester solution in which the phenolic hydroxyl group was protected with a tert-butyl group. Stir for hours. Thereafter, the reaction solution was neutralized with triethylamine, extracted with distilled water and ethyl acetate, and then the organic layer was concentrated to obtain a polyamic acid ester in which the carboxyl group was protected. This is designated as polyimide precursor (A-3).

(Comparative Synthesis Example 1)
After adding 80 g of N-methylpyrrolidone (NMP) as a polymerization solvent to the reaction vessel, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used instead of the diamine compound used in Synthesis Example 1. And using pyromellitic dianhydride instead of the tetracarboxylic dianhydride used in Synthesis Example 1 and reacting in the same manner as in Synthesis Example 1, whereby a solid content concentration of 20% by mass and a solution viscosity of 100 mPa -About 100g of polyamic acid ester solution of s was obtained. This is designated as polyimide precursor (a-1).

<Preparation of radiation-sensitive resin composition>
Example 1
As a component [A], a solution containing the polyimide precursor (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (A-1)), [B] As a component, 4 parts by mass of trifluoromethanesulfonic acid-1,8-naphthalimide (B-1) which is a photoacid generator, and as a [F] component, a silicone surfactant (manufactured by Dow Corning Toray Co., Ltd.) “SH 8400 FLUID”) 0.20 parts by mass, [G] component mixed with 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and filtered through a membrane filter having a pore size of 0.2 μm By doing so, the radiation sensitive resin composition (S-1) was prepared.

(Example 2)
As a component [A], a solution containing the polyimide precursor (A-2) obtained in Synthesis Example 2 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (A-2)), [B] As a component, 4 parts by mass of benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (B-2) which is a photoacid generator, and as a [C] component, di [1-ethyl- (3-oxetanyl) methyl] ether ( C-1) 25 parts by mass, [E] component as a basic compound, 4-dimethylaminopyridine (E-1) 0.01 parts by mass, and [F] component as a silicone surfactant (Corporation) "SH 8400 FLUID" manufactured by Toray Dow Corning) 0.20 parts by mass, and [G] component mixed with 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent The mixture was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a radiation sensitive resin composition (S-2).

(Example 3)
As a component [A], a solution containing the polyimide precursor (A-3) obtained in Synthesis Example 3 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (A-3)) [B] As a component, [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (B-5) 5 parts by mass, [C] component which is a photoacid generator As a phenol novolak type epoxy resin (Epicoat (registered trademark) 152 manufactured by Japan Epoxy Resin Co., Ltd.) (C-2) 15 parts by mass, [D] component, 2-nitrobenzylcyclohexyl carbamate (D-1) 1 part by mass, As component [F], 0.20 parts by mass of a silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) and as component [G] A coupling agent γ- glycinate Doki trimethoxysilane 3.0 part by mass, by filtration through a membrane filter having a pore size of 0.2 [mu] m, the radiation-sensitive resin composition (S-3) was prepared.

Example 4
As a component [A], a solution containing the polyimide precursor (A-2) obtained in Synthesis Example 2 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (A-2)), [B] As a component, [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (“IRGACURE” manufactured by Ciba Specialty Chemicals Co., Ltd.) is used as a photoacid generator. (Registered trademark) PAG 121 ") (B-3) 3 parts by mass, [C] component, di [1-ethyl- (3-oxetanyl) methyl] ether (C-1) 25 parts by mass, [D] component O-carbamoylhydroxyamide (D-2) 1 part by mass, silicone surfactant as “F” component (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) 20 parts by mass, mixed with 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane which is a silane coupling agent as [G] component, and filtered through a membrane filter having a pore size of 0.2 μm, whereby a radiation sensitive resin composition A product (S-4) was prepared.

(Example 5)
As a component [A], a solution containing the polyimide precursor (A-2) obtained in Synthesis Example 2 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (A-2)), [B] As a component, 2 parts by mass of trifluoromethanesulfonic acid-1,8-naphthalimide (B-1), which is a photoacid generator, and as a [C] component, a phenol novolac type epoxy resin (Epicoat (registered trademark) 152 Japan Epoxy Resin) (C-2) 15 parts by mass, [E] component, 0.01 parts by mass of 1,5-diazabicyclo [4,3,0] -5-nonene (E-2) as a basic compound, As component [F], 0.20 part by mass of a silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.), and as component [G], γ-glycidic quip which is a silane coupling agent Pills trimethoxysilane 3.0 part by mass, by filtration through a membrane filter having a pore size of 0.2 [mu] m, the radiation-sensitive resin composition (S-5) was prepared.
The main components used in the above examples are as follows.

[[B] Photoacid generator]
(B-1): trifluoromethanesulfonic acid-1,8-naphthalimide (B-2): benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (B-3): [(5-p-toluenesulfonyloxyimino -5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] ("IRGACURE (registered trademark) PAG 121" manufactured by Ciba Specialty Chemicals)
(B-4): [(Camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (“CGI1380” manufactured by Ciba Specialty Chemicals)
(B-5): [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile]

[[C] Compound having cyclic ether group]
(C-1): Di [1-ethyl- (3-oxetanyl) methyl] ether (C-2): Phenol novolac type epoxy resin (Epicoat (registered trademark) 152 manufactured by Japan Epoxy Resin Co., Ltd.)

[[D] Base generator]
(D-1): 2-nitrobenzylcyclohexyl carbamate (D-2): O-carbamoylhydroxyamide

[[E] basic compound]
(E-1) 4-Dimethylaminopyridine (E-2) 1,5-diazabicyclo [4,3,0] -5-nonene [[F] surfactant]
Silicone surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning)
[[G] Silane coupling agent]
γ-glycidoxypropyltrimethoxysilane

(Comparative example)
As a component [A], a solution containing the polyimide precursor (a-1) obtained in Comparative Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of the polyimide precursor (a-1)) ] As a photoacid generator of the component, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (orthonaphthoquinonediazide (NQD) compound) 1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol), 20 parts by mass, a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd.) as the [F] component. “SH 8400 FLUID”) of 0.20 part by mass, and 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent as [G] component were mixed, and the pore size was 0.2 μm. The radiation sensitive resin composition (S-6) was prepared by filtering with a membrane filter.

<Evaluation of polyimide film>
(Example 6)
Using the respective radiation-sensitive resin compositions (S-1) to (S-6) prepared in Examples 1 to 5 and Comparative Example 1, the properties of the radiation-sensitive resin composition were as follows. And the characteristic of the polyimide film obtained by using them was evaluated. The evaluation results are summarized in Table 2 below.

(1) Evaluation of radiation sensitivity Hexamethyldisilazane (HMDS) was applied on a 550 × 650 mm chromium film and heated at 60 ° C. for 1 minute (hereinafter also referred to as “HMDS treatment”). On the chromium film-forming glass after this HMDS treatment, the respective radiation sensitive resin compositions (S-1) to (S-6) prepared in Examples 1 to 5 and Comparative Example 1 were slit die coater “ TR6320105-CL "was applied, the ultimate pressure was set to 100 Pa, and the solvent was removed under vacuum. Then, the coating film with a film thickness of 3.0 micrometers was formed by prebaking for 2 minutes at 90 degreeC further. Subsequently, using an MPA (registered trademark) -600FA exposure machine manufactured by Canon Inc., the coating film was irradiated with radiation with a proxy gap of 10 μm and a variable exposure amount through a mask having a contact hole pattern of 10 μm. did. Thereafter, development was performed at 25 ° C. for 70 seconds with a tetramethylammonium hydroxide aqueous solution having a developer concentration of 0.4 mass%. Next, washing with running ultrapure water was performed, followed by drying to form a pattern on the glass substrate after the HMDS treatment. At this time, the exposure amount closest to the contact hole diameter of 10 μm was defined as radiation sensitivity. When this value was 500 (J / m ² ) or less, it was judged that the radiation sensitivity was good.

(2) Evaluation of light resistance Using a spinner on a silicon substrate, each radiation-sensitive resin composition (S-1) to (S-6) prepared in Examples 1 to 5 and Comparative Example 1 Then, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a polyimide film. Each obtained polyimide film was irradiated with 800,000 J / m ² at an illuminance of 130 mW with a UV irradiation apparatus (“UVX-02516S1JS01” manufactured by Ushio). It can be said that the light resistance of the polyimide film is good when the amount of film thickness reduction after irradiation is 2% or less compared to the film thickness before irradiation.
In the light resistance evaluation, since the patterning of the polyimide film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the light resistance test, and the heating process were performed for evaluation.

(3) Evaluation of transmittance In the same manner as the evaluation of light resistance, the radiation-sensitive resin compositions (S-1) to (S-1) to (S) prepared in Examples 1 to 5 and Comparative Example 1 were formed on a silicon substrate. A coating film of S-6) was formed. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a polyimide film. About each obtained polyimide film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer ("150-20 type double beam" by Hitachi, Ltd.). At this time, it can be said that transparency is poor when it is less than 85%.

(4) Measurement of thermal weight loss of polyimide film Similar to the above light resistance evaluation, each radiation-sensitive resin composition (S) prepared in Examples 1 to 5 and Comparative Example 1 on a glass substrate. -1) to (S-6) were formed. This substrate was heated in a clean oven at 220 ° C. for 1 hour to form a polyimide film. Each of the obtained substrates having a polyimide film was cut into 1 cm square, heated to 230 ° C. with a temperature programmed desorption analyzer (TDS1200, manufactured by Denki Kagaku), and gas generated when held for 30 minutes. The amount was measured. The amount of gas generated from the polyimide film formed from the radiation sensitive resin composition (S-6) of the comparative example is defined as 100, and the relative values are used to determine the radiation sensitive resin composition (S-1) of the example. ) To (S-5) to evaluate the amount of gas generated from the polyimide film formed. In Table 2 below, which summarizes the evaluation results, the above-mentioned relative values are shown as the thermal weight loss. And when this relative value is 50 or less, it can be judged that there is little decrease in thermal weight, and it can be judged that the amount of gas generated from the polyimide film is small.

As shown in Table 2, the radiation sensitive resin compositions (S-1) to (S-5) of Examples 1 to 5 have good radiation sensitivity, and are formed using the polyimide. The film is excellent in patternability. These polyimide films have good light resistance, good transmittance characteristics, and a small amount of gas generated due to thermal decomposition or the like.
On the other hand, the radiation sensitive resin composition (S-6) of Comparative Example 1 was not good in radiation sensitivity, and the light resistance and transmittance of the formed polyimide film were not good.

DESCRIPTION OF SYMBOLS 1, 20, 102 Substrate 2, 2 'Coating 3 Mask 4 Radiation 5 Exposure part 6, 15, 110, 113 Polyimide film 11 Semiconductor element 12, 106 Semiconductor layer 13, 107 First source-drain electrode 14, 108 First 2 source-drain electrodes 16, 112 through-holes 21, 104 gate electrodes 22, 105 gate insulating film 101 organic EL display element 103 TFT
111 Anode 114 Organic Light-Emitting Layer 115 Cathode 116 Passivation Film 117 Sealing Layer 119 Inorganic Insulating Film 120 Sealing Substrate

Claims (10)

[A] A radiation-sensitive resin composition containing a polyimide precursor having a structural unit represented by the following formula (1), and [B] a photoacid generator ,
A radiation-sensitive resin composition, wherein A in the following formula (1) is at least one structure selected from the following formula (A-1) to the following formula (A-5) .

(In formula (1), A represents a tetravalent organic group, B represents a divalent organic group, and X ¹ and X ² are groups represented by the above formula (2).
In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atoms that the hydrocarbon group having 1 to 30 carbon atoms has Group substituted with a group, a halogen atom or a cyano group (provided that R ¹ and R ² are not both hydrogen atoms). R ³ is a hydroxyl group, a halogen atom or a cyano group in which a part of hydrogen atoms of an ether group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms is substituted. A substituted group. R ¹ and R ³ may be linked to form a ring. )

(In formula (A-1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents hydrogen, fluorine or an organic group having 1 to 4 carbon atoms.) Furthermore, the compound which has a [C] cyclic ether group is contained , The radiation sensitive resin composition of Claim 1 characterized by the above-mentioned. B of said Formula (1) is at least 1 type of structure chosen from following formula (B-1)-following formula (B-10) , The radiation sensitivity of Claim 1 or 2 characterized by the above-mentioned. Resin composition.

(In Formula (B-1) to Formula (B-8), R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group.) [B] The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the photoacid generator is a compound containing an oxime sulfonate group represented by the following formula (3) : .

(In Formula (3), R ⁶ is an alkyl group, a cycloalkyl group, or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.) Furthermore, [D] a base generator is contained , The radiation sensitive resin composition of any one of Claims 1-4 characterized by the above-mentioned. [A] a polyimide precursor having a structural unit represented by the following formula (1), and
[B] Photoacid generator
A radiation sensitive resin composition comprising:
Furthermore, [D] the radiation sensitive resin composition characterized by containing a base generator .

(In formula (1), A represents a tetravalent organic group, B represents a divalent organic group, and X ¹ and X ² are groups represented by the above formula (2).
In Formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atoms that the hydrocarbon group having 1 to 30 carbon atoms has Group substituted with a group, a halogen atom or a cyano group (provided that R ¹ and R ² are not both hydrogen atoms). R ³ is a hydroxyl group, a halogen atom or a cyano group in which a part of hydrogen atoms of an ether group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms is substituted. A substituted group. R ¹ and R ³ may be linked to form a ring. ) A polyimide film obtained by using the radiation-sensitive resin composition according to any one of claims 1 to 6. A semiconductor element comprising the polyimide film according to claim 7. An organic EL device comprising the polyimide film according to claim 7 . The organic EL element according to claim 9, comprising the semiconductor element according to claim 8.

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