JP6056644B2 - Semiconductor device, radiation-sensitive resin composition, cured film, and display device - Google Patents

Description

  The present invention relates to a semiconductor element, a radiation sensitive resin composition, a cured film, and a display element.

  A liquid crystal display element which is a display element is configured by sandwiching liquid crystal between a pair of substrates. An alignment film is provided on the surface of each substrate so as to control the alignment of the liquid crystal. Then, an orientation change is caused in the liquid crystal by applying an electric field between the substrates. In the liquid crystal display element, light is partially transmitted or shielded according to the change in the orientation of the liquid crystal. A liquid crystal display element can display an image using such characteristics. The liquid crystal display element has an advantage that it can be made thinner and lighter than a conventional CRT display element.

  The liquid crystal display elements at the beginning of development were used as display elements for calculators and clocks centered on character displays and the like. After that, the simple matrix method was developed, and the dot matrix display became easy. Subsequently, an active matrix liquid crystal display element was developed by developing a thin film transistor (TFT) which is a semiconductor element. And it has become possible to realize good image quality with excellent contrast ratio and response performance, and has also overcome problems such as high definition, colorization, and viewing angle expansion, so it can also be used for desktop computer monitors, etc. It came to be able to. Recently, a wider viewing angle, faster response of liquid crystal, improved display quality, and the like have been realized, and it has come to be used as a thin display element for television.

  In recent years, liquid crystal display elements are required to have higher performance, for example, a large screen for providing a large television, a flexible display using a flexible substrate, and the like. For this reason, high performance is also required for TFTs which are the main constituent elements of liquid crystal 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 has been studied so that it can be formed at a lower temperature, can be formed on a flexible substrate such as a resin substrate, and the desired mobility can be obtained. .

  For example, Patent Document 1 discloses a TFT technology that uses a transparent oxide semiconductor for a semiconductor layer. In the TFT described in Patent Document 1, 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.

JP 2006-165529 A

  However, a semiconductor using an oxide semiconductor for the semiconductor layer has a problem with light resistance. Specifically, in the case of a semiconductor layer using an oxide semiconductor, the semiconductor layer may have absorption in an ultraviolet region or the like. 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 liquid crystal display element, there is a problem that the characteristics deteriorate due to the influence of light from the outside.

  Such a problem of deterioration of characteristics due to light irradiation is a problem even in a semiconductor element using conventional amorphous silicon or the like as a semiconductor layer, although the degree of weight is different. Therefore, 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 such as a liquid crystal display element.

  The present invention has been made in view of the above problems. In other words, an object of the present invention is to provide a semiconductor element in which a deterioration in characteristics due to the influence of light is reduced.

  Moreover, the objective of this invention is providing the radiation sensitive resin composition used for formation of the cured film of the semiconductor element which reduced the characteristic fall by the influence of light.

  And the objective of this invention is providing the cured film of the semiconductor element which reduced the characteristic fall by the influence of light.

  Furthermore, the objective of this invention is providing the display element which has a semiconductor element which reduced the characteristic fall by the influence of light.

A first aspect of the present invention is a semiconductor layer formed using an oxide containing at least one of indium (In), zinc (Zn), and tin (Sn), and a first surface of the semiconductor layer A semiconductor element having an electrode provided on
A cured film is disposed between the semiconductor layer and the electrode,
The cured film has at least one cross-linked moiety represented by the following formula (1A-1) to the following formula (1A-9).

（式（１Ａ−７）〜式（１Ａ−９）中、Ｒ^０は、水素原子、炭素数１〜６のアルキル基またはフェニル基を示す。）

(In Formula (1A-7) to Formula (1A-9), R ⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.)

In the first aspect of the present invention, the cured film comprises:
[A] a polymer having a structural unit containing a group represented by the following formula (1B) and a structural unit containing an epoxy group in the same or different polymer molecules, and [B] a feeling containing a photoacid generator It is preferably formed using a radiation resin composition.

（式（１Ｂ）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とが連結して環状エーテルを形成してもよい。）

(In Formula (1B), each of R ¹ and R ² independently represents 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 (provided that R ¹ and R ² are not both hydrogen atoms) R ³ is an ether group having 1 to 30 carbon atoms and 1 carbon atom A group in which a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms is substituted with a hydroxyl group, a halogen atom or a cyano group, and R ¹ and R ³ are linked to each other. (Cyclic ethers may be formed.)

In the first aspect of the present invention, the cured film is provided with a through hole,
The first surface of the semiconductor layer and the electrode are preferably connected to each other through the through hole.

  In the first embodiment of the present invention, the semiconductor layer is formed using at least one of zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO). It is preferred that

  1st aspect of this invention WHEREIN: It is preferable that a [B] photo-acid generator contains the oxime sulfonate group represented by following formula (2).

（式（２）中、Ｒ^Ｂ１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 (2), R ^B1 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.)

  1st aspect of this invention WHEREIN: It is preferable that a cured film contains a [C] ultraviolet absorber.

  1st aspect of this invention WHEREIN: It is preferable that a [C] ultraviolet absorber contains 1 type chosen from the group which consists of a compound represented by following formula (3-1) and following formula (3-2). .

（式（３−１）および式（３−２）中、Ｒ^１１〜Ｒ^２５は、各々独立に、水素、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のベンゾイロキシ基または水酸基を表す。）

(In Formula (3-1) and Formula (3-2), R ^{11 to} R ²⁵ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 represents a benzoyloxy group or a hydroxyl group.)

In the first aspect of the present invention, a gate electrode provided on the second surface of the semiconductor layer via a gate insulating film;
It is preferable to form a bottom gate type semiconductor element having a source electrode and a drain electrode provided on the first surface.

  A second aspect of the present invention relates to a radiation-sensitive resin composition that is used for forming a cured film of a semiconductor element according to the first aspect of the present invention.

  A third aspect of the present invention relates to a cured film formed from the radiation-sensitive resin composition of the second aspect of the present invention.

  A fourth aspect of the present invention relates to a display element using the semiconductor element of the first aspect of the present invention.

  According to the first aspect of the present invention, it is possible to obtain a semiconductor element with reduced characteristic deterioration due to the influence of light.

  According to the 2nd aspect of this invention, the radiation sensitive resin composition used for formation of the cured film of the semiconductor element which reduced the characteristic fall by the influence of light is obtained.

  According to the 3rd aspect of this invention, the cured film of the semiconductor element which reduced the characteristic fall by the influence of light is obtained.

  According to the fourth aspect of the present invention, it is possible to obtain a display element having a semiconductor element with reduced characteristic deterioration due to the influence of light.

It is sectional drawing which illustrates the structure of the semiconductor element of this embodiment typically. It is a top view which illustrates typically the principal part structure of the semiconductor substrate of this embodiment. It is sectional drawing which illustrates typically the principal part structure of the liquid crystal display element of this embodiment.

Below, the semiconductor element of embodiment of this invention is demonstrated. Next, a semiconductor substrate configured using the semiconductor element and a liquid crystal display element as a display element having the semiconductor element will be described.
In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

Embodiment 1. FIG.
<Semiconductor element>
FIG. 1 is a cross-sectional view schematically illustrating the structure of the semiconductor device of this embodiment.

FIG. 1 shows an example in which the semiconductor element 1 of this embodiment is provided on one surface of a substrate 10.
The semiconductor element 1 has a semiconductor layer 2 and an electrode provided on the first surface, which is the upper surface of the semiconductor layer 2 in FIG. The electrode includes a source electrode 3 and a drain electrode 4.

  The semiconductor element 1 has a cured film 5 disposed between a semiconductor layer 2 and a source electrode 3 and a drain electrode 4. As will be described in detail later, the cured film 5 is made of a resin. Accordingly, the through hole 6 is provided in the cured film 5, and the electrical connection between the first surface of the semiconductor layer 2 and the source electrode 3, and the electrical connection between the first surface of the semiconductor layer 2 and the drain electrode 4. Each connection is configured to be made through a corresponding through hole 6.

  A semiconductor element 1 in FIG. 1 has a gate electrode 11 on a second surface, which is a lower surface in FIG. 1, of a semiconductor layer 2 via a gate insulating film 12. That is, in the semiconductor element 1, the gate electrode 11 is disposed on the substrate 10, and the gate insulating film 12 is formed on the gate electrode 11. The semiconductor layer 2 is disposed on the gate electrode 11 via the gate insulating film 12 and has a source electrode 3 and a drain electrode 4 connected to the semiconductor layer 2. The semiconductor element 1 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 source electrode and a drain electrode connected to the first surface are arranged on the first surface to be a top gate type. It is also possible.

  In the semiconductor device 1 shown in FIG. 1, the gate electrode 11 can be formed by forming a metal thin film on the substrate 10 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 11 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 11 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 11 is preferably 10 nm to 1000 nm.

The gate insulating film 12 disposed so as to cover the gate electrode 11 can be formed by forming an oxide film or a nitride film by sputtering, CVD, vapor deposition, or the like. The gate insulating film 12 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 12 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.

After the source electrode 3 and the drain electrode 4 connected to the semiconductor layer 2 are formed by using a method such as a sputtering method, a CVD method, or a vapor deposition method in addition to a printing method or a coating method, a conductive film constituting the electrodes, It can be formed by patterning using a photolithography method or the like. Examples of the constituent material of the source electrode 3 and the drain electrode 4 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag, alloys such as Al—Nd and APC, tin oxide, zinc oxide, and indium oxide. And conductive metal oxides such as ITO, IZO, AZO (aluminum-doped zinc oxide), and GZO (gallium-doped zinc oxide), and conductive organic compounds such as polyaniline, polythiophene, and polypyrrole. .
The thicknesses of the source electrode 3 and the drain electrode 4 are preferably 10 nm to 1000 nm.

  The semiconductor layer 2 of the semiconductor element 1 of the present embodiment is formed by using a silicon (Si) material such as a-Si (amorphous-silicon), p-Si (poly-silicon), or microcrystalline silicon, for example. can do.

  Moreover, the semiconductor layer 2 of the semiconductor element 1 of this embodiment can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 2 of the present embodiment include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  As an amorphous oxide applicable to the semiconductor layer 2, an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn) can be given.

  Specific examples of the amorphous oxide applicable to the semiconductor layer 2 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 2 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 2 using the amorphous oxide is preferably 1 nm to 1000 nm.
By using the oxides exemplified above, the semiconductor layer 2 having high mobility can be formed at a low temperature, and the semiconductor element 1 of this embodiment can be provided.

As oxides particularly preferable for forming the semiconductor layer 2 of the semiconductor element 1 of the present 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 1 has the semiconductor layer 2 having excellent mobility formed at a lower temperature, and can exhibit a high ON / OFF ratio.

  In the semiconductor element 1 of this embodiment, a cured film 5 is disposed between the semiconductor layer 2 and the source electrode 3 and the drain electrode 4. The cured film 5 of the present embodiment is an insulating film formed from the radiation-sensitive resin composition of the embodiment of the present invention including a polymer and a photoacid generator, which will be described in detail later.

  The cured film 5 is formed by applying the radiation sensitive resin composition of the embodiment of the present invention on the substrate 10 on which the gate electrode 11, the gate insulating film 12, the semiconductor layer 2, and the like are formed, and forming the through holes 6. After the necessary patterning, it is formed by heat curing. The formed cured film 5 can include a photoacid generator having an absorptivity for light such as ultraviolet rays, and in that case, excellent light shielding properties can be realized. Furthermore, the cured film 5 can also be configured to contain an ultraviolet absorber.

  Therefore, the semiconductor element 1 of this embodiment having the cured film 5 between the semiconductor layer 2 and the source electrode 3 and the drain electrode 4 can shield the semiconductor layer 2 due to the effect of the cured film 5. And the semiconductor element 1 of this embodiment can reduce the fall of the characteristic by the influence of light by the light-shielding effect of the cured film 5. FIG.

  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 1 of the present embodiment uses a cured film 5 containing a suitably selected photoacid generator, so that the balance between visible light transparency (transparency) and light shielding properties required for liquid crystal display elements and the like is achieved. Can be suitably controlled.

  As will be described later, the radiation-sensitive resin composition of the embodiment of the present invention can have a so-called positive radiation sensitivity. The photoacid generator contained in the radiation-sensitive resin composition generates an acid upon irradiation with radiation such as ultraviolet rays, thereby enabling patterning of a formed cured film and formation of a through hole. In that case, the photoacid generator is contained in the cured film remaining after patterning or the like. The photoacid generator contained in the cured film can impart a protection function against light to the cured film.

  As described above, in the semiconductor element 1 of the present embodiment, the cured film 5 exhibits a specific effect and becomes a main constituent element. Then, next, the cured film 5 of the semiconductor element 1 of this embodiment and its formation will be described in more detail. In particular, the radiation sensitive resin composition used for forming the cured film 5 will be described in detail.

<Curing film>
As will be described later, the cured film is formed using a positive radiation-sensitive composition containing [A] a specific polymer and [B] a photoacid generator, and is composed of a resin. . And a cured film has the bridge | crosslinking part by which resin which comprises the cured film is represented by following formula (1A-1)-following formula (1A-9). In the semiconductor element of the present embodiment described above, a cured film having a crosslinked portion represented by the following formula (1A-1) to the following formula (1A-9) between the semiconductor layer and the source electrode and the drain electrode. By providing, it has the outstanding heat resistance and light resistance, As a result, the semiconductor element of this embodiment can have high reliability.

In the above formula (1A-7) to the above formula (1A-9), R ⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

  The crosslinked part represented by the above formula (1A-1) to the above formula (1A-9) is, for example, a polymer having a functional group such as a carboxyl group and an epoxy group, as represented by the following reaction formulas. It is formed by thermally cross-linking with a polymer having a hydrogen atom, or by thermally cross-linking between polymers having a carboxyl group and an epoxy group in one molecule. The functional group such as the carboxyl group corresponds to, for example, a group in which a protecting group represented by the following formula (1B) is deprotected with an acid.

In the above formula (1B), 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 cyclic ether.

<Radiation sensitive resin composition>
In the semiconductor element of the present embodiment, the radiation-sensitive resin composition of the present embodiment, which is disposed between the semiconductor layer and the source electrode and the drain electrode and used for manufacturing a cured film serving as a constituent member, is [A]. Contains a specific polymer (hereinafter sometimes simply referred to as “[A] polymer”) and [B] a photoacid generator (hereinafter sometimes simply referred to as “[B] component”). To do. The radiation sensitive resin composition of the present embodiment can be used as a positive radiation sensitive resin composition.

  And the radiation sensitive resin composition of this embodiment can contain a [C] ultraviolet absorber (Hereinafter, it may only be called "[C] component."). Furthermore, the [D] compound described in detail later (hereinafter sometimes referred to simply as “[D] component”) can be contained, and other optional components (unless it impairs the effects of the present invention). Hereinafter, it may be simply referred to as “[E] component”). The radiation sensitive resin composition of the present embodiment has the above composition and can provide a film having both excellent patterning properties and light shielding properties after formation. About the radiation sensitive resin composition of this embodiment, the detail of each component which it contains is demonstrated below.

<[A] Specific polymer>
[A] A specific polymer (hereinafter referred to as [A] polymer) is a structural unit containing a group represented by the following formula (1B) in the same or different polymer molecule (hereinafter simply referred to as “ It is also referred to as “structural unit (1)”) and an epoxy group-containing structural unit, and may have other structural units as necessary.

[A] The embodiment of the polymer is not particularly limited,
(I) When both the structural unit (1) and the epoxy group-containing structural unit are contained in the same polymer molecule, and [A] one polymer molecule is present in the polymer;
(Ii) having a structural unit (1) in one polymer molecule, and having both an epoxy group-containing structural unit in a different polymer molecule, and [A] two kinds of structural units in the polymer When polymer molecules are present;
(Iii) having both the structural unit (1) and the epoxy group-containing structural unit in one polymer molecule, and having the structural unit (1) in a polymer molecule different from the structural unit (1). When the polymer molecule has an epoxy group-containing structural unit, and [A] three polymer molecules are present in the polymer;
(Iv) In addition to the polymer molecules specified in (i) to (iii), there may be mentioned a case where [A] the polymer further contains one or more polymer molecules.

In the above formula (1B), 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 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 cyclic ether.

In the above formula (1B), 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 (1B), 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, examples of the further substituent include the above alkyl groups.

In the above formula (1B), the ether group having 1 to 30 carbon atoms represented by R ³ 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.

A group obtained by substituting a part of hydrogen atoms of a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms constituting the ether group 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 (1B), 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.

  The structural unit (1) can have an acetal structure or a ketal structure by having a functional group that has an acetal structure or a ketal structure by bonding to another carbon atom.

  Examples of the functional group that should have an acetal structure by bonding to the other carbon atom include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i, and the like. -Propoxyethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (Cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) meth Si group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) ) Methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) ) Methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy The group (benzyl) (i- (Ropoxy) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, 1 -A trimethylsilanyloxyethoxy group, 1-trimethylgermyloxyethoxy group, etc. are mentioned.

  Of these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, and 1-n-propoxyethoxy group are preferable.

  Examples of the functional group having a ketal structure by bonding to the other carbon atom include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl- 1-n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1- sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxy Ethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-naphth Ruoxy) ethoxy group, 1-methyl-1-benzyloxyoxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1- Cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyl Oxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, A phenyl-1-cyclohexyloxyethoxy group, -Phenyl-1-phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxy Ethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2- (2-Methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like can be mentioned.

  Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are preferable.

  Specific examples of the structural unit (1) having the acetal structure or ketal structure include structural units represented by the following formulas (1-1) to (1-3).

In the above formulas (1-1) and (1-3), R ′ is a hydrogen atom or a methyl group. R ¹ , R ² and R ³ have the same meanings as described for the formula (1).

As a monomer having radical polymerizability that gives the structural unit (1) represented by the above formulas (1-1) to (1-3) (hereinafter also simply referred to as “acetal structure-containing monomer”). For example, 1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydro (Meth) acrylate-based acetal structure-containing monomers such as pyranyl (meth) acrylate;
2,3-di (1- (trialkylsilanyloxy) alkoxycarbonyl) -5-norbornene, 2,3-di (1- (trialkylgermyloxy) alkoxycarbonyl) -5-norbornene, 2,3- Di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-norbornene, 2,3-di (1- (aralkyloxy) alkoxycarbonyl)- Norbornene-based acetal structure-containing monomers such as 5-norbornene;
Examples thereof include styrene acetal structure-containing monomers such as 1-alkoxyalkoxystyrene, 1- (haloalkoxy) alkoxystyrene, 1- (aralkyloxy) alkoxystyrene, and tetrahydropyranyloxystyrene.

  Among these, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene, and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable.

Specific examples of the acetal structure-containing monomer that gives the structural unit (1) include, for example,
1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2 -Ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate,
1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) ethyl acrylate, 1- (2 -Ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate,
2,3-di (1- (trimethylsilanyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1- (trimethylgermyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di ( 1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene ,
p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- ( 1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (2-ethylhexyloxy) ethoxystyrene, p or m-1-n-propoxyethoxy Examples include styrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene.

  The structural unit (1) can be used alone or in combination of two or more.

  Among the acetal structure-containing monomers that give the structural unit (1), 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 1-benzyloxyethyl methacrylate are preferable.

  A commercially available thing may be used for the acetal structure containing monomer which gives structural unit (1), and what was synthesize | combined by the well-known method can also be used. For example, the acetal structure-containing monomer that gives the structural unit (1) represented by the above formula (1-1) reacts (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown below. Can be synthesized.

(Wherein, R ', ^{R 1} and ^{R 3} each R in the above formula (1-1)' corresponds to, ^{R 1} and ^{R 3, R 5} and ^{R 6,} -CH ^(R 5) (R ⁶ ) corresponds to R ² in the above formula (1-1).)

  [A] The content of the structural unit (1) in the polymer is not particularly limited as long as the polymer [A] is alkali-soluble by acid and exhibits the desired heat resistance of the cured film. When the polymer molecule contains the structural unit (1) and the epoxy group-containing structural unit, the monomer charge ratio is preferably 5% by mass to 70% by mass with respect to all the structural units contained in the [A] polymer. 10 mass%-60 mass% are more preferable, and 20 mass%-50 mass% are especially preferable.

  On the other hand, when one polymer molecule has the structural unit (1) and another polymer molecule has an epoxy group-containing structural unit, the structural unit in the one polymer molecule having the structural unit (1) The content of (1) is preferably 40% by mass to 99% by mass and more preferably 50% by mass to 98% by mass with respect to the total structural units contained in the polymer molecule. 55 mass% to 95 mass% is particularly preferable.

<Epoxy group-containing structural unit>
[A] A polymer has an epoxy group containing structural unit with the above-mentioned structural unit (1). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer having radical polymerizability, and contains an epoxy group. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). [A] Since the polymer has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the hardness of the cured film obtained from the radiation-sensitive resin composition of the present embodiment is improved and the heat resistance is further increased. be able to.

Specific examples of the epoxy group-containing monomer that gives the above-described epoxy group-containing structural unit include, for example,
Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -3-methyl-3,4-epoxybutyl acrylate, -3-ethyl-3 methacrylate , 4-epoxybutyl, acrylic acid-5,6-epoxyhexyl, methacrylic acid-5,6-epoxyhexyl, methacrylic acid-5-methyl-5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6 -Epoxyhexyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,
3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohex Xylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4 -Oxylanyl group-containing (meth) acrylic compounds such as epoxycyclohexylpropyl acrylate, 3,4-epoxycyclohexylbutyl acrylate, 3,4-epoxycyclohexylhexyl acrylate;
o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3 -Phenyloxetane,
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -3-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3 -Phenyloxetane,
2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane,
2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -2-ethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2 -Oxetanyl group containing (meth) acrylic compounds, such as phenyl oxetane, etc. are mentioned.

  The said epoxy group containing structural unit can be used individually or in combination of 2 or more types.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3-Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane improve copolymerization reactivity with other radical polymerizable monomers and developability of the radiation-sensitive resin composition. It is preferable from the viewpoint.

  [A] The content of the epoxy group-containing structural unit in the polymer is not particularly limited as long as the desired heat resistance of the cured film is exhibited, but the structural unit (1) and the epoxy group are included in one polymer molecule. In the case of containing the containing structural unit, the monomer charge ratio is preferably 10% by mass to 60% by mass, and more preferably 15% by mass to 55% by mass with respect to all the structural units contained in the [A] polymer. 20 mass% to 50 mass% is particularly preferable.

  On the other hand, when one polymer molecule has a structural unit (1) and another polymer molecule has an epoxy group-containing structural unit, it is included in one polymer molecule having an epoxy group-containing structural unit. As content of the epoxy group containing structural unit with respect to all the structural units, 10 mass%-80 mass% are preferable by monomer preparation ratio, 20 mass%-70 mass% are more preferable, 25 mass%-60 mass% Is particularly preferred.

<Other structural units>
Examples of the radical polymerizable monomer that gives other structural units include a carboxyl group or a derivative thereof, a radical polymerizable monomer having a hydroxyl group, and the like.

Examples of the radical polymerizable monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalate. Acids, monocarboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. are mentioned.

Examples of the radical polymerizable monomer having a hydroxyl group include
Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethylcyclohexylmethyl ester;
Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6-hydroxyhexyl ester, methacrylic acid-4- And methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

  Among these radical polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester, from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and heat resistance such as a cured film obtained, Acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid -4-Hydroxymethyl-cyclohexylmethyl ester is preferred.

Examples of other radical polymerizable monomers include
Alkyl acrylates such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6} ] decano-8-yloxy) ethyl, methacrylic acid alicyclic alkyl esters such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates containing 1 atom of oxygen, such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;

4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Unsaturated heterocyclic 5-membered methacrylates containing:
4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxola Unsaturated five-membered heterocyclic acrylic acid esters containing oxygen 2 atoms and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1, Radical polymerizability in which 3-butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate, etc. have the above reactive functional groups It is preferable at the point which makes the copolymerization reactivity with a monomer, and the developability of a radiation sensitive resin composition favorable.

[A] The polystyrene-reduced mass average molecular weight (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably. It is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. [A] By making Mw of a polymer into the said range, the radiation sensitivity and alkali developability of the radiation sensitive resin composition of this embodiment can be improved.

Moreover, the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene by GPC (gel permeation chromatography) of the [A] polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ . Preferably it is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. By setting the Mn of the copolymer within the above range, the curing reactivity during curing of the coating film of the radiation-sensitive resin composition of the present embodiment can be improved.

  Furthermore, the molecular weight distribution (hereinafter referred to as “Mw / Mn”) of the polymer [A] is preferably 3.0 or less, more preferably 2.6 or less. [A] By setting Mw / Mn of the polymer to 3.0 or less, the developability of the resulting cured film can be improved. [A] The radiation-sensitive resin composition containing a polymer can easily form a desired pattern shape without causing a development residue during development.

<[A] Production method of polymer>
[A] The polymer can be produced by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer, and other monomers that give structural units. In the case of producing the [A] polymer containing both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule, a mixture containing at least an acetal structure-containing monomer and an epoxy group-containing monomer May be used for copolymerization. On the other hand, when the [A] polymer having the structural unit (1) in one polymer molecule and the epoxy group-containing structural unit in a different polymer molecule is produced, at least an acetal structure-containing monomer A polymer solution containing the structural unit (1) is obtained by radical polymerization of a polymerizable solution containing, and a polymer solution containing at least an epoxy group-containing monomer is radically polymerized to have an epoxy group-containing structural unit. What is necessary is just to obtain a polymer molecule | numerator and finally mix both to make [A] polymer.

  [A] Examples of the solvent used in the polymerization reaction for producing the polymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

[A] As the polymerization initiator used in the polymerization reaction for producing the polymer, those known as radical polymerization initiators can be used. Examples of radical polymerization initiators include:
2,2′-azobisisobutyronitrile, 2,2′-azobis (methyl 2-methylpropionate), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis -Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile);
Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane;
And hydrogen peroxide.

<[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 [B] a photoacid generator, exhibits positive radiation-sensitive characteristics, and can be used as a positive-type radiation-sensitive resin composition. [B] The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic 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] Photoacid generating groups incorporated as part of polymers or other polymers, or both forms.

  [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 (2) is preferable.

In the above formula (2), R ^B1 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 (2), the alkyl group of R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 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. The aryl group for R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ^B1 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 (2) is more preferably an oxime sulfonate compound represented by the following formula (2-1).

In the above formula (2-1), R ^B1 has the same ^{meaning as} the description of R ^B1 in the formula (2). 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.

  In the above formula (2-1), 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 (2-1), 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 (2) include, for example, compounds (2-1-i) represented by the following formulas (2-1-i) to (2-1-v), respectively. , Compound (2-1-ii), compound (2-1-iii), compound (2-1-iv), compound (2-1-v) and the like.

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

<Sulfonimide compound>
[B] As a preferred sulfonimide compound 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- Trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphor Sulfonyloxy) 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-dicarbo Silimide, 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-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, 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-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Carboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methyl Phenylsulfonyloxy) 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-trifluoromethylphenyls Phonyloxy) 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- (heptylsulfo) Nyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide and the like.

  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 (2). The compound which performs is more preferable, and the oxime sulfonate compound represented by the said Formula (2-1) is further more preferable. Among them, [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5H-octylsulfonyloxyimino-5H-thiophene-2-), which are commercially available. Ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(camphorsulfonyloxyimino-5H- Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile] are particularly preferred.

  [B] One photoacid generator may be used alone, or two or more photoacid generators may be mixed and used. The content as [B] photoacid generator in the radiation sensitive resin composition of the present embodiment is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymer [A]. 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 and a cured film can be formed.

<[C] UV absorber>
The radiation sensitive resin composition of this embodiment contains the above-mentioned [A] specific polymer and [B] photoacid generator as essential components. And [C] an ultraviolet absorber can be contained with them. [C] By containing the ultraviolet absorber, the radiation-sensitive resin composition of the present embodiment can enhance ultraviolet absorption in the cured film after formation. And the influence of the ultraviolet-ray in a semiconductor element can be reduced.

  [C] The ultraviolet absorber is preferably a compound having absorption at 300 nm to 400 nm. [C] The ultraviolet absorber is not particularly limited as long as it has an absorption band in the above-mentioned range, and in particular, [C] a benzotriazole having an absorption band in the above-mentioned range as an easily available ultraviolet absorber. A compound, a benzophenone compound and the like are preferably used.

  A benzotriazole-based compound is a compound having a structure represented by the following formula (3-1). A benzophenone-based compound is a compound represented by the following formula (3-2).

In the above formula (3-1) and the above formula (3-2), R ^{11 to} R ²⁵ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 benzoyloxy groups or hydroxyl groups are represented.

  Specific examples of such benzotriazole compounds include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5- Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, and the like. These benzotriazole compounds may be used alone or in combination of two or more.

  Specific examples of such benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate. 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2,2'- And dihydroxy-4,4′-dimethoxybenzophenone. These benzophenone compounds may be used alone or in combination of two or more.

  It is preferable that the usage-amount of the [C] ultraviolet absorber in the radiation sensitive resin composition of this embodiment is the range of 0.01 mass part-30 mass parts with respect to 100 mass parts of [A] polymers. In particular, it is preferably used in the range of 0.1 to 20 parts by mass. When it is 0.01 part by mass or less, the resulting cured film has a poor shielding effect against ultraviolet rays, and when it is 30 parts by mass or more, the radiation sensitivity of the radiation-sensitive resin composition of the present embodiment is lowered, and pattern formation is performed. May cause trouble.

<[D] Compound>
The radiation-sensitive resin composition of the present embodiment used for forming the cured film of the semiconductor element of the present embodiment contains the above-described [A] specific polymer and [B] photoacid generator as essential components. In addition to the [C] ultraviolet absorber, a [D] compound can be contained.

  [D] A compound is a compound which functions as a hardening | curing agent which accelerates | stimulates hardening of the coating film formed from a radiation sensitive resin composition. Therefore, for the sake of convenience, it may be referred to as [D] compound (curing agent) or simply [D] curing agent. [D] The compound is at least one compound selected from the group consisting of a compound represented by the following formula (4), a phosphonium salt, a thiol compound, and a blocked isocyanate compound. When the radiation sensitive resin composition contains the [D] compound selected from the specific compound group, the curing temperature of the cured film can be more effectively lowered. By containing the [D] compound, the radiation-sensitive resin composition of the present embodiment can produce a cured film at a curing temperature of 200 ° C. or lower, such as 180 ° C. to 200 ° C., for example. Hereinafter, each compound which is a [C] compound is explained in full detail.

[Compound represented by Formula (4)]
[D] The compound is preferably at least one compound selected from the group consisting of compounds represented by the following formula (4). By selecting the above-mentioned specific compound having an amino group and an electron-deficient group as the [D] compound, the curing temperature of the cured film can be lowered more effectively.

In said formula (4), R < ²⁷ > -R < ³⁶ > is a hydrogen atom, an electron withdrawing group, or an amino group each independently. However, at least one of R ^{27 to} R ³⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with an alkylene group having 2 to 6 carbon atoms. Y is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group.

Examples of the electron-withdrawing group represented by R ^{27 to} R ^{36 in} the above formula (4) include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, an alkylsulfonyl group, and an alkyloxysulfonyl group. , Dicyanovinyl group, tricyanovinyl group, sulfonyl group and the like. Of these, a nitro group, an alkyloxysulfonyl group, and a trifluoromethyl group are preferable. The group represented by Y is preferably a sulfonyl group or a methylene group which may be substituted with a fluoroalkyl group.

  Examples of the compound represented by the above formula (4) include 2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, and 4,4′-diaminobenzophenone. 4,4′-diaminophenylbenzoate and 4,4′-diaminodiphenylsulfone are preferred, and 4,4′-diaminodiphenylsulfone and 2,2-bis (4-aminophenyl) hexafluoropropane are more preferred.

  The compounds represented by the above formula (4) can be used alone or in admixture of two or more. As a content rate of the compound represented by the said Formula (4), 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 0.2 mass part-10 mass parts are. More preferred. By making the content rate of the compound represented by the said Formula (4) into the said range, effective hardening acceleration | stimulation of the insulating film formed from a radiation sensitive resin composition is realizable.

[Phosphonium salt]
As the phosphonium salt, at least one selected from the group consisting of compounds represented by the following formula (5) can be used.

In the above formula (5), A ¹ is a phosphorus atom. R ^{41 to} R ⁴⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted. Q ⁻ is a monovalent anion.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁴ in the above formula (5) include a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, Examples include hexyl, heptyl, octyl, nonyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ^{41 to} R ⁴⁴ in the above formula (5) include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ^{41 to} R ⁴⁴ in the above formula (5) include a benzyl group and a phenethyl group.

Examples of the monovalent anion represented by Q ⁻ in the formula (5) include chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, Chlorate ion, chlorate ion, perchlorate ion, permanganate ion, bicarbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carboxylate ion, sulfonate ion, phenoxide ion, tetrafluoroborate Ions, tetraarylborate ions, hexafluoroantimonate ions, and the like.

  Examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, and tetraphenylphosphonium tetra (p-methoxyphenyl). ) Borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-tert-butoxyphenyl) borate, tetraphenylphosphonium tetra (m-tolyl) borate, tetraphenylphosphonium tetra (m -Methoxyphenyl) borate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra (p-tolyl) phosphonium tetra (p-to) E) borate, tri (p-methoxyphenyl) phenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltriphenylphosphonium thiocyanate, p-tolyltriphenylphosphonium thiocyanate .

  Of these phosphonium salts, butyltriphenylphosphonium thiocyanate is preferred. A phosphonium salt can be used individually or in mixture of 2 or more types. As a content rate of the phosphonium salt in a radiation sensitive resin composition, 0.05 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 0.1 mass part-5 mass parts are more. preferable. By setting the content ratio of the phosphonium salt within the above specific range, curing of the radiation-sensitive resin composition can be promoted.

[Thiol compound]
The thiol compound is a compound having two or more mercapto groups in one molecule. The thiol compound is not particularly limited as long as it has two or more mercapto groups in one molecule, but at least one selected from the group consisting of compounds represented by the following formula (6) may be used. it can.

In the above formula ^{(6), R 51} is a methylene group, an alkylene group having 2 to 10 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted with alkyl groups. Y ¹ is a single bond, —CO— or —O—CO— ^* . However, the bond marked with “*” is bonded to R ⁵¹ . n is an integer of 2-10. A ² is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or a group represented by the following formula (7) when n is 3. is there.

In the above formula ^{(7), R} 52 ~R ⁵⁴ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms. “*” Represents a bond.

  As the compound represented by the above formula (6), typically, an esterified product of mercaptocarboxylic acid and a polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylolpropane, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, and pentaerythritol.

  Examples of the compound represented by the above formula (6) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione preferable.

  As the compound having two or more mercapto groups in one molecule of the thiol compound, compounds represented by the following formula (8) to the following formula (10) can also be used.

In said formula (8), ^R61 is a methylene group or a C2-C20 alkylene group. ^R62 is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms. k is an integer of 1-20.

In the formula (9), R ^{63 to} R ⁶⁶ are each independently a hydrogen atom, a hydroxyl group or a group represented by the following formula (10). However, at least one of R ^{63 to} R ⁶⁶ is a group represented by the following formula (10).

In said formula (10), ^R67 is a methylene group or a C2-C6 linear or branched alkylene group.

  A thiol compound can be used individually or in mixture of 2 or more types. As a content rate of the thiol compound in a radiation sensitive resin composition, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 5 mass parts-15 mass parts are more preferable. By setting the content ratio of the thiol compound within the above specific range, it is possible to realize the acceleration of curing of the radiation-sensitive resin composition.

[Block isocyanate compounds]
A block polyisocyanate compound is a compound in which an isocyanate group is reacted with an active hydrogen group-containing compound (blocking agent) to make it inactive at room temperature. When heated, the blocking agent dissociates and the isocyanate group is regenerated. It has something. When the radiation-sensitive resin composition contains the block polyisocyanate, the isocyanate-hydroxyl crosslinking reaction proceeds as an effective crosslinking agent, and the curing of the radiation-sensitive resin composition can be realized.

  The block polyisocyanate compound is obtained by a known reaction between a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (blocking agent).

  Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl-1,6-di- Isocyanatohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, tolidine diisocyanate, xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate Sulfonates, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate.

As a commercial item, for example,
As an isocyanate group blocked with an oxime of methyl ethyl ketone, Duranate (registered trademark) TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (above, Asahi Kasei Kogyo) Company);
As an isocyanate group blocked with active methylene, Duranate (registered trademark) MF-K60X (Asahi Kasei Kogyo Co., Ltd.);
Examples of the block body of an isocyanate compound having a (meth) acryloyl group include Karenz (registered trademark) MOI-BP and Karenz (registered trademark) MOI-BM (shown above, Showa Denko KK).

  Among these, when using Duranate (registered trademark) E402-B80T and MF-B60X, high flexibility is manifested, and its hardness can be controlled freely by using it in a mixed system with others. Is preferable.

  Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, and allophanate type polyisocyanate. From the viewpoint of curability, isocyanurate type polyisocyanate is preferable.

  Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, oxime compounds, Examples include amine compounds, imine compounds, and pyridine compounds.

Examples of alcohol compounds include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like;
Examples of phenolic compounds include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester, and the like;
Examples of active methylene compounds include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like;
Examples of mercaptan compounds include butyl mercaptan and dodecyl mercaptan;
Examples of acid amide compounds include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and the like;
Examples of the acid imide compound include succinimide and maleic imide;
Examples of the imidazole compound include imidazole and 2-methylimidazole;
Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-ethylpyrazole and the like;
Examples of urea compounds include urea, thiourea, ethylene urea, and the like;
Examples of oxime compounds include formaldoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like;
Examples of amine compounds include diphenylamine, aniline, carbazole and the like;
Examples of the imine compound include ethyleneimine and polyethyleneimine;
Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

  A block polyisocyanate compound can be used individually or in mixture of 2 or more types. As a content rate of the block polyisocyanate compound in a radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymers, and 0.5 mass part-5 mass parts. Is more preferable. By making the content rate of a block polyisocyanate compound into the said range, hardening acceleration of a radiation sensitive resin composition is realizable.

<Other optional components>
In addition to the above-mentioned [A] polymer and [B] photoacid generator, the radiation-sensitive resin composition of the present embodiment includes [C] ultraviolet absorber and [D] compound (curing agent), [E ] As a component, a thermal acid generator and other arbitrary components can be contained.

  The thermal acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when the resin is cured by applying heat.

  The radiation-sensitive resin composition of the present embodiment includes other optional components such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver as necessary, as long as the effects of the present invention are not impaired. Can be contained. 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 used for the production of the semiconductor element of the present embodiment is added as necessary in addition to the above [A] polymer and [B] photoacid generator, [ C] It is prepared by mixing an ultraviolet absorber, a [D] compound (curing agent), and other optional components as the [E] component. 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 the present embodiment is preferably prepared and used in a state of being dissolved or dispersed in an appropriate solvent. For example, in a solvent, the [A] component ([A] polymer), the [B] component ([B] photoacid generator), and the optional [C] component ([C] UV absorber) The [D] component ([D] compound (curing agent)), the [E] component, and the like are mixed at a predetermined ratio to prepare a radiation sensitive resin composition.

  The solid content concentration of the radiation-sensitive resin composition of this embodiment (refers to the ratio of the mass of the polymer contained in the polymer solution to the total mass of the polymer 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%. Actually, in the above concentration range, a solid content concentration (a component other than the solvent in the composition solution) corresponding to a desired film thickness value or the like is set.

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

<Solvent>
As a solvent which can be used for preparation of the radiation sensitive resin composition of this embodiment, as above-mentioned, what melt | dissolves or disperse | distributes each component uniformly and does not react with each component is used suitably. Examples of such solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate. , Aromatic hydrocarbons, ketones, esters and the like.

These solvents include
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

  Among these solvents, ethers such as dialkyl ethers, diethylene glycol alkyls, etc. from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, and facilitating film formation. Ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene Recall monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate , Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents can be used alone or in admixture of two or more.

  Among these solvents, ethers such as diisopropyl ether such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether are preferable, and diisopentyl ether is most preferable. . By using such a solvent, at the time of forming a coating film of the radiation-sensitive resin composition of the present embodiment, it is possible to shorten the drying process time and at the same time, further improve the applicability (suppress application unevenness). Become.

  In addition to the above-mentioned solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be used in combination.

  The radiation-sensitive resin composition by the above components and preparation method can form a patterned cured film of a semiconductor element, and in particular, can form a cured film with contact holes by low-temperature curing. And the cured film of the outstanding reliability can be formed, for example by providing favorable solvent resistance with the low curing temperature compared with the past, such as 180 to 200 degreeC.

<Method for forming cured film>
The cured film of the semiconductor element of this embodiment is formed by applying the radiation-sensitive resin composition of this embodiment on a substrate on which a gate electrode, a gate insulating film, a semiconductor layer, and the like are formed, and forming a through hole, etc. After necessary patterning, it is formed by heat curing. The formed cured film includes the above-mentioned [A] polymer and [B] photoacid generator contained in the radiation-sensitive resin composition, and has a suitable light-shielding property.
Below, the formation method of a cured film is demonstrated in detail.

  In forming the cured film of the semiconductor element of this embodiment, first, a coating film of the radiation-sensitive resin composition of this embodiment is formed on the substrate. On this substrate, a gate electrode, a gate insulating film, a semiconductor layer, and the like are formed according to a known method. For example, the semiconductor layer or the like is formed by repeating semiconductor film formation and etching by photolithography on a substrate in accordance with the method described in Patent Document 1 above.

  In the said board | substrate, after apply | coating the radiation sensitive resin composition of this embodiment mentioned above to the surface in which the semiconductor layer etc. were formed, it prebakes and a solvent is evaporated and a coating film is formed.

  Examples of the coating method of the radiation sensitive resin composition include a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), and a slit coating method (slit die coating method). An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

  The prebaking conditions described above vary depending on the types and blending ratios of the components constituting the radiation-sensitive resin composition, but are preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is such as a hot plate or an oven. Although it differs depending on the heating device, it is about 1 to 15 minutes.

  Next, radiation is applied to at least a part of the coating film formed as described above. At this time, in order to irradiate only a part of the coating film, for example, it is performed through a photomask having a pattern corresponding to formation of a desired through hole and formation of a desired shape.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

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

  Next, the coating film after irradiation is developed to remove unnecessary portions, and a coating film in which through holes having a predetermined shape are formed is obtained.

  The developer used for development is preferably an alkaline aqueous solution. Examples of the alkali contained include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Etc.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the alkaline aqueous solution described above. Furthermore, the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability.

  As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

  Next, the coating film on which through holes having a predetermined shape are formed is cured (also referred to as post-baking) by an appropriate heating device such as a hot plate or an oven. Thereby, the cured film of this embodiment is obtained. The thickness of the cured film is preferably 10 nm to 1000 nm. In the cured film, as described above, through holes arranged at desired positions are formed.

  According to the radiation sensitive resin composition of the present embodiment, the curing temperature is preferably 100 ° C. to 250 ° C., and the curing temperature is 200 ° C. or less due to the effect of the added [D] compound (curing agent). It is also possible. For example, the curing time is preferably 5 to 30 minutes on a hot plate, and preferably 30 to 180 minutes in an oven.

  After the cured film of this embodiment is formed, the semiconductor element of this embodiment can be manufactured by forming a source electrode and a drain electrode on the cured film according to a known method. The source electrode and the drain electrode are formed according to a known method by forming a conductive film constituting the electrodes using a printing method, a coating method, a sputtering method, a CVD method, a vapor deposition method, or the like, and then photolithography. It can be formed by patterning using a method or the like.

Embodiment 2. FIG.
<Semiconductor substrate>
FIG. 2 is a plan view schematically illustrating the main structure of the semiconductor substrate of the present embodiment.

  As shown in FIG. 2, on the semiconductor substrate 21 of the present embodiment, data wirings 23 and gate wirings 24 are arranged on the substrate 22 in a matrix. The semiconductor element 1 of the present embodiment described above is disposed in the vicinity of the intersection of the data line 23 and the gate line 24, and the source electrode (not shown in FIG. 2) of the semiconductor element 1 is connected to the data line 23 and the gate The electrode 11 is connected to the gate wiring 24. Thus, each pixel partitioned on the semiconductor substrate 21 is configured. The semiconductor substrate 21 of this embodiment is suitable for the configuration of a display element such as a liquid crystal display element.

  Examples of the material of the substrate 22 include glass substrates such as soda lime glass and non-alkali glass, or resin substrates such as silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. Etc. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

  In the semiconductor substrate 21 of the present embodiment, the data wiring 23 is electrically connected to the source electrode of the semiconductor element 1, and the pixel electrode 25 is electrically connected to the drain electrode (not shown in FIG. 2) of the semiconductor element 1. The Further, the data wiring 23 can also serve as a source electrode, and the pixel electrode 25 can also serve as a drain electrode.

  In the semiconductor substrate 21 of the present embodiment, when the scanning signal is supplied to the gate wiring 24, the semiconductor element 1 is turned on. A video signal from the data wiring 23 is supplied to the pixel electrode 25 through the semiconductor element 1 that is turned on. Here, the gate lines 24 are juxtaposed in the vertical direction in FIG. 2, and the data lines 23 are juxtaposed in the left-right direction in FIG. Then, a pixel electrode 25 having a desired shape is arranged in a region (pixel) surrounded by a pair of adjacent gate lines 24 and a pair of adjacent data lines 23. The pixel electrode 25 shown in FIG. 2 has a solid plate shape. However, as will be described later, when the display element according to the present embodiment is an IPS mode or FFS mode liquid crystal display element, a comb-tooth shape or the like is used. Is possible.

Embodiment 3. FIG.
<Liquid crystal display element>
FIG. 3 is a cross-sectional view schematically illustrating the main structure of the liquid crystal display element of the present embodiment.

  A liquid crystal display element 100 shown in FIG. 3 which is a display element is an active matrix type TN (twisted nematic) mode color liquid crystal display element configured using the semiconductor substrate 21 of the present embodiment described above.

  The liquid crystal display element 100 has a structure in which the semiconductor substrate 21 including the semiconductor element 1 described above and the color filter substrate 30 on which the color filter 40 is formed face each other via a nematic phase liquid crystal 43 that is 90 ° twist aligned. .

  As shown in FIG. 3, in the semiconductor substrate 21, the semiconductor element 1 of this embodiment and a transparent pixel electrode (not shown in FIG. 3) made of ITO are provided on the side of the transparent substrate 22 in contact with the liquid crystal 43. The pixels are arranged in a matrix form. An alignment film 42 that controls the alignment of the liquid crystal 43 is provided on the surface of the semiconductor substrate 21 that is in contact with the liquid crystal 43.

  In the color filter substrate 30, the colored pattern 36 and the like are arranged on the side of the transparent substrate 45 in contact with the liquid crystal 43 to constitute the color filter 40. The color filter 40 includes red, green, and blue coloring patterns 36 provided in the pixel region, and a black matrix 37 that surrounds them. The color filter substrate 30 has a protective layer 38 on the colored pattern 36 of the color filter 40. The color filter substrate 30 has a transparent common electrode 41 made of ITO and an alignment film 42 for controlling the alignment of the liquid crystal 43 on the protective layer 38.

  As described above, the alignment film 42 for controlling the alignment of the liquid crystal 43 is provided on each of the semiconductor substrate 21 and the color filter substrate 30. If necessary, the alignment film 42 is subjected to, for example, an alignment process such as a rubbing process or a photo-alignment process by polarized light irradiation, so that the liquid crystal 43 sandwiched between the semiconductor substrate 21 and the color filter substrate 30 has a uniform alignment. Realize.

  In the semiconductor substrate 21 and the color filter substrate 30, polarizing plates 44 are respectively arranged on the side opposite to the side in contact with the liquid crystal 43. The distance between the semiconductor substrate 21 and the color filter substrate 30 is preferably 2 μm to 10 μm, and these are fixed to each other by a sealing material 46 provided in the peripheral portion.

  In FIG. 3, reference numeral 47 denotes backlight light emitted toward the liquid crystal 43 from a backlight unit (not shown). As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, and a white light that is obtained by mixing a blue LED, a red LED, and a green phosphor to emit white light. A white LED that obtains white light by mixing white LEDs, a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED that obtains white light by mixing colors with a YAG phosphor, A combination of a blue LED, an orange light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED, an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor And white LEDs that obtain white light by color mixing.

  In the liquid crystal display element 100 of the present embodiment, in addition to the above-described TN mode, STN (Super Twisted Nematic) mode, IPS (In-Plane Switching) mode, FFS (Fringe Field Switching) mode, VA (Vertical Alignment) mode or A liquid crystal mode such as an OCB (Optically Compensated Birefringence) mode can be set.

  The semiconductor element of the semiconductor substrate of the liquid crystal display element of the present embodiment has the cured film of the present embodiment between the semiconductor layer and the source electrode and the drain electrode. It is. Therefore, the semiconductor element of the liquid crystal display element of this embodiment can reduce deterioration of characteristics due to the influence of light. As a result, the liquid crystal display element of the present embodiment can suppress display quality degradation due to the influence of light.

  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.

Hereinafter, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis of polymer>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by mass of methacrylic acid, 40 parts by mass of 2-tetrahydropyranyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and 3 parts by mass of α-methylstyrene dimer were charged. After the replacement, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The polystyrene equivalent mass average molecular weight (Mw) of the copolymer (A-1) was 9000. Moreover, the solid content concentration of the polymer solution obtained here was 31.3 mass%.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 85 parts by mass of 2-tetrahydropyranyl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, and 8 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-1). The copolymer (a-1) had a polystyrene-reduced mass average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 29.2 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 52 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate and 48 parts by mass of benzyl methacrylate were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (aa-1). The polystyrene equivalent mass average molecular weight (Mw) of the copolymer (aa-1) was 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by weight of methacrylic acid, 40 parts by weight of 2-tetrahydropyranyl methacrylate, 5 parts by weight of styrene, 40 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane, 10 parts by weight of 2-hydroxyethyl methacrylate and α-methyl After 3 parts by mass of styrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The copolymer (A-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

<Preparation of radiation-sensitive resin composition>
Example 1
In the solution containing copolymer (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of copolymer (A-1)), [(camphorsulfonyl) is used as component [B]. Oxiimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (“CGI1380” manufactured by BASF) 4 parts by mass, Tris- (3,5- 1 part by mass of di-t-butyl-4-hydroxybenzyl) -isocyanurate (“ADEKA STAB (registered trademark) AO-20” manufactured by ADEKA), silicone surfactant (Toray Industries, Inc.) as the [E] component -"SH 8400 FLUID" manufactured by Dow Corning) 0.20 parts by mass, and 3.0 parts by mass of [gamma] -glycidoxypropyltrimethoxysilane as the [E] component were mixed to obtain a 0.2 [mu] m pore size mem. By filtration through membrane filter, the radiation-sensitive resin composition (S-1) was prepared.

Example 2
A solution containing copolymer (a-1) and copolymer (aa-1) obtained in Synthesis Example 2 and Synthesis Example 3 (copolymer (a-1) and copolymer (aa-1), respectively) 50 parts by mass (solid content corresponding to a total of 100 parts by mass in a ratio of 1: 1)) and [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-Methylphenyl) acetonitrile] (“IRGACURE (registered trademark) PAG 103” manufactured by BASF) 4 parts by mass, 4,4′-diaminodiphenylsulfone 0.5 parts by mass as [D] component, [E] component 1 part by weight of tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (“ADEKA STAB (registered trademark) AO-20” manufactured by ADEKA) as an antioxidant as [E ] As an ingredient 0.20 parts by mass of ricone surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) and 3.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as the [E] component were mixed. The radiation sensitive resin composition (S-2) was prepared by filtering with a 0.2 micrometer membrane filter.

Example 3
Instead of using the solution containing the copolymer (A-1) in Example 1, the same procedure as in Example 1 was used except that the solution containing the copolymer (A-2) obtained in Synthesis Example 4 was used. Then, a radiation sensitive resin composition (S-3) was prepared.

<Formation and evaluation of cured film>
Example 4
[Hardened film formed from radiation-sensitive resin compositions (S-1) and (S-3)]
The radiation-sensitive resin composition (S-1) prepared in Example 1 was applied on an alkali-free glass substrate with a spinner, and then pre-baked on a 90 ° C. hot plate for 2 minutes to form a coating film. Next, a high-pressure mercury lamp was used for the obtained coating film, and irradiation was performed with an exposure amount of 500 J / m ² through a photomask having a desired pattern, and a 0.4 mass% tetramethylammonium hydroxide aqueous solution was used. Development was performed at 25 ° C. for 60 seconds. Next, a patterned cured film was formed by post-baking in an oven at a curing temperature of 220 ° C. and a curing time of 1 hour.

  Next, instead of using the radiation sensitive resin composition (S-1) prepared in Example 1, the radiation sensitive resin composition (S-3) prepared in Example 3 was used. In the same manner as in the method using the radiation sensitive resin composition (S-1), a patterned cured film was formed on an alkali-free glass substrate.

Example 5
[Hardened film formed from radiation-sensitive resin composition (S-2)]
The radiation-sensitive resin composition (S-2) prepared in Example 2 was applied onto an alkali-free glass substrate with a spinner, and then pre-baked on a 90 ° C. hot plate for 2 minutes to form a coating film. Next, a high-pressure mercury lamp was used for the obtained coating film, and irradiation was performed with an exposure amount of 500 J / m ² through a photomask having a desired pattern, and a 0.4 mass% tetramethylammonium hydroxide aqueous solution was used. Development was performed at 25 ° C. for 60 seconds. Next, a patterned cured film was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 1 hour.

Example 6
[Evaluation of heat resistance]
About each cured film formed from the radiation sensitive resin compositions (S-1) and (S-3) by the forming method of Example 4, each was further heated in an oven at 230 ° C. for 20 minutes. Was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed about each cured film, and this remaining film rate was made into heat resistance. The residual film ratio was 99% in any cured film, and all the cured films were judged to have good heat resistance.

  Similarly, the cured film by the forming method of Example 5 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after this heating was measured with a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor). It was measured. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Example 7
[Evaluation of light resistance]
For each cured film formed from the radiation-sensitive resin compositions (S-1) and (S-3) by the formation method of Example 4, a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.) was further used. Irradiation with ultraviolet light of 800,000 J / m ² at an illuminance of 130 mW was performed, and the amount of film reduction after irradiation was examined for each cured film. The amount of film reduction was 2% or less in any cured film, and it was judged that any cured film had good light resistance.

Similarly, the cured film obtained by the formation method of Example 5 was further irradiated with 80000 J / m ² of ultraviolet light at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

<Manufacture of liquid crystal display elements>
Example 8
Using the radiation-sensitive resin composition (S-1) obtained in Example 1, a gate electrode and a gate insulating film are formed according to a known method, and a semiconductor layer made of indium gallium zinc oxide (IGZO) is formed thereon. It apply | coated with the slit die coater on the board | substrate with which was arrange | positioned. The semiconductor layer on this substrate is formed according to a known method by referring to the method described in Japanese Patent Application Laid-Open No. 2007-115902, forming a semiconductor film, and repeating etching by a photolithography method. is there.

  Next, a patterned cured film having through holes was formed on the semiconductor layer on the substrate by the formation method of Example 4.

  After that, according to a known method, on the cured film having a through hole, an electrode such as a source electrode and a drain electrode is formed, wiring such as a data wiring and a gate wiring is formed, and then a pixel electrode is patterned and formed. A semiconductor substrate was manufactured. This semiconductor substrate has the same structure as the semiconductor substrate 21 shown in FIG. Therefore, the semiconductor element having the same structure as the semiconductor element 1 shown in FIG. 1 is provided.

  Next, a color filter substrate manufactured by a known method was prepared. In this color filter substrate, a minute coloring pattern of three colors of red, green and blue and a black matrix are arranged in a lattice pattern on a transparent substrate. A transparent common electrode made of ITO is formed on the protective layer.

Next, a photoalignment film was formed on each of the obtained semiconductor substrate and color filter substrate using a liquid crystal aligning agent containing a radiation-sensitive polymer having a photoalignable group. As a method for forming a photo-alignment film, a liquid crystal aligning agent A-1 described in Example 6 of International Publication (WO) 2009/025386 pamphlet is used as a liquid crystal aligning agent including a radiation-sensitive polymer having a photo-aligning group. Is applied onto each substrate by a spinner. Next, after pre-baking for 1 minute on an 80 ° C. hot plate, it was heated at 180 ° C. for 1 hour in an oven in which the inside was replaced with nitrogen to form a coating film having a thickness of 80 nm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from a direction inclined by 40 ° with respect to the direction perpendicular to the substrate surface using a Hg-Xe lamp and a Grand Taylor prism, A semiconductor substrate having a photo-alignment film and a color filter substrate were manufactured.

  A liquid crystal layer was sandwiched between the obtained semiconductor substrate with a photo-alignment film and a color filter substrate to produce a color liquid crystal display element. As the liquid crystal layer, a layer made of nematic liquid crystal and aligned almost in parallel with a very small inclination with respect to the substrate surface was used. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

Example 9
Using the radiation-sensitive resin composition (S-2) obtained in Example 2, a cured film having a patterned through hole is formed on the semiconductor layer on the substrate by the formation method of Example 5. A color liquid crystal display element was manufactured in the same manner as in Example 8 except that. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

Example 10
Using the radiation-sensitive resin composition (S-3) obtained in Example 3, a cured film having a patterned through hole is formed on the semiconductor layer on the substrate by the formation method of Example 4. A color liquid crystal display element was manufactured in the same manner as in Example 8 except that. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

  The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

  The semiconductor element of the present invention can be produced by low-temperature heat treatment, for example, by forming a cured film using the radiation-sensitive resin composition of the present invention, and has excellent mobility characteristics and light resistance. Therefore, it is suitable for formation on a substrate having a heat resistance problem such as a resin substrate, and is suitable for providing a light-weight liquid crystal display element having flexibility. Moreover, since it is excellent in light resistance, it is suitable for outdoor use. Therefore, the semiconductor element, the semiconductor substrate and the display element of the present invention are suitable not only for large liquid crystal TV applications but also for display elements of portable information equipment.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Semiconductor layer 3 Source electrode 4 Drain electrode 5 Cured film 6 Through hole 10, 22, 45 Substrate 11 Gate electrode 12 Gate insulating film 21 Semiconductor substrate 22 Substrate 23 Data wiring 24 Gate wiring 25 Pixel electrode 30 Color filter substrate 36 Coloring pattern 37 Black matrix 38 Protective layer 40 Color filter 41 Common electrode 42 Alignment film 43 Liquid crystal 44 Polarizing plate 46 Sealing material 47 Backlight 100 Liquid crystal display element

Claims (11)

A semiconductor having a semiconductor layer formed using an oxide containing at least one of indium (In), zinc (Zn), and tin (Sn), and an electrode provided on the first surface of the semiconductor layer An element,
A cured film is disposed between the semiconductor layer and the electrode,
The said cured film has at least 1 of the bridge | crosslinking part represented by following formula (1A-1)-following formula (1A-9), The semiconductor element characterized by the above-mentioned.

(In Formula (1A-7) to Formula (1A-9), R ⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.) The cured film is
[A] a polymer having a structural unit containing a group represented by the following formula (1B) and a structural unit containing an epoxy group in the same or different polymer molecules, and [B] a feeling containing a photoacid generator The semiconductor element according to claim 1, wherein the semiconductor element is formed using a radiation resin composition.

(In Formula (1B), each of R ¹ and R ² independently represents 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 (provided that R ¹ and R ² are not both hydrogen atoms) R ³ is an ether group having 1 to 30 carbon atoms and 1 carbon atom A group in which a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms is substituted with a hydroxyl group, a halogen atom or a cyano group, and R ¹ and R ³ are linked to each other. (Cyclic ethers may be formed.) The cured film is provided with a through hole,
The semiconductor element according to claim 1, wherein the first surface of the semiconductor layer and the electrode are connected to each other through the through hole.   The semiconductor layer is formed using at least one of zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO). The semiconductor element according to any one of claims 1 to 3. [B] The semiconductor element according to any one of claims 2 to 4, wherein the photoacid generator includes an oxime sulfonate group represented by the following formula (2).

(In Formula (2), R ^B1 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.)   The semiconductor device according to claim 1, wherein the cured film contains a [C] ultraviolet absorber. [C] The ultraviolet absorber includes one kind selected from the group consisting of compounds represented by the following formula (3-1) and the following formula (3-2). element.

(In Formula (3-1) and Formula (3-2), R ^{11 to} R ²⁵ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 represents a benzoyloxy group or a hydroxyl group.) A gate electrode provided on the second surface of the semiconductor layer via a gate insulating film;
The semiconductor element according to claim 1, wherein the semiconductor element includes a source electrode and a drain electrode provided on the first surface to form a bottom gate type semiconductor element.   The radiation sensitive resin composition used for formation of the cured film of the semiconductor element of any one of Claims 1-8.   A cured film formed from the radiation-sensitive resin composition according to claim 9.   A display element comprising the semiconductor element according to claim 1.

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