JP2014115438A - Radiation-sensitive resin composition for display element, cured film, method for producing cured film, semiconductor element, and display element - Google Patents

Abstract

【選択図】図１The present invention provides a radiation-sensitive resin composition for a display element that forms a cured film excellent in light transmittance and reliability, provides a cured film and a manufacturing method thereof, and provides a semiconductor element and a display element.
[A] A radiation-sensitive resin composition for a display device comprising a polysiloxane having at least one of a group of formula (1) and a group of formula (2) and [B] a photoacid generator is prepared. Then, the coating film 2 is formed on the substrate 1, and a portion of the coating film 2 is irradiated with radiation 4 and developed to form a patterned coating film 2 ′. The coating film 2 ′ is heated to form a cured film 6, which is used for the configuration of a semiconductor element or an organic EL element.

[Selection] Figure 1

Description

  The present invention relates to a radiation-sensitive resin composition for display elements, a cured film, a method for producing a cured film, a semiconductor element, and a display element.

  In recent years, in the field of electronic devices such as semiconductor elements and display elements in which the semiconductor elements can be used as active elements, in addition to conventional films made of inorganic materials, use of films made of resins has become a component. It has been actively studied.

  The film made of resin can be formed as a cured film using, for example, a radiation sensitive resin composition. Some films made of resin can be patterned by a photolithography method, and are used as an insulating film, a protective film, a planarizing film, and the like of semiconductor elements and display elements, and are important constituent elements.

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

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

  For example, in an active organic EL display element, in addition to an insulating film forming a partition wall, an insulation having a flattening function as described in Patent Document 1 and Patent Document 2 can be realized so as to realize a higher aperture ratio. The introduction of membranes is being considered.

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

  Although it is an organic EL display element by the above structure and manufacturing method, it is preferable that the insulating film which functions as a partition of an organic light emitting layer or a planarization film on a TFT is a film made of a resin that can be easily patterned as desired. .

  For the formation of an insulating film made of such a resin, the use of a well-known acrylic resin has been studied. And in patent document 3 and patent document 4, the technique which uses the polyimide film and photosensitive siloxane material which consist of highly reliable polyimide resin for the insulating film of an organic EL element is disclosed. In particular, in the case of a photosensitive siloxane material, quinonediazide is used as a photosensitizer to form a positive pattern, and it exhibits low transmittance due to coloring derived from a quinonediazide compound, and the sensitivity is not sufficient.

JP 2011-107476 A JP 2010-237310 A JP 2009-9934 A Special table 2012-511740 gazette

  Therefore, in the field of semiconductor elements and display elements, in order to improve the performance, in addition to patterning performance, a cured film made of a resin having performance and reliability that can be applied to semiconductor elements and display elements is required. ing. More specifically, there is a need for a cured film made of a resin having excellent light transmission and light resistance, excellent heat resistance, a small amount of gas generated by thermal decomposition, and excellent reliability performance. In order to form the cured film, there is a need for a radiation-sensitive resin composition that enables simple film formation and that can be patterned with high sensitivity using, for example, photolithography. There is also a need for semiconductor elements and display elements having the cured film.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a radiation-sensitive resin composition for a display element that includes a polysiloxane having an acid-dissociable group and a photoacid generator and can form a patterned cured film with high sensitivity. .

  Moreover, the objective of this invention is providing the cured film provided with the patternability and reliability formed from the radiation sensitive resin composition for display elements.

  Moreover, the objective of this invention is providing the manufacturing method of the cured film provided with patterning property and reliability.

  Another object of the present invention is to provide a semiconductor element that is formed using a radiation-sensitive resin composition for display elements and has a cured film having a protective function and excellent in reliability.

  Moreover, the objective of this invention is providing the display element which has the cured film excellent in reliability, such as light transmittance and light resistance, formed using the radiation sensitive resin composition for display elements.

The first aspect of the present invention is:
[A] A polysiloxane having at least one of a group represented by the following formula (1) and a group represented by the following formula (2), and [B] a feeling for a display element comprising a photoacid generator The present invention relates to a radiation resin composition.

（式（１）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。
式（２）中、Ｒ^４〜Ｒ^１０は、それぞれ独立して、水素原子、炭素数１〜１２の炭化水素基である。ｎは１または２の整数である。）

(In formula (1), 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 (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 obtained by substituting a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms with a hydroxyl group, a halogen atom or a cyano group.
In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is an integer of 1 or 2. )

  1st aspect of this invention WHEREIN: It is preferable that [A] polysiloxane has a crosslinkable group further.

  In the first aspect of the present invention, the crosslinkable group is preferably at least one selected from the group consisting of an oxiranyl group and an oxiranyl group.

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

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

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

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

  In the first aspect of the present invention, it is preferable to further contain [D] an antioxidant.

  The 2nd aspect of this invention is related with the cured film characterized by being obtained using the radiation sensitive resin composition for display elements of the 1st aspect of this invention.

According to a third aspect of the present invention, [1] a step of forming a coating film of the radiation-sensitive resin composition for display elements according to the first aspect of the present invention on a substrate,
[2] A step of irradiating at least part of the coating film of the radiation-sensitive resin composition for display elements,
[3] A method for producing a cured film, comprising: a step of developing a coating film irradiated with radiation; and [4] a step of heating and curing the developed coating film.

  A 4th aspect of this invention is related with the semiconductor element characterized by having the cured film of the 2nd aspect of this invention.

  According to a fifth aspect of the present invention, there is provided a display element comprising the cured film according to the second aspect of the present invention.

  In the fifth aspect of the present invention, the semiconductor element of the fourth aspect of the present invention is preferably used as an active element.

  According to the 1st aspect of this invention, the radiation sensitive resin composition for display elements which can form the patterned cured film with high sensitivity is obtained.

  According to the 2nd aspect of this invention, the cured film formed from the radiation sensitive resin composition for display elements and provided with the patternability and reliability is obtained.

  According to the 3rd aspect of this invention, the manufacturing method of the cured film provided with patterning property and reliability is provided.

  According to the 4th aspect of this invention, the semiconductor element which has the cured film which was formed using the radiation sensitive resin composition for display elements, was provided with the protective function, and was excellent in reliability.

  According to the 5th aspect of this invention, the display element which has the cured film excellent in reliability, such as light transmittance and light resistance, formed using the radiation sensitive resin composition for display elements is obtained.

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

  As described above, the present invention relates to a radiation-sensitive resin composition for display elements, a cured film, a method for producing a cured film, a semiconductor element, and a display element. The cured film of the present invention has a sensitivity for a display element of the present invention. It is a cured film formed by using a radiation resin composition and curing it. The semiconductor element of the present invention is composed of the cured film of the present invention using the radiation-sensitive resin composition for display elements of the present invention, and the display element of the present invention activates the semiconductor element of the present invention. It is used as an element as a component, or is formed using the cured film of the present invention in a portion other than a semiconductor element.

Therefore, in describing the present invention, first, a radiation-sensitive resin composition for display elements which is a main component of the present invention will be described, and then the cured film of the present invention using the composition and the semiconductor of the present invention will be described. The device and the display device of the present invention will be described.
In the present invention, “radiation” irradiated upon exposure is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.
Hereinafter, embodiments of the present invention will be described.

<Radiation-sensitive resin composition for display element>
The radiation-sensitive resin composition for a display element according to an embodiment of the present invention is a radiation-sensitive material suitable for forming a film that is a constituent element of an organic EL element that can also form a display element or a film that is a constituent element of a semiconductor element. Resin composition.

  The radiation sensitive resin composition for display elements of the present embodiment includes [A] a polysiloxane having at least one of a group represented by the following formula (1) and a group represented by the following formula (2) (hereinafter simply referred to for convenience). [A] may be referred to as polysiloxane) and [B] a photoacid generator.

（式（１）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。
式（２）中、Ｒ^４〜Ｒ^１０は、それぞれ独立して、水素原子、炭素数１〜１２の炭化水素基である。ｎは１または２の整数である。）

(In formula (1), 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 (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 obtained by substituting a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms with a hydroxyl group, a halogen atom or a cyano group.
In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is an integer of 1 or 2. )

  Furthermore, the radiation-sensitive resin composition for display elements of the present embodiment can independently contain [C] a compound having a cyclic ether group and [D] an antioxidant.

And the radiation sensitive resin composition for display elements of this embodiment can be used as a positive radiation sensitive resin composition, and is suitably used as an insulating film of an organic EL element or an insulating film of a semiconductor element. It can use for formation of the cured film of embodiment.
Hereinafter, the detail of the component contained in the radiation sensitive resin composition for display elements of this embodiment is demonstrated.

[[A] polysiloxane]
[A] polysiloxane contained in the radiation-sensitive resin composition for display elements of this embodiment is at least one of the group represented by the above formula (1) and the acid dissociable group represented by the above formula (2). Having one. The acid dissociable group is a group that can be dissociated from polysiloxane by an acid generated from a photoacid generator described later. [A] When the polysiloxane has at least one of the group represented by the above formula (1) and the group represented by the above formula (2), the polysiloxane can be obtained from the radiation-sensitive resin composition for display elements of this embodiment. As will be described later, the coating film can be patterned by a photolithography method using a [B] photoacid generator.
Unlike conventional pattern formation using positive-type photosensitive polysiloxane materials using quinonediazide compounds, it is possible to form patterns with high sensitivity without using quinonediazide as a photosensitizer. It becomes possible to prevent water absorption into the film by the transmittance and indenecarboxylic acid derived from the quinonediazide compound.

  [A] polysiloxane contained in the radiation-sensitive resin composition for display elements of the embodiment of the present invention is obtained by first synthesizing a polysiloxane having a carboxyl group, and the carboxyl group has the above formula (1) or the above formula. It can be synthesized by introducing an acid dissociable group represented by (2). Details will be described below.

  First, [A] carboxyl group-containing polysiloxane from which polysiloxane can be obtained will be described.

  [A] A carboxyl group-containing polysiloxane from which a polysiloxane can be obtained has a carboxyl group in the molecule. The method for producing the carboxyl group-containing polysiloxane is not particularly limited, but is a polysiloxane obtained by hydrolysis and condensation of the silane compound represented by the following formula (5) and the following formula (6). Is preferred.

In the above formula (5), R ¹⁴ is represented by the following formula (4) by hydrolysis or alcoholysis to generate an organic group. The alcoholysis herein refers to a reaction in which an alcohol present in or generated in a hydrolysis reaction or a condensation reaction reacts with an organic group contained in R ¹⁴ to substitute an alkoxyl group. Examples of the organic group contained in R ¹⁴ include an ester group and an acid anhydride group. When R ¹⁴ is an acid anhydride group, two carboxyl groups are generated by hydrolysis. An acid dissociable group can be introduced into two or one of the carboxyl groups. R ¹⁵ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ¹⁵ may be the same or different. . x represents an integer of 1 to 3.

（上記式（４）中、Ｒ^１１は水素原子または炭素数１〜４のアルキル基、Ｒ^１２はメチレン基、エチレン基を表す。Ｒ^１３は単結合またはメチレン基、炭素数２〜６のアルキレン基を表す。）

(In the above formula (4), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² represents a methylene group or an ethylene group. R ¹³ represents a single bond or a methylene group or an alkylene having 2 to 6 carbon atoms. Represents a group.)

Examples of R ¹⁴ include organic groups containing a succinic anhydride residue or a glutaric anhydride residue.

Specific examples of R ¹⁵ include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, acetyl group, phenyl group and the like. Among these, a methyl group and an ethyl group are preferable in terms of availability and ease of progress of hydrolysis reaction.

  Specific examples of the silane compound represented by the above formula (5) include 2-trimethoxysilylethyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride. Trifunctional such as 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl glutaric anhydride, 3-triethoxysilylsilylpropyl glutaric anhydride, 3-triphenoxysilylpropyl glutaric anhydride, etc. Silane etc. are mentioned. These compounds may be used alone or in combination of two or more.

  The amount of the silane compound represented by the above formula (5) is preferably 1 part by mass to 70 parts by mass, more preferably 5 parts by mass to 50 parts by mass, when the total amount of the co-condensation component is 100 parts by mass. is there. By setting the amount to be used in the above range, the radiation-sensitive resin composition for display elements of the present embodiment can achieve the sensitivity at the time of pattern formation at a high level.

In the above formula ^{(6), R 16} represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having from 6 to 15 carbon atoms, represents either an aralkyl group, a plurality of ^{R 16} is Each may be the same or different.

In the above formula ^{(6), R 17} represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, more ^{R 17} each It can be the same or different. y represents an integer of 0 to 3, and z represents an integer of 0 to 12.

The alkyl group, alkenyl group, aryl group and aralkyl group of R ¹⁶ may have a substituent or may be an unsubstituted form having no substituent. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, 2-glycidoxyethyl group, 3-glycidoxy Examples include propyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 3-glycidoxypropyl group, 3-acryloxy group, 3-methacryloxy group and the like. . Specific examples of the alkenyl group include a vinyl group and an allyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, and a naphthyl group. Specific examples of the aralkyl group include 1- (p-hydroxyphenyl) ethyl group and 2- (p-hydroxyphenyl) ethyl group. Among these, a methyl group is used for imparting high hardness to the cured product, a phenyl group is used for improving the refractive index of the cured product, and 3-glycol is used for imparting adhesion and wettability to the base material and the upper layer film. Sidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 3-glycidoxypropyl group, 3-acryloxy group, 3-methacryloxy group, Each is preferably used.

Specific examples of R ¹⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an acetyl group, and a phenyl group. Among these, a methyl group and an ethyl group are preferably used from the viewpoint of easy availability and easy progress of hydrolysis reaction.

  Specific examples of the silane compound represented by the above formula (6) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-metac Loxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Lan, trifunctional silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, Examples include bifunctional silanes such as dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, and diphenyldimethoxysilane, and monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. These compounds may be used alone or in combination of two or more.

  The amount of the silane compound represented by the above formula (6) is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 50 parts by mass, when the total amount of the co-condensation component is 100 parts by mass. is there. By setting the amount used within the above range, the heat resistance and light transmittance of the cured film obtained using the radiation-sensitive resin composition for display elements of the present embodiment can be achieved at a high level.

Moreover, it is also preferable that the silane compound represented by the said Formula (6) contains the silane compound represented by following formula (7) and / or following formula (8) as an essential component. The silane compound represented by the following formula (7) and / or the following formula (8) plays a role of end-capping that suppresses condensation of polysiloxane. That is, since the silane compound represented by the following formula (7) has a sterically bulky substituent at R ¹⁸ and R ¹⁹ , only one of the two OR ²⁰ can participate in the reaction. Further, the compound represented by the following formula (8) has only one OR ²⁵ . By using such a compound, the radiation-sensitive resin composition for display elements of this embodiment ensures a sufficient pot life without causing a condensation reaction during storage and without easily increasing the viscosity. be able to.

In said formula (7), R < ¹⁸ >, R < ¹⁹ > is a C6-C10 linear alkyl group, a C6-C10 substituted alkyl group, a C6-C15 aryl group, or R < ²¹ > R < ²² > R. A group represented by ²³ C— (R ^{21 to} R ²³ are alkyl groups, which may be the same or different from each other; any one of R ^{21 to} R ²³ may be a hydrogen atom); And the plurality of R ¹⁸ and R ¹⁹ may be the same or different. R ²⁰ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ²⁰ may be the same or different. .

Here, the substituted alkyl group having 6 to 10 carbon atoms refers to a group in which the total number of carbon atoms contained in the main chain alkyl group and the substituent is 6 to 10 carbon atoms. Examples of the substituent in R ¹⁸ and R ¹⁹ include an aryl group, a 3-acryloxy group, a 3-methacryloxy group, an epoxy group, and a hydroxy group.

Specific examples of R ¹⁸ and R ¹⁹ include n-hexyl group, n-decyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 3-glycol. Sidoxypropyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, phenyl group, tolyl group, p-hydroxy A phenyl group, a naphthyl group, etc. are mentioned. The group represented by R ²¹ R ²² R ²³ C— is a group having 3 to 10 carbon atoms, and specific examples thereof include an isopropyl group, a sec-butyl group, and a t-butyl group. Among these, a phenyl group is used to improve the refractive index of the cured product, and a 3-glycidoxypropyl group and 2- (3,4-epoxy are used to provide adhesion and wettability with a base material and an upper layer film. (Cyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, and 3-glycidoxypropyl group are each preferably used.

Specific examples of R ²⁰ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an acetyl group, and a phenyl group. Among these, a methyl group and an ethyl group are preferably used from the viewpoint of easy availability and easy progress of hydrolysis reaction.

  Specific examples of the silane compound represented by the above formula (7) include diphenyldimethoxysilane, diphenyldiethoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, and di-t-butyldimethoxysilane. , Di-t-butyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) propyldimethoxysilane, etc. Silane. These compounds may be used alone or in combination of two or more.

In the formula ^{(8), R 24} represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having from 6 to 15 carbon atoms, an aralkyl group, having 4 to 10 carbon atoms (meth) acryloyl Represents any one of alkyl groups, and the plurality of R ²⁴ may be the same or different. R ²⁵ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms.

  The alkyl group, alkenyl group, aryl group, aralkyl group, and (meth) acryloxyalkyl group may have a substituent or an unsubstituted form having no substituent. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, 2-glycidoxyethyl group, 3-glycidoxy A propyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 3-glycidoxypropyl group and the like can be mentioned. Specific examples of the alkenyl group include a vinyl group and an allyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, and a naphthyl group. Specific examples of the aralkyl group include 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group and the like. . Specific examples of the (meth) acryloxyalkyl group include a 3-acryloxypropyl group and a 3-methacryloxypropyl group. Among these, a methyl group is used for imparting high hardness to the cured product, a phenyl group is used for improving the refractive index of the cured product, and 3-glycol is used for imparting adhesion and wettability to the base material and the upper layer film. Sidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and 3-glycidoxypropyl group are each preferably used.

Specific examples of R ²⁴ include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, acetyl group, phenyl group and the like. Among these, a methyl group and an ethyl group are preferably used from the viewpoint of easy availability and easy progress of hydrolysis reaction.

  Specific examples of the silane compound represented by the above formula (8) include monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane. These compounds may be used alone or in combination of two or more.

  The cocondensation ratio in the case of using the silane compound represented by the above formula (7) and / or the above formula (8) is preferably 1 part by mass or more, more preferably 3 parts by mass or more among monomers used for polymerization. 20 parts by mass or less. By setting the cocondensation ratio within the above range, a stable cured product having high hardness and a stable condensation reaction at room temperature does not proceed.

  The carboxyl group-containing polysiloxane that can be used in the present embodiment is, for example, after hydrolyzing the silane compound represented by the above formula (5) to the above formula (8) or in parallel with the hydrolysis reaction. It can be obtained by subjecting the decomposition product to a condensation reaction.

  Various conditions in the hydrolysis reaction and the condensation reaction include, for example, the acid concentration, the reaction in consideration of the environment of the reaction field such as the reaction scale, the size and shape of the reaction vessel, the intended use and the physical properties suitable for it. Temperature, reaction time, etc. can be set as appropriate. An example is shown below, but is not limited thereto.

The hydrolysis reaction is carried out in a solvent or without solvent, after adding water to the silane compound represented by the above formula (5) to the above formula (8) over 1 minute to 180 minutes, and then at room temperature to 110 ° C. for 1 minute. It is preferable to react for -180 minutes. It is preferable to use ion exchange water or ultrapure water as the water to be added. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 mol to 5.0 mol with respect to 1.0 mol of the alkoxysilane compound. The reaction temperature is more preferably 40 ° C to 105 ° C. In the hydrolysis reaction, the Si—OR groups of the above formulas (5) to (8) are hydrolyzed to become silanol groups. R ¹⁴ of the silane compound of the above formula (5) is also converted into an organic group of the above formula (4) by hydrolysis with added water and alcoholysis generated or present in the reaction system.

  The condensation reaction is carried out at 50 ° C. or more and 200 ° C. or less after obtaining a silanol compound by hydrolysis reaction of the silane compounds represented by the above formulas (5) to (8) or in parallel with the hydrolysis reaction. It is preferable to carry out heating for 1 hour to 50 hours.

  The hydrolysis reaction and condensation reaction proceed autocatalytically by carboxylic acid generated by hydrolysis of the silane compound of the above formula (5) without adding a catalyst, but an acid catalyst may be added separately. Examples of the acid catalyst used here include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. As preferable content of these acid catalysts, Preferably it is 0.05 mass part or more with respect to 100 mass parts of silane compounds represented by the said Formula (5)-said Formula (8) used at the time of a hydrolysis reaction, More preferably, it is 0.1 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less. If the amount of the acid catalyst is less than 0.05 parts by mass, the rate of hydrolysis reaction may be slow, and it may be difficult to control the reaction. Moreover, when the amount of the acid catalyst exceeds 10 parts by mass, the hydrolysis reaction may run away.

  A solvent may be used for the hydrolysis reaction of the silane compound represented by the above formula (5) to the above formula (8) and the condensation reaction of the hydrolyzate. The solvent can be used as a mixture of two or more. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol, 1-t-butoxy-2-propanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol Ethers such as diethyl ether, ethylene glycol dibutyl ether, diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; dimethylformamide, dimethyl Amides such as acetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, Acetates such as ethyl lactate and butyl lactate; aromas such as toluene, xylene, hexane and cyclohexane Or other aliphatic hydrocarbons, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, and dimethyl sulfoxide.

  After the completion of the reaction, it may be adjusted to an appropriate concentration by adding a solvent. Further, for the purpose of increasing the concentration and viscosity of polysiloxane, the produced alcohol or solvent may be distilled and removed under heating and / or under reduced pressure.

  Next, the group represented by the following formula (1) and the acid dissociable group represented by the following formula (2) possessed by the [A] polysiloxane contained in the radiation sensitive resin composition for display elements of the present embodiment. Will be described. [A] When the polysiloxane has at least one of the group represented by the following formula (1) and the group represented by the following formula (2), the radiation-sensitive resin composition for display elements of the present embodiment is used. The obtained coating film can be patterned by a photolithography method using a [B] photoacid generator.

In the above formula (1), 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 that the hydrocarbon group having 1 to 30 carbon atoms has. 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.)

In the above formula (1), R ³ is a hydroxyl group, part of the hydrogen atoms of the ether group having 1 to 30 carbon atoms, the hydrocarbon group having 1 to 30 carbon atoms, or the hydrocarbon group having 1 to 30 carbon atoms. , A group substituted with a halogen atom or a cyano group.

In the above formula (1), the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group. It is.

Specific examples of the linear and branched alkyl groups described above that are R ¹ and R ² in the above formula (1) include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n- Linear alkyl group such as pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, Examples thereof include branched alkyl groups such as a neopentyl group, 2-hexyl group, and 3-hexyl group.

  The alicyclic hydrocarbon group described above is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Specific examples of the alicyclic hydrocarbon 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 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 (1), 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.

The ether group having 1 to 30 carbon atoms represented by R ³ in the above formula (1) 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 part of hydrogen atoms of the hydrocarbon group having 1 to 30 carbon atoms or the hydrocarbon group having 1 to 30 carbon atoms constituting the ether group represented by R ³ is a hydroxyl group, a halogen atom or a cyano group. For the substituted group, the description for R ¹ and R ² can be applied.

In said formula (2), R < ⁴ > -R < ¹⁰ > is respectively independently a hydrogen atom and a C1-C12 hydrocarbon group. n is an integer of 1 or 2.

The hydrocarbon group having 1 to 12 carbon atoms, which is R ^{4 to} R ¹⁰ in the above formula (2), is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, aryl. It is a group.

Specific examples of the linear and branched alkyl groups described above that are R ^{4 to} R ¹⁰ include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Group, n-octyl group, n-dodecyl group, n-tetradecyl group, linear alkyl group such as n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl And branched alkyl groups such as a 3-hexyl group.

The above-described alicyclic hydrocarbon group which is R ^{4 to} R ¹⁰ is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Specific examples of the alicyclic hydrocarbon group described above include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like.

In the above formula (2), n is an integer of 1 or 2. When n is 1, a tetrahydrofuranyl ring is constituted, and when n is 2, a tetrahydropyranyl ring is constituted. Some or all of the hydrogen atoms in the cyclic ether structure are substituted with the above-described substituents which the hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ and R ² in the above formula (1) can have. May be.

  Next, in the [A] polysiloxane contained in the radiation-sensitive resin composition for display elements of this embodiment, the group represented by the above formula (1) and the acid dissociable group represented by the above formula (2) The introduction will be described.

  [A] As the polysiloxane, the carboxyl group-containing polysiloxane described above can be used, and an acid dissociable group represented by the above formula (1) and / or the above formula (2) can be introduced.

  For example, as shown in the following reaction formula, it can be synthesized by reacting a vinyl ether derivative having a desired structure with a carboxyl group of a carboxyl group-containing polysiloxane in the presence of an acid catalyst.

In the above reaction formula, R ′ corresponds to the structure excluding the carboxyl group of the carboxyl group-containing polysiloxane described later. Then, for example, ^{R 1} corresponds to ^{R 1} in the formula (1), OR ^{3 'corresponds} to ^{R 3} in the formula ^{(1), R 31} and ^{R 32,} -CH ^{(R 31)} (R ³² ) corresponds to R ² in the above formula (1).

  In particular, when the [A] polysiloxane has a group represented by the above formula (2), the [A] polysiloxane has a desired cyclic structure in the presence of an acid catalyst as shown in the following reaction formula. It can be synthesized by reacting a vinyl ether derivative with a carboxyl group of a carboxyl group-containing polysiloxane.

In the above reaction formula, R ′ corresponds to the structure of the portion excluding the carboxyl group of the carboxyl group-containing polysiloxane described later. n is an integer of 1 or 2, similar to n in the above formula (2). Then, for example, ^{R 4 corresponds} to ^{R 4} in the formula (2), R 7 ^{to R 10} respectively correspond to ^R 7 ^{to R 10} in the formula (2). R ^5a corresponds to one of R ⁵ and R ⁶ in the above formula (2), and a hydrogen atom corresponds to the other.

  As a more specific example, when the group represented by the above formula (2) contains a tetrahydropyranyl ring structure, the [A] polysiloxane having the group is an acid catalyst as shown in the following reaction formula. Can be synthesized by reacting dihydropyran with the carboxyl group of the carboxyl group-containing polysiloxane in the presence of.

  [A] The polysiloxane can be formed by the following method in addition to the method of protecting the carboxyl group of the carboxyl group-containing polysiloxane as described above by a known method.

  In other words, the above-described carboxyl group-containing polysiloxane can be formed by using the silane compound of the above formula (5) and hydrolyzing and condensing them.

At this time, the group R ¹⁴ of the silane compound of the formula (5) is hydrolyzed or alcoholized to generate the organic group of the formula (4), and the carboxyl group contained in the organic group is known. The organic group having a structure represented by the following formula (4-1) is formed in advance from the organic group of the above formula (4) by protection by a method. The substituents R ¹⁴ are, using a silane compound of the above formula was a group having an organic group in which Kabokishiru group represented by the following formula (4-1) protected (5) with other above-mentioned silane compound They can be hydrolyzed and condensed to form [A] polysiloxane.

  Furthermore, [A] polysiloxane contained in the radiation-sensitive resin composition for display elements of this embodiment is at least one of the group represented by the above formula (1) and the group represented by the above formula (2). In addition, it is preferable to have a crosslinkable group that undergoes a crosslinking reaction by heating. [A] Since the polysiloxane has the above-mentioned crosslinkable group, the coating film obtained from the radiation-sensitive resin composition for display elements of this embodiment is excellent due to the crosslinking reaction of the crosslinkable group generated by heating. A curable cured film can be formed.

  An example of the crosslinkable group is 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] the introduction of the aforementioned crosslinkable groups into the polysiloxane as part of a silane compound represented by the above formula (6), the formula (6) substituents R ¹⁶ are the above-mentioned crosslinkable silane compound This can be realized by using a silane compound which is a group containing a group.

In that case, the co-condensation ratio of the silane compound in which the substituent R ¹⁶ of the silane compound of the formula (6) is replaced with the above-described group having a crosslinkable group is not particularly limited, but the co-condensation ratio of the silane compound is When the cocondensation component used for the polymerization is 100 parts by mass, it is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less. By setting it as the above range, a cured product having sufficient hardness can be obtained.

[A] The polysiloxane may be a blend of two or more polysiloxanes. In that case, one kind of polysiloxane among the polysiloxanes used in the blend can be obtained by using the silane compound represented by the above formula (6). In addition, instead of the silane compound represented by the above formula (6), the substituent R ¹⁶ of the silane compound of the above formula (6) contains the above crosslinkable group in another polysiloxane used in the blend. It is possible to obtain a polysiloxane obtained by using a silane compound substituted for the group (hereinafter simply referred to as a crosslinkable polysiloxane). And [A] siloxane which has a crosslinkable group can be obtained as a blend polymer by mixing and containing them.

  In this case, the amount of the polysiloxane formed using the silane compound represented by the above formula (6) and the crosslinkable group-containing polysiloxane is 100 parts by mass of the co-condensation component used for the polymerization. , Preferably they are 1 mass part or more and 50 mass parts or less, More preferably, they are 3 mass parts or more and 30 mass parts or less. By setting it as the said range, the radiation sensitive resin composition for display elements of this embodiment can form the hardened | cured material which has sufficient hardness.

[[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 for display elements of the present embodiment includes [B] a photoacid generator, and thus exhibits positive radiation sensitive characteristics and is used as a positive radiation sensitive resin composition. can do.

  [B] The photoacid generator is a compound that generates an acid upon irradiation with radiation. Examples of the acid generated include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentasulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, cyclohexanesulfonic acid, Examples thereof include benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, tetrafluoroborate, trifluoroacetate and the like.

  Moreover, such a [B] photo-acid generator can be thermally decomposed and generate | occur | produced by heating at about 200 degreeC. The acid generated by such heat functions as a crosslinking catalyst in the post-bake process. And a highly reliable cured film with high hardness can be obtained from the coating film of the radiation sensitive resin composition for display elements of this embodiment by accelerating | stimulating a crosslinking reaction. More specifically, this promotes the cross-linking reaction, and a film made of polysiloxane having a high cross-linking density can be formed. A film made of polysiloxane having a high crosslinking density has high heat resistance and can suppress the amount of gas generated by thermal decomposition. For this reason, when it uses for the film | membrane which comprises a semiconductor element, an organic EL element, etc., it becomes possible to improve reliability.

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

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

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

In the above formula (3), the R ^a alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of Ra includes ^a C1-C10 alkoxy group or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group). Group) and the like. As the aryl group for ^Ra, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ^a may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing the oxime sulfonate group represented by the above formula (3) is more preferably an oxime sulfonate compound represented by the following formula (3-1) and the following formula (3-2).

In the above formula (3-1) and the above formula (3-2), R ^a has the same ^{meaning as} the description of R ^a in the above formula (3). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, the plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above formula (3-1) and the above formula (3-2), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the above formula (3-1), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Specific examples of the oxime sulfonate compound represented by the above formula (3) include, for example, the following formula (3-1-i) to formula (3-1-iv) and formula (3-2-i) to formula (3): 3-2-ii), compound (3-1-i), compound (3-1-ii), compound (3-1-iii), compound (3-1-iv), compound (3) -2-i) and compound (3-2-ii).

(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- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl Dicarboxylimide, N- (phenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluoro Olophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxyl Imide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octyl) Ruhoniruokishi) naphthyl dicarboxyl imide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like.

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

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

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

  [B] One photoacid generator may be used alone, or two or more photoacid generators may be mixed and used. As content of [B] photo-acid generator in the radiation sensitive resin composition for display elements of this embodiment, Preferably it is 0.1 mass part-15 mass parts with respect to 100 mass parts of [A] polysiloxane. More preferably, it is 1 mass part-10 mass parts. [B] When the content of the photoacid generator is in the above range, the radiation sensitivity of the radiation-sensitive resin composition for display elements can be optimized.

[[C] Compound having cyclic ether group]
The radiation-sensitive resin composition for display elements of the present embodiment contains the above-mentioned [A] polysiloxane and [B] photoacid generator, and further contains a compound having [C] a cyclic ether group. be able to.

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

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

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

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

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

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

[[D] Antioxidant]
The radiation-sensitive resin composition for display elements of this embodiment contains the above-mentioned [A] polysiloxane and [B] photoacid generator, and further has the above-mentioned [C] cyclic ether group. Although a compound can be contained, [D] antioxidant can be contained further.

  [D] The antioxidant can decompose radicals generated by exposure or heating in the photosensitive resin composition of the present embodiment, or peroxide generated by oxidation, and prevents bond breakage of polymer molecules. Is a component that can. As a result, the cured film obtained from the photosensitive resin composition of the present embodiment is used for display elements and semiconductor elements to prevent oxidative deterioration during use, and can improve, for example, light resistance.

  [D] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, a compound having a thioether structure, etc., and particularly has a hindered phenol structure. Compounds are preferred.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione). -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-t-butyl-4- Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3, ', 3', 5 ', 5'-hexa-tert-butyl-a, a', a '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthio) Methyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate, hexa Methylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl ] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3 , 5- Triazine-2-ylamine) phenol, and the like.

  Examples of commercially available compounds having the above-mentioned hindered phenol structure include, for example, ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, and AO-70. AO-80, AO-330 (above, manufactured by ADEKA), sumilizer (registered trademark) GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, Manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD (Registered trademark) 295 (above, manufactured by Ciba Japan), Yoshinox (registered trademark) BHT, BB, 2246G, 425, 250, 30, the SS, the TT, the 917, the 314 (or more, API Corporation Co., Ltd.), and the like.

  Of these [D] antioxidants, compounds having a hindered phenol structure are preferred, and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3, 5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 2,6-di-t-butyl-4-cresol are more preferable.

  These compounds can be used alone or in combination of two or more. In the photosensitive resin composition of the present embodiment, the content of [D] antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 100 parts by mass of [A] polysiloxane. Is 0.2 parts by mass or more and 5 parts by mass or less. [D] By making content of antioxidant into the said specific range, the oxidative degradation of the obtained cured film can be suppressed.

  The radiation-sensitive resin composition for display elements of this embodiment is within the range that does not impair the effects of the present invention, and if necessary, in addition to the [E] basic compound described later, an ultraviolet absorber, a surfactant, and storage. Other optional components such as a stabilizer, an adhesion assistant (including a silane coupling agent), and a heat resistance improver 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 for display element]
The radiation-sensitive resin composition for display elements of the present embodiment includes a compound having a [C] cyclic ether group, which is added as necessary in addition to the above [A] polysiloxane and [B] photoacid generator, D] Prepared by mixing an antioxidant, and [E] a basic compound and other optional ingredients.
[D] As mentioned above, examples of the antioxidant include a compound containing a hindered phenol structure, a compound containing a hindered amine structure, a compound containing an alkyl phosphite structure, and a compound containing a thioether structure. [D] The antioxidant can suppress oxidative deterioration of the cured film due to light irradiation. Of these, compounds containing a hindered phenol structure are particularly preferred.
Moreover, by containing [E] a basic compound, the diffusion length of the acid generated from the acid generator by exposure can be appropriately controlled, and the pattern developability can be improved. [E] The basic compound can be arbitrarily selected from those used in chemically amplified resists. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, carboxylic acid quaternary ammonium Examples include salts. Of these, aliphatic amines and heterocyclic amines are particularly preferred.

  The radiation-sensitive resin composition for display elements of this embodiment is preferably prepared and used in a state where each component contained is dissolved or dispersed in a suitable solvent. For example, in a solvent, the [A] component ([A] polysiloxane), the [B] component ([B] photoacid generator), and the possible [C] component (having a [C] cyclic ether group Compound), [D] component ([D] antioxidant), [E] component (basic compound), and other arbitrary components are mixed at a predetermined ratio, thereby providing a radiation-sensitive resin composition for display elements. Product can be prepared.

  As the solvent that can be used for the preparation of the radiation sensitive resin composition for display element of the present embodiment, as described above, those that uniformly dissolve or disperse each component and do not react with each component are preferably used. .

  As a solvent which can be used for preparation of the radiation sensitive resin composition for display elements of this embodiment, the polymerization solvent illustrated as what is used for the polymerization reaction for obtaining [A] polysiloxane can be mentioned.

  Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, vinegar i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred, propylene glycol monomethyl ether acetate is more preferable.

  These solvents can be used alone or in admixture of two or more.

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

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

<Manufacture of cured film>
Next, the cured film of this embodiment using the radiation sensitive resin composition for display elements of this embodiment mentioned above and its manufacturing method are demonstrated.

  The cured film of the present embodiment can be obtained as a highly reliable cured film manufactured using the radiation-sensitive resin composition for display elements of the present embodiment and patterned into a desired shape by a photolithography method. it can. The manufacturing method of the cured film of this embodiment can be comprised including the following processes as main processes and including the following processes in the following order.

(1) The process of forming the coating film of the radiation sensitive resin composition for display elements of this embodiment on a board | substrate (Hereinafter, it may only be called a coating film formation process.),
(2) A step of irradiating at least a part of the coating film formed in step (1) (hereinafter sometimes simply referred to as a radiation irradiation step),
(3) a step of developing the coating film irradiated with radiation in step (2) (hereinafter, simply referred to as a developing step), and (4) heating the coating film developed in step (3). (Hereinafter, simply referred to as a heating step).

  Fig.1 (a)-(d) is typical sectional drawing which shows each manufacturing process of the manufacturing method of the cured film of embodiment of this invention.

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

(1) Coating film forming step As shown in FIG. 1 (a), in the (1) coating film forming step, the radiation-sensitive resin composition of the present embodiment is applied onto the substrate 1, and preferably prebaked. By removing the solvent, a coating film 2 of the radiation-sensitive resin composition for display elements is formed.

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

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

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

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

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

  In the exposure unit 5, acid is generated by the action of the [B] photoacid generator such as a photoacid generator contained in the coating film 2. At this time, the group represented by the above formula (1) and / or the group represented by the above formula (2) contained in the [A] polysiloxane contained in the coating film 2 is dissociated so that an acid dissociable group is removed by an acid. Shows the reaction. Therefore, in the part where the acid dissociable group of [A] polysiloxane is dissociated, a carboxyl group having an acid dissociable group and having alkali solubility remains. Thus, the part which generated the carboxyl group of the coating film 2 which consists of [A] polysiloxane is removed by a subsequent image development process. On the other hand, no acid is generated by the [B] photoacid generator in the unexposed area. Therefore, the group represented by the above formula (1) and / or the group represented by the above formula (2) possessed by [A] polysiloxane is in a state in which the carboxy group remains protected with an acid dissociable group, Even in the subsequent development process, it is not alkali-developed and is not removed. As a result, a part that dissolves in the developer and a part that does not dissolve are formed in the coating film 2 in accordance with the pattern of exposure (existence of exposure), thereby enabling the coating film 2 to be patterned.

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

  As the developer used in the development processing in this step, for example, an aqueous solution of an alkali (basic compound) such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or the like is used. it can. Also, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition of the present embodiment. Can be used as a developer. As the organic solvent, those mentioned as the polymerization solvent for obtaining the above-mentioned [A] polysiloxane can be used.

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

(4) Heating step As shown in FIG. 1 (d), in the (4) heating step, an appropriate heating device such as a hot plate or an oven is used to form the patterned coating film 2 ′ shown in FIG. 1 (c). Heat. As described above, the [A] polysiloxane constituting the coating film 2 ′ has a group represented by the above formula (1) and / or a group represented by the above formula (2) protected with an acid dissociable group. It remains in a state. On the other hand, in this step, the acid dissociation of the group represented by the above formula (1) and / or the group represented by the above formula (2) in the [A] polysiloxane of the coating film 2 ′ by heating. This causes a dissociation reaction in which the sex group is released. As a result, the [A] polysiloxane constituting the coating film 2 ′ generates an alkali-soluble carboxyl group having no acid-dissociable group. [A] When the polysiloxane contains a crosslinkable group such as the above-described epoxy group, the generated carboxyl group and the epoxy group undergo an addition reaction to form a crosslinked structure. Therefore, by this heating step, the coating film 2 ′ can be made into a cured film 6 having excellent hardness, and a patterned cured film 6 can be formed on the substrate 1.

  The heating temperature in this step is, for example, 120 ° C to 250 ° C. The heating time varies depending on the type of the heating device. For example, when heat treatment is performed on a hot plate, it may be 5 minutes to 30 minutes, and when heat treatment is performed in an oven, it may be 30 minutes to 180 minutes. it can.

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

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

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

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

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

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

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

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

  Examples of the material of the metal oxide conductive film constituting the gate electrode 21 include metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Can be mentioned.

  Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.

  The thickness of the gate electrode 21 is preferably 10 nm to 1000 nm.

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

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

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

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

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

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

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

  For example, when the semiconductor layer 12 using an amorphous oxide is formed using IGZO or ZTO, a semiconductor layer is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method. Etc. are used for patterning by a resist process and an etching process. The thickness of the semiconductor layer 12 using an amorphous oxide is preferably 1 nm to 1000 nm.

  By using the oxides exemplified above, the semiconductor layer 12 with high mobility can be formed at a low temperature, and the semiconductor element 11 of this embodiment including the semiconductor layer 12 can be provided.

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

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

  As described above, the cured film 15 is formed by applying the radiation-sensitive resin composition for display elements of the embodiment of the present invention onto the substrate 20 on which the gate electrode 21, the gate insulating film 22, the semiconductor layer 12, and the like are formed. Then, after performing necessary patterning such as formation of the through hole 16, it is formed by heating. The cured film 15 can be easily formed on the semiconductor layer 12 by the radiation-sensitive resin composition for display elements of the present invention.

  At this time, as an element configured using the semiconductor element 11, for example, there is a liquid crystal display element as described above. In the case of a liquid crystal display element, although not shown, the liquid crystal display element is manufactured by sandwiching a liquid crystal between a semiconductor substrate having the semiconductor element 11 and a color filter substrate having a color filter. In general, a backlight unit is disposed on the semiconductor substrate side to enable image display with a high contrast ratio.

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

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

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

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

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

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

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

  It is also possible to use the semiconductor element of the above-described embodiment of the present invention for the TFT 103. By having such a configuration, in another example of the organic EL display element of the embodiment of the present invention, it is possible to achieve both excellent driving characteristics and reliability. 3 schematically shows the structure of the TFT 103. The gate electrode 104, the gate insulating film 105, the semiconductor layer 106, the first source-drain electrode 107, and the second source-drain electrode 108 of the TFT 103 are shown. Only shown.

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

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

  Since the anode 111 disposed on the cured film 110 that is the first insulating film is connected to the second source-drain electrode 108, a through hole 112 is formed in the cured film 110 so as to pass therethrough. The through hole 112 is formed so as to penetrate the inorganic insulating film 119 under the cured film 110. The cured film 110 can be formed using the radiation sensitive resin composition for display elements of this embodiment described above. Therefore, according to the above-described method for producing a cured film, the cured film 110 having a through hole having a desired shape is formed by irradiating the coating film of the radiation-sensitive resin composition for display elements with radiation, and then the cured film 110 is masked. By performing dry etching on the inorganic insulating film 119, the through hole 112 can be completed. In the case where the inorganic insulating film 119 is not disposed on the TFT 103, the through hole formed in the cured film 110 constitutes the through hole 112. As a result, the anode 111 covers at least a part of the cured film 110 and is connected to the TFT 103 via the through hole 112 provided in the cured film 110 so as to penetrate the cured film 110. 108 can be connected.

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

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

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

  An organic light emitting layer 114 that emits light by applying an electric field is disposed in a region defined by the cured film 113 that is the second insulating film. The organic light emitting layer 114 is a layer containing an organic light emitting material that emits electroluminescence.

  The organic EL display element 101 of this embodiment has a cathode 115 on the organic light emitting layer 114, and the cathode 115 is made of a conductive member.

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

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

  In the organic EL display element 101 of the present embodiment having the above structure, the cured film 110 as the first insulating film and the cured film 113 as the second insulating film, which are constituent elements, are made of polysiloxane and heated. When the water is removed, it does not cause deterioration such as coloring. Therefore, it is possible to reduce a slight amount of moisture contained in the conventional insulating film forming material in the form of adsorbed water from gradually entering the organic light emitting layer 114, thereby preventing deterioration of the organic light emitting layer 114 and inhibition of the light emitting state. Can be reduced.

  Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

<Synthesis of polysiloxane>
(Synthesis Example 1)
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 25 parts by mass of methyltrimethoxysilane, 40 parts by mass of phenyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid (trade name: X (12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts by mass and 15 parts by mass of trimethylmethoxysilane were charged and heated until the solution temperature reached 60 ° C.

  After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (a-1) was obtained. Polysiloxane (a-1) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 4000, and a dispersity (Mw / Mn (number average molecular weight)) of 2.0. In the present specification, the “solid content” means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances.

As a result of conducting FT-IR (Fourier transform infrared spectroscopy) analysis of polysiloxane (a-1), a broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was confirmed. It was confirmed that the succinic acid residue derived from 3-trimethoxysilylpropyl succinic acid was hydrolyzed and had a carboxyl group.

Subsequently, 40 mass parts of ethyl vinyl ether was added to the obtained polysiloxane (a-1) solution, and it stirred at room temperature for 3 hours. Then, as a result of conducting FT-IR analysis of the obtained solution, it was confirmed that the intensity of the broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was decreased. It was confirmed that the carboxyl group reacted with ethyl vinyl ether to form an acid dissociable group. Let the obtained solution be polysiloxane (A-1).

(Synthesis Example 2)
The polysiloxane (A-2) was obtained by the same method except that dihydrofuran was added instead of ethyl vinyl ether to the polysiloxane (a-1) solution obtained in (Synthesis Example 1).

(Synthesis Example 3)
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 30 parts by mass of phenyltrimethoxysilane, 35 parts by mass of 3-methacryloxypropyltrimethoxysilane, and 20-trimethoxysilylpropyl succinic acid. Part by mass and 15 parts by mass of trimethylmethoxysilane were charged and heated until the solution temperature reached 60 ° C.

  After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (a-2) was obtained. Polysiloxane (a-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5000, and a dispersity (Mw / Mn) of 2.0.

As a result of conducting FT-IR (Fourier transform infrared spectroscopy) analysis of polysiloxane (a-2), a broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was confirmed. It was confirmed that the succinic acid residue derived from 3-trimethoxysilylpropyl succinic acid was hydrolyzed and had a carboxyl group.

Subsequently, 40 mass parts of dihydrofuran was added to the obtained polysiloxane (a-2) solution, and it stirred at room temperature for 3 hours. Then, as a result of conducting FT-IR analysis of the obtained solution, it was confirmed that the intensity of the broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was decreased. It was confirmed that the carboxyl group reacted with dihydrofuran to form an acid dissociable group. Let the obtained solution be polysiloxane (A-3).

(Synthesis Example 4)
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 35 parts by mass of phenyltrimethoxysilane, 30 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 3-trimethoxysilylpropyl succinic acid. 20 parts by mass and 15 parts by mass of trimethylmethoxysilane were charged and heated until the solution temperature reached 60 ° C.

  After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (a-3) was obtained. Polysiloxane (a-3) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 5000, and a dispersity (Mw / Mn) of 2.0.

As a result of conducting FT-IR (Fourier transform infrared spectroscopy) analysis of polysiloxane (a-3), a broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was confirmed. It was confirmed that the succinic acid residue derived from 3-trimethoxysilylpropyl succinic acid was hydrolyzed and had a carboxyl group.

Next, 40 parts by mass of dihydrofuran was added to the obtained polysiloxane (a-3) solution, and the mixture was stirred at room temperature for 3 hours. Then, as a result of conducting FT-IR analysis of the obtained solution, it was confirmed that the intensity of the broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm ^{−1 to} 3000 cm ⁻¹ was decreased. It was confirmed that the carboxyl group reacted with dihydrofuran to form an acid dissociable group. Let the obtained solution be polysiloxane (A-4).

(Synthesis Example 5)
In a vessel equipped with a stirrer, 24 parts by mass of propylene glycol monomethyl ether was charged, followed by 40 parts by mass of phenyltrimethoxysilane, 40 parts by mass of 3-glycidoxypropyltrimethoxysilane, 5 parts by mass of trimethylmethoxysilane, methyl 15 parts by mass of trimethoxysilane was charged and heated until the solution temperature reached 60 ° C.

  After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, polysiloxane (a-4) was obtained. Polysiloxane (a-4) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 4000, and a dispersity (Mw / Mn) of 2.0.

<Preparation of radiation-sensitive resin composition for display element>
Example 1
As the component [A], the solution containing the polysiloxane (A-1) obtained in Synthesis Example 1 (the amount corresponding to 100 parts by mass (solid content) of the polysiloxane (A-1)) 4 parts by mass of trifluoromethanesulfonic acid-1,8-naphthalimide (B-1) as a photoacid generator and 0.01 part by mass of 4-dimethylaminopyridine as a basic compound are mixed, and the pore size is 0.2 μm. The membrane was filtered through a membrane filter to prepare a radiation-sensitive resin composition for display elements (S-1).

(Example 2)
As a component [A], a solution containing the polysiloxane (A-2) obtained in Synthesis Example 2 (amount corresponding to 100 parts by mass (solid content) of the polysiloxane (A-2)) is added as a component [B]. 4 parts by weight of benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (B-2) which is a photoacid generator, and di [1-ethyl- (3- By mixing 25 parts by mass of oxetanyl) methyl] ether (C-1) and 0.01 parts by mass of 4-dimethylaminopyridine, which is a basic compound, the mixture is filtered through a membrane filter having a pore size of 0.2 μm. A radiation sensitive resin composition (S-2) was prepared.

(Example 3)
As the component [B], the solution containing the polysiloxane (A-3) obtained in Synthesis Example 3 as the component [A] (the amount corresponding to 100 parts by mass (solid content) of the polysiloxane (A-3)) (B-4) which is a photoacid generator: 4 parts by mass of (5-methylsulfonyloxyimino) -phenylacetonitrile, and a compound having a cyclic ether group as the [C] component (C-2): phenol novolak Type epoxy resin (Epicoat 152 (registered trademark) manufactured by Japan Epoxy Resin Co., Ltd.), 10 parts by mass, [D] component, 2,6-di-t-butyl-4-cresol (D-1) 0 as an antioxidant .5 parts by mass and 0.01 part by mass of 4-dimethylaminopyridine, which is a basic compound, are mixed and filtered through a membrane filter having a pore size of 0.2 μm, thereby providing a radiation-sensitive tree for display elements. Composition (S-3) was prepared.

Example 4
As a component [A], a solution containing the polysiloxane (A-4) obtained in Synthesis Example 4 (amount corresponding to 100 parts by mass (solid content) of the polysiloxane (A-4)) is added as a component [B]. (B-4) :( 5-methylsulfonyloxyimino) -phenylacetonitrile], which is a photoacid generator, 4 parts by mass, and as a [C] component, di [1-ethyl- ( 3-Oxetanyl) methyl] ether (C-1) 15 parts by mass, and as component [D], 0.5 parts by mass of 2,6-di-t-butyl-4-cresol (D-1) as an antioxidant Then, 0.01 parts by mass of 4-dimethylaminopyridine which is a basic compound is mixed and filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (S-4) for display elements. did.

(Example 5)
[A] As a component, obtained in Synthesis Example 5 with a solution containing polysiloxane (A-2) obtained in Synthesis Example 2 (an amount corresponding to 50 parts by mass (solid content) of polysiloxane (A-2)). A solution containing polysiloxane (a-4) (a quantity corresponding to 50 parts by mass (solid content) of polysiloxane (a-4)), a component [B], which is a photoacid generator as described above. Compound (3-1-iv) ([(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile]) (B-3) 5 parts by mass, [C] As components, 25 parts by mass of di [1-ethyl- (3-oxetanyl) methyl] ether (C-1) which is a compound having a cyclic ether group, 0.01 parts by mass of 4-dimethylaminopyridine which is a basic compound The pore size By filtration through a membrane filter of .2Myuemu, the display device for radiation-sensitive resin composition (S-5) was prepared.

  The main components used in the above examples are summarized as follows.

[Photoacid generator: [B] component]
(B-1): trifluoromethanesulfonic acid-1,8-naphthalimide (B-2): benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (B-3): compound (3-1-iv)
(B-4): (5-Methylsulfonyloxyimino) -phenylacetonitrile]

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

[Antioxidant: [D] component]
(D-1) 2,6-di-t-butyl-4-cresol

[Basic compound]: 4-dimethylaminopyridine The basic compound is mentioned as the above-mentioned [E] component, and is added in a small amount for the purpose of controlling the diffusion of the acid generated from the photoacid generator.

(Comparative Example 1)
[A] solution containing polysiloxane (a-4) having no acid dissociable group obtained in Synthesis Example 5 as component (amount corresponding to 100 parts by mass (solid content) of polysiloxane (a-4)) Was used. To this, 35 parts by mass of a quinonediazide compound (d-1) (compound shown below) is mixed, dissolved in diethylene glycol ethyl methyl ether, filtered through a membrane filter having a diameter of 0.2 μm, and radiation sensitive for a display element. Resin composition (s-1).

<Evaluation of cured film>
Using each of the radiation-sensitive resin compositions for display elements prepared in Examples 1 to 4 and Comparative Example 1, according to the following method, the characteristics of the radiation-sensitive resin composition for display elements, and those The properties of the cured film obtained by using were evaluated. The evaluation results are summarized in Table 1 below.

(1) Evaluation of radiation sensitivity Hexamethyldisilazane (HMDS) was applied on a 550 × 650 mm chromium film and heated at 60 ° C. for 1 minute (hereinafter also referred to as HMDS treatment). On the chromium film-forming glass after this HMDS treatment, each of the radiation sensitive resin compositions for display elements ((S-1) to (S-5)) prepared in Examples 1 to 5 and Comparative Example 1 and (S-1)) was applied using a spin coater. Then, the coating film with a film thickness of 3.0 micrometers was formed by further prebaking for 3 minutes at 90 degreeC. Subsequently, using a MPA-600FA exposure machine manufactured by Canon Inc., the coating film was irradiated with radiation with a proxy gap of 10 μm and an exposure amount as a variable amount through a mask having a contact hole pattern of 10 μm. Thereafter, development was performed at 25 ° C. for 70 seconds with a tetramethylammonium hydroxide aqueous solution having a developer concentration of 0.4 mass%. Next, washing with running ultrapure water was performed, followed by drying to form a pattern on the glass substrate after the HMDS treatment. At this time, the exposure amount closest to the contact hole diameter of 10 μm was defined as radiation sensitivity. When this value was 500 (J / m ² ) or less, it was judged that the radiation sensitivity was good.

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

(3) Evaluation of transmittance In the same manner as the evaluation of light resistance, each radiation-sensitive resin composition for display elements ((S-) prepared on Examples 1 to 5 and Comparative Example 1 on a silicon substrate. The coating films of 1) to (S-5) and (s-1)) were formed. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. About each obtained cured film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer ("150-20 type double beam" by Hitachi, Ltd.). At this time, if it is less than 90%, it can be said that the transparency is poor.

(4) Measurement of thermogravimetric reduction amount of cured film Similar to the above-described evaluation of light resistance, each of the radiation-sensitive resin compositions for display elements prepared in Examples 1 to 5 and Comparative Example 1 on a glass substrate. The coating film of the thing ((S-1)-(S-5) and (s-1)) was formed. This substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. Each of the obtained substrates having a cured film was cut into 1 cm squares, heated to 230 ° C. with a temperature programmed desorption analyzer (TDS1200, manufactured by Denki Kagaku), and gas generated when held for 30 minutes. The amount was measured. Radiation-sensitive resin for display elements of Examples using relative values, with the amount of gas generated from the cured film formed from the radiation-sensitive resin composition for display elements (s-1) of Comparative Example being 100 The amount of gas generated from the cured film formed from the composition ((S-1) to (S-5)) is evaluated. Table 1 below, which summarizes the evaluation results, shows the above-mentioned relative values as the thermogravimetric reduction amount. And when this relative value is 70 or less, it can be judged that there is little thermogravimetric reduction, and it can be judged that the amount of gas generated from a cured film is small.

(5) Evaluation of film thickness change rate (storage stability)
About the cured film formation composition immediately after preparation, the film thickness of the cured film formed similarly to "(1) Evaluation of radiation sensitivity" was measured (in the following formula, it is called "film thickness immediately after preparation").

Further, the composition was stored at 25 ° C. for 5 days, and the film thickness of a cured film similarly formed after 5 days was measured (referred to as “film thickness after 5 days” in the following formula). The film thickness increase rate (%) was calculated from the following formula. When the film thickness increase rate was 3% or less, it was judged that the storage stability was good.

  As shown in Table 1, the radiation-sensitive resin compositions (S-1) to (S-5) for display elements of Examples 1 to 5 have good radiation sensitivity and are formed using them. The cured film is excellent in patternability. And these hardened | cured films have favorable light resistance, favorable transmittance | permeability characteristics, and also there are few gas generation amounts by thermal decomposition.

  On the other hand, the radiation sensitive resin composition for display element (s-1) of Comparative Example 1 was not good in radiation sensitivity, and the light resistance and transmittance of the formed cured film were not good.

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

Claims (11)

[A] A polysiloxane having at least one of a group represented by the following formula (1) and a group represented by the following formula (2), and [B] a feeling for a display element comprising a photoacid generator Radiation resin composition.

(In formula (1), 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 (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 obtained by substituting a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms with a hydroxyl group, a halogen atom or a cyano group.
In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is an integer of 1 or 2. )   [A] The radiation-sensitive resin composition for display elements according to claim 1, wherein the polysiloxane further has a crosslinkable group.   The radiation-sensitive resin composition for display elements according to claim 1, wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxiranyl group.   The radiation-sensitive resin composition for display elements according to any one of claims 1 to 3, further comprising a compound having [C] a cyclic ether group (excluding the component [A]). [B] The radiation-sensitive element for a display element according to any one of claims 1 to 4, wherein the photoacid generator is a compound containing an oxime sulfonate group represented by the following formula (3). Resin composition.

(In Formula (3), R ^a is an alkyl group, an alicyclic hydrocarbon group, or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.)   Furthermore, [D] antioxidant is contained, The radiation sensitive resin composition for display elements of any one of Claims 1-5 characterized by the above-mentioned.   A cured film obtained by using the radiation-sensitive resin composition for display elements according to any one of claims 1 to 6. [1] A step of forming a coating film of the radiation-sensitive resin composition for display elements according to any one of claims 1 to 6 on a substrate,
[2] A step of irradiating at least a part of the coating film of the radiation-sensitive resin composition for display elements,
[3] A method for producing a cured film, comprising: a step of developing the coating film irradiated with radiation; and [4] a step of heating and curing the developed coating film.   A semiconductor device comprising the cured film according to claim 7.   A display element comprising the cured film according to claim 7.   The display element according to claim 10, wherein the semiconductor element according to claim 9 is used as an active element.

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