JP2014174406A - Radiation-sensitive resin composition, cured film, light-emitting display element and method for producing light-emitting layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of easily forming a highly reliable cure film which contains a quantum dot composed of a safety material and has patternability and excellent fluorescent characteristics, and to provide a cured film, a light-emitting display element and a method for producing a light-emitting layer.SOLUTION: A radiation-sensitive resin composition is obtained by incorporating [A] an alkali-soluble resin, [B] a photo-acid generating body and [C] a semiconductor quantum dot. A cure film is formed on a substrate 12 using the radiation-sensitive resin composition. A wavelength conversion substrate 11 is formed by using the cured film as a light-emitting layer 13 and a light-emitting display element 100 is constituted in combination with a light source substrate 18 provided with a light source 17.

Description

  The present invention relates to a radiation-sensitive resin composition, a cured film, a light-emitting display element, and a method for forming a light-emitting layer.

  Extremely small particles (dots) formed to confine electrons are called quantum dots and have recently attracted attention. The size of one quantum dot is several nanometers to several tens of nanometers in diameter, and is composed of about 10,000 atoms.

  When quantum dots are dispersed in a semiconductor thin film of a solar cell panel, energy conversion efficiency can be greatly improved, so application to solar cells has been studied (for example, see Patent Document 1). .) In addition, by changing the size of the quantum dots (changing the band gap), it is possible to change the color (emission wavelength) of the emitted fluorescence (wavelength conversion), so fluorescent probes in bio research (see Non-Patent Document 1) And application to a display element as a wavelength conversion material (see Patent Document 2 and Patent Document 3).

JP 2006-216560 A JP 2008-112154 A JP 2009-251129 A

Shintaka, “Semiconductor quantum dots, their synthesis and application to life science,” Production and Technology, Vol. 63, No. 2, 2011, p58-p65

  As shown in Examples of Non-Patent Document 1 and Patent Document 1, typical quantum dots are semiconductors made of II-V semiconductors such as CdSe (cadmium selenide), CdTe (cadmium telluride), and PbS. It is a quantum dot.

  However, for example, lead (Pb), which is the main component, is a material that is well known for its concern for toxicity. Further, cadmium (Cd) and its compounds are extremely toxic even at low concentrations, and are materials for which renal dysfunction and carcinogenicity are a concern. Therefore, there is a demand for the formation of semiconductor quantum dots made of a safer material.

  In addition, when semiconductor quantum dots are to be applied to a solar cell panel, a display of a display element, or the like, formation of a film or a layer composed of semiconductor quantum dots in a particle form may be required in order to utilize the fluorescence emission. That is, the formation of a wavelength conversion film (wavelength conversion film) or a light emitting layer that exhibits fluorescence may be required.

  As a method for forming a light emitting layer using semiconductor quantum dots in the form of particles, for example, as shown in the examples of Patent Document 1 and Patent Document 2, a layer made of semiconductor quantum dots is directly formed on an appropriate substrate. Methods of forming are known. However, in such a formation method, the stability of the obtained light emitting layer is poor. In particular, there is concern about the binding property between the layer made of semiconductor quantum dots and the substrate.

  Therefore, a method of forming a layer or a film by mixing or embedding semiconductor quantum dots in a particle form in a resin material has been proposed. However, a method for forming a layer or a film together with a resin using a semiconductor quantum dot while maintaining its fluorescence characteristics has not been sufficiently studied.

  Therefore, there is a need for a technique for using a semiconductor quantum dot together with a resin material to form a semiconductor quantum dot layer without reducing the fluorescence emission characteristics of the semiconductor quantum dot and to form a highly reliable light emitting layer. In particular, there is a demand for a resin material that is used together with semiconductor quantum dots and that is suitable for forming a light emitting layer made of semiconductor quantum dots and a resin.

  In that case, it is desirable that the resin material be used together with a semiconductor quantum dot made of a safe material and be suitable for forming a light emitting layer.

In addition, the light-emitting layer made of the semiconductor quantum dots and the resin material can be easily formed, and preferably has high productivity. Therefore, it is preferable that a simple forming method such as coating can be used for forming the light emitting layer made of the semiconductor quantum dots and the resin material. And it is preferable that the light emitting layer can be formed using methods, such as application | coating, from the liquid resin composition containing a semiconductor quantum dot and a resin component, for example.
Therefore, there is a demand for a resin composition that contains a semiconductor quantum dot and a resin component, and that can form a light emitting layer by using a method such as coating.

Furthermore, it is preferable that the resin composition has an excellent patterning property. That is, the resin composition for forming the light emitting layer is preferably capable of forming a patterned light emitting layer so that it can be suitably used for the structure of a light emitting display element, for example. In that case, the formation of the patterned light-emitting layer can be performed easily, for example, by using a photolithography method or the like.
Therefore, there is a demand for a radiation-sensitive resin composition that can easily form a patterned light-emitting layer using a known patterning method such as a photolithography method.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a radiation-sensitive resin composition that includes a semiconductor quantum dot made of a safe material, has a patterning property, and can easily form a highly reliable cured film having excellent fluorescence characteristics. It is to be.

  Another object of the present invention is to provide a cured film that is formed using a radiation-sensitive resin composition having a patterning property including a semiconductor quantum dot made of a safe material, having excellent fluorescence characteristics and high reliability. It is to be.

  Moreover, the objective of this invention is providing the light emitting display element which has a light emitting layer formed using the radiation sensitive resin composition provided with patterning property including the semiconductor quantum dot which consists of a safe material.

  Furthermore, the objective of this invention is providing the formation method of the light emitting layer of a light emitting display element using the radiation sensitive resin composition which has the patternability including the semiconductor quantum dot which consists of a safe material.

  Other objects and advantages of the present invention will become apparent from the following description.

The first aspect of the present invention is:
[A] alkali-soluble resin,
[B] A photoacid generator, and [C] a radiation sensitive resin composition comprising a semiconductor quantum dot.

  In the first aspect of the present invention, the [C] semiconductor quantum dot is at least two kinds selected from the group consisting of a group 2 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element. It is preferable to consist of a compound containing an element.

  1st aspect of this invention WHEREIN: It is preferable that a [C] semiconductor quantum dot consists of a compound which contains In as a structural component.

In the first aspect of the present invention, the [C] semiconductor quantum dot comprises an InP / ZnS compound, a CuInS ₂ / ZnS compound, an AgInS ₂ compound, a (ZnS / AgInS ₂ ) solid solution / ZnS compound, a Zn-doped AgInS ₂ compound, and a Si It is preferably at least one selected from the group consisting of compounds.

  In the first aspect of the present invention, the [A] alkali-soluble resin is preferably at least one selected from the group consisting of an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin.

  1st aspect of this invention WHEREIN: It is preferable that a [B] photo-acid generator consists of a quinonediazide compound.

  1st aspect of this invention WHEREIN: It is preferable that content of [C] semiconductor quantum dot with respect to 100 mass parts of [A] alkali-soluble resin is 0.1 mass part-100 mass parts.

  The second aspect of the present invention relates to a cured film characterized by being formed using the radiation-sensitive resin composition of the first aspect of the present invention.

  According to a third aspect of the present invention, there is provided a light emitting display device comprising a light emitting layer formed using the radiation sensitive resin composition of the first aspect of the present invention.

A fourth aspect of the present invention is a method for forming a light emitting layer of a light emitting display element according to the third aspect of the present invention,
(1) The process of forming the coating film of the radiation sensitive resin composition of the 1st aspect of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) It is related with the formation method of the light emitting layer which has the process of developing the coating film irradiated with the radiation in process (2), and (4) The process of heating the coating film developed at process (3).

  According to the first aspect of the present invention, the radiation-sensitive resin composition includes a semiconductor quantum dot made of a safe material, has a patterning property, and can easily form a highly reliable cured film having excellent fluorescence characteristics. Things are provided.

  In addition, according to the second aspect of the present invention, it is formed using a radiation-sensitive resin composition having a patterning property including a semiconductor quantum dot made of a safe material, having excellent fluorescence characteristics and high reliability. A cured film is provided.

  In addition, according to the third aspect of the present invention, there is provided a light emitting display element having a light emitting layer formed using a radiation sensitive resin composition having a patterning property including a semiconductor quantum dot made of a safe material. Is done.

  In addition, according to the fourth aspect of the present invention, there is provided a method for forming a light emitting layer of a light emitting display element using a radiation sensitive resin composition having patternability including semiconductor quantum dots made of a safe material. The

It is sectional drawing of the board | substrate explaining the coating-film formation process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing which illustrates typically the radiation irradiation process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing of the board | substrate explaining the image development process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing of the cured film and board | substrate explaining the heating process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing which shows typically the light emitting display element of 3rd Embodiment of this invention.

The radiation sensitive resin composition of the present invention is a radiation sensitive resin composition comprising [A] an alkali-soluble resin, [B] a photoacid generator, and [C] a semiconductor quantum dot. The radiation-sensitive resin composition of the present invention can be patterned using, for example, a photolithography method based on the radiation sensitivity.
In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

  Also, in the photolithography method, a resist composition is formed by applying a resist composition to the surface of a substrate to be processed or processed, and a resist pattern is exposed by irradiating light or an electron beam to expose a predetermined resist pattern. An exposure step for forming a pattern latent image, a heat treatment step if necessary, a development step for developing the pattern to form a desired fine pattern, and a process such as etching on the substrate using the fine pattern as a mask. The process to perform etc. are included.

  The radiation-sensitive resin composition of the present invention is patterned when necessary, and then heated to form the cured film of the present invention. The cured film of the present invention is constituted by including [C] semiconductor quantum dots in a resin.

The cured film of the present invention has a fluorescence emission (wavelength conversion) function based on [C] semiconductor quantum dots. Therefore, it can be used as a wavelength conversion film or a light emitting layer that emits fluorescence having a wavelength different from that of excitation light.
In particular, the cured film of the present invention is suitable for use as a light emitting layer of a light emitting display element, and can be used for the configuration of the light emitting display element of the present invention described later.

  Hereinafter, the radiation sensitive resin composition, the cured film, the method for forming the light emitting layer of the light emitting display element, and the light emitting display element of the present invention will be described.

Embodiment 1 FIG.
<Radiation sensitive resin composition>
As described above, the radiation-sensitive resin composition of the first embodiment of the present invention contains [A] an alkali-soluble resin, [B] a photoacid generator, and [C] semiconductor quantum dots as essential components. .

  By having such a composition, the radiation-sensitive resin composition of the present embodiment can have patterning properties, and has an excellent fluorescence emission (wavelength conversion) function (hereinafter simply referred to as fluorescence or fluorescence characteristics). Etc.)) can be formed.

And the radiation sensitive resin composition of this embodiment can contain the hardening accelerator which accelerates | stimulates hardening of the film | membrane formed, and also contains other arbitrary components, unless the effect of this invention is impaired. can do.
Below, the component of the radiation sensitive resin composition of 1st Embodiment of this invention is demonstrated.

[[A] alkali-soluble resin]
The [A] alkali-soluble resin contained in the radiation-sensitive resin composition of the present embodiment is a resin that is soluble in an alkaline solvent and has alkali developability. [A] The alkali-soluble resin is preferably one selected from, for example, an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin. Hereinafter, each of [A] an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin, which is preferable as the alkali-soluble resin, will be described in more detail.

[Acrylic resin having carboxyl group]
[A] The acrylic resin having a carboxyl group, which is preferable as the alkali-soluble resin, preferably contains a structural unit having a carboxyl group and a structural unit having a polymerizable group. In that case, it is not particularly limited as long as it includes a structural unit having a carboxyl group and a structural unit having a polymerizable group and has alkali developability (alkali solubility).

  The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. When the acrylic resin having a carboxyl group contains the specific structural unit, a film having excellent surface curability and deep part curability can be formed, and the cured film of the embodiment of the present invention can be formed.

  The structural unit having a (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer By a method of reacting (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in a copolymer, a method of reacting (meth) acrylic acid hydroxy ester at an acid anhydride site in the copolymer, etc. Can be formed. Among these, a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.

  The acrylic resin containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is at least one selected from the group consisting of (A1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “a”). It can be synthesized by copolymerizing “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”). In this case, the acrylic resin having a carboxyl group is a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.

  The acrylic resin having a carboxyl group is, for example, copolymerizing a compound (A1) that gives a carboxyl group-containing structural unit and a compound (A2) that gives an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer. Further, in the production of an acrylic resin having a carboxyl group, the (A4) compound (the (A1) compound, the (A2) compound and the (A3) described above) together with the above (A1) compound, (A2) compound and (A3) compound. Further, an unsaturated compound that gives structural units other than the structural unit derived from the compound) can be added to make a copolymer. Next, each compound of (A1) to (A3) will be described in detail.

((A1) Compound)
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
These (A1) compounds may be used alone or in combination of two or more.

  The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-25 mass% are more preferable. (A1) By making the usage rate of a compound 5 mass%-30 mass%, while being able to optimize the solubility with respect to the alkaline aqueous solution of the acrylic resin which has a carboxyl group, the film | membrane excellent in a radiation sensitivity can be formed. .

((A2) Compound)
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. Epoxy heptyl, methacrylic acid 6,7-epoxy heptyl, α-ethylacrylic acid-6,7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the insulating film and the like.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

  Of these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-50 mass% are more preferable. (A2) By making the usage-amount of a compound into 5 mass%-60 mass%, the cured film of this embodiment which has the outstanding sclerosis | hardenability etc. can be formed.

((A3) Compound)
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

  Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.

  Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

  As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5 mass%-25 mass% are more preferable.

((A4) Compound)
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

  These (A4) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound).

[Polyimide resin]
The polyimide resin preferable as the [A] alkali-soluble resin used in the radiation-sensitive resin composition of the present embodiment is selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the structural unit of the polymer. It is a polyimide resin having at least one kind. Having these alkali-soluble groups in the structural unit provides alkali developability (alkali-solubility), and can suppress the occurrence of scum in the exposed area during alkali development.

  In addition, it is preferable that the polyimide resin has a fluorine atom in the structural unit, since water repellency is imparted to the interface of the film and development of the interface is suppressed when developing with an alkaline aqueous solution. The fluorine atom content in the polyimide resin is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing the penetration of the interface, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

A polyimide resin preferable as the [A] alkali-soluble resin used in the radiation-sensitive resin composition of the present embodiment is, for example, a polyimide resin obtained by condensing an acid component and an amine component. Tetracarboxylic dianhydride is preferably selected as the acid component, and diamine is preferably selected as the amine component.
[A] The structure of a polyimide resin preferable as an alkali-soluble resin is not particularly limited, but preferably has a structural unit represented by the following formula (I-1).

In the above formula (I-1), R ¹ represents a tetravalent to 14-valent organic group, and R ² represents a divalent to 12-valent organic group.
R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different. a and b represent the integer of 0-10.

In the formula ^(I-1), R 1 represents the residue of a tetracarboxylic dianhydride used in the formation of a polyimide resin, a tetravalent to 14-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Examples of tetracarboxylic dianhydrides used for forming polyimide resins include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3-Di Ruboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, Preference is given to 9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride or an acid dianhydride having the structure shown below. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ⁶ and R ⁷ represent a hydrogen atom, a hydroxyl group or a thiol group.

In the above formula (I-1), R ² represents the residue of the diamine used for forming the polyimide resin, and is a divalent to 12-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of the diamine used for forming the polyimide resin include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis ( 4-aminophenyl) fluorene or shown below Diamine of the structure is preferable. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ^{6 to} R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

In addition, in order to improve the adhesion between the cured film formed thereafter and the substrate by forming a coating film of the radiation-sensitive resin composition of the present embodiment on the substrate, R is within a range where the heat resistance is not lowered. it may be copolymerized aliphatic groups with a siloxane structure ¹ or R ^2. Specifically, as the diamine which is an amine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane or the like copolymerized by 1 mol% to 10 mol%, etc. Can be mentioned.

In the above formula (I-1), R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group. a and b show the integer of 0-10. Although a and b are preferably 0 from the stability of the resulting radiation-sensitive resin composition, a and b are preferably 1 or more from the viewpoint of solubility in an aqueous alkali solution.

By adjusting the amount of the alkali-soluble group of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a radiation-sensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

In the case where both R ³ and R ⁴ are phenolic hydroxyl groups, in order to make the dissolution rate in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution more suitable, It is preferable to contain 2 mol to 4 mol of phenolic hydroxyl group in 1 kg of (a). By setting the amount of phenolic hydroxyl group within this range, a radiation-sensitive resin composition with higher sensitivity and contrast can be obtained.

  Moreover, it is preferable that the polyimide which has a structural unit represented by the said formula (I-1) has an alkali-soluble group in the principal chain terminal. Such polyimide has high alkali solubility. Specific examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Introduction of an alkali-soluble group at the end of the main chain can be carried out by imparting an alkali-soluble group to the end capping agent. As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.

  Monoamines used as end capping agents include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy. -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4 -Aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds used as end-capping agents include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid Acid anhydrides such as acid anhydrides, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Mo Carboxylic acids and monoacid chloride compounds in which these carboxyl groups are acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- A monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene- Active ester compounds obtained by reaction with 2,3-dicarboximide are preferred. Two or more of these may be used.

  The introduction ratio of the monoamine used for the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  In the polyimide resin having the structural unit represented by the formula (I-1), the number of repeating structural units is preferably 3 or more, more preferably 5 or more, and preferably 200 or less, more preferably 100 or less. If it is this range, it will become possible to use the photosensitive resin composition of this embodiment by a thick film.

  In the present embodiment, [A] the polyimide resin preferable as the alkali-soluble resin may be composed only of the structural unit represented by the above formula (I-1), or a copolymer with another structural unit. Or a mixture may be sufficient. In that case, it is preferable to contain the structural unit represented by the said formula (I-1) 10 mass% or more of the whole polyimide resin. If it is 10 mass% or more, the shrinkage | contraction at the time of thermosetting can be suppressed, and it is suitable for preparation of a thick cured film. The type and amount of the structural unit used for copolymerization or mixing is preferably selected within a range that does not impair the heat resistance of the polyimide resin obtained by the final heat treatment. Examples include benzoxazole, benzimidazole, and benzothiazole. These structural units are preferably 70% by mass or less in the polyimide resin.

  In the present embodiment, for example, a preferable polyimide resin can be synthesized by using a method in which a polyimide precursor is obtained using a known method and is imidized using a known imidization reaction method. As a known synthesis method of the polyimide precursor, a part of the diamine is replaced with a monoamine which is a terminal blocking agent, or a part of the acid dianhydride is a monocarboxylic acid or an acid anhydride which is a terminal blocking agent. It can be obtained by reacting an amine component and an acid component in place of a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting tetracarboxylic dianhydride and diamine (partially substituted with monoamine) at low temperature, tetracarboxylic dianhydride (partially acid anhydride, monoacid chloride compound or monoactivity at low temperature) A method in which an ester compound is substituted) and a diamine, a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then a reaction is performed in the presence of a diamine (partially substituted with a monoamine) and a condensing agent, tetracarboxylic acid There is a method in which a diester is obtained with a dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with a diamine (partially substituted with a monoamine).

Moreover, the imidation ratio of the polyimide resin of this embodiment can be easily calculated | required with the following method, for example. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, the polymer was heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum was measured, and the peak intensity around 1377 cm ⁻¹ was compared to calculate the content of imide groups in the polymer before heat treatment. Find the rate.

  In the present embodiment, the imidation ratio of the polyimide resin is preferably 80% or more from the viewpoint of chemical resistance and a high shrinkage residual film ratio.

  Moreover, the terminal blocker introduce | transduced into the preferable polyimide resin in this embodiment can be easily detected with the following method. For example, a polyimide resin introduced with a terminal blocking agent is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polyimide resin, and this is measured by gas chromatography (GC) or NMR. Thus, the end-capping agent used for forming the polyimide resin can be easily detected. Apart from this, the polymer component into which the end-capping agent has been introduced can also be easily detected by directly measuring it with a pyrolysis gas chromatograph (PGC), an infrared spectrum and a 13C-NMR spectrum.

[Polysiloxane]
A preferred polysiloxane as a resin used in the radiation sensitive resin composition of the present embodiment is a polysiloxane having a radical reactive functional group. When the polysiloxane is a polysiloxane having a radical reactive functional group, the polysiloxane is not particularly limited as long as it has a radical reactive functional group in the main chain or side chain of a polymer having a siloxane bond. In that case, the polysiloxane can be cured by radical polymerization, and cure shrinkage can be minimized. Examples of the radical reactive functional group include unsaturated organic groups such as vinyl group, α-methylvinyl group, acryloyl group, methacryloyl group, and styryl group. Among these, those having an acryloyl group or a methacryloyl group are preferable because the curing reaction proceeds smoothly.

  In the present embodiment, the preferred polysiloxane is preferably a hydrolysis condensate of a hydrolyzable silane compound. The hydrolyzable silane compound constituting the polysiloxane includes (s1) a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as “(s1) compound”), and (s2) the following formula. A hydrolyzable silane compound including the hydrolyzable silane compound (hereinafter also referred to as “(s2) compound”) represented by (S-2) is preferable.

In the above formula ^{(S-1), R 11} is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. ^{However, if R 11} and ^{R 12} is plural, ^{R 11} and ^{R 12} are each, independently.

In the above formula ^{(S-2), R 13} is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0-3. ^{However, if R 13} and ^{R 14} is plural, ^{R 13} and ^{R 14} are each, independently.

  In the present invention, the “hydrolyzable silane compound” is usually hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water. It refers to a compound having a group capable of forming a silanol group or a group capable of forming a siloxane condensate. In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (S-1) and (S-2), some hydrolyzable groups are not hydrolyzed in the polysiloxane to be formed. It may remain in the state. Here, the “hydrolyzable group” means a group capable of forming a silanol group by hydrolysis as described above or a group capable of forming a siloxane condensate. In addition, in the radiation-sensitive resin composition of the present embodiment, some hydrolyzable silane compounds have some or all of the hydrolyzable groups in the molecule unhydrolyzed and other hydrolysable groups. It may remain in a monomer state without condensing with the decomposable silane compound. The “hydrolysis condensate” means a hydrolysis condensate obtained by condensing some silanol groups of a hydrolyzed silane compound. Hereinafter, the (s1) compound and the (s2) compound will be described in detail.

((S1) compound)
In the above formula ^{(S-1), R 11} is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. ^{However, if R 11} and ^{R 12} is plural, ^{R 11} and ^{R 12} are each, independently.
Examples of the alkyl group having 1 to 6 carbon atoms that is R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said p, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

Examples of the organic group having a radical reactive functional group include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with the above radical reactive functional group, A 6-12 aryl group, a C7-12 aralkyl group, etc. are mentioned. When a plurality of R ¹² are present in the same molecule, these are independent of each other. Further, the organic group represented by R ¹² may have a hetero atom. Examples of such an organic group include an ether group, an ester group, and a sulfide group.

  Examples of the compound (s1) in the case of p = 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, and m-styryltrimethoxysilane. M-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, methacryloxytripropoxysilane, Acryloxytrimethoxysilane, acryloxytriethoxysilane, acryloxytripropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, -Methacryloxyethyl tripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltri Ethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane Trifluoro-butyl trimethoxy silane, 3-trialkoxysilane compounds such as (trimethoxysilyl) propyl succinic anhydride and the like.

  Examples of the compound (s1) in the case of p = 2 include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, phenyltri And dialkoxysilane compounds such as fluoropropyldimethoxysilane.

  Examples of the compound (s1) in the case of p = 3 include allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-acryloxypropyldimethyl. Methoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3′-dimethacryloxypropyldimethoxysilane, 3,3′-diaacryloxypropyldimethoxysilane, 3,3 ′, Monoalkoxysilane compounds such as 3 ″ -trimethacryloxypropylmethoxysilane, 3,3 ′, 3 ″ -triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane, etc. It is below.

  Among these (s1) compounds, scratch resistance and the like can be achieved at a high level, and condensation reactivity is increased. Therefore, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane. 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and 3- (trimethoxysilyl) propyl succinic anhydride are preferable.

((S2) compound)
In the above formula ^{(S-2), R 13} is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0-3. ^{However, if R 13} and ^{R 14} is each one, the plurality of ^{R 13} and ^{R 14} are each, independently.

Examples of the alkyl group having 1 to 6 carbon atoms as R ¹³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said q, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

When R ¹⁴ described above is an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl Group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2- Dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methyl Tylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethyl Butyl group, 1,2,3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1- Methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n Heptadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. Preferably it is a C1-C10 alkyl group, More preferably, it is a C1-C3 alkyl group.

  As the compound (s2) in the case of q = 0, for example, as a silane compound substituted with four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra -I-propoxysilane etc. are mentioned.

  As the compound (s2) in the case of q = 1, as a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, for example, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyl Trimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane 3 isocyanoacetate trimethoxysilane, 3-isocyanoacetate triethoxysilane o- tolyl trimethoxysilane, m- tolyl trimethoxysilane p- tolyl trimethoxysilane, and the like.

  As the compound (s2) in the case of q = 2, examples of the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, and ditolyl. Examples include dimethoxysilane and dibutyldimethoxysilane.

  As the compound (s2) in the case of q = 3, examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include trimethylmethoxysilane, triphenylmethoxysilane, Examples include tolylmethoxysilane and tributylmethoxysilane.

  Of these (s2) compounds, a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is preferred. More preferred are silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups. Particularly preferred hydrolyzable silane compounds include, for example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, ethyltrisilane. Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-isocyanate And propyltrimethoxysilane. Such hydrolyzable silane compounds may be used alone or in combination of two or more.

  Regarding the mixing ratio of the (s1) compound and the (s2) compound, it is desirable that the (s1) compound exceeds 5 mol%. When the compound (s1) is 5 mol% or less, the exposure sensitivity when forming a protective film as a cured film is low, and the scratch resistance and the like of the resulting protective film tend to be reduced.

(Hydrolytic condensation of (s1) compound and (s2) compound)
The conditions for hydrolyzing and condensing the compound (s1) and the compound (s2) include hydrolyzing at least a part of the compound (s1) and the compound (s2) to convert a hydrolyzable group into a silanol group and condensing the compound. Although it will not specifically limit as long as it raise | generates reaction, As an example, it can implement as follows.

  As water used for the hydrolysis condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 2 mol, with respect to 1 mol of the total amount of hydrolyzable groups of the (s1) compound and (s2) compound. Particularly preferred is 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  Examples of the solvent used for hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers. Examples include propionates, aromatic hydrocarbons, ketones, and other esters. These solvents can be used alone or in combination of two or more.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol monomethyl ether and butyl methoxyacetate are preferred.

  The hydrolysis condensation reaction is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, etc.), base Catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; Carboxylic acid salts such as sodium acetate; various Lewis bases) or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, etc.) are used in the presence of a catalyst. For example, tri-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.001 mol per mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. 1 mole.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the above-mentioned hydrolysis-condensation product is preferably 500 to 10,000, more preferably 1000 to 5000. By making Mw 500 or more, the film formability of the radiation sensitive resin composition of the present embodiment can be improved. On the other hand, by setting Mw to 10,000 or less, it is possible to prevent the developability of the radiation-sensitive resin composition from decreasing.

  The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) by GPC of the above-mentioned hydrolysis-condensation product is preferably 300 to 5000, and more preferably 500 to 3000. By making Mn of polysiloxane into the said range, the cure reactivity at the time of hardening of the coating film of the radiation sensitive resin composition of this embodiment can be improved.

  The molecular weight distribution “Mw / Mn” of the hydrolysis-condensation product is preferably 3.0 or less, and more preferably 2.6 or less. By setting Mw / Mn of the hydrolysis condensate of the (s1) compound and the (s2) compound to 3.0 or less, the developability of the formed film can be enhanced. The radiation-sensitive resin composition of the present embodiment containing polysiloxane can easily form a desired pattern shape with little occurrence of development residue during development.

[Novolac resin]
A novolak resin preferable as a resin used in the radiation-sensitive resin composition of the present embodiment can be obtained by polycondensing phenols with aldehydes such as formalin by a known method.

  Examples of phenols for obtaining a preferred novolak resin in the present embodiment include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol, m-methoxy Enol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol and the like can be mentioned. Two or more of these may be used.

  In the present embodiment, examples of aldehydes for obtaining a preferred novolak resin include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like in addition to formalin. Two or more of these may be used.

  The weight average molecular weight of the novolak resin preferable as the resin used in the radiation-sensitive resin composition of the present embodiment is preferably 2000 to 50000 in terms of polystyrene by GPC (gel permeation chromatography), more preferably 3000 to 40000. .

[[B] Photoacid generator]
[B] The photoacid generator, which is an essential component of the radiation-sensitive resin composition of the embodiment of the present invention, is a compound that generates an acid upon irradiation with radiation. Here, as described above, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam), X-ray or the like can be used. When the radiation sensitive composition of this embodiment contains a [B] photo-acid generator, the radiation sensitive resin composition of this embodiment can exhibit a positive radiation sensitive characteristic.

  [B] The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. [B] The content of the photoacid generator in the radiation-sensitive resin composition of the present embodiment is a photoacid generator (hereinafter also referred to as “[B] photoacid generator”) which is a compound as described later. It may be in the form of [A] a photoacid generator group incorporated as part of a polymer or other polymer, or both forms.

  [B] Examples of the photoacid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds.

(Oxime sulfonate compound)
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (1) is preferable.

In the above formula (1), R ²¹ is an alkyl group, a cycloalkyl group or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the above formula (1), the alkyl group represented by R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group). Group) and the like. The aryl group for R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

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

In said formula (2), R < ²¹ > is synonymous with description of R < ²¹ > in said formula (1). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. When m is 2 or 3, the plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above formula (2), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the above formula (2), 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 formula (2) include, for example, the compounds (3-i) and (3-ii) represented by the following formulas (3-i) to (3-v), respectively. ), Compound (3-iii), compound (3-iv), compound (3-v) and the like.

  These can be used alone or in combination of two or more, and can also be used in combination with other photoacid generators as the component [B]. Compound (3-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (3-ii) [(5H-octylsulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (3-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound ( 3-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] and compound (3-v) [(5-octylsulfonyloxyimino)-( 4-methoxyphenyl) acetonitrile] is available as a commercial product Coming.

(Onium salt)
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluoro Tansulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. Can be mentioned.

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

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4 Examples include-(benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, and dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenyl. Sulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl Examples include -4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenyl. Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3 -Chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and the like.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy). Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include, for example, 4,7-di-n-butoxy-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoro L-methanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1, 1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxy) Bicyclo [2.2.1] heptan-2-yl) -1,1 2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptane-2- Yl) -1,1,2,2-tetrafluoroethanesulfonate.

(Sulfonimide compound)
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, and N- (2-trifluoromethylphenyl). Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphe Rumaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutane Sulfonyloxy) bicyclo [2.2 1] Hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenyls) Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2, -Dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy -2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (Phenylsulfonyloxy) naphthyl dicarboxylimide N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (hepta Fluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (Butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl di Examples thereof include carboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxyimide, N- (octylsulfonyloxy) naphthyl dicarboxyimide, N- (nonylsulfonyloxy) naphthyl dicarboxyimide, and the like.

(Halogen-containing compounds)
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

(Diazomethane compound)
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-trisulfonyl) diazomethane, and bis (2,4-xylylsulfonyl). ) Diazomethane, bis (p-chlorophenissulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl ( And benzoyl) diazomethane.

(Sulfone compound)
Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryl disulfone compounds, and the like.

(Sulfonate compound)
Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate.

(Carboxylic acid ester compound)
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

Among the oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds and carboxylic acid ester compounds of the [B] photoacid generator described above, the radiation sensitivity From the viewpoint of solubility, an oxime sulfonate compound is preferable, a compound containing an oxime sulfonate group represented by the above formula (1) is more preferable, and an oxime sulfonate compound represented by the above formula (2) is more preferable. However, commercially available [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5H-octylsulfonyloxyimino-5H-thiophen-2-ylidene) )-(2-Methyl Phenyl) acetonitrile], [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)- (2-Methylphenyl) acetonitrile] and [(5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile] are particularly preferred.
Also, onium salts are preferred [B] photoacid generators, more preferably tetrahydrothiophenium salts and benzylsulfonium salts, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate. And benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate is particularly preferred.

  [B] When the photoacid generator is any one of an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carboxylic acid ester compound, You may use individually, and may mix and use 2 or more types. [B] When the photoacid generator is one of an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carboxylic acid ester compound, this embodiment The content of [B] photoacid generator in the radiation sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 100 parts by mass of [A] alkali-soluble resin. 1 part by mass to 5 parts by mass. When the content of the above-mentioned [B] photoacid generator is in the above-mentioned range, the radiation sensitivity of the radiation-sensitive resin composition of the present embodiment can be optimized, exhibiting good patternability, This is suitable for forming the cured film of the embodiment.

(Quinonediazide compound)
Examples of the [B] photoacid generator of the radiation-sensitive resin composition of the present embodiment include quinonediazide compounds in addition to the oxime sulfonate compounds described above. This quinonediazide compound can be particularly preferably used as the [B] photoacid generator of the radiation-sensitive resin composition of the present embodiment.

  A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, Examples include 3,4,2′-tetrahydroxy-4′-methylbenzophenone and 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone.

  Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone.

  Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone, and the like.

  Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p- Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, bis (2,5- Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi Nden -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  Examples of other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [ 4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl)- 4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- {4- (1- [ 4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol is preferably used.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphtho. Quinonediazide-4-sulfonic acid amide and the like are also preferably used.

These quinonediazide compounds can be used alone or in combination of two or more.
Moreover, it can also be used in combination with the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonic acid ester compound and carboxylic acid ester compound described above.

  As content of the quinonediazide compound in the radiation sensitive resin composition of this embodiment, Preferably it is 5 mass parts-100 mass parts with respect to 100 mass parts of [A] alkali-soluble resin, More preferably, 10 mass parts- 50 parts by mass. By setting the content of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer can be increased, and the patterning performance can be improved. Moreover, the solvent resistance of the cured film obtained using this radiation sensitive resin composition can also be made favorable.

[[C] Semiconductor quantum dots]
The [C] semiconductor quantum dot, which is an essential component of the radiation-sensitive resin composition of the embodiment of the present invention, does not contain Cd or Pb as a constituent component, for example, In (indium), Si (silicon), or the like. This is a semiconductor quantum dot made of a safe material.

  [C] The semiconductor quantum dot is at least two elements selected from the group of elements represented by Group 2 element, Group 11 element, Group 12 element, Group 13 element, Group 14 element, Group 15 element and Group 16 element It is preferable that it is a semiconductor quantum dot which consists of a compound containing this.

  More specifically, elements such as Pb and Cd, which are of great concern for human safety, are excluded, and Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (Barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), C (Carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen), S (Sulfur), Se (selenium), Te (tellurium), and a semiconductor quantum dot which consists of a compound containing at least 2 or more types of elements chosen from Po (polonium) group are preferable.

  At this time, it is preferable that the [C] semiconductor quantum dot consists of a compound (A) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a compound (B) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm.

  [C] The semiconductor quantum dot is composed of the compound (A) and / or the compound (B) having such fluorescence emission characteristics, so that the wavelength range of 500 nm to 600 nm and / or the wavelength range of 600 nm to 700 nm is obtained. It can have a fluorescence maximum. As a result, the radiation sensitive resin composition of this embodiment containing [C] semiconductor quantum dots is a cured film suitable for the structure of the light emitting layer of a light emitting display element that displays an image using light in the visible range. Can be formed.

  Furthermore, it is more preferable that the [C] semiconductor quantum dot contained in the radiation sensitive resin composition of the present embodiment is a semiconductor quantum dot made of a compound containing In as a constituent component. In addition, the [C] semiconductor quantum dots may include Si compounds.

  [C] Examples of the Si compound preferable as the semiconductor quantum dot include Si.

  [C] By making the component constitution of the semiconductor quantum dots as described above, the radiation-sensitive resin composition of the present embodiment can form a cured film having a safe and excellent fluorescence property, and further, A light emitting layer of a light emitting display element that is safe and has excellent fluorescence characteristics can be formed.

  In addition, the [C] semiconductor quantum dots contained in the radiation-sensitive resin composition of the present embodiment are at least selected from a homogeneous structure type composed of one compound and a core-shell structure type composed of two or more compounds. One structure type semiconductor quantum dot is preferable.

  The core-shell structure type [C] semiconductor quantum dot is formed by forming a core structure with one kind of compound and coating the periphery of the core structure with another compound. For example, by covering the core semiconductor with a semiconductor having a larger band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the quantum dot is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of the [C] semiconductor quantum dot are improved.

[C] semiconductor quantum dots contained in the radiation-sensitive resin composition of the present embodiment are InP / ZnS, CuInS ₂ / ZnS, and (ZnS), which are core-shell structure type semiconductor quantum dots, in consideration of the component structure and structure. / AgInS ₂ ) Solid solution / ZnS, and at least one selected from the group consisting of AgInS ₂ and Zn-doped AgInS ₂ which are homogeneous structure type semiconductor quantum dots are preferable.

From the above, [C] a semiconductor quantum dots contained in the radiation-sensitive resin composition of the present embodiment, InP / ZnS compounds, CuInS ₂ / ZnS compounds, AgInS ₂ compound, (ZnS / AgInS ₂₎ solid solution / ZnS compound It is preferable that at least one selected from the group consisting of Zn-doped AgInS ₂ compound and Si compound.

  With the [C] semiconductor quantum dots exemplified above, the radiation-sensitive resin composition of the present embodiment containing the same forms a cured film having a safe and superior fluorescence property, and more excellent. A light-emitting layer of a light-emitting display element having fluorescent characteristics can be formed.

  In addition, the [C] semiconductor quantum dots contained in the radiation-sensitive resin composition of the present embodiment preferably have an average particle size of 0.5 nm to 20 nm, and more preferably 1.0 nm to 10 nm. . When the average particle size is less than 0.5 nm, it is difficult to prepare the [C] semiconductor quantum dot, and even if it can be prepared, the fluorescence characteristics of the [C] semiconductor quantum dot may become unstable. is there. [C] If the average particle diameter of the semiconductor quantum dots exceeds 20 nm, the quantum confinement effect due to the size of the semiconductor quantum dots may not be obtained, and the desired fluorescence characteristics cannot be obtained, which is not desirable.

  The shape of the semiconductor quantum dots is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disk shape, or other shapes. Information such as the particle size, shape, and dispersion state of the quantum dots can be obtained by a transmission electron microscope (TEM).

  As a method of obtaining the [C] semiconductor quantum dot contained in the radiation sensitive resin composition of embodiment of this invention, utilizing the well-known method of thermally decomposing an organometallic compound in a coordination organic solvent. it can. For core-shell structure type semiconductor quantum dots, after forming a homogeneous core structure by reaction, a precursor for forming a shell on the core surface is added to the reaction system, and the reaction is stopped after the shell formation. And can be obtained by separating from the solvent. A commercially available product can also be used.

  As content of the [C] semiconductor quantum dot in the radiation sensitive resin composition of this embodiment, Preferably it is 0.1 mass part-100 mass parts with respect to 100 mass parts of [A] alkali-soluble resin. Preferably they are 0.2 mass part-50 mass parts. [C] By setting the content of the semiconductor quantum dots in the above range, a cured film having excellent fluorescence characteristics can be formed, and as a result, a light emitting layer of a light emitting display element having excellent fluorescence characteristics can be formed. . [C] If the content of the semiconductor quantum dots is less than 0.1 parts by mass with respect to 100 parts by mass of the [A] alkali-soluble resin, the desired fluorescent properties cannot be obtained in the formed cured film. The light emitting layer of the light emitting display element cannot be formed. Moreover, when it exceeds 100 mass parts with respect to 100 mass parts of [A] alkali-soluble resin, stability of the cured film formed will be impaired and the light emitting layer of a stable light emitting display element cannot be formed.

[Other ingredients]
The radiation-sensitive resin composition of the present embodiment contains [A] alkali-soluble resin, [B] photoacid generator, and [C] semiconductor quantum dots as essential components, as well as a curing accelerator and thermal acid generator. An agent and other optional components can be contained.

  The curing accelerator is a compound that functions to promote curing of a film formed by the radiation-sensitive resin composition of the present embodiment.

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

  The radiation-sensitive resin composition of the present embodiment includes other optional components such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver as necessary, as long as the effects of the present invention are not impaired. Can be contained. Each of these optional components may be used alone or in combination of two or more.

[Method for preparing radiation-sensitive resin composition]
The radiation sensitive resin composition of this embodiment is prepared by uniformly mixing [A] alkali-soluble resin, [B] photoacid generator and [C] semiconductor quantum dots. Further, when a curing accelerator, a thermal acid generator and other optional components are selected as necessary, and they are contained, [A] an alkali-soluble resin, [B] a photoacid generator, and [C] a semiconductor quantum dot As well as those optional ingredients. And the radiation sensitive resin composition of this embodiment is preferably dissolved in an appropriate solvent and used in the form of a solution. A solvent can be used individually or in mixture of 2 or more types.

  As a solvent used for the preparation of the radiation sensitive resin composition of the present embodiment, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used. Examples of such solvents include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol mono Examples include alkyl ether propionates, ketones, esters and the like.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 2% by mass from the viewpoints of applicability and stability of the resulting radiation-sensitive resin composition. The amount of ˜50 mass% is preferred, and the amount of 5˜40 mass% is more preferred. When preparing a solution of a radiation-sensitive resin composition, the solid content concentration (components other than the solvent occupying in the composition solution) is actually set in the above-mentioned concentration range according to the desired film thickness value, etc. Is done.

  The solution-like radiation-sensitive resin composition of the present embodiment prepared in this way is 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. Is preferred.

Embodiment 2. FIG.
<Curing film>
The cured film of the second embodiment of the present invention is formed by applying the radiation sensitive resin composition of the above-described embodiment of the present invention on a suitable substrate, patterning if necessary, and then heat curing. Is done. Below, the cured film of this embodiment and its formation method are demonstrated.

  In the method for forming a cured film of this embodiment, it is preferable that at least the following steps (1) to (4) are included in the following order so that the cured film is formed on the substrate.

(1) The coating-film formation process which forms the coating film of the radiation sensitive resin composition of 1st Embodiment of this invention on a board | substrate.
(2) A radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
(3) A development step of developing the coating film irradiated with radiation in step (2).
(4) A heating step of heating the coating film developed in step (3).

  1 to 4 are diagrams illustrating a method for forming a cured film according to the second embodiment of the present invention.

  FIG. 1 is a cross-sectional view of a substrate for explaining a coating film forming step in forming a cured film according to a second embodiment of the present invention.

  FIG. 2 is a cross-sectional view schematically illustrating a radiation irradiation step in forming a cured film according to the second embodiment of the present invention.

  FIG. 3 is a cross-sectional view of a substrate for explaining a development process in forming a cured film according to the second embodiment of the present invention.

  FIG. 4 is a cross-sectional view of a cured film and a substrate for explaining a heating step in forming a cured film according to the second embodiment of the present invention.

  Hereinafter, each of the above-described steps (1) (coating film forming step) to (4) step (heating step) will be described.

[(1) Process]
In the process (1) (coating film forming process) of the method for forming a cured film of the present embodiment, as shown in FIG. 1, the coating film 1 of the radiation sensitive resin composition of the present embodiment is formed on the substrate 2. .
For the substrate 2 on which the coating film 1 is formed, a substrate made of glass, quartz, or a transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, or the like) is used. it can. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

  In the substrate 2, after the radiation sensitive resin composition of the present embodiment is applied to one surface, prebaking is performed, and when the radiation sensitive resin composition contains a solvent, the solvent evaporates, and the coating film 1. Is formed.

  Examples of the coating method of the radiation-sensitive resin composition in this step include a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), a slit coating method (slit die). Appropriate methods such as a coating method), a bar coating method, and an inkjet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

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

[(2) Process]
Next, in step (2) (radiation irradiation step) of the method for forming a cured film of the present embodiment, as shown in FIG. 2, at least part of the coating film 1 formed on the substrate 2 in step (1) is formed. Radiation 4 is irradiated. At this time, in order to irradiate only a part of the coating film 1 with the radiation 4a, for example, it is performed through the photomask 3 having a pattern corresponding to formation of a desired shape. By using this photomask 3, a part of the irradiated radiation 4 passes through the photomask, and a part of the radiation 4 a is irradiated onto the coating film 1.

  Examples of the radiation 4 used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

The dose of radiation 4 (exposure amount), the intensity at the wavelength 365nm radiation 4 as a value measured by a luminometer (OAI model 356, Optical Associates Ltd. ^Inc.), be 10J / ^{m 2} ~10000J / m 2 can be ^{preferably 100J / m 2 ~5000J / m 2} , 200J / m 2 ~3000J / m 2 is more preferable.

[[3] Process]
Next, in step (3) (development step) of the method for forming a cured film of the present embodiment, as shown in FIG. 3, the coating film 1 of FIG. 2 after irradiation is developed to remove unnecessary portions. The coating film 1a patterned into a predetermined shape is obtained.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, An aqueous solution of an alkaline compound such as 8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, a spraying method, etc., and the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[[4] Process]
Next, in step (4) (heating step) of the method for forming a cured film of this embodiment, the patterned coating film 1a shown in FIG. 3 is cured (post-posted) by an appropriate heating device such as a hot plate or oven. Also called bake.) Thereby, as shown in FIG. 4, the cured film 5 of this embodiment formed on the board | substrate 2 is obtained. As described above, the cured film 5 is patterned so as to have a desired shape.

  For the formation of the cured film 5 of the present embodiment, the radiation-sensitive resin composition of the first embodiment described above is used, and the heating temperature in this step is preferably 100 ° C to 250 ° C. In addition, due to the effect of the curing accelerator added to the radiation-sensitive resin composition of the first embodiment, the cured film 5 can be formed at a heating temperature of 200 ° C. or lower. For example, the curing time is preferably 5 to 30 minutes on a hot plate, and preferably 30 to 180 minutes in an oven.

The cured film of this embodiment formed by the cured film forming method including the above steps (1) to (4) is configured to include [C] semiconductor quantum dots in the resin, and [C] semiconductor quantum. Fluorescence emission (wavelength conversion) function based on dots. Therefore, it can be used as a wavelength conversion film or a light emitting layer that emits fluorescence having a wavelength different from that of excitation light.
In particular, the cured film of the present embodiment is suitable for use as a light emitting layer of a light emitting display element, and can be used for the structure of the light emitting display element.

  Therefore, the resin has a total light transmittance (JIS K7105) at a thickness of 0.1 mm, preferably 75% to 95%, more preferably, so that the cured film can enhance the light utilization efficiency. Is 78% to 95%, more preferably 80% to 95%. When the total light transmittance is within such a range, the obtained cured film can constitute a wavelength conversion film or a light emitting layer with excellent light utilization efficiency.

Embodiment 3 FIG.
<Light-emitting display element and light-emitting layer thereof>
The light emitting display element which is 3rd Embodiment of this invention is comprised using the wavelength conversion board | substrate which uses the cured film of 2nd Embodiment of this invention mentioned above as a light emitting layer.

  FIG. 5 is a cross-sectional view schematically showing a light-emitting display element according to an embodiment of the present invention.

  The light emitting display device 100 according to the first embodiment of the present invention includes a wavelength conversion substrate 11 configured by providing a light emitting layer 13 (13a, 13b, 13c) and a black matrix 14 on a substrate 12, and a wavelength conversion substrate 11. And a light source substrate 18 bonded through an adhesive layer 15.

  The substrate 12 is made of glass, quartz, or a transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).

  The light emitting layer 13 of the wavelength conversion substrate 11 utilizes the above-described cured film of the second embodiment of the present invention. That is, the light emitting layer 13 is formed by patterning using the radiation sensitive resin composition of the first embodiment of the present invention described above.

About the formation method of a light emitting layer, since they are formed using the cured film of 2nd Embodiment of this invention, it becomes the same as the formation method of 2nd Embodiment of this invention mentioned above.
That is, the cured film of the second embodiment of the present invention is formed on the substrate 12, and these serve as the light emitting layer 13 to constitute the wavelength conversion substrate 11 of the light emitting display element 100. Therefore, the method for forming the light emitting layer 13 preferably includes the following steps (1) to (4) similar to those described above in this order.

(1) The coating-film formation process which forms the coating film of the radiation sensitive resin composition of 1st Embodiment of this invention on a board | substrate.
(2) A radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
(3) A development step of developing the coating film irradiated with radiation in step (2).
(4) A heating step of heating the coating film developed in step (3).

  And each of (1) process-(4) process for forming the light emitting layer 13 is as having demonstrated using FIGS. 1-4 in formation of the cured film of 2nd Embodiment of this invention. . Therefore, although the details are omitted, the cured film 5 patterned so as to have a desired shape shown in FIG. 4 becomes the light emitting layer 13 of the wavelength conversion substrate 11 of FIG.

  In the wavelength conversion substrate 11, each of the light emitting layers 13 uses semiconductor quantum dots contained therein, converts the wavelength of excitation light from the excitation light source 17 of the light source substrate 18, and emits fluorescence having a desired wavelength.

  And in the wavelength conversion board | substrate 11, the light emitting layer 13a, the light emitting layer 13b, and the light emitting layer 13c are respectively comprised including a different semiconductor quantum dot, and can light-emit different fluorescence.

For example, in the wavelength conversion substrate 11, the light emitting layer 13a converts excitation light into red light, the light emitting layer 13b converts excitation light into green light, and the light emitting layer 13c converts excitation light into blue light. Can be configured.
In that case, the semiconductor quantum dots to be contained are selected so that each of the light emitting layers 13a, 13b, and 13c has a desired fluorescence characteristic. Therefore, in the formation of the light emitting layers 13a, 13b, and 13c of the wavelength conversion substrate 11, for example, three types of radiation sensitive resin compositions of the first embodiment including semiconductor quantum dots having different light emission characteristics are prepared.

  And the formation method of the light emitting layer 13 containing the process (1)-process (4) mentioned above using each of the three types of radiation sensitive resin compositions of 1st Embodiment is repeated, and the light emitting layer 13a, light emission A layer 13b and a light emitting layer 13c are sequentially formed. Then, the light emitting layer 13 is formed on the substrate 12 to obtain the wavelength conversion substrate 11.

  The thickness of the light emitting layer 13 of the wavelength conversion substrate 11 is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. If the thickness is less than 100 nm, the excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, so that the luminance of the light emitting display element cannot be sufficiently secured. Furthermore, in order to enhance absorption of excitation light and sufficiently secure the luminance of the light emitting display element, the film thickness is preferably 1 μm or more.

  A black matrix 14 is disposed between the light emitting layers 13 on the substrate 12. The black matrix 14 can be formed by using a known light-shielding material and patterning it according to a known method. Note that the black matrix 14 is not an essential component in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may be configured without the black matrix 14.

  The adhesive layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light having a wavelength described later. As shown in FIG. 5, the adhesive layer 15 does not have to be provided on the substrate 12 so as to cover the entire surface of the light emitting layers 13a, 13b, 13c, and can be provided only around the wavelength conversion substrate 11. It is.

  The light source substrate 18 includes a substrate 16 and a light source 17 disposed on the wavelength conversion substrate 11 side of the substrate 16. Each of the light sources 17 emits ultraviolet light or blue light as excitation light.

  As the light source 17, an ultraviolet light-emitting organic EL element and a blue light-emitting organic EL element having a known structure can be used. The light source 17 is not particularly limited, and can be manufactured using a known material or a known manufacturing method. It is. Here, as the ultraviolet light, light emission having a main emission peak of 360 nm to 435 nm is preferable, and as the blue light, light emission having a main emission peak of 435 nm to 480 nm is preferable. The light source 17 desirably has directivity so that each emitted light irradiates the light emitting layer 13 facing each other.

  The light emitting display element 100 of this embodiment converts the wavelength of the excitation light from the light source 17a by the semiconductor quantum dots of the light emitting layer 13a of the wavelength conversion substrate 11 that faces the light emitting display element 100. Similarly, the wavelength of excitation light from the light source 17b is converted by the semiconductor quantum dots of the light emitting layer 13b of the opposing wavelength conversion substrate 11, and the light emission layer 13c of the wavelength conversion substrate 11 of the opposing wavelength conversion substrate 11 is converted. Wavelength conversion is performed by using semiconductor quantum dots. In this way, the excitation light from the light source 17 is converted into visible light having a desired wavelength and used for display.

  In the wavelength conversion substrate 11, the excitation light is converted into blue light in the light emitting layer 13c, as will be described later. At this time, instead of the light emitting layer 13c, the wavelength conversion substrate 11 may use a light scattering layer configured by dispersing photoacid scattering particles in a resin. By doing so, when the excitation light is blue light, the excitation light can be used as it is without converting the wavelength.

  As described above, the wavelength conversion substrate 11 of the light-emitting display element 100 is provided with the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c made of semiconductor quantum dots and resin, respectively, patterned on the substrate 12. Is. The light emitting layers 13a, 13b, and 13c are each formed from the radiation sensitive resin composition of the first embodiment including semiconductor quantum dots.

  In the light emitting display element 100, the portion where the light emitting layer 13a is provided constitutes a sub-pixel that performs red display. That is, the light emitting layer 13 a of the wavelength conversion substrate 11 converts the excitation light from the light source 17 a facing the light source substrate 18 into red. Further, the portion where the light emitting layer 13b is provided constitutes a sub-pixel that performs green display. That is, the light emitting layer 13b converts the excitation light from the light source 17b facing the light source substrate 18 to green. Further, the portion where the light emitting layer 13c is provided constitutes a sub-pixel that performs blue display. That is, the light emitting layer 13c converts the excitation light from the light source 17c facing the light source substrate 18 into blue.

  The light-emitting display element 100 includes one pixel that is a minimum unit constituting an image by three types of a sub-pixel including the light-emitting layer 13a, a sub-pixel including the light-emitting layer 13b, and a sub-pixel including the light-emitting layer 13c. Configure.

  The light-emitting display element 100 of the present embodiment having the above configuration has red, green, or blue color for each of the sub-pixel including the light-emitting layer 13a, the sub-pixel including the light-emitting layer 13b, and the sub-pixel including the light-emitting layer 13c. Light emission is controlled. Then, the emission of red, green, and blue light is controlled for each pixel composed of three types of sub-pixels, and a full color display is performed.

  In the light emitting display element according to the embodiment of the present invention, a color filter can be provided between the light emitting layer 13 and the substrate 12. That is, a red color filter is provided between the light emitting layer 13a and the substrate 12, a green color filter is provided between the light emitting layer 13b and the substrate 12, and a red color filter is provided between the light emitting layer 13c and the substrate 12. Can be provided.

  The light emitting display element according to the third embodiment of the present invention can improve the color purity of display by providing a color filter. Here, as a color filter, what is known for liquid crystal display elements etc. can be formed and used by a well-known method.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In addition, the measuring method of the molecular weight of used resin is as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
(B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.

<Semiconductor quantum dots>
The semiconductor quantum dots used in this example are shown below.
Semiconductor quantum dot A: InP / ZnS core-shell quantum dot semiconductor quantum dot B: InCuS ₂ / ZnS core-shell quantum dot semiconductor quantum dot C: Si quantum dot

The semiconductor quantum dots A: InP / ZnS core-shell quantum dots, semiconductor quantum dots B: InCuS ₂ / ZnS core-shell quantum dots, and semiconductor quantum dots C: Si quantum dots used in the following examples are generally known. It can be synthesized by the method.

For example, regarding the semiconductor quantum dot A: InP / ZnS core-shell type quantum dot, the technical literature “Journal of American Chemical Society. 2007, 129, 15432-15433” and the semiconductor quantum dot B: InCuS ₂ / ZnS core-shell type quantum dot In the technical document “Journal of American Chemical Society. 2009, 131, 5691-5697” and the technical document “Chemistry of Materials. 2009, 21, 2422-2429”, as for the technical quantum dot C: Si compound quantum dot of American Chemical Society. 2010, 132, 248-253 ”. Can be synthesized with reference to the method.

Synthesis example 1
[Synthesis of Resin (α-I)]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and n- After charging 10 parts by mass of lauryl methacrylate and substituting with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 5 hours, whereby a resin (α- A solution containing I) was obtained. The Mw of the resin (α-I) as a copolymer was 8000.

Synthesis example 2
[Synthesis of Resin (α-II)]
Under a dry nitrogen stream, 29.30 g (0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Glass), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1 .24 g (0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) as an end-capping agent is N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Dissolved in 80 g. Bis (3,4-dicarboxyphenyl) ether dianhydride (Manac) 31.2 g (0.1 mol) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. I let you. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a resin (α-II) as a polymer having a structure represented by the following formula.

Synthesis example 3
[Synthesis of Resin (α-III)]
In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane, and heated until the solution temperature reached 60 ° C. . After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 4 hours. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a resin (α-III) was obtained as a siloxane polymer which is a hydrolysis-condensation product. The Mw of the resin (α-III) which is a siloxane polymer was 5000.

Example 1
[Preparation of radiation-sensitive resin composition (β-I)]
A solution containing the resin (α-I) of Synthesis Example 1 was added in an amount corresponding to 100 parts by mass (solid content) of the copolymer and a quinonediazide compound [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene) -(2-Methylphenyl) acetonitrile] was mixed with 5 parts by mass, and 10 parts by mass of semiconductor quantum dots A were mixed to prepare a radiation sensitive resin composition (β-I).

Example 2
[Preparation of radiation-sensitive resin composition (β-II)]
2 g of novolak resin (trade name, XPS-4958G, m-cresol / p-cresol ratio = 55/45 (weight ratio), Gunei Chemical Industry Co., Ltd.) was added to 8 g of the resin (α-II) of Synthesis Example 2. . Further, 2.4 g of a compound represented by the following formula (β1) and 0.6 g of a compound represented by the following formula (β2) are added as a thermally crosslinkable compound that undergoes a crosslinking reaction by heat, and 2 g of a quinonediazide compound (β3) is added. It was. Next, 10 parts by mass of semiconductor quantum dots B were mixed, and γ-butyrolactone was added thereto as a solvent to prepare a radiation sensitive resin composition (β-II).

Example 3
[Preparation of radiation-sensitive resin composition (β-III)]
4,4 ′-[1- {as a quinonediazide compound was added to the solution containing siloxane polymer resin (α-III) obtained in Synthesis Example 3 (amount corresponding to 100 parts by mass (solid content) of siloxane polymer). Condensation of 4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol) 12 parts by mass of the product and 10 parts by mass of the semiconductor quantum dot C were added, and propylene glycol monomethyl ether was added as a solvent to prepare a radiation sensitive resin composition (β-III).

Example 4
[Formation of cured film using radiation-sensitive resin composition (β-I)]
After coating the radiation-sensitive resin composition (β-I) prepared in Example 1 on an alkali-free glass substrate by spin coating, a coating film is formed by pre-baking on a 90 ° C. hot plate for 2 minutes. did.
Next, radiation was applied to the obtained coating film through a photomask having a predetermined pattern at an exposure amount of 700 J / m ² using a high pressure mercury lamp. Next, development was performed at 25 ° C. for 60 seconds with a 0.4 mass% tetramethylammonium hydroxide aqueous solution.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 5
[Formation of cured film using radiation-sensitive resin composition (β-II)]
After applying the radiation sensitive resin composition (β-II) prepared in Example 2 on a non-alkali glass substrate with a spinner, a coating film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 1000 J / m ² through a photomask having a predetermined pattern using a high-pressure mercury lamp, and a 0.4 mass% tetramethylammonium hydroxide aqueous solution Then, development was carried out at 25 ° C. for 150 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 6
[Formation of cured film using radiation-sensitive resin composition (β-III)]
The radiation-sensitive resin composition (β-III) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Then, development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 7
[Evaluation of patterning properties]
Using each of the radiation-sensitive resin compositions (β-I to β-III) prepared in Examples 1 to 3, spin coating was performed on a glass substrate (“Corning (registered trademark) 7059” (manufactured by Corning)). After coating using the method, each coating film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes.

  Next, the obtained coating film on each glass substrate is exposed through a mask having a pattern of 5 cm × 8 cm using a PLA (registered trademark) -501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Went. Then, it developed for 60 second at 25 degreeC with the 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, running water was washed with ultrapure water for 1 minute to form a cured film patterned to have a 5 cm × 8 cm opening.

The edge part of each patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the pattern was formed linearly.
As a result, the patterning properties of the cured films formed by patterning using the radiation-sensitive resin compositions (β-I to β-III) prepared in Examples 1 to 3 were all good. .

Example 8
[Evaluation of heat resistance]
About the cured film by the formation method of Example 4, it heated at 230 degreeC for 20 minute (s) further in oven, and measured the film thickness before and behind this heating with the stylus type film thickness measuring device (alpha step IQ, KLA Tencor). . And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

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

  Similarly, the cured film by the forming method of Example 6 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after this heating was measured with a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor). It was measured. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Example 9
[Evaluation of light resistance]
About the cured film by the formation method of Example 4, further, UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.) was used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and the film reduction after irradiation I investigated. The amount of film loss was 2% or less, and light resistance was judged to be good.

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

Similarly, the cured film obtained by the formation method of Example 6 was further irradiated with UV light of 800000 J / m ² at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Example 10
[Evaluation of fluorescence characteristics]
About the cured film by the formation method of Example 4, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C9920-02G, Hamamatsu Photonics). The fluorescence quantum yield was 80%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 5 was further examined using an absolute PL quantum yield measuring apparatus (C9920-02G, Hamamatsu Photonics). The fluorescence quantum yield was 71%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 6 was further examined using an absolute PL quantum yield measuring apparatus (C9920-02G, Hamamatsu Photonics). The fluorescence quantum yield was 63%, and the fluorescence characteristics were judged to be good.

  The cured film formed using the radiation-sensitive resin composition of the present invention is excellent in reliability such as heat resistance and light resistance, is easy to pattern, and other than display elements and electronic devices using the same. It can also be used in the field of LEDs and solar cells.

1, 1a Coating 2, 12, 16 Substrate 3 Photomask 4, 4a Radiation 5 Cured film 11 Wavelength conversion substrate 13, 13a, 13b, 13c Light emitting layer 14 Black matrix 15 Adhesive layer 17, 17a, 17b, 17c Light source 18 Light source substrate 100 Light emitting display element

Claims (10)

[A] alkali-soluble resin,
[B] A radiation-sensitive resin composition comprising a photoacid generator, and [C] a semiconductor quantum dot.   [C] The semiconductor quantum dot is made of a compound containing at least two elements selected from the group consisting of a group 2 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element. The radiation sensitive resin composition according to claim 1.   [C] The radiation-sensitive resin composition according to claim 1 or 2, wherein the semiconductor quantum dots are composed of a compound containing In as a constituent component. [C] At least one semiconductor quantum dot is selected from the group consisting of InP / ZnS compound, CuInS ₂ / ZnS compound, AgInS ₂ compound, (ZnS / AgInS ₂ ) solid solution / ZnS compound, Zn-doped AgInS ₂ compound and Si compound. The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition is a seed.   [A] The alkali-soluble resin is at least one selected from the group consisting of an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin. The radiation sensitive resin composition as described.   [B] The radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the photoacid generator comprises a quinonediazide compound.   [A] Content of [C] semiconductor quantum dot with respect to 100 mass parts of alkali-soluble resin is 0.1 mass part-100 mass parts, The feeling of any one of Claims 1-6 characterized by the above-mentioned. Radiation resin composition.   A cured film formed using the radiation-sensitive resin composition according to claim 1.   A light-emitting display element comprising a light-emitting layer formed using the radiation-sensitive resin composition according to claim 1. A method for forming a light emitting layer of a light emitting display element according to claim 9,
(1) The process of forming the coating film of the radiation sensitive resin composition of any one of Claims 1-7 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3). .

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