JP6171927B2 - Radiation sensitive resin composition, cured film, light emitting element, and method for forming light emitting layer - Google Patents

Description

  The present invention relates to a radiation sensitive resin composition, a cured film, a light emitting 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 (for example, 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 with a well-known concern about 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 directly on an appropriate substrate A method of forming is 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, a film, or the like together with a resin while using semiconductor quantum dots and stably maintaining the fluorescence characteristics peculiar to the semiconductor quantum dots has not been sufficiently studied.

  Therefore, there is a demand for a technique for using a semiconductor quantum dot together with a resin material to form a highly reliable light emitting layer by forming a layer or film without deteriorating the fluorescence emission characteristics. 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, such a resin material is particularly suitable for a semiconductor quantum dot made of a safe material, and is desirably suitable for forming a light emitting layer or the like. And it is preferable that the resin material protects the semiconductor quantum dot contained in formation of a light emitting layer etc., suppresses deterioration of a fluorescence characteristic, and also makes it possible to improve reliability.

In addition, the light-emitting layer made of semiconductor quantum dots and resin can be easily formed, and preferably has high productivity. That is, it is preferable that a simple forming method such as coating can be used for forming such a light emitting layer. And it is preferable that the light emitting layer etc. 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 is prepared containing semiconductor quantum dots and a resin component, and that can form a light emitting layer or a light emitting film by forming a cured film by using a method such as coating.

  Further, the resin composition preferably has excellent patterning properties. That is, the resin composition forming the light emitting layer or the like is preferably capable of forming a patterned light emitting layer or the like so that it can be suitably used for the structure of a light emitting element such as a light emitting display element. In that case, the formation of the patterned light-emitting layer or the like 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 is excellent in radiation sensitivity and can easily form a patterned light-emitting layer or the like 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 and can easily form a highly reliable cured film having excellent fluorescence characteristics.

  Another object of the present invention is to provide a cured film that is formed using a radiation-sensitive resin composition containing semiconductor quantum dots and has excellent fluorescence characteristics and high reliability.

  Another object of the present invention is to provide a light-emitting element formed using a radiation-sensitive resin composition containing semiconductor quantum dots and having a light-emitting layer having excellent fluorescence characteristics and reliability.

  Furthermore, the objective of this invention is providing the formation method of the light emitting layer using the radiation sensitive resin composition containing a semiconductor quantum dot.

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

The first aspect of the present invention is:
[A] at least one alkali-soluble resin selected from the group consisting of polyimide, polyimide precursor and polysiloxane,
[B] It is related with the radiation sensitive resin composition characterized by including a semiconductor quantum dot and [C] a polymerization initiator.

  In the first aspect of the present invention, [B] the 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 [B] semiconductor quantum dot consists of a compound which contains In as a structural component.

In the first aspect of the present invention, the [B] 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.

  1st aspect of this invention WHEREIN: It is preferable that content of [B] 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.

  A third aspect of the present invention relates to a light emitting device having a light emitting layer formed using the first radiation sensitive resin composition of the present invention.

A fourth aspect of the present invention is a method for forming a light emitting layer of a light emitting device 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) 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). About.

  According to the first aspect of the present invention, there is provided a radiation-sensitive resin composition that includes a semiconductor quantum dot and can easily form a highly reliable cured film having excellent fluorescence characteristics.

  Moreover, according to the 2nd aspect of this invention, the cured film which is formed using the radiation sensitive resin composition containing a semiconductor quantum dot, is excellent in the fluorescence characteristic, and has high reliability is provided.

  Moreover, according to the 3rd aspect of this invention, the light emitting element which is formed using the radiation sensitive resin composition containing a semiconductor quantum dot and has a light emitting layer excellent in the fluorescence characteristic and reliability is provided.

  Furthermore, according to the 4th aspect of this invention, the formation method of the light emitting layer of a light emitting element using the radiation sensitive resin composition containing a semiconductor quantum dot is provided.

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 hardening 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 comprises at least one alkali-soluble resin selected from the group consisting of [A] polyimide, polyimide precursor and polysiloxane (hereinafter simply referred to as [A] component or [A] alkali-soluble resin. ), [B] semiconductor quantum dots (hereinafter also simply referred to as [B] component), and [C] a polymerization initiator (hereinafter also simply referred to as [C] component). Resin composition.

  The radiation-sensitive resin composition of the present invention contains [A] an alkali-soluble resin and [B] semiconductor quantum dots, and can be formed of a resin material to form a layer or film containing semiconductor quantum dots. . [A] component of the radiation sensitive resin composition of this invention is at least 1 sort (s) of alkali-soluble resin chosen from the group which consists of a polyimide, a polyimide precursor, and polysiloxane. That is, the layer and film | membrane formed from the radiation sensitive resin composition of this invention are formed using the outstanding heat resistant resin, and are provided with high reliability. And these layers etc. can protect the semiconductor quantum dot to contain, suppress the characteristic deterioration at the time of layer formation, and can improve the reliability further.

  Moreover, the radiation sensitive resin composition of this invention contains a [C] polymerization initiator and can have desired radiation sensitivity. And the radiation sensitive resin composition of this invention becomes possible [patterning using the photolithographic method etc. based on 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 so-called resist composition is applied to the surface of a substrate to be processed or processed to form a resist film, and a predetermined resist pattern is exposed by irradiating light or an electron beam. An exposure process for forming a resist pattern latent image, a heating process as necessary, a development process for developing the resist pattern to form a desired fine pattern, and a process such as etching the substrate using the fine pattern as a mask The process etc. which perform are included.

  And the radiation sensitive resin composition of this invention can be patterned as needed, and can form the cured film of this invention. The cured film of the present invention is constituted by including [B] semiconductor quantum dots in an excellent heat-resistant resin.

  The cured film of the present invention has a fluorescence emission (wavelength conversion) function based on [B] semiconductor quantum dots. Therefore, it can be used as a light emitting layer or a light emitting film (wavelength conversion film) 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 element, and can be used for the structure of the light emitting element of the present invention described later.

  Hereinafter, the radiation-sensitive resin composition, cured film, light-emitting element, and method for forming the light-emitting layer 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 semiconductor quantum dot, and [C] a polymerization initiator 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 component for improving the tolerance of the film | membrane formed and improving reliability as arbitrary components, and also the effect of this invention As long as the above is not impaired, other optional components can be contained.
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 is a resin having alkali developability. [A] The alkali-soluble resin of this embodiment is at least one selected from the group consisting of polyimide, a polyimide precursor, and polysiloxane, and is an alkali-soluble resin. Hereinafter, polyimide, polyimide precursor, and polysiloxane, which are preferable as the [A] alkali-soluble resin, will be described in more detail.

[Polyimide]
A preferred polyimide as the [A] alkali-soluble resin of the radiation-sensitive resin composition of the present embodiment is a polyimide having an alkali-soluble group in the structural unit of the polymer. Examples of the alkali-soluble group include a carboxyl group. Having an alkali-soluble group, for example, a carboxyl group, in the structural unit provides alkali developability (alkali-solubility), and suppresses the occurrence of scum in the exposed area during alkali development. Similarly, for example, the polyimide precursor can also have alkali-solubility having an alkali-soluble group such as a carboxyl group, and is suitable as the [A] alkali-soluble resin of the radiation-sensitive resin composition of the present embodiment. Can be used.

  In addition, it is preferable that the polyimide has a fluorine atom in the structural unit because water repellency is imparted to the interface of the film and the penetration of the interface is suppressed when developing with an alkaline aqueous solution. The fluorine atom content in the polyimide 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 aqueous alkali solution.

  A preferred polyimide as the [A] alkali-soluble resin used in the radiation-sensitive resin composition of the present embodiment is, for example, a polyimide 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 the polyimide that can be used as the 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 above formula (I-1), R ¹ represents a residue of tetracarboxylic dianhydride used for forming the polyimide, and is 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 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′-benzophenonetetracarboxylic Acid 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-Zical Xylphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ) Hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9- Bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride or an acid dianhydride having the structure shown below is preferred. 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 a residue of diamine used for forming the polyimide, 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 include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, and 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 the structure shown below The preferred diamine of. 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 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 carboxyl groups of R ³ and R ^4, the dissolution rate with respect to the aqueous alkaline solution is changed, so that a radiation-sensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

  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 having the structural unit represented by the above 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] a polyimide preferable as the alkali-soluble resin may be composed only of the structural unit represented by the above formula (I-1), or may be 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. 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 are preferably selected within a range that does not impair the heat resistance of the polyimide 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.

  In the present embodiment, for example, a preferable polyimide 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 tetracarboxylic dianhydride and an alcohol, and then a reaction is carried out in the presence of a diamine (partially substituted with a monoamine) and a condensing agent, tetracarboxylic There is a method of obtaining a diester with an acid dianhydride and an alcohol, then converting the remaining dicarboxylic acid into an acid chloride, and reacting with a diamine (partially substituted with a monoamine). In addition, the polyimide precursor which is the precursor of the polyimide mentioned above can also be used suitably as [A] alkali-soluble resin by containing alkali-soluble groups, such as a carboxyl group, and providing alkali solubility, for example.

Moreover, the imidation ratio of the polyimide 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 this embodiment, the imidation ratio of polyimide 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 in this embodiment can be easily detected with the following method. For example, by dissolving a polyimide having an end capping agent dissolved in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polyimide, and measuring this by gas chromatography (GC) or NMR The end-capping agent used for forming the polyimide 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.

  In addition, as mentioned above, the polyimide that is preferable as the [A] alkali-soluble resin of the radiation-sensitive resin composition of the present embodiment is, for example, a polyimide having a carboxyl group in the constituent unit of the polymer. Further, it is possible to use a polyimide having at least one selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the structural unit of the polymer. Such a polyimide has alkali developability (alkali solubility) by having an alkali-soluble group such as a phenolic hydroxyl group in the structural unit, and in the same manner as a polyimide having a carboxyl group in the polymer structural unit, It is possible to suppress the occurrence of scum in the exposed area during development.

[Polysiloxane]
In the radiation-sensitive resin composition of the present embodiment, a preferred polysiloxane as a resin component (hereinafter also simply referred to as polysiloxane) is a polysiloxane having a radical reactive functional group.

  When the polysiloxane of the resin component is a polysiloxane having a radical reactive functional group, it is not particularly limited as long as it has a radical reactive functional group in the main chain or side chain of the polymer of the compound having a siloxane bond. Absent. 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” refers to a group capable of forming a silanol group upon 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.

[[B] Semiconductor quantum dots]
The [B] semiconductor quantum dot of the radiation-sensitive resin composition of the first embodiment of the present invention does not contain Cd or Pb as a constituent component, and is composed of, for example, In (indium) or Si (silicon). In addition, it is a semiconductor quantum dot made of a safe material.

  [B] The semiconductor quantum dot is at least two elements selected from the group consisting of 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 [B] the semiconductor quantum dot is composed 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.

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

  Furthermore, it is more preferable that the [B] 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, as the [B] semiconductor quantum dots, Si compounds can be exemplified.

  [B] Si is preferable as the Si compound preferable as the semiconductor quantum dot.

  [B] By making the component configuration of the semiconductor quantum dots as described above, the radiation-sensitive resin composition of the present embodiment can form a cured film that is safe and has excellent fluorescence characteristics. A light emitting layer or a light emitting film (wavelength conversion film) of a light emitting element that is safe and has excellent fluorescence characteristics can be formed.

  [B] The 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 [B] 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 [B] semiconductor quantum dot are improved.

The [B] 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, the [B] semiconductor quantum dots contained in the radiation-sensitive resin composition of this embodiment are InP / ZnS compound, CuInS ₂ / ZnS compound, 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 [B] 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 wavelength conversion film (wavelength conversion film) having a fluorescent property or a light emitting layer of a light emitting element can be formed.

  The [B] 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 [B] semiconductor quantum dots, and even if the preparation is completed, the fluorescence characteristics of the [B] semiconductor quantum dots may become unstable. is there. [B] If the average particle size 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.

  Moreover, the shape of [B] semiconductor quantum dot is not specifically limited, For example, spherical shape, rod shape, disk shape, and other shapes may be sufficient. 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 for obtaining [B] semiconductor quantum dots contained in the radiation-sensitive resin composition of the first embodiment of the present invention, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent is used. be able to. 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 [B] 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] component mentioned above. Preferably they are 0.2 mass part-50 mass parts. [B] By setting the content of the semiconductor quantum dots in the above range, a cured film having excellent fluorescence characteristics is formed. As a result, the light emitting layer and the light emitting film (wavelength conversion film) of the light emitting element having excellent fluorescence characteristics ) Can be formed. [B] 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 component [A], desired fluorescence characteristics cannot be obtained in the formed cured film, and light emission The light emitting layer of the element cannot be formed. Moreover, when it is more than 100 parts by mass with respect to 100 parts by mass of the [A] component, the stability of the cured film to be formed is impaired, and a light-emitting layer or the like of a stable light-emitting element cannot be formed.

[[C] polymerization initiator]
The radiation sensitive resin composition of this embodiment is comprised including a [C] polymerization initiator. A polymerization initiator is an agent that produces an active species capable of initiating polymerization of a polymerizable compound.

  As the [C] polymerization initiator of this embodiment, it is preferable to use a radiation-sensitive polymerization initiator. The radiation-sensitive polymerization initiator is a component that is used together with a polymerizable compound such as a polyfunctional acrylate described later, and generates an active species that can start polymerization of the polymerizable compound in response to radiation.

  [C] The polymerization initiator is, for example, a radical photopolymerization initiator. Examples of such [C] polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound described above include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  As the acetophenone compound, an α-aminoketone compound is preferable, and in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

[C] As described above, the polymerization initiator can be used alone or in admixture of two or more.
[C] The content of the polymerization initiator is preferably 1 part by mass to 40 parts by mass and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the component [A]. [C] By setting the content of the polymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition of the present embodiment has a high solvent resistance, a high hardness and a low exposure amount. A cured film having high adhesion can be formed.

[Optional ingredients]
The radiation sensitive resin composition of the present embodiment includes [A] at least one alkali-soluble resin selected from the group consisting of polyimide, polyimide precursor, and polysiloxane, [B] semiconductor quantum dots, and [C] polymerization initiation. In addition to the agent, [D] a polyfunctional acrylate or an organic solvent can be contained as an optional component. Furthermore, the radiation-sensitive resin composition of the present embodiment can contain other optional components such as surfactants and adhesion assistants, as needed, within a range that does not impair the effects of the present invention. These optional components may be used as a mixture of two or more. Hereinafter, each component will be described.

[[D] polyfunctional acrylate]
As described above, the radiation-sensitive resin composition of the present embodiment can contain [D] polyfunctional acrylate as an optional component.

  And as a [D] polyfunctional acrylate of the radiation sensitive resin composition of this embodiment, the polymeric compound which has several (meth) acryloyl group in a molecule | numerator can be mentioned.

  [D] As one of the functions of the polyfunctional acrylate, when the radiation-sensitive resin composition of this embodiment is irradiated with light as radiation, it polymerizes to form a high molecular weight or form a crosslinked structure. Can be mentioned. By containing such a polymerizable compound, the entire coating film of the radiation sensitive resin composition can be cured, the strength of the formed cured film can be improved, and the protective function of the contained semiconductor quantum dots can be enhanced. . Furthermore, it is possible to improve the contrast between the light irradiated portion and the non-irradiated portion, thereby preventing peeling during development and suppressing the formation of residues.

  Here, “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, and “having a plurality of (meth) acryloyl groups in a molecule” means an acryloyl group present in the molecule. The total of group and methacryloyl group is 2 or more. In that case, the total number of these groups should just be 2 or more, and either an acryloyl group and a methacryloyl group do not need to exist.

  Examples of the polymerizable compound having a plurality of (meth) acryloyl groups in the molecule include the following.

  Examples of the polymerizable compound having two (meth) acryloyl groups in the molecule include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) Acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene Recall di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, full orange (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, oligopropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, bis (2-hydride) Kishiechiru) isocyanurate di (meth) acrylate.

  Examples of polymerizable compounds having three (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri {(meth) acryloyloxypropyl} ether, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( (Meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri {(meth) acryloyloxy Chill} isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

  Polymerizable compounds having four (meth) acryloyl groups in the molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetrapropionate (meth). ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol triacrylate and the like.

  Examples of the polymerizable compound having five (meth) acryloyl groups in the molecule include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of polymerizable compounds having six (meth) acryloyl groups in the molecule include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol. Examples include hexa (meth) acrylate.

  [D] The polyfunctional acrylate may be a polymerizable compound having 7 or more (meth) acryloyl groups. [D] The polyfunctional acrylate may be (meth) acrylates having a hydroxyl group among the above-described polymerizable compounds, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups. Good. Furthermore, as [D] polyfunctional acrylate, as long as it is a compound having two or more (meth) acryloyl groups, oligoester (meth) acrylates, oligoether (meth) acrylates, and oligoepoxy (meth) acrylates Etc. can be used.

  Among these [D] polyfunctional acrylates, among these, pentaerythritol tri (meth) acrylate, full orange (meth) acrylate, oligoester (meth) acrylate {dendrimer (meth) acrylate} are excellent in polymerizability. More preferred.

  About the commercial item of the polymeric compound illustrated as above [D] polyfunctional acrylate, for example, Toronsei Co., Ltd. Aronix (registered trademark) M-400, M-404, M-408, M-450, M -305, M-309, M-310, M-313, M-315, M-321, M-402, M-350, M-360, M-208, M-210, M-215, M-220 M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M -203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, TO-1450, TO 1382, KAYARAD (registered trademark) D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295 manufactured by Nippon Kayaku Co., Ltd. SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR -9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610 , SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGD , PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, RP-1040, RP -2040, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. Light Acrylate PE-4A, DPE-6A, DTMP-4A, Osaka Organic Examples include Biscoat # 802 manufactured by Chemical Industry Co., Ltd .; a mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate.

  As for content of [D] polyfunctional acrylate in the radiation sensitive resin composition of this embodiment, 1 mass%-20 mass% are preferable with respect to the whole radiation sensitive resin composition. Moreover, when the radiation sensitive resin composition of this embodiment contains an organic solvent, content of [D] polyfunctional acrylate in a radiation sensitive resin composition is 5 with respect to the sum total of the component except an organic solvent. The content is preferably in the range of mass% to 50 mass% or less, and more preferably in the range of 10 mass% to 40 mass%. [D] By containing the polyfunctional acrylate in the above range, a cured film having high hardness can be obtained from the radiation-sensitive resin composition.

[Surfactant]
In the radiation-sensitive resin composition of the present embodiment, the surfactant which is another optional component is for improving the coating property of the radiation-sensitive resin composition, reducing coating unevenness, and improving the developability of the radiation irradiated portion. Can be added. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hex Fluoroalkanes such as fluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorinated alkyl esters.

Commercially available products of these fluorosurfactants include Ftop (registered trademark) EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac (registered trademark) F171, 172, and 173 (DIC Corporation). Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG (registered trademark) 710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC-101, 102, 103, 104 , 105, 106 (manufactured by AGC Seimi Chemical Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.
Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.).

  When using a surfactant as an optional component, the content thereof is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the component [A]. Part. By making the usage-amount of surfactant into 0.01 mass part-10 mass parts, the applicability | paintability of a radiation sensitive resin composition can be optimized.

[Adhesion aid]
In the radiation-sensitive resin composition of the present embodiment, an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a glass such as silicate and quartz, and a metal such as gold, copper, and aluminum Adhesion aids can be used to improve the adhesion to the insulating film. Examples of such adhesion assistants include functional silane coupling agents. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.

  Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples include propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Among these, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  In the radiation-sensitive resin composition of the present embodiment, such an adhesion assistant is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the component [A]. Used in an amount of 10 parts by weight. By setting the amount of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is improved.

[Preparation of radiation-sensitive resin composition]
The radiation sensitive resin composition of the present embodiment includes [A] at least one alkali-soluble resin selected from the group consisting of polyimide, polyimide precursor, and polysiloxane, [B] semiconductor quantum dots, and [C] polymerization initiation. In addition to [D] polyfunctional acrylate, if necessary, it is prepared by uniformly mixing other optional components such as a surfactant. At this time, an organic solvent can be used to prepare a radiation-sensitive resin composition in a dispersion state.

  That is, the radiation-sensitive resin composition of the present embodiment can be prepared in a state of being dissolved or dispersed in an appropriate solvent, and can be used as it is in a dispersion state. For example, in the organic solvent, the [A] component, the [B] component and the [C] component, and if necessary, the [D] component and other optional components are mixed at a predetermined ratio. A radiation sensitive resin composition in the form can be prepared. At this time, an organic solvent can be used individually or in mixture of 2 or more types.

  Examples of the function of the organic solvent include adjusting the viscosity and the like of the radiation-sensitive resin composition, and improving operability and moldability in addition to improving applicability to a substrate and the like.

  Examples of the organic solvent that can be used in the radiation-sensitive resin composition of the present embodiment include those that dissolve or disperse other components and that do not react with other components. Examples of such organic solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propio. Examples thereof include nates, aromatic hydrocarbons, ketones, esters and the like.

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

  Among these organic solvents, ethers such as dialkyl ethers and diethylene glycol alkyl ethers from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of film formation. , Ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate , Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These organic solvents can be used alone or in combination.

  Among these organic solvents, ethers such as diisopropyl ether such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether and di n-hexyl ether are preferred, and diisopentyl ether is most preferred. preferable. By using such a solvent, when applying the radiation-sensitive resin composition of the present embodiment to a large glass substrate by the slit coating method, the drying process time is shortened and the coating property is further improved (coating unevenness). Can be suppressed).

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

  The content of the organic solvent used in the radiation sensitive resin composition of the present embodiment can be appropriately determined in consideration of viscosity and the like. That is, the solid content concentration of the radiation-sensitive resin composition of the present embodiment can be arbitrarily set according to the purpose of use and the desired film thickness, but is preferably 5% by mass to 50% by mass, more preferably Is 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass.

  When the radiation-sensitive resin composition of the present embodiment thus prepared is liquid, it 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. It is preferable to do.

Embodiment 2. FIG.
<Curing film>
The cured film of the second embodiment of the present invention uses the radiation-sensitive resin composition of the first embodiment of the present invention described above, applies it on a substrate, performs patterning when necessary, and then heat cures. Formed. The cured film of the second embodiment of the present invention has a fluorescence emission (wavelength conversion) function based on [B] semiconductor quantum dots and can be used as a wavelength conversion film (wavelength conversion film) or a light emitting layer of a light emitting element. It is. Below, the cured film and its formation method of 2nd Embodiment of this invention are demonstrated.

  In the cured film forming method of the present embodiment, it is preferable to include at least the following steps (1) to (4) in this 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 curing 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 curing process in forming a cured film according to the second embodiment of the present invention.

  Hereinafter, the above-mentioned process (1) (coating film forming process) to process (4) (curing process) will be described.

[Step (1)]
In the coating film forming process which is the process (1) of the cured film forming method of the present embodiment, the coating film 1 of the radiation-sensitive resin composition of the first embodiment of the present invention is applied to the substrate 2 as shown in FIG. Form on top.

  The substrate 2 on which the coating film 1 is formed has glass, quartz, silicon, or resin (for example, polyimide, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyester, cyclic olefin ring opening weight) For example, a substrate made of a coalescence and hydrogenated product thereof may be used. 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, components such as a solvent contained in the radiation sensitive resin composition are evaporated, 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.

[Step (2)]
Next, in the radiation irradiation process which is the process (2) of the method for forming a cured film of the present embodiment, as shown in FIG. 2, at least a part of the coating film 1 formed on the substrate 2 in the process (1) is applied. 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.

[Step (3)]
Next, in the development step which is step (3) of the method for forming a cured film of this 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, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, and tetramethylammonium hydroxide and tetraethylammonium hydroxide. Aqueous solutions of alkaline compounds such as quaternary ammonium salts, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 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 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.

[Step (4)]
Next, in the curing step which is step (4) of the cured film forming method of the present embodiment, the patterned coating film 1a shown in FIG. 3 is cured (post-posted) by a suitable 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 above-described radiation-sensitive resin composition of the first embodiment of the present invention is used, and the heating temperature in this step is preferably 100 ° C to 250 ° C. 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 [B] semiconductor quantum dots in the resin, and [B] semiconductor quantum. Fluorescence emission (wavelength conversion) function based on dots. Therefore, it can be used as a wavelength conversion film that emits fluorescence having a wavelength different from that of excitation light. Therefore, the wavelength conversion film of the embodiment of the present invention can be formed by using the radiation-sensitive resin composition of the first embodiment of the present invention according to the cured film forming method of the present embodiment described above. And the wavelength conversion film of this embodiment has a fluorescence emission (wavelength conversion) function based on [B] semiconductor quantum dots.

  Moreover, it is also possible to provide a light emitting element using the cured film of this embodiment as a light emitting layer.

  In particular, as described later, the cured film of the second embodiment of the present invention is suitable for use as a light emitting layer of a light emitting display element that is an example of a light emitting element, and can be used for the configuration of the light emitting display element. In that case, the light emitting layer of the light emitting device of the embodiment of the present invention is formed in the same manner using the radiation sensitive resin composition of the first embodiment of the present invention according to the above-described cured film forming method of the present embodiment. be able to. And the light emitting layer of the light emitting element of this embodiment has the fluorescence emission (wavelength conversion) function based on [B] semiconductor quantum dot.

  Therefore, in the cured film of this embodiment, the total light transmittance (JIS K7105) at a thickness of 0.1 mm is preferably 75% to a resin constituting the cured film so that the light use efficiency can be increased. 95%, more preferably 78% to 95%, still 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 having excellent light utilization efficiency and a light emitting layer of a light emitting element.

Embodiment 3 FIG.
<Light-emitting display element and light-emitting layer thereof>
In this invention, light emitting elements, such as an illuminating device and a light emitting display element, can be provided by using the cured film of 2nd Embodiment of this invention mentioned above and using it as a wavelength conversion film or a light emitting layer.

  Therefore, the light emitting display element which is 3rd Embodiment of this invention is an example of the light emitting element of this invention. 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 element 100 according to the third 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 is formed by using the cured film of the second embodiment of the present invention described above. 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 curing 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 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 excitation light from the light source 17a, which is one of the light sources 17, by the semiconductor quantum dots of the light emitting layer 13a of the opposing wavelength conversion substrate 11. 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-described 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 100 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 100 according to the third embodiment of the present invention can increase the purity of display color 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.

<Semiconductor quantum dots>
The [B] 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 as follows: It can be synthesized by a generally known 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”, regarding the semiconductor quantum dot C: American Chemical Society. 2010, 132, 248-253 ”. It can be synthesized with reference to the method.

<Preparation of radiation-sensitive resin composition>
Synthesis example 1
[Synthesis of Resin (α-I)]
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 three times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a resin (α-I) as a polymer having a structure represented by the following formula.

Synthesis example 2
[Synthesis of Resin (α-II)]
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. As a result, a resin (α-II) was obtained as polysiloxane which is a hydrolysis-condensation product. The Mw of the resin (α-II) that is polysiloxane was 5000.

Example 1
[Preparation of radiation-sensitive resin composition (β-I)]
The solution containing the resin (α-I) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dot A 10 mass parts mixed, radiation sensitive A resin composition (β-I) was prepared.

Example 2
[Preparation of radiation-sensitive resin composition (β-II)]
The solution containing the resin (α-I) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dot B 10 mass parts mixed, radiation sensitive A resin composition (β-II) was prepared.

Example 3
[Preparation of radiation-sensitive resin composition (β-III)]
The solution containing the resin (α-I) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dots C 10 mass parts mixed, radiation sensitive A resin composition (β-III) was prepared.

Example 4
[Preparation of radiation-sensitive resin composition (β-IV)]
The solution containing the resin (α-II) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dots C 10 mass parts mixed, radiation sensitive A resin composition (β-IV) was prepared.

Example 5
[Preparation of radiation-sensitive resin composition (β-V)]
The solution containing the resin (α-II) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dot B 10 mass parts mixed, radiation sensitive A resin composition (β-V) was prepared.

Example 6
[Preparation of radiation-sensitive resin composition (β-VI)]
The solution containing the resin (α-II) was added in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime). )] (BASF Irgacure (registered trademark) OXE01) 10 mass, tricyclodecane dimethanol diacrylate 30 mass parts mixed, dissolved in methylcyclohexane, semiconductor quantum dots C 10 mass parts mixed, radiation sensitive A resin composition (β-VI) was prepared.

Comparative Example 1
[Preparation of Radiation Sensitive Resin Composition (β-VII)]
A solution containing polyisoprene-terminated acrylate (trade name “UC-203” manufactured by Kuraray Co., Ltd.) in an amount corresponding to 100 parts by mass (solid content) of the polymer, and 1,2-octanedione-1- [4 -(Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) 10 parts, 30 parts by weight of tricyclodecane dimethanol diacrylate, dissolved in methylcyclohexane, and semiconductor quantum dots 10 parts by mass of B was mixed to prepare a radiation sensitive resin composition (β-VII).

<Evaluation of cured film>
The radiation-sensitive resin compositions ((β-I) to (β-VI)) prepared in Examples 1 to 6 and the radiation-sensitive resin composition (β-VII) prepared in Comparative Example 1 were used. The cured film was formed as follows, and the characteristics were evaluated.

Example 7
[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 with 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation-sensitive resin composition (β-I) was good.

Example 8
[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 Development was performed 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation-sensitive resin composition (β-II) was good.

Example 9
[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. 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation sensitive resin composition (β-III) was good.

Example 10
[Formation of cured film using radiation-sensitive resin composition (β-IV)]
A radiation-sensitive resin composition (β-IV) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then prebaked 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. 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation sensitive resin composition (β-IV) was good.

Example 11
[Formation of cured film using radiation-sensitive resin composition (β-V)]
A radiation-sensitive resin composition (β-V) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then prebaked 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. 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation sensitive resin composition (β-V) was good.

Example 12
[Formation of cured film using radiation-sensitive resin composition (β-VI)]
A radiation-sensitive resin composition (β-VI) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then prebaked 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. 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation-sensitive resin composition (β-VI) was good.

Comparative Example 2
[Formation of cured film using radiation-sensitive resin composition (β-VII)]
On the alkali-free glass substrate, the radiation sensitive resin composition (β-VII) prepared in Comparative Example 1 was applied with a spinner, and then prebaked 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. 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 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the 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 linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the radiation-sensitive resin composition (β-VII) was good.
Example 13
[Evaluation of curing shrinkage]
The cured film obtained by the forming method of Example 7 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 8 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 9 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film by the forming method of Example 10 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 11 was further subjected to an exposure process of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 12 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring device (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film formed by the formation method of Comparative Example 2 is further subjected to an exposure process of 1 J / cm ² , and the film thickness before and after this exposure is measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. 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 hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Example 14
[Evaluation of light resistance]
About the cured film by the formation method of Example 7, 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 8 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 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 formed by the formation method of Example 9 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 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 10 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 11 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 12 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 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 formed by the formation method of Comparative Example 2 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.

Example 15
[Evaluation of fluorescence characteristics]
For the cured film obtained by the formation method of Example 7, the fluorescence quantum yield at 25 ° C. was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 79%, 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 8 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 72%, 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 9 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 64%, 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 10 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, 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 11 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, 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 12 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 64%, 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 Comparative Example 2 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 13%, which resulted in a significant decrease in fluorescence characteristics.

  A cured film formed using the radiation-sensitive resin composition of the present invention is excellent in reliability such as light resistance and is easy to pattern, and as a wavelength conversion layer or wavelength conversion film, a display element and the same In addition to the electronic devices used, the present invention can also be used in the fields of LEDs, lighting devices using the 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 (8)

[A] at least one alkali-soluble resin selected from the group consisting of polyimide, polyimide precursor and polysiloxane,
[B] semiconductor quantum dots
[ C] a polymerization initiator , and
[D] A radiation-sensitive resin composition comprising a polymerizable compound .   [B] 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.   [B] 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. [B] The semiconductor quantum dot is at least one selected from the group consisting of 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 compound. The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition is a seed.   [A] Content of [B] 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 1-4 characterized by the above-mentioned. Radiation resin composition.   A cured film formed using the radiation-sensitive resin composition according to any one of claims 1 to 5. A light-emitting element comprising a light-emitting layer that emits fluorescence by excitation light formed using the radiation-sensitive resin composition according to claim 1. It is a formation method of the light emitting layer of the light emitting element of Claim 7, Comprising:
(1) The process of forming the coating film of the radiation sensitive resin composition of any one of Claims 1-5 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). .

Images