JPWO2019181698A1 - Photosensitive resin composition, cured film, color conversion substrate, image display device, and method for manufacturing the cured film. - Google Patents

Abstract

The photosensitive resin composition according to one aspect of the present invention contains at least a photopolymerization initiator, a pyromethene derivative, a photopolymerizable compound, a photopolymerization initiator and an alkali-soluble resin. The h-ray absorption coefficient of this photopolymerization initiator is 100 mL / g · cm or more. Further, a cured film made of a cured product of this photosensitive resin composition can be applied to, for example, a color conversion substrate. The color conversion substrate provided with this cured film can be applied to, for example, an image display device.

Description

The present invention relates to a photosensitive resin composition containing a specific photopolymerization initiator and a pyrromethene derivative, a cured film thereof, a color conversion substrate and an image display device using the same, and a method for producing the cured film.

In recent years, organic EL (electroluminescence) displays have been attracting attention as one of the new thin displays, and have begun to appear on the market as display displays for mobile phones, mobile devices, televisions, and the like.

As a method for making an organic EL display full-color, the development of an RGB coating method for forming a film of each of red (R), green (G), and blue (B) light emitting materials has been promoted. Various other methods are being studied because of the increase in cost due to the enormous size of the film forming apparatus and the limitation of high definition due to the increase in size and definition. In particular, full-color technology using a color conversion (CCM) method that converts the light of a blue backlight into green light emission or red light emission is being actively studied. For example, a self-luminous photosensitive composition for forming a color conversion layer, which comprises a fluorescent dye, a highly refracting material, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. A resin composition (see, for example, Patent Document 1) and a curable composition containing a quantum dot and a binder resin (see, for example, Patent Document 2) have been proposed.

On the other hand, as a technique for improving the luminous efficiency of a display device or a lighting device, a color conversion composition containing a pyromethene compound and a binder resin and converting incident light into long-wavelength light (see, for example, Patent Document 3) has been proposed. There is.

Japanese Unexamined Patent Publication No. 2016-71360 Japanese Unexamined Patent Publication No. 2016-157114 International Publication No. 2016/190283

However, in the prior art disclosed in Patent Documents 1 and 2, although a color conversion layer having higher brightness than a color conversion layer using a pigment or dye having no light emitting property can be formed, the obtained brightness is obtained. It was still insufficient. Further, Patent Document 3 does not disclose anything about forming a patterned color conversion film, and has not studied improvement of brightness, which is a problem of conventional organic EL displays.

Further, although the brightness can be expected to be improved by increasing the optical path length of the color conversion layer by thickening the color conversion layer, the compositions described in Patent Documents 1 to 3 use the thickened color conversion layer. It was difficult to form a fine pattern.

The present invention has been made in view of the above circumstances, and is a photosensitive resin composition capable of forming a fine pattern with high brightness, a cured film thereof, a color conversion substrate using the same, and an image display device. , As well as a method for producing a cured film.

In order to solve the above-mentioned problems and achieve the object, the photosensitive resin composition according to the present invention has at least a photopolymerization initiator, a pyrromethene derivative, and light having an h-ray extinction coefficient of 100 mL / g · cm or more. It is characterized by containing a polymerizable compound and an alkali-soluble resin.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the photopolymerization initiator is a phosphine oxide-based compound.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the extinction coefficient of the photopolymerization initiator at the absorption maximum wavelength of the pyrromethene derivative is 20 mL / g · cm or less. ..

Further, the photosensitive resin composition according to the present invention is further characterized in that, in the above invention, it further contains fine particles having a refractive index of 1.40 or more and 3.00 or less.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the number average particle diameter of the fine particles is 10 nm or more and 300 nm or less.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the weight ratio of the content of the fine particles to the content of the pyrromethene derivative is 5/1 or more and 100/1 or less. ..

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the pyrromethene derivative is a compound represented by the following general formula (1).

（一般式（１）において、Ｘは、Ｃ−Ｒ^７またはＮである。Ｒ^１〜Ｒ^９は、それぞれ同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、スルホ基、ホスフィンオキシド基、および隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。）

(In the general formula (1), X is C-R ⁷ or N. R ^{1 to} R ⁹ may be the same or different, respectively, and hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl. Group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester It is selected from a fused ring and an aliphatic ring formed between a group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siroxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent. )

Further, in the photosensitive resin composition according to the present invention, in the above invention, in the general formula (1), X is C-R ⁷ and R ⁷ is a group represented by the following general formula (2). It is characterized by being.

（一般式（２）において、ｒは、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、チオール基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、ボリル基、スルホ基、ホスフィンオキシド基からなる群より選ばれる。ｋは、１〜３の整数である。ｋが２以上である場合、ｒは、それぞれ同じでも異なってもよい。）

(In the general formula (2), r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, aryl. Thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siroxanyl group, boryl group, sulfo group, phosphine oxide Selected from the group consisting of groups. K is an integer from 1 to 3. When k is 2 or more, r may be the same or different.)

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the pyrromethene derivative exhibits light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm due to excitation light.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the pyrromethene derivative exhibits light emission observed in a region having a peak wavelength of 580 nm or more and less than 750 nm due to excitation light.

Further, the photosensitive resin composition according to the present invention is characterized in that, in the above invention, it further contains an ultraviolet absorber having an absorption maximum wavelength in a wavelength region of 360 nm or less.

Further, the cured film according to the present invention is characterized by being composed of a cured product of the photosensitive resin composition according to any one of the above inventions.

Further, the cured film according to the present invention is characterized in that, in the above invention, the film thickness is 5 μm or more and 50 μm or less.

Further, the method for producing a cured film according to the present invention is a method for producing a cured film made of a cured product of a photosensitive resin composition, wherein the photosensitive resin composition according to any one of the above inventions is used. It includes an exposure step of exposing using an ultra-high pressure mercury lamp, and the exposure amount of the photosensitive resin composition in the exposure step is 60 mJ / cm ² or more and 250 mJ / cm ² or less in terms of i-line. To do.

Further, the color conversion substrate according to the present invention is characterized by including the cured film according to any one of the above inventions.

Further, the image display device according to the present invention is characterized by including the color conversion substrate according to the above invention.

According to the photosensitive resin composition according to the present invention, there is an effect that a fine pattern can be formed with high brightness. Further, by using the photosensitive resin composition according to the present invention, it is possible to realize a high-luminance cured film, a color conversion substrate, and an image display device.

Hereinafter, preferred embodiments of the photosensitive resin composition, the cured film, the color conversion substrate, the image display device, and the method for producing the cured film according to the present invention will be described, but the present invention is limited to the following embodiments. It can be changed and implemented in various ways according to the purpose and application.

<Photosensitive resin composition>
The photosensitive resin composition according to the embodiment of the present invention will be described in detail. The photosensitive resin composition according to the embodiment of the present invention contains at least a photopolymerization initiator, a pyromethene derivative, a photopolymerizable compound, and an alkali-soluble resin having an h-ray extinction coefficient of 100 mL / g · cm or more. When the photosensitive resin composition according to the present embodiment contains the above-mentioned photopolymerization initiator, photopolymerizable compound and alkali-soluble resin, radicals are generated by ultraviolet irradiation to cure the photosensitive resin composition. The difference in alkali solubility between the ultraviolet-irradiated portion and the non-ultraviolet-irradiated portion of the photosensitive resin composition can impart pattern processability to the photosensitive resin composition. The pyrromethene derivative has a color conversion function of converting incident light into light having a wavelength longer than that of the incident light. In the present invention, as described above, the photosensitive resin composition contains such a pyrromethene derivative and a photopolymerization initiator having an h-ray extinction coefficient of 100 mL / g · cm or more.

As described above, in order to improve the brightness, it is effective to thicken the color conversion layer to increase the optical path length of the color conversion layer. However, since it is difficult to sufficiently cure the bottom of the thick color conversion layer by exposure, it is difficult for the conventional composition to achieve both brightness and fine pattern processability. In the present invention, since the wavelength is longer than that of the i-line, attention is paid to the h-line that reaches the bottom more linearly, and the extinction coefficient of the h-line is used as a photopolymerization initiator contained in the photosensitive resin composition. A photopolymerization initiator having a value of 100 mL / g · cm or more has been selected. As a result, the curability of the bottom of the photosensitive resin composition due to exposure can be dramatically improved. As a result, the photosensitive resin composition according to the present embodiment can form a fine pattern even if it is a thick film.

In the present invention, the photosensitive resin composition further comprises a photopolymerization initiator, an ultraviolet absorber, fine particles, an organic solvent, an adhesion improver, a surfactant, and a dispersant having an h-ray absorption coefficient of less than 100 mL / g · cm. , A polymerization inhibitor and the like may be contained. In particular, the fine particles contained in the photosensitive resin composition are preferably fine particles having a refractive index of 1.40 or more and 3.00 or less. Such fine particles appropriately scatter incident light and light emitted from the pyrromethene derivative to improve the light conversion efficiency, so that the brightness can be further improved.

(Components of Photosensitive Resin Composition)
Hereinafter, each component constituting the photosensitive resin composition according to the embodiment of the present invention will be described in detail.

The "photopolymerization initiator" in the present invention refers to a compound that decomposes or reacts with light (including ultraviolet rays or electron beams) or decomposes and reacts to generate radicals. In the photosensitive resin composition according to the embodiment of the present invention, the photopolymerization initiator has an h-ray extinction coefficient of 100 mL / g · cm or more. If the extinction coefficient of the h-line is less than 100 mL / g · cm, the absorption of the h-line is reduced and the curability of the bottom due to the exposure of the thick film becomes insufficient. As a result, it becomes difficult to form a fine pattern on the thick film. Therefore, the h-ray absorption coefficient of the photopolymerization initiator needs to be 100 mL / g · cm or more. The h-ray absorption coefficient of the photopolymerization initiator is preferably 200 mL / g · cm or more from the viewpoint of forming a finer pattern. On the other hand, the h-ray absorption coefficient of the photopolymerization initiator is preferably 1000 mL / g · cm or less from the viewpoint of ease of handling.

Here, the extinction coefficient refers to the value of the absorbance of the photopolymerization initiator solution when the optical path length is 1 cm and the concentration is converted into a 1 g / mL solution. For the absorbance coefficient of the photopolymerization initiator, prepare a diluted solution obtained by diluting the photopolymerization initiator with PGMEA (propylene glycol monomethyl ether acetate), and use a cell with an optical path length of 1 cm to obtain an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). , MultiSpec-1500), and the absorbance at the h line (405 nm) is measured, and the measured value can be obtained by converting the measured value into a solution having a concentration of 1 g / mL.

Examples of the photopolymerization initiator having an h-ray absorption coefficient of 100 mL / g · cm or more include phosphine oxide compounds, benzophenone compounds, acetophenone compounds, oxime ester compounds, and thioxanthene compounds. The photosensitive resin composition according to the present embodiment may contain two or more of these as a photopolymerization initiator.

Examples of the phosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE” (registered trademark) 819), 1800, 1870, and “DAROCUR” (registered trademark) 4265 ( (Made by BASF) and the like. Hereinafter, "IRGACURE" 819, which is an example of a phosphine oxide compound, is abbreviated as IC819 as appropriate. Examples of the benzophenone compound include 4,4'-(bis) dimethylaminobenzophenone and the like. Examples of the acetophenone-based compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (“IRGACURE” (registered trademark) 369, manufactured by BASF Corporation). Examples of the oxime ester compound include "ADEKA ARKULS" (registered trademark) NCI-831 (manufactured by ADEKA). Examples of the thioxanthene compound include 2,4-diethylthioxanthene-9-one.

The structure of the photopolymerization initiator having an h-ray absorption coefficient of 100 mL / g · cm or more is not particularly limited. As the photopolymerization initiator, a phosphine oxide compound is preferable, a compound represented by the following general formula (8) is more preferable, and "IRGACURE" 819 is more preferable, from the viewpoint of bottom curability and transparency.

In the above general formula (8), R ^{16 to} R ¹⁸ may be the same or different, respectively, and hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group and thiol. Group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl It is selected from a fused ring and an aliphatic ring formed between a group, a siroxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent. Of these, an aryl group is preferable. Of the above groups, at least a part of hydrogen may be substituted, and the substituents when substituted include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group and an alkynyl group. Hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thio ether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro A group, a silyl group, a siloxanyl group, a boryl group, a sulfo group and a phosphine oxide group are preferable. The carbon number of R ^{16 to} R ¹⁸ including the substituent is preferably 0 to 20, respectively.

In the present invention, the photosensitive resin composition contains a pyrromethene derivative as described above. In order to make the pyrromethene derivative in the photosensitive resin composition emit light efficiently, the photopolymerization initiator (the h-ray extinction coefficient of 100 mL / g · cm or more) in the photosensitive resin composition is used. It is preferable that the pyrromethene derivative described later has a low absorption coefficient at the absorption maximum wavelength. Specifically, the extinction coefficient of the photopolymerization initiator at the maximum absorption wavelength of the pyrromethene derivative is preferably 20 mL / g · cm or less. When the extinction coefficient of the photopolymerization initiator at the absorption maximum wavelength of the pyrromethene derivative is 20 mL / g · cm or less, the pyrromethene derivative can efficiently absorb light, so that the luminescence characteristics of the pyrromethene derivative are sufficiently exhibited. , The brightness can be further improved.

Here, the maximum absorption wavelength of the pyrromethene derivative means the wavelength at which the absorption spectrum is maximum in the wavelength region of 300 nm or more and 800 nm or less. The absorption maximum wavelength of this pyrromethene derivative can be measured using an ultraviolet-visible spectrophotometer (MultiSpec-1500, manufactured by Shimadzu Corporation).

In the present invention, the content of the photopolymerization initiator contained in the photosensitive resin composition is the solid content of the photosensitive resin composition (other components other than the organic solvent) from the viewpoint of suppressing surface roughness during development. It is preferably 1% by weight or more out of 100% by weight. Further, the content of the photopolymerization initiator is preferably 10% by weight or less based on 100% by weight of the solid content from the viewpoint of compatibility. Further, the photosensitive resin composition may contain a chain transfer agent together with the photopolymerization initiator.

In the present invention, the pyrromethene derivative contained in the photosensitive resin composition is preferably a compound represented by the following general formula (1).

In the general formula (1), X is CR ⁷ or N. R ^{1 to} R ⁹ may be the same or different, respectively, and hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, It is selected from a fused ring and an aliphatic ring formed between a sulfo group, a phosphine oxide group, and an adjacent substituent.

In all the above groups, the hydrogen may be deuterium. This also applies to the compounds described below or their partial structures. Further, in the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms has all carbon atoms of 6 to 40 including the carbon number contained in the substituent substituted with the aryl group. It is an aryl group. The same applies to other substituents that specify the number of carbon atoms.

Further, in all the above groups, the substituents in the case of substitution include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group and an alkylthio group. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group. , Sulf group and phosphine oxide group are preferable, and specific substituents which are preferable in the description of each substituent are preferable. Further, these substituents may be further substituted with the above-mentioned substituents.

"Unsubstituted" in the case of "substituted or unsubstituted" means that a hydrogen atom or a deuterium atom has been substituted. The same applies to the case of "substituted or unsubstituted" in the compound described below or its partial structure.

Of all the above groups, the alkyl group is a saturated aliphatic hydrocarbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Shows a group, which may or may not have a substituent. The additional substituent when substituted is not particularly limited, and examples thereof include an alkyl group, a halogen, an aryl group, and a heteroaryl group, and this point is also common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 or more and 20 or less, more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.

The cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc., which may or may not have a substituent. .. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is preferably in the range of 3 or more and 20 or less.

The heterocyclic group refers to an aliphatic ring having an atom other than carbon such as a pyran ring, a piperidine ring, and a cyclic amide in the ring, which may or may not have a substituent. Good. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkenyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, a butadienyl group, etc., which may or may not have a substituent. .. The carbon number of the alkenyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, etc., even if it has a substituent. You do not have to have it.

The alkynyl group refers to an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. The carbon number of the alkynyl group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkoxy group refers to a functional group to which an aliphatic hydrocarbon group is bonded via an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group has a substituent. You do not have to have. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.

The alkylthio group is one in which the oxygen atom of the ether bond of the alkoxy group is replaced with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. The number of carbon atoms of the alkylthio group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.

The aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. May be good. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

The arylthio ether group is one in which the oxygen atom of the ether bond of the aryl ether group is replaced with a sulfur atom. The aromatic hydrocarbon group in the arylthioether group may or may not have a substituent. The number of carbon atoms of the arylthioether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

The aryl group is, for example, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthryl group, an anthrasenyl group, a benzophenanthryl group, a benzoanthrase. It shows an aromatic hydrocarbon group such as an Nyl group, a chrysenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthrasenyl group, a perylenel group and a helisenyl group. Of these, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, a fluoranthenyl group and a triphenylenyl group are preferable. The aryl group may or may not have a substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less, and more preferably 6 or more and 30 or less.

When R ^{1 to} R ⁹ are substituted or unsubstituted aryl groups, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthrasenyl group, preferably a phenyl group or a biphenyl group. Groups, turphenyl groups and naphthyl groups are more preferred. More preferably, it is a phenyl group, a biphenyl group, a terphenyl group, and a phenyl group is particularly preferable.

When each substituent is further substituted with an aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group or an anthrasenyl group, preferably a phenyl group, a biphenyl group or a ter. A phenyl group and a naphthyl group are more preferable. Particularly preferred is a phenyl group.

The heteroaryl group is, for example, a pyridyl group, a furanyl group, a thienyl group, a quinolinyl group, an isoquinolinyl group, a pyrazinyl group, a pyrimidyl group, a pyridadinyl group, a triazine group, a naphthyldinyl group, a synnolinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, Benzofuranyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzoflocarbazolyl group, benzothienocarbazolyl Non-carbon atoms such as groups, dihydroindenocarbazolyl groups, benzoquinolinyl groups, acridinyl groups, dibenzoacrydinyl groups, benzoimidazolyl groups, imidazoly pyridyl groups, benzoxazolyl groups, benzothiazolyl groups, phenanthrolinyl groups, etc. Indicates a cyclic aromatic group having one or more rings in the ring. However, the naphthyldinyl group is any of 1,5-naphthylidineyl group, 1,6-naphthylidineyl group, 1,7-naphthylidineyl group, 1,8-naphthylidineyl group, 2,6-naphthylidineyl group and 2,7-naphthylidineyl group. Indicates. The heteroaryl group may or may not have a substituent. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 or more and 40 or less, and more preferably 2 or more and 30 or less.

When R ^{1 to} R ⁹ are substituted or unsubstituted heteroaryl groups, the heteroaryl groups include pyridyl group, furanyl group, thienyl group, quinolinyl group, pyrimidyl group, triazine group, benzofuranyl group, benzothienyl group and indrill. Group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzoimidazolyl group, imidazole pyridyl group, benzoxazolyl group, benzothiazolyl group, phenanthrolinyl group are preferable, and pyridyl group, furanyl group, thienyl group, quinolinyl group More preferred. Particularly preferred is a pyridyl group.

When each substituent is further substituted with a heteroaryl group, the heteroaryl group includes pyridyl group, furanyl group, thienyl group, quinolinyl group, pyrimidyl group, triazinyl group, benzofuranyl group, benzothienyl group, indolyl group, dibenzo. A furanyl group, a dibenzothienyl group, a carbazolyl group, a benzoimidazolyl group, an imidazole pyridyl group, a benzoxazolyl group, a benzothiazolyl group and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a thienyl group and a quinolinyl group are more preferable. Particularly preferred is a pyridyl group.

Halogen refers to an atom selected from fluorine, chlorine, bromine and iodine. Further, the carbonyl group, the carboxyl group, the ester group and the carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group and the like, and these substituents may be further substituted.

The amino group is a substituted or unsubstituted amino group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group and the like. As the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group and a quinolinyl group are preferable. These substituents may be further substituted. The number of carbon atoms is not particularly limited, but is preferably 2 or more and 50 or less, more preferably 6 or more and 40 or less, and particularly preferably 6 or more and 30 or less.

The silyl group is, for example, an alkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a propyldimethylsilyl group or a vinyldimethylsilyl group, a phenyldimethylsilyl group, a tert-butyldiphenylsilyl group or a tri. Indicates an arylsilyl group such as a phenylsilyl group and a trinaphthylsilyl group. Substituents on silicon may be further substituted. The number of carbon atoms of the silyl group is not particularly limited, but is preferably in the range of 1 or more and 30 or less.

The siloxanyl group refers to, for example, a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted. The boryl group is a substituted or unsubstituted boryl group. Examples of the substituent in the case of substituting the boryl group include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group, a hydroxyl group and the like. Of these, aryl groups and aryl ether groups are preferable. The sulfo group is a substituted or unsubstituted sulfo group. Examples of the substituent when substituting the sulfo group include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group and the like. Of these, linear alkyl groups and aryl groups are preferable. The phosphine oxide group is a group represented by −P (= O) R ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ are selected from the same group as R ^{1 to} R ⁹ .

The condensed ring and the aliphatic ring formed between the adjacent substituents are conjugated or unconjugated by any adjacent bisubstituted groups (for example, R ¹ and R ² of the general formula (1)) bonded to each other. It means to form a circular skeleton of. The constituent elements of such a fused ring and the aliphatic ring may contain elements selected from nitrogen, oxygen, sulfur, phosphorus and silicon in addition to carbon. Further, these fused rings and aliphatic rings may be fused with yet another ring.

Since the compound represented by the general formula (1) exhibits a high emission quantum yield and a small half-value width of the emission spectrum, both efficient color conversion and high color purity can be achieved. Furthermore, the compound represented by the general formula (1) has various properties such as luminous efficiency, color purity, thermal stability, photostability and dispersibility by introducing an appropriate substituent at an appropriate position. And physical properties can be adjusted. For example, at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group or substituted or unsubstituted compared to the case where R ¹ , R ³ , R ⁴ and R ⁶ are all hydrogen. The aryl group, substituted or unsubstituted heteroaryl group, shows better thermal stability and photostability.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group, the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl. Alkyl groups having 1 to 6 carbon atoms such as groups, sec-butyl groups, tert-butyl groups, pentyl groups and hexyl groups are preferable. Further, as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group are preferable from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, the tert-butyl group having a high sterically bulk is more preferable as the alkyl group. A methyl group is also preferably used as the alkyl group from the viewpoint of ease of synthesis and availability of raw materials.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, and more preferably. Is a phenyl group and a biphenyl group. The aryl group is particularly preferably a phenyl group.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolinyl group, or a thienyl group, and more preferably. It is a pyridyl group and a quinolinyl group. The heteroaryl group is particularly preferably a pyridyl group.

All of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and when they are substituted or unsubstituted alkyl groups, the solubility in an alkali-soluble resin or a solvent is improved. preferable. In this case, the alkyl group is preferably a methyl group from the viewpoint of easiness of synthesis and availability of raw materials.

Better thermal stability when all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, respectively, and are substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups. And because it shows photostability, it is preferable. In this case, all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and are more preferably substituted or unsubstituted aryl groups.

Although some substituents improve several properties, only a limited number of substituents exhibit sufficient performance. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, by introducing a plurality of types of substituents into the compound represented by the general formula (1), it is possible to obtain a compound having a good balance in light emission characteristics, color purity and the like.

In particular, all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, respectively, and when substituted or unsubstituted aryl groups are used, for example, R ¹ ≠ R ⁴ , R ³ ≠ R ⁶ , R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ , and so on, it is preferable to introduce a plurality of types of substituents. Here, "≠" indicates that the bases have different structures. For example, R ¹ ≠ R ⁴ indicates that R ¹ and R ⁴ are groups of different structures. By introducing a plurality of types of substituents as described above, an aryl group that affects color purity and an aryl group that affects luminous efficiency can be introduced at the same time, so that fine adjustment is possible.

Above all, it is preferable that R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ from the viewpoint of improving the luminous efficiency and the color purity in a well-balanced manner. In this case, for the compound represented by the general formula (1), one or more aryl groups that affect the color purity are introduced into the pyrrole rings on both sides, and the aryl that affects the luminous efficiency at other positions. Since the group can be introduced, both of these properties can be maximized. Further, when R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ , it is more preferable that R ¹ = R ⁴ and R ³ = R ⁶ from the viewpoint of improving both heat resistance and color purity.

As the aryl group that mainly affects the color purity, an aryl group substituted with an electron donating group is preferable. An electron-donating group is an atomic group that donates an electron to an atomic group substituted by an inductive effect or a resonance effect in organic electron theory. Examples of the electron-donating group include those having a negative value as the substituent constant (σp (para)) of Hammett's law. The substituent constant (σp (para)) of Hammett's rule can be quoted from the 5th edition of the Basics of Chemistry Handbook (page II-380).

Specific examples of the electron donating group include an alkyl group (methyl group σp: −0.17), an alkoxy group (methoxy group σp: −0.27), and an amino group (−NH ₂ σp: −”. 0.66) and the like can be mentioned. In particular, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, a tert-butyl group and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable, and when these are used as the above-mentioned electron-donating groups, in the compound represented by the general formula (1), quenching due to aggregation of molecules is prevented. be able to. The substitution position of the substituent is not particularly limited, but since it is necessary to suppress the twist of the bond in order to enhance the photostability of the compound represented by the general formula (1), the meta is relative to the bond position with the pyrromethene skeleton. It is preferable to combine with the position or para position. On the other hand, as the aryl group that mainly affects the light emission efficiency, an aryl group having a bulky substituent such as a tert-butyl group, an adamantyl group, or a methoxy group is preferable.

If R ¹ , R ³ , R ⁴ and R ⁶ are the same or different, respectively, and are substituted or unsubstituted aryl groups, then R ¹ , R ³ , R ⁴ and R ⁶ are the same or different, respectively. It may be a substituted or unsubstituted phenyl group, and is preferable. At this time, it is more preferable that R ¹ , R ³ , R ⁴ and R ⁶ are selected from the following Ar-1 to Ar- ⁶ , respectively. In this case, preferred combinations of R ¹ , R ³ , R ⁴ and R ⁶ include, but are not limited to, the combinations shown in Tables 1-1 to 1-11.

Further, in the general formula (1), R ² and R ⁵ are preferably any one of hydrogen, an alkyl group and an aryl group. Among them, as R ² and R ⁵ , hydrogen or an alkyl group is preferable from the viewpoint of thermal stability of the compound represented by the general formula (1), and hydrogen is easily obtained from the viewpoint of easily obtaining a narrow full width at half maximum in the emission spectrum. Is more preferable.

Further, in the general formula (1), R ⁸ and R ⁹ are preferably an alkyl group, an aryl group, a heteroaryl group, a fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group. In particular, R ⁸ and R ⁹ are more preferably fluorine or fluorine-containing aryl groups because they are stable with respect to excitation light and a higher emission quantum yield can be obtained. Further, from the viewpoint of ease of synthesis, it is more preferable that R ⁸ and R ⁹ are fluorine.

Here, the fluorine-containing aryl group is an aryl group containing fluorine. Examples of the fluorine-containing aryl group include a fluorophenyl group, a trifluoromethylphenyl group and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a fluorine-containing heteroaryl group. Examples of the fluorine-containing heteroaryl group include a fluoropyridyl group, a trifluoromethylpyridyl group and a trifluoropyridyl group. The fluorine-containing alkyl group is an alkyl group containing fluorine. Examples of the fluorine-containing alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

Further, in the general formula (1), it is preferable that X is CR ⁷ from the viewpoint of light stability. When X is C-R ⁷ , the durability of the compound represented by the general formula (1) tends to be easily affected by the substituent R ⁷ . Specifically, when R ⁷ is hydrogen, the reactivity of this portion is high, so that this portion tends to easily react with moisture and oxygen in the air. Further, when R ⁷ is a substituent having a large degree of freedom of movement of the molecular chain such as an alkyl group, the compounds tend to aggregate with time in the photosensitive resin composition. Therefore, it is preferable that R ⁷ is a group that is rigid, has a small degree of freedom of movement, and is unlikely to cause aggregation. Specifically, R ⁷ is preferably either a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

From the viewpoint of giving a higher emission quantum yield, making it more difficult to pyrolyze, and from the viewpoint of photostability, it is preferable that X is C-R ⁷ and R ⁷ is a substituted or unsubstituted aryl group. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group and an anthrasenyl group are preferable from the viewpoint of not impairing the emission wavelength.

Furthermore, to increase the photostability of the compound represented by the general formula (1), the carbon of R ⁷ and pyrromethene skeleton - is preferably suppressed moderately twisting of carbon bonds. From this point of view, R ⁷ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group, and is preferably substituted or unsubstituted. Phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group are more preferable. Particularly preferably, R ⁷ is a substituted or unsubstituted phenyl group.

Further, R ⁷ is preferably a moderately bulky substituent. When R ⁷ has a certain bulk height, molecular aggregation can be prevented. As a result, the luminous efficiency and durability of the compound represented by the general formula (1) are further improved.

A more preferable example of R ⁷ which is such a bulky substituent is a group having a structure represented by the following general formula (2). That is, in the general formula (1), when X is C-R ^7, it is preferable that R ⁷ is a group represented by the following general formula (2).

In the general formula (2), r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, arylthioether. Group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siroxanyl group, boryl group, sulfo group, phosphine oxide group Selected from the group consisting of. k is an integer of 1-3. When k is 2 or more, r may be the same or different.

From the viewpoint that a higher emission quantum yield can be obtained, r is preferably a substituted or unsubstituted aryl group. Among these aryl groups, a phenyl group and a naphthyl group are particularly preferable examples. When r is an aryl group, k in the general formula (2) is preferably 1 or 2, and more preferably 2 from the viewpoint of further preventing molecular agglutination. Further, when k is 2 or more, it is preferable that at least one of the plurality of r is substituted with an alkyl group. As the alkyl group in this case, a methyl group, an ethyl group and a tert-butyl group are particularly preferable examples from the viewpoint of thermal stability.

Further, from the viewpoint of controlling the emission wavelength and absorption wavelength of the compound represented by the general formula (1) and enhancing the compatibility with the solvent, r is a substituted or unsubstituted alkyl group, substituted or absent. It is preferably a substituted alkoxy group or halogen, and more preferably a methyl group, an ethyl group, a tert-butyl group or a methoxy group. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable as this r. The fact that r is a tert-butyl group or a methoxy group is more effective in preventing quenching due to aggregation of molecules.

Further, as a further aspect of the compound represented by the general formula (1), it is preferable that at least one of R ^{1 to} R ⁷ is an electron attracting group. In particular, the first to third aspects shown below are preferable. As a first preferred embodiment, at least one of R ^{1 to} R ⁶ is an electron attracting group. A second preferred embodiment is that R ⁷ is an electron attracting group. As a third preferred embodiment, at least one of R ^{1 to} R ⁶ is an electron attracting group, and R ⁷ is an electron attracting group. As described above, by introducing an electron attracting group into the pyrromethene skeleton of the compound represented by the general formula (1), the electron density of the pyrromethene skeleton can be significantly reduced. As a result, the stability of the compound represented by the general formula (1) to oxygen is further improved, and as a result, the durability of the compound represented by the general formula (1) can be further improved.

An electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from an atomic group substituted by an inductive effect or a resonance effect in organic electron theory. Examples of the electron-withdrawing group include those having a positive value as the substituent constant (σp (para)) of Hammett's law. The substituent constant (σp (para)) of Hammett's rule can be quoted from the 5th edition of the Basics of Chemistry Handbook (page II-380). The phenyl group also has an example of taking a positive value as described above, but in the present invention, the phenyl group is not included in the electron attracting group.

Examples of electron attracting groups include -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18), -CO ₂ R ¹² (σp: +0.45 when R ¹² is an ethyl group), -CONH ₂ (σp: +0.38), -COR ¹² (σp: +0.49 when R ¹² is a methyl group),- Examples thereof include CF ₃ (σp: +0.50), −SO ₂ R ¹² (σp: +0.69 when R ¹² is a methyl group), −NO ₂ (σp: +0.81) and the like. R ¹² is a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 substituted or unsubstituted ring-forming atoms, a heterocyclic group having 5 to 30 substituted or unsubstituted ring-forming atoms, and a substituted or unsubstituted carbon number. Represents an alkyl group of 1 to 30, a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of each of these groups include the same examples as described above.

Preferred electron-withdrawing groups include fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group, a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted amide group, and the like. Examples include substituted or unsubstituted sulfonyl or cyano groups. This is because they are difficult to decompose chemically.

More preferred electron attractants include fluoroalkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups or cyano groups. This is because they have the effect of preventing concentration quenching and improving the emission quantum yield. A particularly preferred electron attractant is a substituted or unsubstituted ester group.

As one of the preferred examples of the compound represented by the general formula (1), all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, respectively, and are substituted or unsubstituted alkyl groups. Further, there is a case where X is C-R ⁷ and R ⁷ is a group represented by the general formula (2). In this case, it is particularly preferable that R ⁷ is a group represented by the general formula (2) in which r is contained as a substituted or unsubstituted phenyl group.

Further, as a further preferable example of the compound represented by the general formula (1), all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, respectively, and the above-mentioned Ar-1 to Ar may be used. Further, there is a case where X is selected from -6, X is C-R ⁷ , and R ⁷ is a group represented by the general formula (2). In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is contained as a tert-butyl group or a methoxy group, and is represented by the general formula (2) in which r is contained as a methoxy group. It is particularly preferable that it is a group to be produced.

Further, as a further preferable example of the compound represented by the general formula (1), all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, respectively, and the above-mentioned Ar-1 to Ar may be used. It is selected from −6, and R ² and R ⁵ may be the same or different, respectively, and are substituted or unsubstituted ester groups. Further, X is CR ⁷ and R ⁷ is a general formula. The group represented by (2) may be used. In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is contained as a tert-butyl group or a methoxy group, and is represented by the general formula (2) in which r is contained as a methoxy group. It is particularly preferable that it is a group to be produced.

Examples of the compound represented by the general formula (1) include compounds having the following structures.

The compound represented by the general formula (1) can be synthesized, for example, by the method described in JP-A-8-509471 and JP-A-2000-208262. That is, the desired pyrromethene-based metal complex can be obtained by reacting the pyrromethene compound and the metal salt in the presence of a base.

Regarding the synthesis of the pyrromethene-boron trifluoride complex, refer to J. Org. Chem. , Vol. 64, No. 21, pp. 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, pp. The compound represented by the general formula (1) can be synthesized with reference to the method described in 1333-1335 (1997) and the like. For example, the compound represented by the following general formula (5) and the compound represented by the general formula (6) are heated in 1,2-dichloroethane in the presence of phosphorus oxychloride, and then the following general formula (7) is used. A method of reacting the represented compound in 1,2-dichloroethane in the presence of triethylamine to obtain the compound represented by the general formula (1) can be mentioned. However, the present invention is not limited to this. Wherein, R ^'1 ~R' ⁹ is the same as ^R 1 to R ⁹ in the above description. J represents halogen.

Further, when introducing an aryl group or a heteroaryl group, a method of forming a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned. , Not limited to this. Similarly, when introducing an amino group or a carbazolyl group, for example, a method of forming a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or carbazole derivative under a metal catalyst such as palladium is used. However, the present invention is not limited thereto.

When the pyrromethene derivative in the present invention is used in a green photosensitive resin composition, it is preferable that the pyromethene derivative exhibits light emission observed in a region where the maximum emission wavelength (peak wavelength) is 500 nm or more and less than 580 nm due to excitation light. Hereinafter, the emission observed in the region where the maximum emission wavelength is 500 nm or more and less than 580 nm is referred to as “green emission”. Here, the maximum emission wavelength can be measured using, for example, an F-2500 type spectrofluorometer (manufactured by Hitachi, Ltd.).

When the pyrromethene derivative in the present invention is used in a green photosensitive resin composition, it preferably emits green light by excitation light in a wavelength range of 430 nm or more and less than 500 nm. In general, the greater the energy of excitation light, the more likely it is to cause material decomposition. However, the excitation light in the wavelength range of 430 nm or more and less than 500 nm has a relatively small excitation energy. Therefore, by using the excitation light in the wavelength range as the light absorbed by the pyrromethene derivative, the decomposition of the pyrromethene derivative in the photosensitive resin composition can be suppressed. As a result, green light with good color purity can be obtained from the pyrromethene derivative.

When the pyrromethene derivative in the present invention is used in a red photosensitive resin composition, it is preferable that the pyromethene derivative exhibits light emission observed in a region where the maximum emission wavelength (peak wavelength) is 580 nm or more and less than 750 nm due to excitation light. Hereinafter, the light emission observed in the region where the maximum emission wavelength is 580 nm or more and less than 750 nm is referred to as “red emission”.

When the pyrromethene derivative in the present invention is used in a red photosensitive resin composition, it preferably emits red light by excitation light in a wavelength range of 430 nm or more and less than 580 nm. In general, the greater the energy of excitation light, the more likely it is to cause material decomposition. However, the excitation light in the wavelength range of 430 nm or more and less than 580 nm has a relatively small excitation energy. Therefore, by using the excitation light in the wavelength range as the light absorbed by the pyrromethene derivative, the decomposition of the pyrromethene derivative in the photosensitive resin composition can be suppressed. As a result, red light with good color purity can be obtained from the pyrromethene derivative.

The content of the pyromethene derivative in the photosensitive resin composition can be appropriately set according to the molar extinction coefficient of the compound, the emission quantum yield and the absorption intensity at the excitation wavelength, and the film thickness and transmittance of the cured film to be produced. .. For example, the content of this pyrromethene derivative is preferably 0.1% by weight or more and 10% by weight or less based on 100% by weight of the solid content of the photosensitive resin composition. By setting the content of the pyrromethene derivative to 0.1% by weight or more in the solid content, the color purity and the brightness can be further improved. The content of the pyrromethene derivative in the photosensitive resin composition is more preferably 0.3% by weight or more based on the solid content. On the other hand, by setting the content of the pyrromethene derivative in the photosensitive resin composition to 10% by weight or less in the solid content, the solubility of the pyrromethene derivative in the alkali-soluble resin is improved, and the color conversion effect is further improved. Can be done. The content of the pyrromethene derivative in the photosensitive resin composition is more preferably 1.5% by weight or less based on the solid content.

The "alkali-soluble resin" in the present invention means a resin having an acidic group. As the acidic group, a carboxyl group, a hydroxyl group and the like are preferable. Examples of the alkali-soluble resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, polyamide resin, polyamideimide resin, and polyester resin. In the present invention, the photosensitive resin composition may contain two or more of these as alkali-soluble resins. Among these, acrylic resin is more preferable from the viewpoint of stability.

The acrylic resin more preferably has an alicyclic hydrocarbon group. Since the acrylic resin has an alicyclic hydrocarbon group, it is possible to improve the chemical resistance to an alkaline developer, an organic solvent, or the like. For example, acrylic resin has a structural unit represented by the following general formula (3) having a carboxyl group in the side chain and a structural unit represented by the following general formula (4) having an alicyclic hydrocarbon group in the side chain. It is more preferable to have. By having the structural unit represented by the following general formula (3), the acrylic resin can further improve the solubility in an alkaline developer. Further, since the acrylic resin has a structural unit represented by the following general formula (4), it is possible to further improve the chemical resistance and brightness against an alkaline developer, an organic solvent and the like.

In the above general formula (3), R ¹³ represents a hydrogen atom or a methyl group. In the above general formula (4), R ¹⁴ represents a hydrogen atom or a methyl group, and R ¹⁵ represents an organic group having 1 to 6 carbon atoms. n is an integer of 1 to 3. When n is 2 or more, the plurality of R ^15s may be the same or different. The organic group represented by R ^15, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, aryl ether group, aryl thioether group, an aryl group, a heteroaryl Examples thereof include a fused ring and an aliphatic ring formed between a group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group and an adjacent substituent. Among these, a carboxyl group and an ester group are preferable from the viewpoint of solubility in an alkaline developer.

The acrylic resin having the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) is, for example, a copolymer constituting the structural unit represented by the general formula (3). It can be obtained by copolymerizing a component with a copolymerization component constituting a structural unit represented by the general formula (4). Other copolymerization components may be further copolymerized with respect to these copolymerization components.

Examples of the copolymerization component constituting the structural unit represented by the above general formula (3) include (meth) acrylic acid. Here, "(meth) acrylic acid" means acrylic acid or methacrylic acid. Two or more of these may be used as the copolymerization component. Of these, methacrylic acid is preferred.

Examples of the copolymerization component constituting the structural unit represented by the above general formula (4) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyloxyethyl (meth). Acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] Decane-8-yloxyethyl (meth) acrylate and the like can be mentioned. Two or more of these may be used as the copolymerization component. Among these, dicyclopentanyl (meth) acrylate is preferable.

As the other copolymerization component described above, an ethylenically unsaturated compound is preferable. This is because the sensitivity of the photosensitive resin composition can be improved. Examples of the ethylenically unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl (meth). Unsaturated carboxylic acid alkyl esters such as acrylates, iso-butyl (meth) acrylates, tert-butyl (meth) acrylates, n-pentyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, and benzyl (meth) acrylates; , Aromatic vinyl compounds such as p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene; unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate; unsaturated carboxylics such as glycidyl (meth) acrylate. Acid glycidyl ester; carboxylic acid vinyl ester such as vinyl acetate and vinyl propionate; vinyl cyanide compound such as (meth) acrylonitrile and α-chloroacrylonitrile; aliphatic conjugated diene such as 1,3-butadiene and isoprene; Examples thereof include polystyrene having a meta) acryloyl group, polymethyl (meth) acrylate, polybutyl (meth) acrylate, and macromonomer such as polysilicone. As the "other copolymerization component", two or more of these may be used. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, styrene, and glycidyl methacrylate are particularly preferable.

The content of the structural unit represented by the general formula (3) in the acrylic resin is preferably 5% by weight or more in 100% by weight of the acrylic resin from the viewpoint of further improving the alkali solubility. Further, the content of the structural unit represented by the general formula (3) in the acrylic resin is 60% by weight or less out of 100% by weight of the acrylic resin from the viewpoint of forming a finer pattern. preferable.

On the other hand, the content of the structural unit represented by the general formula (4) in the acrylic resin is preferably 5% by weight or more out of 100% by weight of the acrylic resin from the viewpoint of further improving the brightness. More preferably, it is 15% by weight or more. Further, the content of the structural unit represented by the general formula (4) in the acrylic resin is 60% by weight or less out of 100% by weight of the acrylic resin from the viewpoint of forming a finer pattern. It is preferably 45% by weight or less, more preferably 45% by weight or less.

The glass transition temperature (Tg) of the alkali-soluble resin in the present invention is preferably 30 ° C. or higher and 180 ° C. or lower. By setting the Tg of the alkali-soluble resin to 30 ° C. or higher, the molecular motion of the alkali-soluble resin due to the heat generated by the incident light from the light source or the driving heat of the device can be suppressed, and the dispersed state of the pyrromethene derivative can be stabilized. Thereby, the durability of the photosensitive resin composition can be improved. The Tg of the alkali-soluble resin is more preferably 50 ° C. or higher, and even more preferably 90 ° C. or higher. On the other hand, by setting the Tg of the alkali-soluble resin to 180 ° C. or lower, the flexibility of the cured film described later can be improved. The Tg of the alkali-soluble resin is more preferably 150 ° C. or lower, and even more preferably 140 ° C. or lower.

Examples of the method for synthesizing an acrylic resin, which is an example of such an alkali-soluble resin, include the methods described in JP-A-2006-124664.

The weight average molecular weight of the alkali-soluble resin in the present invention is preferably 10,000 to 800,000. By setting the weight average molecular weight of the alkali-soluble resin to 10,000 or more, the strength of the alkali-soluble resin can be improved. As a result, a finer pattern of the photosensitive resin composition containing the alkali-soluble resin can be formed. On the other hand, by setting the weight average molecular weight of the alkali-soluble resin to 800,000 or less, the viscosity of the photosensitive resin composition can be appropriately suppressed. Here, the weight average molecular weight of the alkali-soluble resin can be measured by GPC (gel permeation chromatography).

The acid value of the alkali-soluble resin in the present invention is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more, from the viewpoint of suppressing residues and forming a finer pattern. On the other hand, the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less, from the viewpoint of further improving the alkali solubility. Here, the acid value of the alkali-soluble resin can be determined by titrating a solution of the alkali-soluble resin in orthocresol at 25 ° C. using a 0.1 mol / L potassium hydroxide / ethanol aqueous solution. ..

In the present invention, the content of the alkali-soluble resin in the photosensitive resin composition is 20 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight in total of the alkali-soluble resin and the photopolymerizable compound described later. Is preferable. By setting the content of the alkali-soluble resin to 20 parts by weight or more, it is possible to form a higher brightness and finer pattern of the photosensitive resin composition. The content of the alkali-soluble resin is more preferably 30 parts by weight or more. On the other hand, by setting the content of the alkali-soluble resin to 80 parts by weight or less, the sensitivity and alkali solubility of the photosensitive resin composition can be improved. The content of the alkali-soluble resin is more preferably 60 parts by weight or less.

The "photopolymerizable compound" in the present invention refers to a compound having an ethylenically unsaturated group. Examples of the photopolymerizable compound include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipanoic acid 1,6-hexanediol (meth) acrylic acid ester, and the like. Polypropylene phthalic acid propylene oxide (meth) acrylic acid ester, diethylene glycol (meth) acrylic acid ester of trimellitic acid, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate and other oligomers, tripropylene glycol di (meth) acrylate, 1,6-Hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethyl propanthyl (meth) acrylate, tetratrimethylol propanthyl (meth) acrylate, pentaerythritol tri (meth) acrylate, Triacrylic formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, bisphenoxyethanol full orange acrylate, dicyclopentanedienyldiacrylate, alkyl modified products of these, Examples thereof include an alkyl ether modified product and an alkyl ester modified product. In the present invention, the photosensitive resin composition may contain two or more of these as photopolymerizable compounds.

The photosensitive resin composition according to the embodiment of the present invention may further contain fine particles in addition to the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerization compound and alkali-soluble resin. By containing the fine particles, the photosensitive resin composition can appropriately scatter the incident light from the light source and the light emitted from the pyrromethene derivative to improve the light conversion efficiency and further improve the brightness. Hereinafter, the fine particles contained in the photosensitive resin composition according to the embodiment of the present invention will be abbreviated as fine particles as appropriate.

In the present invention, the fine particles contained in the photosensitive resin composition are preferably white fine particles. Here, white refers to a color in which the brightness of the Munsell display system measured in accordance with JIS Z 8717 (1989) is 8.0 to 10.0. Examples of white fine particles include minerals such as talc, mica, and kaolin clay; metal oxides such as titania (titanium oxide), zirconia (zirconium dioxide), alumina (aluminum oxide), silica (silicon oxide), and zinc oxide; sulfate. Metallic sulfates such as barium and calcium sulfate; metal carbonates such as barium carbonate, calcium carbonate, magnesium carbonate and strontium carbonate, sodium metasilicate; sodium stearate and the like can be mentioned. The photosensitive resin composition may contain two or more of these as fine particles. Among these, fine particles of titanium oxide, zirconium dioxide, aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, and sodium metasilicate are preferable from the viewpoint of electrical reliability. Titanium oxide, zirconium dioxide, and aluminum oxide are more preferable from the viewpoint of further improving the refractive index and brightness. Examples of commercially available titanium oxide fine particles include JR-301 and JR-600A (manufactured by TAYCA). Examples of the zirconia dioxide fine particles include "UEP" (registered trademark) 100 (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.). Examples of aluminum oxide include "AEROXIDE" (registered trademark) Alu C (Nippon Aerosil Co., Ltd.).

In the present invention, the refractive index of the fine particles contained in the photosensitive resin composition is preferably 1.40 or more and 3.00 or less. By setting the refractive index of the fine particles to 1.40 or more, the brightness of the photosensitive resin composition can be further improved. The refractive index of the fine particles is more preferably 1.60 or more. As a result, the difference in refractive index between the other components in the photosensitive resin composition and the fine particles becomes large, so that the light conversion efficiency can be improved and the brightness of the photosensitive resin composition can be further improved. On the other hand, by setting the refractive index of the fine particles to 3.00 or less, the light conversion efficiency can be further improved and a finer pattern of the photosensitive resin composition can be formed. The refractive index of the fine particles is more preferably 1.80 or less, which can further improve the fine pattern processability of the photosensitive resin composition. Here, the refractive index of the fine particles in the present invention refers to the Abbe refractometer (DR-M2,) under the condition of a temperature of 25 ° C. using the sodium D line (589 nm) as a light source for 30 randomly selected fine particles. Refers to the number average value of the refractive index measured by the immersion method (Becke line method) using (manufactured by Atago).

Examples of the shape of the fine particles in the present invention include a spherical shape, an ellipsoidal shape, a needle shape, a polygonal shape, and a star shape. Further, the shape of the fine particles may have irregularities or pores on the surface, or may be hollow.

The particle size of the fine particles in the present invention is preferably 5 nm or more and 300 nm or less. By setting the particle size of the fine particles to 5 nm or more, the dispersion stability of the fine particles in the photosensitive resin composition can be improved, and the brightness of the photosensitive resin composition can be further improved. The particle size of the fine particles is more preferably 10 nm or more. On the other hand, by setting the particle size of the fine particles to 300 nm or less, the scattering intensity of light by the fine particles in the photosensitive resin composition can be appropriately suppressed, and a finer pattern of the photosensitive resin composition can be formed. The particle size of the fine particles is more preferably 100 nm or less. Here, the particle size of the fine particles in the present invention refers to the number average value of the primary particle diameter (that is, the number average particle diameter), and the primary particle diameter refers to the average value of the maximum diameter and the minimum diameter of the primary particles. ..

The particle size of the fine particles can be determined by the following method. For example, 100 particles randomly selected from among the particles for which the whole image is observed in a field of view magnified at a magnification of 10,000 times using an electron microscope (S-4800, manufactured by Hitachi High Technology). The primary particle size of each is measured. When the cross-sectional shape of the particle is not a circle, the maximum diameter and the minimum diameter of the particle are measured respectively, and the average value is taken as the primary particle diameter. It is not necessary to measure the primary particle size of 100 particles in one measurement, and a total of 100 particles may be selected from a plurality of fields of view. The particle size of the fine particles can be obtained by calculating the number average value of the primary particle diameters of the 100 measured particles.

Examples of the method for producing fine particles include a pulverization method in which a mineral or the like as a raw material is pulverized to be finely divided; a chemical method in a gas phase, a liquid phase or a solid layer; a physical method and the like. Examples of the crushing method include a jet method, a hammer method, and a mill method. Examples of the chemical method in the gas phase include a chemical vapor deposition method (CVD method), an electric furnace method, a chemical flame method, and a plasma method. Examples of the chemical method in the liquid phase include a precipitation method, an alkoxide method, and a hydrothermal method. Examples of the chemical method in the solid phase include a crystallization method. Examples of the physical method include a spray method, a solution combustion method, a freeze-drying method, and the like. Among these, the precipitation method is preferable because the particle size of the fine particles can be easily adjusted to a desired range.

In the present invention, the content of the fine particles contained in the photosensitive resin composition is defined by the weight ratio to the content of the pyrromethene derivative contained in the photosensitive resin composition. For example, when the weight of the fine particles contained in the photosensitive resin composition is Ma and the weight of the pyrromethene derivative contained in the photosensitive resin composition is Mb, the content of the fine particles is the content of the fine particles relative to the content of the pyrromethene derivative. The weight ratio of the content (Ma / Mb) is adjusted to be within a predetermined range. In the present invention, the weight ratio (Ma / Mb) of the content of the fine particles to the content of the pyrromethene derivative in the photosensitive resin composition is preferably 5/1 or more and 100/1 or less. By setting the weight ratio (Ma / Mb) to 5/1 or more, the scattering intensity of light by the fine particles can be improved, and the brightness of the photosensitive resin composition can be further improved. The weight ratio (Ma / Mb) is more preferably 20/1 or more. On the other hand, by setting the weight ratio (Ma / Mb) to 100/1 or less, the scattering intensity of light by the fine particles can be appropriately suppressed, and a finer pattern of the photosensitive resin composition can be formed. The weight ratio (Ma / Mb) is more preferably 80/1 or less.

The photosensitive resin composition according to the embodiment of the present invention may further contain an ultraviolet absorber in addition to the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerization compound and alkali-soluble resin. The photosensitive resin composition absorbs light in the wavelength range of the j-line by containing an ultraviolet absorber. Therefore, it is possible to suppress the line width thickening at the bottom of the photosensitive resin composition and form a finer pattern.

In the present invention, the ultraviolet absorber contained in the photosensitive resin composition preferably has an absorption maximum wavelength in a wavelength region of 360 nm or less. The maximum absorption wavelength can be measured using an ultraviolet-visible spectrophotometer (MultiSpec-1500, manufactured by Shimadzu Corporation). Examples of the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds. The photosensitive resin composition may contain two or more of these as an ultraviolet absorber.

Examples of the benzotriazole-based compound include 2- (2H-benzotriazole-2-yl) -p-cresol and 2- (2H-benzotriazole-2-yl) -4-6-bis (1-methyl-1). -Phenylethyl) phenol, 2- [5 chloro (2H) -benzotriazole-2-yl] -4-methyl-6- (tert-butylphenol), 2,4 di-tert-butyl-6- (5-chloro) Bentotriazole-2-yl) phenol, 2- (2H-benzotriazole-2-yl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-tert-pentylphenol, 2- (2H-) Bentriazole-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol, 2 [2-hydroxy -3- (3,4,5,6 tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole and the like can be mentioned. Examples of the benzophenone-based compound include octabenzone and 2-hydroxy-4-n-octoxybenzophenone. Examples of the triazine-based compound include 2- (4,6-diphenyl-1,3,5 triazine-2-yl) -5-[(hexyl) oxy] -phenol, BASF's "Tinuvin". "(Registered trademark) 400, 405 and the like.

In the present invention, the content of the ultraviolet absorber contained in the photosensitive resin composition is preferably 0.05% by weight or more and 10% by weight or less based on 100% by weight of the solid content of the photosensitive resin composition. By setting the content of the ultraviolet absorber to 0.05% by weight or more in 100% by weight of the solid content, the line width thickening of the photosensitive resin composition is further suppressed and the fine pattern processability is further improved. Can be done. The content of the ultraviolet absorber is more preferably 0.1% by weight or more based on 100% by weight of the solid content. On the other hand, the sensitivity of the photosensitive resin composition can be improved by setting the content of the ultraviolet absorber to 10% by weight or less based on 100% by weight of the solid content. The content of the ultraviolet absorber is more preferably 5.0% by weight or less based on 100% by weight of the solid content.

The photosensitive resin composition according to the embodiment of the present invention may further contain an organic solvent in addition to the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerization compound and alkali-soluble resin. Examples of the organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate and ethyl acetoacetate. , Cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propionate, pentyl acetate, propylene glycol monomethyl Ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, monoethyl ether, methyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tasher Lee Butyl ether, dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, isopentylbutanol acetate, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone, xylene, ethylbenzene, solventnaphtha, etc. Can be mentioned. The photosensitive resin composition may contain two or more of these as an organic solvent.

In the present invention, the content of the organic solvent contained in the photosensitive resin composition is preferably 40% by weight or more, preferably 40% by weight or more, out of 100% by weight of the photosensitive resin composition from the viewpoint of improving the coatability. More preferably, it is by weight% or more. On the other hand, the content of the organic solvent is preferably 90% by weight or less, preferably 80% by weight or less, based on 100% by weight of the photosensitive resin composition from the viewpoint of applying the resist to the thick film. More preferred.

The photosensitive resin composition according to the embodiment of the present invention contains a adhesion improver in addition to the above-mentioned photopolymerization initiator, pyrromethene derivative, photopolymerization compound and alkali-soluble resin, thereby forming a cured film described later. Adhesion to the substrate can be improved. Examples of the adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-). Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples thereof include silane coupling agents such as ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. The photosensitive resin composition may contain two or more of these as adhesion improvers.

The photosensitive resin composition according to the embodiment of the present invention further contains a surfactant in addition to the above-mentioned photopolymerization initiator, pyrromethene derivative, photopolymerization compound and alkali-soluble resin, so that the coating property and the coating surface can be coated. Uniformity can be improved. Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide, Amphoteric surfactants such as laurylcarboxymethyl hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate; fluorosurfactants; silicon surfactants And so on. The photosensitive resin composition may contain two or more of these as surfactants.

In the present invention, the content of the surfactant contained in the photosensitive resin composition is 0.001% by weight or more and 10% by weight in 100% by weight of the photosensitive resin composition from the viewpoint of in-plane uniformity of the coating film. % Or less is preferable.

The photosensitive resin composition according to the embodiment of the present invention may further contain a dispersant in addition to the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerization compound and alkali-soluble resin. Examples of the dispersant include low molecular weight dispersants such as pigment intermediates and pigment derivatives, and polymer dispersants. The photosensitive resin composition may contain two or more of these as a dispersant. Examples of the pigment derivative include an alkylamine modified product of the pigment skeleton, a carboxylic acid derivative, a sulfonic acid derivative, and the like, which contribute to appropriate wetting and stabilization of the pigment. Of these, a sulfonic acid derivative having a pigment skeleton, which has a remarkable effect on stabilizing fine pigments, is preferable. Examples of the polymer dispersant include polymers such as polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, and polyamideimide, and copolymers thereof. Among these polymer dispersants, those having an amine value of 5 to 200 mgKOH / g in terms of solid content and an acid value of 1 to 100 mgKOH / g are preferable. In particular, a polymer dispersant having a basic group is more preferable. This is because the storage stability of the photosensitive resin composition can be improved. Examples of commercially available polymer dispersants having a basic group include "Solspers" (registered trademark) 24000 (manufactured by Abyssia), "EFKA" (registered trademark) 4300, 4330 (manufactured by Fuka), and 4340 ( Fuka), "Ajispar" (registered trademark) PB821, PB822 (Ajinomoto Fine-Techno), "BYK" (registered trademark) 161-163, 2000, 2001, 6919, 21116 (Big Chemie), etc. ..

The photosensitive resin composition according to the embodiment of the present invention is intended to improve stability by further containing a polymerization inhibitor in addition to the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerization compound and alkali-soluble resin. Can be done. Polymerization inhibitors generally have the effect of prohibiting or stopping polymerization by radicals generated by heat, light, radical initiators, etc., and are used to prevent gelation of thermosetting resins and to stop polymerization during polymer production. Will be done. Examples of the polymerization inhibitor in the present invention include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, and 2,5-bis (1,1-dimethylbutyl). ) Hydroquinone, catechol, tert-butylcatechol and the like. The photosensitive resin composition may contain two or more of these as a polymerization inhibitor.

In the photosensitive resin composition of the present invention, for example, the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerizable compound and alkali-soluble resin are mixed, and if necessary, the above-mentioned other components are mixed, whereby the above-mentioned other components are mixed. Obtainable.

<Cured film>
The cured film according to the embodiment of the present invention is a film made of a cured product of the above-mentioned photosensitive resin composition. Hereinafter, the term "cured film" means a film made of a cured product of the photosensitive resin composition according to the embodiment of the present invention, unless otherwise specified.

The film thickness of the cured film is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of sufficiently exerting the color conversion function of the pyrromethene derivative and further improving the brightness. On the other hand, from the viewpoint of suppressing missing pixels in the image display device, the film thickness of the cured film is preferably 50 μm or less.

The film thickness of such a cured film can be calculated by measuring the height of the step using a stylus type film thickness measuring device. More specifically, a part of the cured film is scratched with a needle or the like to expose the lower layer of the substrate, etc., and the film thickness is observed vertically from above the cured film using a stylus type film thickness meter. Can be obtained.

The line width of the cured film is preferably 30 μm or more. Here, the line width of the cured film refers to the width of the bottom of the narrowest portion of the width of the cured film processed into a desired pattern on the substrate. Since the thicker stripe pattern is less likely to cause missing pixels in the image display device, it is possible to suppress missing pixels in the image display device by setting the line width of the cured film to 30 μm or more. Further, from the viewpoint of fineness when the cured film is incorporated into an image display device or the like, the line width of the cured film is preferably 400 μm or less. The line width of such a cured film can be measured by magnifying and observing the pattern of the cured film at a magnification of 50 times using an optical microscope.

For the components contained in the cured film, a sample of the cured film is taken with a manipulator and analyzed by laser Raman (for example, HOLIBA Jobin Yvon's Ramanor T-64000) or FT-IR (for example, SPECTR-TECH's FT). -IR MICROSCOPE) can be identified by performing an analysis and comparing it with a specimen. Further, if necessary, it can be identified with high accuracy by combining centrifugation, filtration, sampling method such as GPC preparative collection, NMR and the like. When the cured film contains a metal, the metal can be detected by ICP emission spectroscopic analysis and LDI-MS analysis.

<Color conversion board>
The color conversion substrate according to the embodiment of the present invention includes a cured film made of a cured product of the above-mentioned photosensitive resin composition, and color conversion that converts incident light into light having a longer wavelength than the incident light. Has a function. Such a color conversion substrate is preferably formed by a combination of the substrate and the above-mentioned cured film. The substrate used for the color conversion substrate is preferably a transparent substrate. Transparency in the present invention means that the light transmittance at wavelengths of 400 nm, 550 nm, 633 nm, and 800 nm is 90% or more. Examples of the transparent substrate include a glass plate, a resin plate, and a resin film. As the material of the glass plate, non-alkali glass is preferable. As the material of the resin plate and the resin film, polyester resin, acrylic resin, transparent polyimide resin, polyether sulfone resin and the like are preferable. The thickness of the glass plate and the resin plate is preferably 1 mm or less, and more preferably 0.6 mm or less. The thickness of the resin film is preferably 100 μm or less.

<Manufacturing method of cured film and color conversion substrate>
Next, a method for manufacturing the cured film and the color conversion substrate according to the embodiment of the present invention will be described. Hereinafter, as an example of these manufacturing methods, a manufacturing method in the case of forming a cured film on a substrate will be described.

In the method for producing a cured film and a color conversion substrate according to the embodiment of the present invention, first, a coating step of applying the photosensitive resin composition according to the present embodiment onto the substrate is performed. As a method for applying the photosensitive resin composition in this coating step, for example, a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, or the like is used to apply the photosensitive resin composition to the substrate. , A method of immersing the substrate in the photosensitive resin composition, a method of spraying the photosensitive resin composition onto the substrate, and the like.

In this coating step, it is preferable to form a coating film of the photosensitive resin composition by drying the photosensitive resin composition coated on the substrate. Examples of the drying method include air drying, heat drying, vacuum drying and the like.

Next, an exposure step is performed in which the photosensitive resin composition on the substrate is exposed using a predetermined light source. In this exposure step, the coating film of the photosensitive resin composition formed on the substrate is selectively exposed to the coating film of the photosensitive resin composition by irradiating the coating film of the photosensitive resin composition with light such as ultraviolet rays through a mask. It is preferable to do so. Examples of the light source used in this exposure step include an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a chemical lamp. Among these, from the viewpoint of the exposure wavelength, an ultra-high pressure mercury lamp or a high-pressure mercury lamp is preferable, and an ultra-high pressure mercury lamp is more preferable. Examples of the exposure machine include an exposure machine that employs methods such as proximity, mirror projection, and lens scanning. Among these, a lens scan type exposure machine is preferable from the viewpoint of accuracy.

The exposure amount of the photosensitive resin composition in this exposure process, it is preferable in terms of i-line is 60 mJ / cm ² or more 250 mJ / cm ² or less. When the exposure amount is 60 mJ / cm ² or more, a finer pattern of the photosensitive resin composition can be formed. On the other hand, when the exposure amount is 250 mJ / cm ² or less, the decomposition of the pyrromethene derivative in the photosensitive resin composition due to exposure can be suppressed, and the brightness of the photosensitive resin composition can be further improved.

After that, in the exposure step, it is preferable to develop the photosensitive resin composition with a developing solution as necessary to form a desired fine pattern on the photosensitive resin composition. As the developing solution, an alkaline developing solution is preferable. Examples of the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; alkaline substances such as organic alkalis such as tetramethylammonium hydroxide, and aqueous solutions thereof. The alkaline developer may be one in which two or more of these are used.

Next, a curing step is performed in which the photosensitive resin composition after exposure is cured to form a cured film. In this curing step, the patterned photosensitive resin composition obtained by the above-mentioned exposure step is cured by heat treatment, thereby forming a cured film made of the cured product of the photosensitive resin composition. Is preferable. In this curing step, the heat treatment can be performed in air, a nitrogen atmosphere, a vacuum, or the like. The heating temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of adhesion of the cured film to the substrate. On the other hand, the heating temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, from the viewpoint of heat resistance of the pyrromethene derivative. The heating time is preferably 0.5 hours or more and 5 hours or less.

As described above, a cured film made of a cured product of the photosensitive resin composition is produced. That is, the method for producing a cured film according to the embodiment of the present invention includes the above-mentioned exposure step. Further, by forming a cured film of the photosensitive resin composition on the substrate, a color conversion substrate provided with the cured film is manufactured. The color conversion substrate produced in this way can be suitably used for, for example, electronic materials, automobile lamps, various lighting devices, various displays, and the like. Since the color conversion substrate according to the embodiment of the present invention has high brightness and high definition, it can be suitably used for an image display device such as an organic EL display, a micro LED display device, a liquid crystal display, and electronic paper.

<Image display device>
The image display device according to the embodiment of the present invention includes the above-mentioned color conversion substrate. Specifically, in the present invention, it is preferable that the image display device includes a color conversion substrate having a cured film of the photosensitive resin composition described above, a color filter substrate, and a light emitting element. In this case, the color conversion substrate is preferably arranged between the color filter substrate and the light emitting element. For example, when the image display device is an organic EL display, the organic EL display preferably includes a partially driven blue organic electroluminescent element light source, a color conversion substrate, and a color filter substrate. This organic EL display may have an organic protective layer or an inorganic oxide film between the color filter substrate and the partially driven blue organic electroluminescent device light source. Further, the organic EL display may be a passive drive system or an active drive system. On the other hand, when the image display device is a micro LED display, the micro LED display preferably includes a partially driven blue LED light source, a color conversion substrate, and a color filter substrate.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. The measurement methods and evaluation methods in Examples 1 to 24 and Comparative Examples 1 to 7 below are as shown below.

< ¹ Measurement of ¹ H-NMR>
¹ H-NMR measurement of the pyrromethene derivative was carried out in a deuterated chloroform solution using a superconducting FT-NMR apparatus EX-270 (manufactured by JEOL Ltd.).

<Measurement of weight average molecular weight>
The weight average molecular weight of the alkali-soluble resin in Synthesis Examples 3 and 4 described later was measured by GPC (gel permeation chromatography).

<Measurement of acid value>
The acid value of the alkali-soluble resin in Synthesis Examples 3 and 4 was determined by titrating a solution of the alkali-soluble resin in orthocresol at 25 ° C. using a 0.1 mol / L potassium hydroxide / ethanol aqueous solution. It was.

<Measurement of refractive index>
In the measurement of the refractive index, the fine particles used in Examples 1 to 9, 11 to 24 and Comparative Examples 1 to 2, 5 to 7 were subjected to Abbe under the condition of a temperature of 25 ° C. using the sodium D line (589 nm) as a light source. The refractive index was measured by the immersion method (Becke line method) using a refractometer (DR-M2, manufactured by Atago Co., Ltd.).

<Measurement of number average particle size>
In the measurement of the number average particle diameter of the fine particles, an electron microscope (S-4800, manufactured by Hitachi High-Technology Co., Ltd.) was used to magnify and observe the fine particles used in each Example and Comparative Example at a magnification of 10,000 times. The primary particle size of each of 100 fine particles randomly selected from the fine particles whose overall image was observed was measured. The number average value of the measured primary particle diameters of 100 fine particles was calculated, and the obtained value was taken as the number average particle diameter of the fine particles.

<Measurement of maximum absorption wavelength>
In the measurement of the maximum absorption wavelength, a diluted solution prepared by diluting the light emitting material used in each Example and Comparative Example with PGMEA (propylene glycol monomethyl ether acetate) was prepared, and a cell having an optical path length of 1 cm was used to obtain ultraviolet-visible spectral light intensity. The absorption spectrum of 300 nm to 800 nm was measured with a meter (MultiSpec-1500 manufactured by Shimadzu Corporation), and the wavelength having the maximum absorbance was read as the absorption maximum wavelength.

<Measurement of absorption coefficient>
In the measurement of the absorption coefficient, a diluted solution prepared by diluting the photopolymerization initiator used in each Example and Comparative Example with PGMEA (propylene glycol monomethyl ether acetate) was prepared, and an ultraviolet-visible spectroscopy was performed using a cell having an optical path length of 1 cm. Absorption by measuring the absorption spectrum from 300 nm to 800 nm with a photometer (MultiSpec-1500, manufactured by Shimadzu Corporation) and converting the absorbance at the h-line (405 nm) and the absorption maximum wavelength of the luminescent material into a 1 g / mL solution. The coefficient was calculated.

<Measurement of maximum emission wavelength>
In the measurement of the maximum emission wavelength, the surface of the cured film of the color conversion substrate produced in each Example and Comparative Example is irradiated with light having a wavelength of 460 nm using an F-2500 type spectral fluorescence photometer (manufactured by Hitachi, Ltd.). Then, the fluorescence spectrum when excited was measured, and the wavelength at which the fluorescence emission intensity was maximized was read as the emission maximum wavelength.

<Measurement of brightness>
In the measurement of brightness, a color conversion substrate produced by each Example and Comparative Example and a yellow color filter substrate that transmits a wavelength of 500 nm or more are mounted on a planar light emitting device equipped with a commercially available blue LED (emission maximum wavelength 450 nm). I put it. A current of 10 mA was passed through the planar light emitting device to light a blue LED, and the brightness (unit: cd / m ² ) was measured using a spectral radiance meter (SR-LEDW, manufactured by Topcon Techno House). For Examples 1 to 16 and Comparative Examples 1, 3 and 4, the relative value when the brightness in Comparative Example 2 was 1.00 was taken as the brightness, and Examples 17 to 24 and Comparative Examples 5 and 6 were compared. The relative value when the brightness in Example 7 was 1.00 was defined as the brightness.

<Measurement of film thickness>
In the film thickness measurement, a part of the cured film was scratched with a needle to expose the glass coated with the photosensitive resin composition, and a stylus type film thickness meter (Surfcom 1400d, manufactured by Tokyo Seimitsu Co., Ltd.) was used. The height of the step between the cured film and the glass was measured, and the obtained measured value was taken as the film thickness.

<Measurement of line width>
In the measurement of the line width, the pattern of the cured film of the color conversion substrate produced in each Example and Comparative Example was magnified and observed at a magnification of 50 times using an optical microscope (MX61L, manufactured by Olympus Corporation), and the line width was 50 μm. The line width at the bottom of the pattern was measured, and the obtained measured value was used as the line width.

<Evaluation of fine pattern workability>
In the evaluation of fine pattern processability, the pattern of the cured film of the color conversion substrate produced in each Example and Comparative Example was magnified and observed at a magnification of 50 times using an optical microscope (MX61L, manufactured by Olympus Corporation), and the following Based on the criteria, the pattern processability of this cured film was evaluated.
⊚: No chipping or thickening of the line width is observed in the pattern having a line width of 20 μm.
◯: No chipping is observed in the pattern having a line width of 20 μm, but thick line width is observed.
Δ: A pattern having a line width of 20 μm is chipped, but a pattern having a line width of 30 μm is not chipped.
X: A pattern with a line width of 30 μm is chipped.

<Compounds in Examples and Comparative Examples>
In the following Examples and Comparative Examples, the compounds G1 and G2 and the compounds R1 and R2 are the compounds shown below.

<Raw materials in Examples and Comparative Examples>
The raw materials used in the following examples and comparative examples are as shown below.

(Synthesis Example 1)
In Synthesis Example 1, a method for synthesizing compound G1, which is an example of a pyrromethene derivative in the present invention, will be described. In the method for synthesizing compound G1, 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), and Potassium carbonate (2.0 g) was placed in a flask and replaced with nitrogen. To this, degassed toluene (30 mL) and degassed water (10 mL) were added, and the mixture was refluxed for 4 hours. The obtained reaction solution was cooled to room temperature, the organic layer was separated from the cooled reaction solution, and then the organic layer was washed with saturated brine. The washed organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g) as a white solid.

Next, the above 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were added to the reaction solution, and dehydrated dichloromethane (200 mL) and tri Fluoroacetic acid (1 drop) was added, and the mixture was stirred under a nitrogen atmosphere for 4 hours. Subsequently, a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, and then water (100 mL) was further added and stirred to separate the organic layer. did. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography, and as a result, 0.4 g of compound G1 was obtained (yield 18%). The ¹ H-NMR analysis result of the obtained compound G1 is as shown below.
^{1 1} H-NMR (CDCl ₃ (d = ppm)): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s) , 6H), 1.50 (s, 6H), 1.37 (s, 18H)

(Synthesis Example 2)
In Synthesis Example 2, a method for synthesizing compound R1, which is an example of a pyrromethene derivative in the present invention, will be described. In the method for synthesizing compound R1, a mixed solution of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole (300 mg), 2-methoxybenzoyl chloride (201 mg) and toluene (10 mL) is prepared. , Heated at 120 ° C. for 6 hours under a stream of nitrogen. Subsequently, the mixed solution was cooled to room temperature and then evaporated. Subsequently, after washing with ethanol (20 mL) and vacuum drying, 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole (260 mg) is obtained. It was.

Next, the obtained 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole (260 mg) and 4- (4-t-butylphenyl) were obtained. A mixed solution of -2- (4-methoxyphenyl) pyrrole (180 mg), methanesulfonic anhydride (206 mg) and degassed toluene (10 mL) was heated at 125 ° C. for 7 hours under a nitrogen stream. Subsequently, the mixed solution was cooled to room temperature, water (20 mL) was injected, and the organic layer was extracted with dichloromethane (30 mL). The organic layer was washed twice with water (20 mL) and evaporated to give a pyrromethene as a residue after vacuum drying.

Next, diisopropylethylamine (305 mg) and boron trifluoride diethyl ether complex (670 mg) were added to the obtained mixed solution of pyrromethene and toluene (10 mL) under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. .. Then water (20 mL) was injected and the organic layer was extracted with dichloromethane (30 mL). The organic layer was washed twice with water (20 mL), dried over magnesium sulfate, and then evaporated. The obtained product was purified by silica gel column chromatography, vacuum dried, and then a magenta powder (0.27 g) was obtained (yield 70%). The ¹ H-NMR analysis result of the obtained reddish purple powder is as follows, and it was confirmed that the reddish purple powder obtained above is the compound R1 represented by the above structural formula.
^{1 1} H-NMR (CDCl ₃ (d = ppm)): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H)

(Synthesis Example 3)
Synthesis Example 3 describes a method for synthesizing resin A, which is an example of the alkali-soluble resin in the present invention. In the method for synthesizing the resin A, propylene glycol monomethyl ether acetate (202 g) was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Then, nitrogen gas was introduced into the flask through the gas introduction pipe, and the atmosphere in the flask was replaced with nitrogen gas. Then, after the solution in the flask was heated to 100 ° C., dicyclopentanyl methacrylate (59.4 g (0.27 mol)), benzyl methacrylate (68.7 g (0.39 mol)) and methacrylic acid were added. A mixture of acid (37.8 g (0.5 mol)), azobisisobutyronitrile (4.0 g) and propylene glycol monomethyl ether acetate (101 g) over 2 hours using a dropping funnel. The mixture was added dropwise to the flask, and after the addition was completed, stirring was continued at 100 ° C. for 5 hours. At this time, FA-513M manufactured by Hitachi Chemical Co., Ltd. was used as the dicyclopentanyl methacrylate.

After the above stirring is completed, air is introduced into the flask through the gas introduction pipe to make the atmosphere in the flask air, and then glycidyl methacrylate (31.2 g (0.25 mol)) and trisdimethylamino Methylphenol (1.0 g) and hydroquinone (0.16 g) were placed in a flask, and the reaction was continued at 110 ° C. for 6 hours, so that the weight average molecular weight was 12,000, the acid value was 108 mgKOH / g, and the resin solid was formed. A solution of an alkali-soluble resin (resin A) of 40.0% by weight was obtained. The above-mentioned glycidyl methacrylate has a molar fraction of 50 mol% with respect to the methacrylic acid used in this reaction.

(Synthesis Example 4)
Synthesis Example 4 describes a method for synthesizing resin B, which is an example of the alkali-soluble resin in the present invention. In the method for synthesizing the resin B, a styrene / methyl methacrylate / methacrylic acid copolymer (weight ratio 33/33/34) was synthesized by the same method as in Synthesis Example 3 except that the raw material monomer and the composition ratio were changed. By adding glycidyl methacrylate (33 parts by weight), a solution of an alkali-soluble resin (resin B) having a weight average molecular weight of 23,000, an acid value of 75 mgKOH / g, and a resin solid content of 45.0% by weight was obtained.

<Example 1>
(Preparation of fine particle dispersion)
The method for producing the fine particle dispersion liquid of Example 1 will be described. In Example 1, barium sulfate (BF-20, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 30 nm, refractive index: 1.64) (96 g) was used as fine particles, and resin A obtained by Synthesis Example 3 as an alkali-soluble resin. (60 g), γ-butyrolactone (114 g), N-methyl-2pyrrolidone (598 g), and 3methyl-3methoxybutyl acetate (132 g) were charged in a tank and stirred with a homomixer for 1 hour. Using an ultra-apex mill equipped with a centrifuge separator filled with 70% of 0.05 mmφ zirconia beads, dispersion was performed at a rotation speed of 8 m / s for 2 hours. As a result, a fine particle dispersion having a solid content concentration of 12% by weight and a weight ratio of fine particles to resin (fine particles / resin) of 80/20 was obtained.

(Preparation of photosensitive resin composition)
The method for producing the photosensitive resin composition of Example 1 will be described. In Example 1, 5.0 parts by weight of "IRGACURE" (registered trademark) 819 manufactured by BASF was used as a photopolymerization initiator, and 0.5 parts by weight of the pyromethene derivative (Compound G1) obtained in Synthesis Example 1 was used. As a polymerizable compound, 36.8 parts by weight of "Kayarad" (registered trademark) DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. was used, and as an alkali-soluble resin, a solution of resin A obtained in Synthesis Example 3 was prepared. 67 parts by weight, 1.0 part by weight of BASF's "Tinuvin" (registered trademark) 400 as an ultraviolet absorber, 208.8 parts by weight of the fine particle dispersion obtained by the above method as fine particles, and PGMEA as an organic solvent. (Propylene glycol monomethyl ether acetate) was added in an amount of 50.7 parts by weight, and the mixture was stirred and mixed. Then, these mixtures were filtered through a 0.45 μm syringe filter to prepare the photosensitive resin composition of Example 1. The above "IRGACURE" 819 is abbreviated as "IC819" as appropriate.

(Making a color conversion board)
The method of manufacturing the color conversion substrate of Example 1 will be described. In Example 1, non-alkali glass (manufactured by Asahi Glass Co., Ltd., AN100) having a thickness of 0.5 mm is used as a glass substrate, and the photosensitivity of Example 1 is set on the glass substrate so that the film thickness after curing is 20 μm. The resin composition was applied and vacuum dried. The photosensitive resin composition of Example 1 using a mask aligner (PLA-501F manufactured by Canon Inc.), using an ultrahigh pressure mercury lamp as a light source, and having an exposure of 100 mJ / cm ² (i-line) without using a photomask. The entire surface of (coating film) was exposed. Subsequently, it was heat-cured at 170 ° C. for 30 minutes to form a cured film of the photosensitive resin composition of Example 1 on a glass substrate.

Further, the photosensitive resin composition of Example 1 was applied onto a glass substrate (non-alkali glass having a thickness of 0.5 mm) similar to the above glass substrate so that the film thickness after curing was 20 μm. Vacuum dried. Using a mask aligner (PLA-501F manufactured by Canon Inc.), an exposure amount of 100 mJ / cm ² (i) is passed through a photomask designed to be exposed to a line pattern of 10 μm to 50 μm using an ultrahigh pressure mercury lamp as a light source. It was exposed with a line) and developed with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds. Then, it was heat-cured at 170 ° C. for 30 minutes to form a cured film pattern of the photosensitive resin composition of Example 1 on a glass substrate. As described above, the color conversion substrate of Example 1 was obtained.

The photosensitive resin composition and the color conversion substrate of Example 1 were evaluated by the above-mentioned methods. The evaluation results of Example 1 are shown in Table 2 described later.

<Example 2>
In Example 2, the photosensitive resin composition and the color conversion substrate were used in the same manner as in Example 1 except that "ADEKA Arklus" (registered trademark) NCI-831 manufactured by ADEKA was used as the photopolymerization initiator. Made. Then, the photosensitive resin composition and the color conversion substrate of Example 2 were evaluated in the same manner as in Example 1. The evaluation results of Example 2 are shown in Table 2.

<Example 3>
In Example 3, the photosensitive resin composition and the photosensitive resin composition and the same as in Example 1 except that titanium oxide (JR-600A, manufactured by TAYCA Corporation, particle size: 250 nm, refractive index: 2.40) was used as the fine particles. A color conversion substrate was produced. Then, the photosensitive resin composition and the color conversion substrate of Example 3 were evaluated in the same manner as in Example 1. The evaluation results of Example 3 are shown in Table 2.

<Example 4>
In Example 4, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 3 except that no ultraviolet absorber was added. Then, the photosensitive resin composition and the color conversion substrate of Example 4 were evaluated in the same manner as in Example 1. The evaluation results of Example 4 are shown in Table 2.

<Example 5>
In Example 5, except that aluminum oxide (“AEROXIDE” (registered trademark) Alu C, manufactured by Nippon Aerosil Co., Ltd., particle size: 13 nm, refractive index: 1.76) was used as fine particles and no ultraviolet absorber was added. Made a photosensitive resin composition and a color conversion substrate in the same manner as in Example 1. Then, the photosensitive resin composition and the color conversion substrate of Example 5 were evaluated in the same manner as in Example 1. The evaluation results of Example 5 are shown in Table 2.

<Example 6>
In Example 6, barium sulfate (BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64) was used as the fine particles, and the ultraviolet absorber was not added. In the same manner, a photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 6 in the same manner as in Example 1. The evaluation results of Example 6 are shown in Table 2.

<Example 7>
In Example 7, barium sulfate (B-30, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 300 nm, refractive index: 1.64) was used as the fine particles, and the ultraviolet absorber was not added. In the same manner, a photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 7 in the same manner as in Example 1. The evaluation results of Example 7 are shown in Table 2.

<Examples 8 and 9>
In Examples 8 and 9, the amount of fine particles added (content of fine particles in the photosensitive resin composition) was changed as shown in Tables 2 and 3, and the addition of the ultraviolet absorber was not added. In the same manner, a photosensitive resin composition and a color conversion substrate were prepared. Then, the photosensitive resin compositions and color conversion substrates of Examples 8 and 9 were evaluated in the same manner as in Example 1. The evaluation results of Example 8 are shown in Table 2. The evaluation results of Example 9 are shown in Table 3 described later.

<Example 10>
In Example 10, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that fine particles and an ultraviolet absorber were not added. Then, the photosensitive resin composition and the color conversion substrate of Example 10 were evaluated in the same manner as in Example 1. The evaluation results of Example 10 are shown in Table 3.

<Example 11>
In Example 11, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that no ultraviolet absorber was added. Then, the photosensitive resin composition and the color conversion substrate of Example 11 were evaluated in the same manner as in Example 1. The evaluation results of Example 11 are shown in Table 3.

<Examples 12 and 13>
In Examples 12 and 13, a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 1 except that the exposure amount was changed as shown in Table 3. Then, the photosensitive resin compositions and color conversion substrates of Examples 12 and 13 were evaluated in the same manner as in Example 1. The evaluation results of Examples 12 and 13 are shown in Table 3.

<Examples 14 and 15>
In Examples 14 and 15, the same as in Example 1 except that the photosensitive resin composition of Example 1 was applied onto the glass substrate so that the film thickness after curing was as shown in Table 3. , A photosensitive resin composition and a color conversion substrate were prepared. Then, the photosensitive resin compositions and color conversion substrates of Examples 14 and 15 were evaluated in the same manner as in Example 1. The evaluation results of Examples 14 and 15 are shown in Table 3.

<Example 16>
In Example 16, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 11 except that the resin B synthesized in Synthesis Example 4 was used as the alkali-soluble resin and no ultraviolet absorber was added. did. Then, the photosensitive resin composition and the color conversion substrate of Example 16 were evaluated in the same manner as in Example 1. The evaluation results of Example 16 are shown in Table 3.

<Example 17>
In Example 17, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that compound R1 was used as the pyrromethene derivative. Then, the photosensitive resin composition and the color conversion substrate of Example 17 were evaluated in the same manner as in Example 1. The evaluation results of Example 17 are shown in Table 4 described later.

<Example 18>
In Example 18, a photosensitive resin composition was prepared in the same manner as in Example 17 except that NCI-831 was used as an initiator and no ultraviolet absorber was added. Further, a color conversion substrate was produced in the same manner as in Example 17 except that the photosensitive resin composition produced was applied onto a glass substrate so that the film thickness after curing was 2.5 μm. Then, the photosensitive resin composition and the color conversion substrate of Example 18 were evaluated in the same manner as in Example 1. The evaluation results of Example 18 are shown in Table 4.

<Example 19>
In Example 19, aluminum oxide (“AEROXIDE” (registered trademark) Alu C, manufactured by Nippon Aerosil Co., Ltd., particle size: 13 nm, refractive index: 1.76) was used as the fine particles in the same manner as in Example 18. , A photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 19 in the same manner as in Example 1. The evaluation results of Example 19 are shown in Table 4.

<Example 20>
In Example 20, the photosensitive resin composition was the same as in Example 18 except that barium sulfate (BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64) was used as the fine particles. An object and a color conversion substrate were produced. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 20 in the same manner as in Example 1. The evaluation results of Example 20 are shown in Table 4.

<Example 21>
In Example 21, the photosensitive resin composition was the same as in Example 18 except that barium sulfate (B-30, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 300 nm, refractive index: 1.64) was used as the fine particles. An object and a color conversion substrate were produced. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 21 in the same manner as in Example 1. The evaluation results of Example 21 are shown in Table 4.

<Examples 22 and 23>
In Examples 22 and 23, the same as in Example 18 except that the photosensitive resin composition of Example 18 was applied onto the glass substrate so that the film thickness after curing was as shown in Table 4. A photosensitive resin composition and a color conversion substrate were prepared. Then, the photosensitive resin compositions and color conversion substrates of Examples 22 and 23 were evaluated in the same manner as in Example 1. The evaluation results of Examples 22 and 23 are shown in Table 4.

<Example 24>
In Example 24, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 18 except that the resin B synthesized in Synthesis Example 4 was used as the alkali-soluble resin. Then, each evaluation was performed on the photosensitive resin composition and the color conversion substrate of Example 24 in the same manner as in Example 1. The evaluation results of Example 24 are shown in Table 4.

<Comparative example 1>
In Comparative Example 1, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that “IRGACURE” (registered trademark) OXE02 manufactured by BASF was used as a photopolymerization initiator. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 1 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 1 are shown in Table 5 described later. The "luminescent material" in Table 5 includes a pyrromethene derivative as an example.

<Comparative example 2>
In Comparative Example 2, the photosensitive resin composition was applied in the same manner as in Comparative Example 1 except that the photosensitive resin composition of Comparative Example 1 was applied onto the glass substrate so that the film thickness after curing was 3 μm. And a color conversion substrate was prepared. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 2 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 2 are shown in Table 5.

<Comparative example 3>
In Comparative Example 3, a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 10 except that compound G2 was used as the light emitting material. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 3 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 3 are shown in Table 5.

<Comparative example 4>
In Comparative Example 4, a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 10 except that quantum dots (CdSeS / ZnS: dot diameter 6 nm, manufactured by Sigma-Aldrich) were used as the light emitting material G3. did. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 4 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 4 are shown in Table 5.

<Comparative example 5>
In Comparative Example 5, a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Comparative Example 1 except that compound R1 was used as the light emitting material. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 5 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 5 are shown in Table 6 described later.

<Comparative Example 6>
In Comparative Example 6, the photosensitive resin composition was applied in the same manner as in Comparative Example 5, except that the photosensitive resin composition of Comparative Example 1 was applied onto the glass substrate so that the film thickness after curing was 3 μm. And a color conversion substrate was prepared. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 6 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 6 are shown in Table 6.

<Comparative Example 7>
In Comparative Example 7, a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 18 except that compound R2 was used as the light emitting material. Then, the photosensitive resin composition and the color conversion substrate of Comparative Example 7 were evaluated in the same manner as in Example 1. The evaluation results of Comparative Example 7 are shown in Table 6.

As described above, the photosensitive resin composition, the cured film, the color conversion substrate, the image display device, and the method for producing the cured film according to the present invention have a photosensitive resin composition capable of forming a fine pattern with high brightness. It is suitable for objects, cured films thereof, color conversion substrates using the same, and image display devices.

Claims (16)

It contains at least a photopolymerization initiator, a pyrromethene derivative, a photopolymerizable compound and an alkali-soluble resin having an h-ray extinction coefficient of 100 mL / g · cm or more.
A photosensitive resin composition characterized by the above. The photopolymerization initiator is a phosphine oxide compound.
The photosensitive resin composition according to claim 1. The extinction coefficient of the photopolymerization initiator at the absorption maximum wavelength of the pyrromethene derivative is 20 mL / g · cm or less.
The photosensitive resin composition according to claim 1 or 2. Further, it contains fine particles having a refractive index of 1.40 or more and 3.00 or less.
The photosensitive resin composition according to any one of claims 1 to 3. The number average particle diameter of the fine particles is 10 nm or more and 300 nm or less.
The photosensitive resin composition according to claim 4. The weight ratio of the content of the fine particles to the content of the pyrromethene derivative is 5/1 or more and 100/1 or less.
The photosensitive resin composition according to claim 4 or 5. The pyrromethene derivative is a compound represented by the following general formula (1).
The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitive resin composition is characterized by this.

(In the general formula (1), X is C-R ⁷ or N. R ^{1 to} R ⁹ may be the same or different, respectively, and hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl. Group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester It is selected from a fused ring and an aliphatic ring formed between a group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siroxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent. ) In the general formula (1), X is CR ⁷ and R ⁷ is a group represented by the following general formula (2).
The photosensitive resin composition according to claim 7.

(In the general formula (2), r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, aryl. Thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siroxanyl group, boryl group, sulfo group, phosphine oxide Selected from the group consisting of groups. K is an integer from 1 to 3. When k is 2 or more, r may be the same or different.) The pyrromethene derivative exhibits light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm due to excitation light.
The photosensitive resin composition according to any one of claims 1 to 8, wherein the photosensitive resin composition is characterized by this. The pyrromethene derivative exhibits light emission observed in a region having a peak wavelength of 580 nm or more and less than 750 nm due to excitation light.
The photosensitive resin composition according to any one of claims 1 to 9, wherein the photosensitive resin composition is characterized by this. Further, it contains an ultraviolet absorber having an absorption maximum wavelength in a wavelength region of 360 nm or less.
The photosensitive resin composition according to any one of claims 1 to 10. The product comprises a cured product of the photosensitive resin composition according to any one of claims 1 to 11.
A cured film characterized by that. The film thickness is 5 μm or more and 50 μm or less.
The cured film according to claim 12, wherein the cured film is characterized by the above. A method for producing a cured film made of a cured product of a photosensitive resin composition.
An exposure step of exposing the photosensitive resin composition according to any one of claims 1 to 11 using an ultra-high pressure mercury lamp is included.
The exposure amount of the photosensitive resin composition in the exposure step is 60 mJ / cm ² or more and 250 mJ / cm ² or less in terms of i-line.
A method for producing a cured film. The cured film according to claim 12 or 13.
A color conversion board characterized by that. The color conversion substrate according to claim 15 is provided.
An image display device characterized by this.