CN116802528A - Method for manufacturing photocurable green resin composition, display device, and laminate of organic light-emitting element and external light anti-reflection film - Google Patents

Abstract

The photocurable green resin composition of the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element. The photocurable green resin composition contains a colorant, a photopolymerizable compound, and a light Initiator, the above-mentioned color material includes a blue pigment and a yellow pigment, and the halogenated metal phthalocyanine pigment is less than 10 mass % relative to the total color material. When a cured film is formed with a film thickness of 3.0 μm, the wavelength range is 380 nm to 480 nm. The spectral transmittance is 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm is 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm is 40% or more and 80% or less.

Description

Photocurable green resin composition, display device, organic light-emitting element and external light Method for manufacturing an anti-reflection film laminate

Technical field

The present invention relates to a photocurable green resin composition, a display device containing a cured product of the photocurable green resin composition, and an organic light-emitting element and an external light reflection prevention film using the photocurable green resin composition. The manufacturing method of the laminated body.

Background technique

In recent years, as display elements for mobile devices and televisions, organic light-emitting elements, which are advantageous in being thinner and more flexible than conventional liquid crystal display elements and have in principle higher light utilization efficiency, have attracted attention.

Such organic light-emitting elements, especially in mobile devices that are supposed to be used outdoors, are equipped with a circularly polarizing plate as an anti-reflection film in order to prevent deterioration in visibility due to reflection of external light. However, the circularly polarizing plate not only reduces external light, but also reduces the light emitted by the organic light-emitting element, so the light utilization efficiency is greatly reduced. Furthermore, since the circularly polarizing plate has relatively hard characteristics and therefore its flexibility is reduced, it is not conducive to flexibility. Therefore, it is expected to develop a display device using an organic light-emitting element that has good visibility outdoors even without using a circular polarizing plate.

On the other hand, Patent Document 1 describes a green photosensitive resin combination for pixel formation that can suppress external light reflection with a color filter that can replace a polarizing plate, and can also achieve high color reproducibility while replacing a polarizing plate. It discloses a green photosensitive resin composition, which is characterized in that it contains a pigment dispersion composition, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the above-mentioned pigment dispersion composition includes a green pigment, a yellow pigment, and a yellow pigment. Pigment and black pigment, when the green photosensitive resin composition is formed into a cured film having a thickness of 2.2 μm, the spectral transmittance in the wavelength of 380 nm to 480 nm and the spectral transmittance in the wavelength of 580 nm to 780 nm are 25% or less , the spectral transmittance in the wavelength of 500nm to 560nm is 30% or more and less than 70%.

On the other hand, Patent Document 2 discloses a green colorant composition for color filters that contains a blue pigment and a yellow pigment so as to be halogen-free. However, this Patent Document 2 aims to provide a halogen-free, high-contrast composition. , and the technology of the color filter substrate with high adhesion force does not describe the use as a substitute for the polarizing plate at all, nor does it describe the problems that arise when used as a substitute for the polarizing plate.

In addition, Patent Document 3 discloses a coloring composition in which the colorant contains at least one selected from the group consisting of Dye Index Pigment Blue 15:3 and Dye Index Pigment Blue 15:4 and Dye Index Pigment Yellow 150. 100 parts by mass of Index Pigment Yellow 150 contains a total of 35 to 55 parts by mass of dye Index Pigment Blue 15:3 and dye Index Pigment Blue 15:4, and the above-mentioned coloring composition has an absorbance of light with a wavelength of 400 to 700 nm. , has the minimum value of absorbance in the wavelength range of 495 to 525 nm. When the absorbance for light with a wavelength of 450 nm is set to 1, the wavelengths at which the absorbance reaches 0.14 exist in the range of 474 to 494 nm and the range of 530 to 570 nm, respectively. The ratio of the absorbance A ⁴⁵⁰ for light with a wavelength of 450 nm and the absorbance A ⁶²⁰ for light with a wavelength of 620 nm, that is, A ⁴⁵⁰ /A ⁶²⁰ , is 1.08 to 2.05. However, Patent Document 3 does not describe at all the use of a cured film formed on an organic light-emitting element as a substitute for a polarizing plate, and does not describe at all the problems that arise when used as a substitute for a polarizing plate.

existing technical documents

patent documents

Patent Document 1: Japanese Patent Application Publication No. 2017-182067

Patent document 2: Japanese Patent Application Publication No. 2011-242568

Patent Document 3: International Publication No. 2020-196393

Contents of the invention

Invent the problem to be solved

The color filter of the polarizing plate substitute of Patent Document 1 is formed on a glass substrate. Therefore, there is a further problem in manufacturing a display device with improved thickness and flexibility.

In addition, conventionally, halogenated metal phthalocyanine pigments such as Pigment Green (PG) 7, 36, 58, and 59 have been frequently used as green pigments in green resin compositions for color filters. The color filter of the polarizing plate substitute in Patent Document 1 also utilizes a halogenated metal phthalocyanine pigment to realize green color. However, display devices using organic light-emitting elements are usually used by bonding glass or film as a covering material to the surface using a transparent adhesive. As a result, a photocurable green resin composition containing a large amount of halogenated metal phthalocyanine pigments is used. The green colored layer formed on the organic light-emitting element has the following problem: even if a sealing film is interposed, the transmittance decreases when a weather resistance test is performed with glass attached.

On the other hand, as for the green colored layer specifically disclosed in Patent Documents 2 and 3, as shown in the following comparative examples, the spectral characteristics are not sufficient to be used as a color filter for a polarizing plate substitute for suppressing external light reflection, and are difficult to withstand. There are also problems with solvent properties.

The present invention was made in view of the above actual situation, and its object is to provide a photocurable green resin composition that can produce an organic light-emitting display with excellent weather resistance, suppressed external light reflection, and a thin film with improved flexibility. device. In addition, an object of the present invention is to provide a display device containing a cured product of the photocurable green resin composition, having excellent weather resistance, suppressing external light reflection, and improving the flexibility of the film; and a display device using the photocurable green resin composition. A method for manufacturing a laminate of an organic light-emitting element of a photocurable green resin composition and an anti-reflection film for external light.

Technical means to solve problems

The photocurable green resin composition of the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element,

The above-mentioned photocurable green resin composition contains a colorant, a photopolymerizable compound, and a photoinitiator,

The above-mentioned color materials include blue pigments and yellow pigments, and the halogenated metal phthalocyanine pigment is less than 10% by mass relative to the total amount of color materials.

When the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength range of 380 nm to 480 nm becomes 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm becomes 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm becomes The spectral transmittance within becomes 40% or more and 80% or less.

The display device of the present invention has a cured film of the photocurable green resin composition of the present invention on an organic light-emitting element.

The manufacturing method of a laminate of an organic light-emitting element and an external light anti-reflection film of the present invention includes the step of forming a cured film of the photocurable green resin composition of the present invention on the organic light-emitting element by including the following steps:

The process of forming a coating film by coating the above-mentioned photocurable green resin composition of the present invention on an organic light-emitting element;

The process of illuminating the above-mentioned coating film;

The above-mentioned illuminated film is subjected to a heating post-baking process; and

The step of developing the film after the above-mentioned irradiation.

Invention effect

According to the present invention, it is possible to provide a photocurable green resin composition that can produce an organic light-emitting display device that has excellent weather resistance, suppresses external light reflection, and has a thin film with improved flexibility. In addition, the present invention can provide a display device that contains a cured product of the photocurable green resin composition, has excellent weather resistance, suppresses external light reflection, and improves the flexibility of the film; and uses the photocurable resin composition. A method for manufacturing a laminate of an organic light-emitting element of a green resin composition and an anti-reflection film for external light.

Description of the drawings

FIG. 1 is a schematic cross-sectional view showing an example of a display device including an organic light-emitting element of the present invention.

Detailed ways

Hereinafter, embodiments, examples, and the like of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in many different forms, and is not limited to the description of the embodiments, examples, etc. illustrated below. In addition, for the sake of clearer explanation, the drawings may schematically show the width, thickness, shape, etc. of each part compared with the actual form. However, this is only an example and is not intended to limit the interpretation of the present invention. In addition, in this specification and each drawing, the same elements as those described above with respect to the drawings that have appeared are sometimes denoted by the same reference numerals, and detailed descriptions may be omitted as appropriate. In addition, for convenience of explanation, the words "upper" or "lower" are sometimes used for explanation, but the upper and lower directions may also be reversed.

In this specification, when a certain component, such as a certain member or a certain region, is located "above (or below)" another member, another region, etc., unless otherwise specified, this case is not limited to This includes being located immediately above (or immediately below) another component, and also includes being located above (or below) another component, that is, it also includes including other components between it and above (or below) another component. elements.

It should be noted that in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and rays. The rays include, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less.

In the present invention, (meth)acryloyl represents each of acryloyl and methacryloyl, (meth)acrylic acid represents each of acrylic acid and methacrylic acid, and (meth)acrylate represents acrylate and methacrylate. Everyone.

In addition, in this specification, "～" indicating a numerical range is used in the sense of including the numerical values described before and after it as the lower limit and the upper limit.

In addition, in the present invention, the spectral transmittance Z% or less in the wavelength range of X nm to Y nm means that the spectral transmittance is Z% or less in the entire wavelength range of X nm to Y nm.

Hereinafter, the method for manufacturing the photocurable green resin composition, the display device, and the laminate of the organic light-emitting element and the external light anti-reflection film of the present invention will be described in detail in this order.

I. Photocurable green resin composition

The photocurable green resin composition of the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element,

The above-mentioned photocurable green resin composition contains a colorant, a photopolymerizable compound, and a photoinitiator,

The above-mentioned color materials include blue pigments and yellow pigments, and the halogenated metal phthalocyanine pigment is less than 10% by mass relative to the total amount of color materials.

When the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength range of 380 nm to 480 nm becomes 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm becomes 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm becomes The spectral transmittance within becomes 40% or more and 80% or less.

In the photocurable green resin composition of the present invention, the color material includes a blue pigment and a yellow pigment, the halogenated metal phthalocyanine pigment is 10 mass % or less relative to the total amount of the color material, and the color material satisfies the specific requirements in the specific wavelength range. Spectral transmittance, the cured film of the photocurable green resin composition can effectively reduce the transmittance of the film, and can be used as a substitute for a polarizing plate to suppress external light reflection.

Furthermore, the photocurable green resin composition of the present invention is characterized in that it is used for a cured film formed on an organic light-emitting element. That is, the photocurable green resin composition of the present invention is used for a cured film formed directly on an element substrate provided with an organic light-emitting element. The photocurable green resin composition of the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element adjacently or with at least one layer interposed therebetween. Therefore, it is possible to produce a display device that combines Compared with a display device in which an externally mounted color filter formed on a substrate such as a glass substrate and bonded to an organic light-emitting element is thinner and more flexible.

Furthermore, the content of the halogenated metal phthalocyanine pigment in the cured film formed on the organic light-emitting element formed using the photocurable green resin composition of the present invention is 10 mass % or less relative to the total amount of the colorant, so that even if it is green, By conducting a weather resistance test with glass bonded with a transparent adhesive, the decrease in transmittance is suppressed, and a display device with excellent weather resistance can be realized.

The photocurable green resin composition of the present invention contains at least a colorant, a photopolymerizable compound, and a photoinitiator, and may further contain other components within a range that does not impair the effects of the present invention.

Hereinafter, each component of the photocurable green resin composition of the present invention will be described in detail in order.

＜Color＞

In the present invention, the color material is not particularly limited as long as it can develop the required color when forming the colored layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, and dyes can be used. The salt-forming compound is used by mixing two or more kinds thereof, and is characterized in that it contains at least a blue pigment and a yellow pigment, and the halogenated metal phthalocyanine pigment is 10 mass % or less relative to the total amount of the color material.

Among them, organic pigments are preferably used as colorants because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the C.I. (Published by The Society of Dyers and Colourists). Specifically, compounds with the following C.I. numbers are included. .

Examples of blue pigments include C.I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80, and the like.

The blue pigment is preferably selected from the group consisting of C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, and C.I. At least one of Pigment Blue 16.

C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, and C.I. Pigment Blue 16 have different rising wavelengths in the transmission spectrum that gradually shift from the long wavelength side to the short wavelength side, so they are considered to be combined for external light reflection. It is preferable to select appropriately the spectrum of the green light-emitting layer of the organic light-emitting element and use one type alone or a combination of two or more types. From the viewpoint of weather resistance, C.I. Pigment Blue 15:4 is preferred among them.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62: 1, 63, 65, 71, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231, and derivative pigments of C.I. Pigment Yellow 150, etc.

As a yellow pigment, when combined with a blue pigment, it is easy to satisfy the specific spectral transmittance in the above-mentioned specific wavelength range, and it is easy to reduce the half-peak width of the peak indicating the maximum transmittance of the transmission spectrum, and it is easy to change the transmission spectrum. The wavelength of the maximum transmittance is set within the range of 525nm to 545nm, and it is preferable to include C.I. Pigment Yellow 139 from the viewpoint of easily improving the suppression effect of external light reflection.

As a yellow pigment, when combined with a blue pigment, it is easy to satisfy the specific spectral transmittance in the above-mentioned specific wavelength range, and it is easy to reduce the half-peak width of the peak indicating the maximum transmittance of the transmission spectrum, and it is easy to change the transmission spectrum. The wavelength of the maximum transmittance is set within the range of 525nm to 545nm to easily improve the suppression effect of external light reflection. Pigment Yellow 139 can be included, and it can also include Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 185. At least one, more preferably Pigment Yellow 139, and Pigment Yellow 150 are included.

From the viewpoint of adjusting the suppression effect of external light reflection, other colorants may also be used as the colorant. Examples of other colorants include green pigments, purple pigments, orange pigments, and the like.

Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, 63, and the like. However, even when a green pigment is used, from the viewpoint of improving weather resistance, the halogenated metal phthalocyanine pigment is set to 10 mass % or less relative to the total amount of the color material.

Examples of purple pigments include C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, and the like.

Examples of orange pigments include: C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73 etc.

Regarding the content ratio of the blue pigment and the yellow pigment used in the present invention, and other color materials that may be included as needed, when the photocurable green resin composition is used to form a cured film with a film thickness of 3.0 μm, the content ratio is 380 nm to 3.0 μm. The spectral transmittance in the wavelength range of 480nm is 20% or less, the spectral transmittance in the wavelength range of 580nm to 700nm is 30% or less, and the spectral transmittance in the wavelength range of 510nm to 550nm is 40% or more and 80% or less way to adjust.

When the cured film is formed with a film thickness of 3.0 μm, if the spectral transmittance in the wavelength of 380 nm to 480 nm is 20% or less, the decrease in color purity of green can be suppressed, and the decrease in color purity and reflection from the light-emitting element can also be easily suppressed. The prevention performance is easily excellent. When the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength of 380 nm to 480 nm may be 18% or less, and may be 13% or less.

On the other hand, when the cured film is formed with a film thickness of 3.0 μm, if the spectral transmittance in the wavelength of 510 nm to 550 nm is 40% or more and 80% or less, it is easy to suppress reduction in brightness of the display device and poor visibility. When the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength of 510 nm to 550 nm may be 45% or more, and may be 75% or less, and further may be 70% or less.

In addition, when the cured film is formed with a film thickness of 3.0 μm, if the spectral transmittance in the wavelength of 580 nm to 700 nm is 30% or less, the anti-reflection performance is likely to be excellent. When the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength of 580 nm to 700 nm may be 25% or less, 20% or less, or 18% or less.

In addition, in the present invention, the spectral transmittance when forming a cured film with a film thickness of 3.0 μm can be measured by the method specifically described in the Examples.

In addition, from the viewpoint of improvement in anti-reflection performance, when the cured film is formed with a film thickness of 3.0 μm, it is preferable that the half-peak width of the peak showing maximum transmittance in the wavelength range of 380 nm to 700 nm of the transmission spectrum is 70 nm or less. When the cured film is formed with a film thickness of 3.0 μm, the half-maximum width of the peak indicating the maximum transmittance of the transmission spectrum may be 65 nm or less, 63 nm or less, or 60 nm or less.

In addition, from the viewpoint of excellent color separation from blue and red, when the cured film is formed with a film thickness of 3.0 μm, the wavelength of the peak showing maximum transmittance at a wavelength in the range of 380 nm to 700 nm is preferably 510 nm to 550 nm. Within the range, it is more preferably within the range of 525nm to 545nm, further preferably within the range of 526nm to 540nm, and may also be within the range of 527nm to 535nm.

The content of the colorant used in the present invention is not particularly limited as long as it satisfies the specific spectral transmittance in the above-mentioned specific wavelength region.

In the colorant used in the present invention, the content of the blue pigment relative to the total amount of the colorant can be, for example, 1 mass% or more and 60 mass% or less, preferably 5 mass% or more, and more preferably 10 mass%. The content may be 15 mass% or more, preferably 50 mass% or less, and more preferably 40 mass% or less.

In the colorant used in the present invention, the content of the yellow pigment relative to the total amount of the colorant can be, for example, 20 mass% or more and 90 mass% or less, preferably 30 mass% or more, and more preferably 40 mass%. % or more, more preferably 50 mass% or more, more preferably 60 mass% or more, and preferably 85 mass% or less, more preferably 80 mass% or less.

When Pigment Yellow 139 is contained as the yellow pigment, the content of Pigment Yellow 139 may be 1 mass% or more, more preferably 5 mass% or more, and further preferably 10 mass% or more relative to the total amount of yellow pigment. , and may be 50 mass% or less, preferably 30 mass% or less.

When Pigment Yellow 139 and Pigment Yellow 150 are included as yellow pigments, the total content of Pigment Yellow 139 and Pigment Yellow 150 may be 40 mass% or more, and more preferably 60 mass% or more, relative to the total amount of yellow pigments, More preferably, it may be 80 mass% or more, 100 mass%, or 40 mass% or less.

In the colorant used in the present invention, the content ratio of the blue pigment relative to the total of the blue pigment and the yellow pigment is not particularly limited as long as it satisfies the specific spectral transmittance in the above-mentioned specific wavelength region. For example, it can be 1 Mass% or more and 60 mass% or less, preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, and preferably 50 mass% or less, more preferably The ground content may be 40% by mass or less.

In the colorants used in the present invention, the total content of the blue pigment and the yellow pigment relative to the total amount of the colorants can usually be 80 mass% or more, preferably 90 mass% or more, and more preferably 95 mass%. % or more, and may be 100 mass%, but when containing other colorants different from halogenated metal phthalocyanine pigments, it may be 90 mass% or less.

Among the colorants used in the present invention, the total content of other colorants relative to the total amount of colorants may be 0% by mass, may be 1% by mass or more, or may be 5% by mass or more. On the other hand, it is usually 20 mass% or less, preferably 10 mass% or less.

Among them, when using halogenated metal phthalocyanine pigments as other colorants, the total content is 10% by mass or less relative to the total amount of colorants. It can usually be 0.1% by mass or more and 10% by mass or less, and preferably it can be 1% by mass or more. , more preferably 3% by mass or more, and preferably 9.5% by mass or less. The halogenated metal phthalocyanine pigment may be 0% by mass relative to the total amount of colorants.

The average primary particle size of the colorant used in the present invention is such that when it is formed into a cured film, it can suppress external light reflection and transmit the required light from the light-emitting element to suppress the damage of the display device. It is not particularly limited as long as the brightness is reduced, and it varies depending on the type of color material used. However, it is preferably in the range of 10 nm to 200 nm, and more preferably 15 nm to 100 nm. When the average primary particle size of the colorant is within the above range, a display device including a cured film produced using the photocurable green resin composition of the present invention can suppress external light reflection, have excellent color separation properties, and be of high quality.

In addition, the average dispersed particle size of the colorant in the photocurable green resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 200 nm, and more preferably in the range of 15 nm to 100 nm.

The average dispersed particle size of the colorant in the photocurable green resin composition is the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured using a laser scattering particle size distribution meter. As a measurement of the particle size using a laser scattering particle size distribution meter, the photocurable green resin composition can be appropriately diluted to a concentration that can be measured using a laser scattering particle size distribution meter using a solvent used in the photocurable green resin composition ( For example, 1000 times, etc.), and measured at 23°C by the dynamic light scattering method using a laser scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.

The colorant used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. In addition, commercially available coloring materials can also be used after being finely processed.

In the photocurable green resin composition of the present invention, the content of the colorant is not particularly limited. The content of the colorant is preferably in the range of, for example, 3 to 65 mass%, and more preferably 4 mass% relative to the total solid content of the photocurable green resin composition from the viewpoint of dispersion and dispersion stability. The content is in the range of % to 60 mass%, more preferably in the range of 5 to 55 mass%, and more preferably in the range of 6 to 50 mass%. The content of the colorant may be 10% by mass to 45% by mass or 10% by mass to 35% by mass based on the total solid content of the photocurable green resin composition from the viewpoint of dispersion and dispersion stability. %. If it is more than the above lower limit, the cured film when the photocurable green resin composition is applied to a specific film thickness (usually 1.0 μm to 5.0 μm, such as 3.0 μm) has sufficient color density and reflects external light. The inhibitory effect is easy to be good. Moreover, if it is below the said upper limit, the cured film which will be excellent in storage stability, and will have sufficient hardness and adhesion to a board|substrate can be obtained.

In addition, in this invention, a solid content is all except the solvent mentioned below, and also includes the monomer etc. dissolved in a solvent.

＜Photopolymerizable compound＞

Examples of the photopolymerizable compound used in the photocurable green resin composition include compounds having a photopolymerizable group in the molecule. The photopolymerizable group is not particularly limited as long as it can be polymerized with a photoinitiator. Examples of the photopolymerizable group include ethylenically unsaturated double bonds, such as vinyl, allyl, acryl, or Methacryloyl etc. Among them, from the viewpoint of ultraviolet curability, an acryloyl group or a methacryloyl group can be suitably used as the photopolymerizable group.

The photopolymerizable compound preferably contains a compound having two or more photopolymerizable groups per molecule from the viewpoint of curability, and more preferably contains a compound having three or more photopolymerizable groups per molecule.

As the photopolymerizable compound, a compound having two or more ethylenically unsaturated double bonds can be suitably used, and a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferred.

As such a polyfunctional (meth)acrylate, any one appropriately selected from conventionally known ones may be used. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when excellent photocurability (high sensitivity) is required for the photocurable green resin composition of the present invention, the polyfunctional (meth)acrylate preferably has three or more (trifunctional) polymerizable double bonds. Preferred are poly(meth)acrylates of trivalent or higher polyhydric alcohols and dicarboxylic acid modified products thereof. Specifically, trimethylolpropane tri(meth)acrylate and pentaerythritol triacrylate are preferred. (Meth)acrylate, succinic acid modification of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , succinic acid modification of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The content of the photopolymerizable compound used in the photocurable green resin composition is not particularly limited, but is preferably in the range of 5 to 60 mass% relative to the total solid content of the photocurable green resin composition. Within, more preferably within the range of 10 mass% to 40 mass%. If the content of the photopolymerizable compound is more than the above lower limit, photocuring can be sufficiently performed, and the elution of the exposed part during development can be suppressed. In addition, if the content of the photopolymerizable compound is less than the above upper limit, alkali development can be achieved. Full of sex.

＜Photoinitiator＞

As the photoinitiator used in the photocurable green resin composition of the present invention, one or a combination of two or more of various conventionally known photoinitiators can be used.

Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazole compounds, N,N-dimethylaminobenzophenone, Halomethyl-S-triazine compounds, thioxanthone, oxime esters, etc. As such a photoinitiator, conventionally known photoinitiators can be used, and examples include the photoinitiator described in International Publication No. 2018/062105.

In addition, as the oxime ester photoinitiator used in the present invention, for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyl oxime), Japanese Patent Application Laid-Open 2 -80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Publication No. 2013-041153, International Publication No. 2015/152153, Japan Select appropriately from the oxime ester photoinitiators described in Japanese Patent Application Laid-Open No. 2010-256891 and the like.

When a cured film is formed on an element substrate as shown in the present invention, since the heat resistance of the organic light-emitting element is low, the heating in the manufacturing process requires low-temperature heating of 130°C or lower, and further 100°C or lower. Treatment is considered preferred. In a normal color filter manufacturing process, a cured film is cured by heat treatment at about 230° C. on a glass substrate. In contrast, it is difficult to cure the cured film with heat in a heat treatment of 130° C. or lower. That is, the cured film produced by low-temperature heat treatment has a problem that substrate adhesion and solvent resistance tend to become insufficient.

In view of this problem, the photoinitiator preferably contains at least one of the compounds represented by the following general formula (A) from the viewpoint that the substrate adhesion and solvent resistance of the cured film are good even if a low-temperature heat treatment is performed. A sort of.

[Chemical formula 1]

General formula (A)

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterogenous group having 2 to 20 carbon atoms. Ring group,

The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are optionally further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN, or halogen atom,

R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterogeneous group having 2 to 20 carbon atoms. Ring group,

The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ are optionally further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups,

The alkylene part of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ optionally contains 1 to 5 -O-, -S- under the condition that the oxygen atoms are not adjacent. , -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-,

R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

The alkyl part of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have branched side chains or may be a cyclic alkyl group,

R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. The group represented by R ³ The alkyl part of the group may have a branched side chain or may be a cyclic alkyl group. In addition, R ³ and R ⁷ and R ³ and R ⁸ may together form a ring, respectively.

The hydrogen atom of the group represented by R ³ may be further substituted with R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl, nitro, CN, or halogen atom,

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, CN or halogen atom, R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ can form a ring together respectively,

R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl part of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ may have a branched side chain or may be a cyclic alkane. Base, R ⁸ represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl, CN or halogen atom,

k means 0 or 1)

The oxime ester compound represented by the above general formula (A) includes geometric isomers formed by the double bonds of the oxime, but these are not distinguished. That is, in this specification, the compound represented by the above-mentioned general formula (A), and the compound represented by the following general formula (A'), which is a preferred form of the compound, and its exemplary compounds represent a mixture or any of the two. One is not limited to the structure showing an isomer.

As the carbon number 1 to 20 represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-amyl, hexyl, and heptyl Base, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl Alkyl, octadecyl, eicosanyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

Examples of the aryl group having 6 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (A) include benzene. base, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted by one or more of the above alkyl groups.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (A) include: Benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, etc.

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , and R ²⁴ in the general formula (A) include : Pyridyl, pyrimidinyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, 5-7 membered heterocycles such as thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl, morpholinyl, etc.

In the general formula (A), R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ may form a ring, for example, preferably Examples include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.

In addition, as the halogen atom represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (A), and the substitutable R ³ , R ¹¹ and R ¹² in the above general formula (A), , R ¹³ , R ²¹ , R ²² and R ²³ halogen atoms include fluorine, chlorine, bromine and iodine.

The alkylene part of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the above general formula (A) optionally contains 1 to 5 under the condition that the oxygen atoms are not adjacent to each other. -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-. In this case, the divalent group contained may be one type or two or more groups. In the case of a group that can be included continuously, two or more groups may be included continuously.

In addition, the alkyl (alkylene) part of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) may have a branched side chain, It can also be a cyclic alkyl group.

Among the compounds represented by the general formula (A), those in which R ³ is an optionally condensed aromatic ring or the compounds represented by the following general formula (A') are preferred because they are highly sensitive and can be easily produced.

[Chemical formula 2]

General formula (A′)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and k are the same as the above general formula (A), and R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently represents R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxyl, nitro, CN or Halogen atoms, R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ and R ³⁴ and R ³⁵ can form a ring together respectively)

Examples of the rings formed together by R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , and R ³⁴ and R ³⁵ include R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R Examples of the rings that can be formed together by ⁶ and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ are the same rings listed above.

In the above general formulas (A) and (A'), R ¹ is an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 15 carbon atoms, and R ¹¹ is an aryl group having 6 to 12 carbon atoms. Alkyl groups with 1 to 8 numbers are preferred because of their high solubility in solvents. R ² is preferably a methyl group, an ethyl group or a phenyl group because of its high reactivity. R ⁴ to R ⁷ are hydrogen atoms or A cyano group, especially a hydrogen atom, is preferred because it is easy to synthesize. R ⁸ is a hydrogen atom, which is preferred because it is easy to synthesize. K is 1, which is preferred because of its high sensitivity. In the above general formula (A'), If at least one of R ³¹ to R ³⁵ is a nitro group, CN, halogen atom, or COR ¹¹ , and R ¹¹ is an aryl group with 6 to 12 carbon atoms or an alkyl group with 1 to 8 carbon atoms, the sensitivity is higher. Preferably, at least one of R ³¹ to R ³⁵ is a nitro group, CN or a halogen atom, and particularly preferably, R ³³ is a nitro group, a CN or a halogen atom.

Preferable specific examples of the compound represented by the general formula (A) include the following compounds. In addition, compounds No. 1 to No. 212 described in International Publication No. 2015/152153 can be cited.

[Chemical formula 3]

The compound represented by the general formula (A) can be synthesized, for example, by referring to International Publication No. 2015/152153 and appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the materials used. In addition, you can also obtain commercially available products appropriately and use them.

As long as the effects of the present invention are not impaired, the total content of the photoinitiators used in the photocurable green resin composition of the present invention is not particularly limited, but relative to the total solid content of the photocurable green resin composition, preferably It is in the range of 0.1 mass% to 15.0 mass%, and more preferably in the range of 1.0 mass% to 10.0 mass%. If the content is equal to or more than the above-mentioned lower limit, photocuring can be sufficiently performed, and solvent resistance and substrate adhesion can easily be improved. On the other hand, if it is less than the above-mentioned upper limit, line width deviation can be suppressed, and it is easy to Form high-definition patterns.

Regarding the total content of at least one type of compound represented by the general formula (A), the cured film having excellent substrate adhesion and solvent resistance can be formed even with low-temperature heat treatment, compared with photoinitiation. The total amount of the agent is preferably 30.0 mass% or more, more preferably 50.0 mass% or more, still more preferably 70.0 mass% or more, and may be 100 mass%.

The photocurable green resin composition of the present invention contains a colorant, a photopolymerizable compound, and a photoinitiator. By using a liquid photopolymerizable compound, a coating film can be formed even without a solvent, for example, by using an inkjet method. A patterned colored layer can be formed by a method such as pattern coating.

The photocurable green resin composition of the present invention may further contain an alkali-soluble resin and a solvent, and may have alkali developability.

＜Alkali-soluble resin＞

The alkali-soluble resin used in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected and used from those soluble in an alkaline developer used for pattern formation.

In the present invention, the alkali-soluble resin can have an acid value of 40 mgKOH/g or more as a standard.

As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used. For example, the alkali-soluble resin described in International Publication No. 2016/104493 can be appropriately selected and used.

Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually a carboxyl group. Specific examples thereof include acrylic resins such as acrylic copolymers having a carboxyl group and styrene-acrylic copolymers having a carboxyl group, Acrylic resins such as an epoxy (meth)acrylate resin having a carboxyl group, an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group can be suitably used. Among these, those having a carboxyl group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferred. The reason for this is that the film strength of the cured film formed by containing the photopolymerizable functional group is improved. In addition, two or more types of these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be mixed and used.

The alkali-soluble resin used in the photocurable green resin composition may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the alkali-soluble resin is not particularly limited, but it is preferably in the range of 5 to 60 mass %, and more preferably 10 to 40 mass % relative to the total solid content of the photocurable green resin composition. %In the range. If the content of the alkali-soluble resin is not less than the above-mentioned lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is not more than the above-mentioned upper limit, film roughness and pattern loss can be suppressed during development.

＜Solvent＞

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photocurable green resin composition and can dissolve or disperse these components. The solvent can be used alone or in combination of two or more types.

Specific examples of the solvent include alcohol-based solvents such as methanol, ethanol, N-propanol, isopropyl alcohol, methoxyalcohol, and ethoxyalcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol solvents such as ethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethoxyethylpropionate, ethyl lactate, methyl hydroxypropionate, Ester solvents such as ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate; acetone, methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-acetate Glycol ether acetate solvents such as butyl ester, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol acetate solvents such as carbitol acetate (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc. Glycol ether solvents such as glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether. ; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran Solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; aromatic hydrocarbons such as toluene and xylene and other organic solvents. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetate from the viewpoint of solubility of other components and coating suitability. (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethoxyethyl propionate, ethyl lactate, and 3-methoxybutyl acetate.

In the photocurable green resin composition of the present invention, the content of the solvent may be appropriately set within a range in which a colored layer can be formed with high accuracy. The content of the solvent is usually preferably in the range of 55 to 95 mass%, and more preferably in the range of 65 to 88 mass% relative to the total amount of the photocurable green resin composition containing the solvent. When the content of the above-mentioned solvent is within the above-mentioned range, the coating property can be excellent.

＜Dispersant＞

In the photocurable green resin composition of the present invention, when the colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability.

In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine and other surfactants can be used. Among surfactants, polymer dispersants are preferred because they can be dispersed uniformly and finely.

Examples of polymer dispersants include: (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethylene oxides; Amine derivatives (amides obtained by the reaction of poly(lower alkylene imine) and free carboxyl-containing polyesters or bases of these); polyallylamine derivatives (polyallylamines are reacted with polyesters having free carboxyl groups) The reaction product obtained by reacting one or more of the three compounds of ester, polyamide, or co-condensate of ester and amide (polyester amide), etc.

In the present invention, it is preferable to use a (meth)acrylate copolymer-based dispersant as the dispersant because the solvent resistance is easily good even in low-temperature heat treatment. It is presumed that the (meth)acrylate copolymer-based dispersant has good compatibility between the photopolymerizable compound and the photoinitiator containing the compound represented by the general formula (A), and therefore the initiator is likely to be uniformly present in the colored layer. , the colored layer is uniformly solidified, thereby reducing unreacted components and the internal stress of the colored layer is also reduced, so the change of the colored layer when immersed in a solvent is reduced.

In the present invention, a (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a structural unit derived from (meth)acrylate.

The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a colorant adsorption site and a structural unit that functions as a solvent affinity site, and preferably serves as a solvent affinity site. The functional structural units include at least a structural unit derived from (meth)acrylate.

Examples of the structural unit that functions as a colorant adsorption site include a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with a structural unit derived from (meth)acrylate. The colorant adsorption site may be a structural unit derived from an acidic group-containing ethylenically unsaturated monomer or a structural unit derived from a basic group-containing ethylenically unsaturated monomer.

The structural unit derived from the basic group-containing ethylenically unsaturated monomer is preferably a structural unit represented by the following general formula (I) from the viewpoint of excellent dispersibility.

[Chemical formula 4]

(In the general formula (I), R ⁷¹ represents a hydrogen atom or a methyl group, A ¹ represents a divalent linking group, R ⁷² and R ⁷³ each independently represent a hydrogen atom, or a hydrocarbon group optionally containing a heteroatom, R ⁷² and R ⁷³ can also bond with each other to form a ring structure)

In general formula (I), A ¹ is a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof, etc. It should be noted that in the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain. Conversely, -NH may be on the carbon side of the main chain. atom side and -CO is the nitrogen atom side of the side chain.

Among them, from the perspective of dispersion, A ¹ in the general formula (I) is preferably a divalent linking group containing a -CONH- group or -COO- group, and more preferably a divalent linking group containing a -CONH- group or -COO- group and carbon A divalent linking group for an alkylene group with a number of 1 to 10.

Examples of the hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R ⁷² and R ⁷³ include an alkyl group, an aralkyl group, an aryl group, and the like.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is preferably: 1 to 18, among which, methyl or ethyl is more preferred.

Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl, biphenylmethyl, and the like. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12. It should be noted that the above preferred carbon number does not include the carbon number of the substituent.

The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is substituted with a hetero atom, or a hydrogen atom in the hydrocarbon group is substituted with a substituent containing a hetero atom. Examples of heteroatoms that the hydrocarbon group may contain include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like.

In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

The fact that R ⁷² and R ⁷³ are bonded to each other to form a ring structure means that R ⁷² and R ⁷³ form a ring structure through a nitrogen atom. The ring structure formed by R ⁷² and R ⁷³ may optionally contain a heteroatom. The ring structure is not particularly limited, and examples include a pyrrolidine ring, a piperidine ring, a morpholine ring, and the like.

In the present invention, it is preferable that R ⁷² and R ⁷³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or that R ⁷² and R ⁷³ are bonded to form a pyrrolidine ring or a piperidine ring. , morpholine ring.

Examples of the monomer from which the structural unit represented by the general formula (I) is derived include: (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid dimethylaminopropyl ester, (meth)acrylic acid Diethylaminoethyl, diethylaminopropyl (meth)acrylate and other alkyl-substituted amino-containing (meth)acrylates; dimethylaminoethyl (meth)acrylamide, dimethylamino Propyl (meth)acrylamide and other alkyl-substituted amino-containing (meth)acrylamide, etc. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate can be preferably used from the viewpoint of improving dispersibility and dispersion stability. base) acrylamide.

In the polymer, the structural unit represented by the general formula (I) may contain one type, or two or more types of structural units.

In addition, as a structural unit that functions as a colorant adsorption site, at least a part of the nitrogen site of the structural unit represented by the general formula (I) may form a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. (Hereinafter, this copolymer may be referred to as a salt type copolymer).

As the organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferred, and as the halogenated hydrocarbon, a compound represented by the following general formula (2) is preferred. the compound represented. That is, as at least one compound selected from the above-mentioned organic acid compounds and halogenated hydrocarbons, one or more compounds selected from the following general formulas (1) to (3) can be preferably used.

[Chemical formula 5]

(In the general formula (1), R ^a represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , and R ^e represents A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms. In the general formula (2), R ^b , R ^b ', and R ^b ″ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a straight chain, branched chain or ring having 1 to 20 carbon atoms which may have a substituent. an alkyl group, a vinyl group that may have a substituent, a phenyl group or a benzyl group that may have a substituent, or -OR ^f , where R ^f represents a linear, branched or cyclic carbon number of 1 to 20 that may have a substituent. an alkyl group, an optionally substituted vinyl group, an optionally substituted phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or Iodine atom. In the general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or benzene which may have a substituent. group or benzyl group, or -OR ^e , ^Re represents a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group that may have a substituent, or a carbon group with 1 to 20 carbon atoms. 4 alkylene (meth)acryloyl group. Wherein, at least one of R ^c and R ^d contains a carbon atom)

Each symbol of the above general formulas (1) to (3) may be the same as described in International Publication No. 2016/104493.

From the viewpoint of excellent dispersibility and dispersion stability of the colorant, the organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid and phenylphosphinic acid. Specific examples of the organic acid compound used in such a dispersant include those described in Japanese Patent Application Laid-Open No. 2012-236882 and the like.

In addition, the halogenated hydrocarbon is preferably at least one of allyl halogens such as allyl bromide and benzyl chloride and halogenated aralkyl groups, in terms of excellent dispersibility and dispersion stability of the colorant.

In the salt type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen site of the structural unit represented by the general formula (I). The total of the terminal nitrogen sites of the structural unit represented by formula (I) is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. The amount is 0.1 mol or more, particularly preferably 0.2 mol or more. If it is the above lower limit value or more, the effect of improving the dispersibility of the colorant by salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, particularly preferably 0.6 mol or less. If it is below the upper limit, development adhesion and solvent re-solubility can be excellent.

It should be noted that at least one type selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone, or two or more types may be combined. When two or more types are combined, the total content is preferably within the above range.

Examples of a method for preparing a salt-type copolymer include adding at least one selected from the above organic acid compounds and halogenated hydrocarbons to a solvent in which the copolymer before salt formation is dissolved or dispersed, and stirring. , and then heat as needed.

It should be noted that the terminal nitrogen site of the structural unit represented by the general formula (I) of the copolymer forms a salt with at least one selected from the above-mentioned organic acid compound and halogenated hydrocarbon, and the ratio thereof can be, for example, Confirmation by known methods such as NMR (Nuclear Magnetic Resonance).

From the aspects of dispersion and dispersion stability, the copolymer having the structural unit represented by the above general formula (I) is more preferably at least one of the following: having the structural unit represented by the above general formula (I), and in A graft copolymer having a structural unit derived from (meth)acrylate in the graft polymer chain; and an A block containing a structural unit represented by the above general formula (I) and a block containing a structural unit derived from (meth)acrylate. A block copolymer of the B block of structural units.

Hereinafter, the above-mentioned graft copolymer and the above-mentioned block copolymer will be described in order.

Examples of a graft copolymer having a structural unit represented by the above general formula (I) and having a structural unit derived from a (meth)acrylate in the graft polymer chain include a graft copolymer having the above general formula (I) A graft copolymer of the structural unit represented by the represented structural unit and the structural unit represented by the following general formula (II), and at least a part of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer. At least one of the salt-type graft copolymers forming a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons.

[Chemical formula 6]

(In the general formula (II), R ⁷¹ ' represents a hydrogen atom or a methyl group, A ² represents a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain contains (methyl) Structural unit of acrylate)

In the above general formula (II), A ² is a direct bond or a divalent linking group. The divalent linking group in A ² is not particularly limited as long as it can connect a carbon atom derived from an ethylenically unsaturated double bond and a polymer chain. Examples of the divalent linking group in A ² include the same divalent linking groups as those in A ¹ described above.

Among them, from the perspective of dispersion, A ² in the general formula (II) is preferably a divalent linking group containing a -CONH- group or -COO- group, and more preferably a divalent linking group containing a -CONH- group or -COO- group and carbon A divalent linking group for an alkylene group with a number of 1 to 10.

In the above general formula (II), Polymer represents a polymer chain, and the structural units of the polymer chain include structural units derived from (meth)acrylate. By containing the structural unit represented by the above-mentioned general formula (II) with a specific polymer chain, the graft copolymer has good solvent affinity, good dispersion and dispersion stability of colorants, and is compatible with the above-mentioned photoinitiator. Sex is also good.

Examples of structural units of the polymer chain include structural units represented by the following general formula (III).

[Chemical Formula 7]

(In the general formula (III), R ⁷⁴ ″ is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ⁸⁰ is a hydrogen atom or a hydrocarbon group optionally containing a heteroatom)

Examples of the divalent linking group of A ⁴ include the same divalent linking groups as those of the above-mentioned A ¹ . In the present invention, as the structural unit derived from (meth)acrylate, at least the structural unit represented by the general formula (III) in which A ⁴ in the general formula (III) is a divalent linking group containing a -COO- group is included. . From the viewpoint of solubility in organic solvents used for color filters, A ⁴ in the general formula (III) may also contain a divalent linking group containing a -CONH- group.

Examples of the hydrocarbon group in R ⁸⁰ that may contain a heteroatom include an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkyl-substituted aryl group, and combinations thereof. Examples of the hydrocarbon group in the hydrocarbon group in R ⁸⁰ that may contain a hetero atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and an aralkyl group or an alkyl substituted group. Aryl and other combinations of these.

The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6.

The above-mentioned alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond exists at the terminal of the alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 12, more preferably 2 to 8.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12.

Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl, biphenylmethyl, and the like, and may optionally further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

In addition, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded to the aromatic ring such as the aryl group or aralkyl group as a substituent.

Among them, from the viewpoint of dispersion stability, the hydrocarbon group in R ⁸⁰ is preferably selected from an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 12 carbon atoms in which the alkyl group is optionally substituted, and an alkyl group with optional substitutions. One or more substituted aralkyl groups having 7 to 14 carbon atoms is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-hard The aliphatic group and the alkyl group may be at least one of optionally substituted phenyl and benzyl groups.

Examples of heteroatoms optionally included in the hydrocarbon group include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and the like. Examples of the hydrocarbon group that optionally contains a heteroatom include -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO in the carbon chain of the hydrocarbon group. -, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O The structure of -NH- and other linking groups.

In addition, the hydrocarbon group may optionally have a substituent within a range that does not interfere with the dispersion performance of the graft copolymer. Examples of the substituent include: halogen atom, hydroxyl group, carboxyl group, alkoxy group, nitro group, and cyano group. , epoxy group, isocyanate group, thiol group, etc.

In addition, the hydrocarbon group in R ⁸⁰ that may contain a hetero atom may have a structure in which a polymerizable group such as an alkenyl group is added to the terminal via a linking group containing a hetero atom in the hydrocarbon group. For example, the structural unit represented by the general formula (III) may have a structure in which glycidyl (meth)acrylate and a structural unit derived from (meth)acrylic acid are reacted. That is, the structure of -A ⁴ -R ⁸⁰ in the general formula (III) may be -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (here, R is a hydrogen atom or a methyl group) the structure represented. In addition, the structural unit represented by the general formula (III) may be a structure in which 2-isocyanatoalkyl (meth)acrylate and a structural unit derived from hydroxyalkyl (meth)acrylate are reacted. That is, R ⁸⁰ in the general formula (III) may be -R'-OCONH-R”-OCO-CR=CH ₂ (here, R’ and R” are each independently an alkylene group, and R is a hydrogen atom. or methyl).

As a monomer from which the structural unit represented by the general formula (III) is derived, for example, those derived from methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) n-Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate Base) cyclohexyl acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate Ester, (meth)acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy(meth)acrylate Butyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxy polyethylene glycol ( Structural units of meth)acrylate, polyethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, etc. However, it is not limited to these.

In the present invention, as the above-mentioned R ⁸⁰ , one having excellent solubility in the organic solvent described below is preferably used, and it may be appropriately selected according to the organic solvent used in the color dispersion liquid. Specifically, for example, when the organic solvent is an ether alcohol acetate-based, ether-based, ester-based, alcohol-based organic solvent that is commonly used as an organic solvent for color dispersions, methyl or ethyl is preferred. , isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxypolyethylene glycol, methyl Oxygen-based polypropylene glycol, polyethylene glycol, etc.

Regarding the graft copolymer, it is preferable that the cured product of the photocurable green resin composition has better solvent resistance and the development time of the photocurable green resin composition is shortened. The structural units of the polymer chain among the structural units represented include at least one structural unit selected from the structural units represented by the following general formula (IV) and the structural units represented by the following general formula (IV'). .

The structural unit represented by the following general formula (IV) and the structural unit represented by the following general formula (IV') are structural units included in the structural unit represented by the above-mentioned general formula (III).

[Chemical formula 8]

(In the general formula (IV), R ⁷⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁷⁵ is an ethylene group or a propylene group, R ⁷⁶ is a hydrogen atom or a hydrocarbon group, m represents 3 or more and Numbers below 80.

In the general formula (IV′), R ⁷⁴ ′ is a hydrogen atom or a methyl group, A ³ ′ is a divalent linking group, R ⁷⁷ is an alkylene group having 1 to 10 carbon atoms, and R ⁷⁸ is an alkylene group having 3 to 7 carbon atoms. Alkyl group, R ⁷⁹ is a hydrogen atom or a hydrocarbon group, n represents a number from 1 to 40)

Examples of the divalent linking group in A ³ include the same divalent linking groups as those in A ¹ described above. Among them, A ³ in the general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group from the viewpoint of solubility in an organic solvent used for color filters, and is more preferably -CONH- group or -COO- group, more preferably -COO- group.

The above-mentioned m represents the number of repeating units of the ethylene oxide chain or the propylene oxide chain, and represents a number of 3 or more. Among them, from the viewpoint of suppressing the occurrence of water stains and solvent resistance, it is preferably 19 or more, and more preferably 21 or more.

When m is 19 or more, the graft copolymer contains a main chain portion having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). The structural unit represented includes a structural unit represented by the general formula (IV) in a polymer chain, and the structural unit includes a polyethylene oxide chain or a polypropylene oxide chain with a specific repeat number. In the specific graft copolymer used in the present invention, the structural units of the polymer chain grafted in this way include the following structural units, which contain polyethylene oxide chains or polypropylene oxide having a specific repeat number. chain, and the grafted polymer chain itself has a branched structure. It is presumed that the grafted plurality of polymer chains three-dimensionally diffuse in the film and increase the specific surface area, thereby further suppressing the solvent from penetrating into the coating film and reaching the colorant.

On the other hand, the upper limit of m is 80 or less, but from the viewpoint of solubility in an organic solvent used for color filters, it is preferably 50 or less.

The hydrocarbon group in R ⁷⁶ may be the same as the hydrocarbon group in R ⁸⁰ described above.

Among them, from the viewpoint of dispersion stability or compatibility, the hydrocarbon group in R ⁷⁶ is preferably selected from an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 12 carbon atoms in which the alkyl group is optionally substituted, and The alkyl group is optionally substituted with one or more aralkyl groups having 7 to 14 carbon atoms, preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, and n-lauryl group, n-stearyl group, alkyl group, one or more of optionally substituted phenyl group and benzyl group.

In addition, examples of the divalent linking group for A ³ ′ in the general formula (IV′) include the same divalent linking groups as those for A ¹ . Among them, A ³ ′ in the general formula (IV′) is preferably a divalent linking group including a -CONH- group or a -COO- group from the viewpoint of solubility in an organic solvent used for color filters, and more preferably A -CONH- group or a -COO- group is preferable, and a -COO- group is more preferable.

In the general formula (IV′), R ⁷⁷ is an alkylene group having 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferred from the viewpoint of re-solubility in a solvent.

R ⁷⁸ is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms and further an alkylene group having 5 carbon atoms is preferred from the viewpoint of substrate adhesion.

R ⁷⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group in R ⁷⁹ may be the same as the hydrocarbon group in R ⁷⁶ .

The above-mentioned n in the above-mentioned general formula (IV′) represents the number of repeating units of the ester chain, and represents a number of 1 or more. Among them, it is preferably 2 or more from the viewpoint of satisfying both the shortening of the development time and excellent solvent resistance. More preferably, it is 3 or more.

On the other hand, the upper limit of n is 40 or less, but from the viewpoint of solubility in an organic solvent used for color filters, it is preferably 20 or less.

In the above polymer chain, at least one structural unit selected from the structural unit represented by the above general formula (IV) and the structural unit represented by the following general formula (IV′) may be a single type, but may also be Mix two or more types.

From the viewpoints of making the role of the solvent affinity portion utilizing oxygen atoms more significant, shortening the development time of the photocurable green resin composition, and improving solvent resistance, it is preferable that the polymer chain includes the above-mentioned pass Structural unit represented by formula (IV).

Among them, among the structural units of the polymer chain in the structural unit represented by the above-mentioned general formula (II), it is more preferable to include the selected ones in combination from the viewpoints of improved solvent resistance, improved water spot suppressing effect, and improved development residue suppressing effect. At least one selected from the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less, and selected from the structural units represented by the general formula (IV) in which m is 3 or more and 10 or less. At least one type, more preferably, at least one type of structural unit represented by the general formula (IV) selected from the group consisting of m being 19 or more and 50 or less, and at least one type selected from the group consisting of the above general formula (IV) with m being 3 or more and 8 or less are included in combination. At least one of the structural units represented by formula (IV).

When the structural unit of the polymer chain among the structural units represented by the above general formula (II) contains at least one selected from the structural units represented by the above general formula (IV) in which m is 19 or more and 80 or less. When m is 19 or more and 80 or less, the total proportion of the structural units represented by the general formula (IV) is considered from the viewpoint of the water stain inhibitory effect when all the structural units of the polymer chain are taken as 100 mass %. , preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more. On the other hand, from the viewpoint of solvent re-solubility and water stain inhibition effect, it is preferably 75% by mass or less, More preferably, it is 65 mass % or less, and still more preferably, it is 50 mass % or less.

Among the structural units of the polymer chain among the structural units represented by the above general formula (II), the combination contains at least one selected from the structural units represented by the above general formula (IV) in which m is 19 or more and 80 or less. and at least one selected from the structural units represented by the general formula (IV) in which m is 3 or more and 10 or less, when all the structural units of the polymer chain are taken as 100% by mass, m is The total ratio of the structural units represented by the general formula (IV) between 3 and 10 is preferably 20% by mass or more. On the other hand, from the viewpoint of solvent re-solubility, in the above-mentioned polymer chain, m is the above-mentioned general formula (IV) in which m is 3 or more and 10 or less when all the structural units of the polymer chain are taken as 100 mass %. The total ratio of the represented structural units is preferably 80 mass% or less, and more preferably 60 mass% or less.

In addition, in the above-mentioned polymer chain, regarding the structural unit represented by the above-mentioned general formula (IV) in which m is 19 or more and 80 or less, and the structural unit represented by the above-mentioned general formula (IV) in which m is 3 or more and 10 or less, The mixing ratio of the structural unit represented by the above-mentioned general formula (IV) in which m is 19 to 80, and the above-mentioned general formula (IV) in which m is 3 to 10 is considered to improve the development residue suppressing effect. When the total of the structural units represented is 100 parts by mass, the total of the structural units represented by the general formula (IV) with m being 19 or more and 80 or less is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, And it is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.

From the viewpoint of satisfying dispersion stability, high contrast, shortened development time, and excellent solvent resistance at the same time, when all the structural units of the above-mentioned polymer chain are taken as 100 mass %, a compound selected from the group consisting of the above-mentioned general formula (IV The total proportion of at least one structural unit represented by ) and the structural unit represented by the general formula (IV′) is preferably 1 mass% or more, more preferably 2 mass% or more, and still more preferably 4 mass% %above. From the perspective of solvent re-solubility, when all the structural units of the above-mentioned polymer chain are taken as 100% by mass, the structural unit represented by the above-mentioned general formula (IV) and the structure represented by the above-mentioned general formula (IV′) are selected. The total proportion of at least one structural unit among the units is preferably 80 mass% or less, more preferably 70 mass% or less, and still more preferably 60 mass% or less.

In the above-mentioned polymer chain, the structural unit represented by the above-mentioned general formula (III) including the structural unit represented by the above-mentioned general formula (IV) and the above-mentioned structural unit represented by the above-mentioned general formula (IV′) may be a single type, However, two or more types may be mixed.

From the viewpoint of the dispersibility and dispersion stability of the colorant, when all the structural units of the polymer chain are taken as 100 mass %, the total proportion of the structural units represented by the above general formula (III) is preferably 70 mass % or more. , more preferably 90 mass% or more. On the other hand, in terms of satisfying both dispersion stability and excellent solvent resistance, in the above-mentioned polymer chain, when all structural units of the polymer chain are taken as 100% by mass, the above-mentioned general formula (III) The total proportion of the structural units shown may be 100% by mass.

Among them, from the viewpoint of dispersion stability, solvent resistance, and compatibility with the initiator, when all the structural units of the polymer chain are taken as 100% by mass, the total number of structural units derived from (meth)acrylate The proportion is preferably 60 mass% or more, more preferably 80 mass% or more. On the other hand, in terms of satisfying both dispersion stability and excellent solvent resistance, in the above-mentioned polymer chain, when all structural units of the polymer chain are taken as 100% by mass, the amount of the polymer derived from (meth)acrylic acid The total ratio of the structural units of the ester may be 100% by mass.

The structural units of the polymer chain among the structural units represented by the general formula (II) of the graft copolymer may contain other structural units in addition to the structural units represented by the general formula (III).

Examples of other structural units include structural units derived from a monomer having an unsaturated double bond copolymerizable with a monomer from which the structural unit represented by the general formula (III) is derived.

Examples of monomers from which other structural units are derived include styrenes such as styrene and α-methylstyrene; vinyl ethers such as phenyl vinyl ether; and the like.

In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, from the viewpoint of the effect of the present invention, when all the structural units of the polymer chain are 100% by mass, The total proportion of other structural units is preferably 30 mass% or less, and more preferably 10 mass% or less.

From the perspective of the dispersion and dispersion stability of the colorant, the mass average molecular weight Mw of the polymer chain in the Polymer is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and more preferably 15,000 or less. More preferably, it is 12,000 or less.

By being in the above range, the sufficient steric repulsion effect of the dispersant can be maintained, and the specific surface area of the solvent affinity portion of the dispersant can be increased, thereby easily suppressing the solvent from penetrating into the coating film and reaching the colorant.

In addition, as a standard, the solubility of the polymer chain in the Polymer at 23°C is preferably 20 (g/100g solvent) or more with respect to the organic solvent used in combination.

The solubility of this polymer chain can be based on the above-mentioned solubility of the raw material introduced into the polymer chain when preparing the graft copolymer. For example, in order to introduce a polymer chain into a graft copolymer, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal is used, The polymerizable oligomer only needs to have the above-mentioned solubility. In addition, after forming a copolymer using a monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer is used to introduce the polymer In the case of a chain, the polymer chain containing the reactive group only needs to have the above-mentioned solubility.

In the graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a proportion of 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% by mass. ~30% by mass. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity part with the colorant in the graft copolymer becomes more appropriate, and the resistance to organic solvents can be suppressed. The solubility is reduced, so it has good adsorption to colorants, and it is easy to obtain excellent dispersion and dispersion stability.

On the other hand, in the above-mentioned graft copolymer, the structural unit represented by the above-mentioned general formula (II) is preferably contained in a proportion of 40 mass % to 97 mass %, more preferably 55 mass % to 94 mass %, and still more preferably It is 70 mass % - 91 mass %. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the proportion of the solvent affinity portion in the graft copolymer becomes more appropriate, and sufficient three-dimensionality as a dispersant can be maintained. The repulsion effect and the specific surface area of the solvent affinity part of the dispersant increase, thereby easily inhibiting the solvent from penetrating into the coating film and reaching the colorant.

The above-mentioned graft copolymer used in the present invention may optionally contain, in addition to the structural unit represented by the above-mentioned general formula (I) and the structural unit represented by the above-mentioned general formula (II) within the scope that does not impair the effect of the present invention. Have other structural units. As other structural units, an ethylenically unsaturated double bond-containing monomer capable of being copolymerized with an ethylenically unsaturated double bond-containing monomer or the like from which the structural unit represented by the general formula (I) is derived may be appropriately selected and copolymerized, and other structural units may be introduced. Structural units.

Examples of other structural units copolymerized with the structural unit represented by the general formula (I) include the structural unit represented by the general formula (III).

It should be noted that the content ratio of the above structural units is based on the structural unit represented by the above general formula (I), the structural unit represented by the above general formula (II), and the derivation of the above general formula when synthesizing the graft copolymer during production. The added amount of the monomer such as the structural unit represented by the formula (III) is calculated.

In addition, from the viewpoint of dispersibility and dispersion stability, the mass average molecular weight Mw of the graft copolymer is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more. On the other hand, from the viewpoint of solvent re-solubility, it is preferably 50,000 or less, and more preferably 30,000 or less.

In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). HLC-8120GPC manufactured by Tosoh was used for the measurement. The elution solvent was N-methylpyrrolidone added with 0.01 mol/L of lithium bromide. The polystyrene standards used for the standard curve were Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are the Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh), and the measurement column is TSK-GEL ALPHA-M × 2 (manufactured by Tosoh). conduct.

(Production method of graft copolymer)

In the present invention, the method for producing the graft copolymer is any method that can produce a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). That’s it, there are no special restrictions. When producing a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II), for example, the following method can be used: containing the following general formula (Ia) The monomer shown and the polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal are copolymerized as copolymerization components to produce a graft copolymer. .

If necessary, other monomers may be used, and the graft copolymer may be produced using a known polymerization method.

[Chemical formula 9]

(In the general formula (Ia), R ⁷¹ , A ¹ , R ⁷² and R ⁷³ are the same as in the general formula (I))

In addition, when producing a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II), it is also possible to make the graft copolymer represented by the above general formula (Ia) After the monomer is added-polymerized with another monomer containing a group having an ethylenically unsaturated double bond to form a copolymer, a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer is used, Import polymer chains. Specifically, for example, a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanato group, a hydrogen bond forming group, etc. may be synthesized and then reacted with a copolymer containing the substituent The functional groups of the polymer chain react and are introduced into the polymer chain.

For example, a polymer chain having a carboxyl group at the terminal can be reacted with a copolymer having a glycidyl group in a side chain, or a polymer chain having a hydroxyl group at the terminal can be reacted with a copolymer having an isocyanate group in a side chain to introduce it into the polymer chain.

In addition, in the above-mentioned polymerization, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, chain transfer agents, etc. may also be used.

Next, a block copolymer having an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from (meth)acrylate will be described.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Among these, AB block copolymers or ABA block copolymers are preferable from the viewpoint of excellent dispersibility.

The A block is a block that functions as a colorant adsorption site and contains at least the structural unit represented by the general formula (I). The block copolymer may also be a salt-type block copolymer in which at least a part of the nitrogen site of the structural unit represented by the general formula (I) forms a salt with at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons. things.

Within the scope of achieving the object of the present invention, the A block may also have structural units other than the structural units represented by the general formula (I), as long as they are structural units that can be copolymerized with the structural units represented by the general formula (I), that is, May contain. Specific examples include the structural unit represented by the above general formula (III) and the like.

In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably 50 mass % to 100 mass % with respect to the total mass of all structural units of the A block. %, more preferably 80 mass% to 100 mass%, most preferably 100 mass%. The reason for this is that the higher the ratio of the structural unit represented by the general formula (I), the higher the adsorption force for the colorant is, and the better the dispersibility and dispersion stability of the block copolymer are. In addition, the content ratio of the said structural unit is calculated based on the added mass when synthesizing the A block which has the structural unit represented by general formula (I).

In the block copolymer before salt formation, from the viewpoint of good dispersibility and dispersion stability, the amount of the structural unit represented by the general formula (I) relative to the total mass of all the structural units of the block copolymer is The total content ratio of all the structural units of the A block is preferably 5 to 60 mass%, and more preferably 10 to 50 mass%.

In addition, in the block copolymer before salt formation, from the viewpoint of good dispersibility and dispersion stability, the structural unit represented by the general formula (I) is smaller than the total mass of all structural units of the block copolymer. The content ratio of is preferably 5% to 60% by mass, more preferably 10% to 50% by mass. In addition, the content ratio of each structural unit in the said block copolymer is calculated based on the added mass when synthesizing the block copolymer before salt formation.

It should be noted that the structural unit represented by the general formula (I) only needs to have affinity with the colorant, and may include one type, or two or more types of structural units.

The B block is a block that functions as a solvent affinity site and contains at least a structural unit derived from (meth)acrylate.

The structural unit derived from (meth)acrylate may be the same as described above.

As the B block, it is preferable to select and use it appropriately according to the solvent so as to have solvent affinity from monomers having unsaturated double bonds that can be copolymerized with the monomer from which the structural unit represented by the general formula (I) is derived. As a standard, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. becomes 20 (g/100 g solvent) or more with respect to the solvent used in combination. The structural unit constituting the B block part may include one type, or two or more types of structural units.

Examples of the structural unit contained in the B block include the structural unit represented by the above general formula (III).

In the block copolymer used as the dispersant of the present invention, the relationship between the number m of the structural unit represented by the general formula (I) and the number n of the other structural units constituting the solvent-affinity block part is The ratio m/n is preferably in the range of 0.01 or more and 1 or less, and more preferably in the range of 0.05 or more and 0.7 or less from the viewpoint of the dispersibility and dispersion stability of the color material.

The block copolymer used as the dispersant of the present invention preferably contains the following blocks from the viewpoint of achieving good substrate adhesion and solvent resistance even in a low-temperature heat-treated cured film and suppressing the generation of development residue. At least one of a copolymer and a salt-type block copolymer containing an A block containing a structural unit represented by the above general formula (I) and a structural unit derived from a carboxyl group-containing monomer and a block copolymer derived from ( The B block of the structural unit of methacrylate, the salt type block copolymer is composed of at least a part of the nitrogen site of the structural unit represented by the above general formula (I) of the block copolymer and is selected from the group consisting of At least one of the organic acid compound and the halogenated hydrocarbon forms a salt, and at least one of the above-mentioned block copolymer and the salt-type block copolymer has an acid value of 1 mgKOH/g to 18 mgKOH/g, and a glass transition temperature of 30°C above. In addition, this specific dispersant is preferably combined with a photoinitiator containing a compound represented by the above-mentioned general formula (A) in that the solvent resistance is further improved.

The B block in this case contains a structural unit derived from (meth)acrylate as an essential component, and may be the same as the B block in International Publication No. 2016/104493.

As the above-mentioned carboxyl group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by general formula (I) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include: (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and diacrylic acid. Polymer etc. In addition, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic acid anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used. ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the carboxyl group precursor, acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among these, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before the salt is formed, the content ratio of the structural unit derived from the carboxyl group-containing monomer can be appropriately set so that the acid value of the block copolymer falls within the range of the above-mentioned specific acid value, and there is no particular requirement. It is limited to preferably 0.05 mass% to 4.5 mass%, and more preferably 0.07 mass% to 3.7 mass% based on the total mass of all structural units of the block copolymer.

When the content ratio of the structural unit derived from the carboxyl group-containing monomer is not less than the above-mentioned lower limit, the inhibitory effect of development residue is exhibited, and when it is not more than the above-mentioned upper limit, deterioration of development adhesion and deterioration of solvent re-solubility can be prevented.

In addition, as long as the structural unit derived from a carboxyl group-containing monomer has the said specific acid value, it may contain one type, and may contain two or more types of structural units.

In addition, the B block of the block copolymer preferably contains a structural unit derived from a hydroxyl-containing monomer from the viewpoint of improving development adhesion. When the B block contains a structural unit derived from a hydroxyl-containing monomer, the development speed is further improved. In addition, the hydroxyl group here refers to the alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from the hydroxyl-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with a monomer from which the structural unit represented by the general formula (I) is derived can be used. Examples of such monomers include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 2-hydroxybutyl ester, (meth)acrylic acid 4 -Hydroxybutyl ester, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, 1 mole adduct of ε-caprolactone of 2-hydroxyethyl (meth)acrylate, (meth)acrylate base) 2-hydroxy-3-phenoxypropyl acrylate, etc.

Among them, from the viewpoint of improving development adhesion, one or more types selected from 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate are preferred.

In the block copolymer before salt formation, the content ratio of the structural units derived from the hydroxyl-containing monomer is preferably 1 mass % or more, and more preferably 2 mass % or more relative to the total mass of all structural units of the block copolymer. , more preferably 3 mass% or more, particularly preferably 4 mass% or more. If it is more than the said lower limit, the development adhesiveness can become preferable. Similarly, the content is preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, and particularly preferably 40 mass% or less. If it is below the above-mentioned upper limit, it is preferable in that the introduction ratio of other useful monomers can be increased. In addition, the content ratio of the said structural unit is calculated based on the added mass when synthesizing the block copolymer before salt formation.

The lower limit of the acid value of at least one of the block copolymer and the salt type block copolymer is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more from the viewpoint of the inhibitory effect of development residue. In addition, the upper limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 18 mgKOH/g from the viewpoint of preventing deterioration of development adhesion or deterioration of solvent re-solubility. or less, more preferably 16 mgKOH/g or less, still more preferably 14 mgKOH/g or less.

The acid value of at least one of the block copolymer and the salt type block copolymer can be determined by the method described in International Publication No. 2016/104493.

The glass transition temperature of at least one of the above-mentioned block copolymers and salt-type block copolymers is preferably 30°C or higher from the viewpoint of development adhesion, especially 32°C or higher, and more preferably 35°C. above. On the other hand, from the viewpoint of operability during use such as easy and accurate weighing, the temperature is preferably 200° C. or lower.

The glass transition temperature of at least one of the above-mentioned block copolymer and salt-type block copolymer is determined by measuring by differential scanning calorimetry (DSC) in accordance with JISK7121. When two or more peaks indicating the glass transition temperature are observed, the peak with the largest peak area, that is, the area of the portion protruding from the reference line of the obtained graph is set as the representative value of the glass transition temperature.

The mass average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, but from the viewpoint of improving color material dispersibility and dispersion stability, it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 12,000. .

Here, the mass average molecular weight (Mw) can be measured in the same manner as above.

In addition, regarding the total ratio of the structural units derived from (meth)acrylate, from the viewpoint of dispersion stability, solvent resistance, and compatibility with the photoinitiator, the ratio of the B block in the block copolymer to When the total structural units are 100% by mass, it is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. On the other hand, from the viewpoint of satisfying both dispersion stability and excellent solvent resistance, when all the structural units in the B block are taken as 100% by mass, the total of the structural units derived from (meth)acrylate The proportion may also be 100% by mass. When the above structural unit derived from the carboxyl group-containing monomer is included in the B block, the difference in the B block is derived from (methane The total ratio of the structural units of acrylic acid ester may be 100% by mass.

In the block copolymer before salt formation, from the viewpoint of good dispersibility and dispersion stability, the total content ratio of all the structural units of the B block relative to the total mass of all the structural units of the block copolymer is preferably: 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass.

In addition, in the block copolymer before salt formation, from the viewpoint of improving the dispersibility of the colorant, the content ratio of the structural unit represented by the above general formula (III) relative to the total mass of all structural units of the block copolymer is Preferably it is 40 mass % - 95 mass %, More preferably, it is 50 mass % - 90 mass %. In addition, the content ratio of the said structural unit is calculated based on the added mass when synthesizing the block copolymer before salt formation.

The (meth)acrylate copolymer containing the structural unit represented by the general formula (I) preferably has an amine value of 40mgKOH/g～120mgKOH/g copolymer.

When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and the alkali developability and solvent re-solubility are also excellent. In the present invention, regarding the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I), the amine value is preferably 80 mgKOH/g or more, and more preferably 90 mgKOH/g or more. . On the other hand, from the viewpoint of solvent re-solubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, and more preferably 105 mgKOH/g. the following.

The amine value refers to the number of mg of potassium hydroxide equivalent to the perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with an organic acid compound in the dispersant, the organic acid compound usually dissociates, so the amine value of the block copolymer itself used as the dispersant can be measured.

The content ratio (mol%) of each structural unit in the copolymer in the dispersant can be determined based on the amount of raw materials added during production, and can be measured using an analysis device such as NMR. In addition, the structure of the dispersant can be measured using NMR, various mass spectrometry analyses, and the like. In addition, if necessary, the dispersant can be decomposed by thermal decomposition or the like, and the obtained decomposition products can be determined using high performance liquid chromatography, gas chromatography mass spectrometry, NMR, elemental analysis, XPS/ESCA, TOF-SIMS, etc.

In the photocurable green resin composition of the present invention, the content of the dispersant is not particularly limited as long as it is selected so as to have excellent dispersibility and dispersion stability of the colorant. The total solid content is, for example, preferably in the range of 2 to 30 mass%, and more preferably in the range of 3 to 25 mass%. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of a photocurable green resin composition will be more excellent. Moreover, if it is below the said upper limit, the developability will be good. Especially when forming a cured film with a high colorant concentration, the content of the dispersant relative to the total solid content of the photocurable green resin composition is preferably in the range of 2 to 25 mass%, and more preferably It is in the range of 3% by mass to 20% by mass.

＜Thiool compound＞

From the viewpoint of improving solvent resistance and substrate adhesion after low-temperature heat treatment, the photocurable green resin composition of the present invention preferably further contains a thiol compound.

Examples of thiol compounds include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. From the viewpoint of suppressing line width deviation and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having one thiol group.

Examples of the monofunctional thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto -5-Methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, etc.

Examples of polyfunctional thiol compounds include: 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 ,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), etc.

The thiol compound may be used alone or in combination of two or more. Among them, 2-mercaptobenzoxazole or 2-mercapto is preferred from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion. Benzothiazole.

The content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, and preferably in the range of 1% by mass to 5% by mass relative to the total solid content of the photocurable green resin composition. If it is the said lower limit value or more, it will become easy to improve the solvent resistance after low-temperature heat processing, and the adhesiveness of a board|substrate. On the other hand, if it is less than the above-mentioned upper limit, the photocurable green resin composition of the present invention will tend to have good developability and suppress line width deviation.

＜Other ingredients＞

The photocurable green resin composition of the present invention may further contain various additives as necessary. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, and adhesion accelerators.

Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Laid-Open No. 2013-029832.

From the viewpoint of suppressing the line width shift of the cured film, the photocurable green resin composition of the present invention preferably further contains an antioxidant. The photocurable green resin composition of the present invention, for example, by containing an antioxidant in combination with a compound represented by the general formula (A) above, can control excessive radical chain reactions without impairing curability when forming a cured film. Therefore, when forming a thin line pattern, the linearity is further improved, or the ability to form a thin line pattern according to the design of the mask line width is improved. In addition, heat resistance can be improved, and brightness reduction after exposure and post-baking can be suppressed, thereby improving brightness.

The antioxidant used in the present invention is not particularly limited and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc., and are formed according to the design of the mask line width. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to pattern fine lines and considering heat resistance. It may also be a potential antioxidant as described in International Publication No. 2014/021023.

Examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), isocyanate Uric acid 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) ester (trade name: IRGANOX3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5 -Di-tert-butylbenzyl) mesitylene (trade name: IRGANOX1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP- S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxy Diethyl benzylphosphonate (trade name: Irgamod 195, manufactured by BASF), etc. Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferred from the viewpoint of heat resistance and light resistance.

The antioxidant content is usually in the range of 0.1 to 10.0 mass%, preferably 0.5 to 5.0 mass%, based on the total solid content of the photocurable green resin composition. If it is more than the said lower limit value, the ability to form a fine line pattern according to the design of a mask line width will be improved, and it will be excellent in heat resistance. On the other hand, if it is the said upper limit or less, it will become easy to make the photocurable green resin composition of this invention a highly sensitive photocurable green resin composition.

Examples of the silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, and KBE-402. , KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicones Co., Ltd.), etc. Among them, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacryloyl group or an acryl group are preferred from the viewpoint of adhesion to the SiN substrate.

The content of the silane coupling agent is usually in the range of 0.05 to 10.0 mass%, preferably 0.1 to 5.0 mass%, based on the total solid content in the photocurable green resin composition. If it is more than the said lower limit value and less than the said upper limit value, the board|substrate adhesiveness improvement effect will tend to be good.

<Production method of photocurable green resin composition>

The method for producing the photocurable green resin composition of the present invention can be prepared by mixing a colorant, a photopolymerizable compound, a photoinitiator, and various additional components as necessary using a known mixing method.

When the photocurable green resin composition of the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components used as necessary, as the resin combination Examples of preparation methods include: (1) First, add a colorant and a dispersant to a solvent to prepare a colorant dispersion, and mix an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator into the dispersion. and various methods of adding ingredients as needed; (2) simultaneously adding colorants, dispersants, alkali-soluble resins, photopolymerizable compounds, photoinitiators, and various additive ingredients as needed into the solvent and mixing method; (3) a method of adding a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additional ingredients as needed to a solvent and mixing them, and then adding a colorant and dispersing it; ( 4) Add a colorant, a dispersant, and an alkali-soluble resin to a solvent to prepare a colorant dispersion, and further add an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various other components as needed to the dispersion. Methods for adding ingredients and mixing, etc.

Among these methods, the above-mentioned methods (1) and (4) are preferable from the viewpoint of being able to effectively prevent aggregation of the colorant and uniformly disperse the colorant.

The method for preparing the color material dispersion liquid can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt of an amino group contained in the dispersant and an organic acid compound. Mix it with colorants and other ingredients as needed, and use a known mixer or disperser to disperse; (2) Mix the dispersant in the solvent and stir to prepare a dispersant solution, and then mix the colorants and mix as needed The organic acid compound and other components as needed are dispersed using a known mixer or disperser; (3) Mix the dispersant in the solvent and stir to prepare a dispersant solution, and then mix the colorant and If other components are required, a known mixer or disperser is used to prepare a dispersion liquid, and then an organic acid compound is added as required.

Examples of the disperser used for the dispersion treatment include roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibration ball mills; paint conditioners, continuous disc bead mills, and continuous ring bead mills. Mill and other bead mills. As the preferred dispersion conditions of the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

＜Use＞

Since the cured film of the photocurable green resin composition of the present invention has an external light reflection suppressing effect, it can be suitably used to form a colored cured film as a substitute for a circularly polarizing plate. When the cured film of the photocurable green resin composition of the present invention is used as a substitute for a circularly polarizing plate, a display device without a polarizing plate can be produced. Therefore, the photocurable green resin composition of the present invention can be suitably used. For use in display devices without polarizing plates.

In addition, the photocurable green resin composition of the present invention is a photocurable green resin composition used for a cured film formed on an organic light-emitting element, and therefore can be suitably used for displays that do not include externally mounted color filter substrates. Device application, film and organic light-emitting display device application with improved flexibility.

In addition, by appropriately selecting components as described above, the photocurable green resin composition of the present invention can form a cured film with good solvent resistance and excellent substrate adhesion even if it is subjected to low-temperature heat treatment, so it can be suitably used in Use for forming a cured film on a substrate on which an element with low heat resistance is formed by low-temperature heat treatment at 130°C or lower, further 100°C or lower, or 90°C or lower.

II.Display device

The display device of the present invention is characterized by having a cured film of the photocurable green resin composition of the present invention on an organic light-emitting element.

The display device of the present invention has a cured film of a photocurable green resin composition formed on an organic light-emitting element. The photocurable green resin composition is used to form a cured film on the organic light-emitting element of the present invention. Therefore, there is no need for an externally mounted circular polarizing plate or an externally mounted color filter substrate, and these are not required.

The display device of the present invention uses the photocurable green resin composition for forming the cured film on the organic light-emitting element of the present invention to form the cured film on the organic light-emitting element. Therefore, there is no gap between the organic light-emitting element and the cured film. It is used for substrates such as externally mounted color filter substrates, so thinning and flexibility are improved.

This organic light-emitting display device including the organic light-emitting element of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a display device including an organic light-emitting element of the present invention. As illustrated in FIG. 1 , the display device 100 of the present invention includes an element substrate 30 of an organic light-emitting element, and an external light anti-reflection film 20 including a colored cured film (9R, 9G, 9B) on the element substrate 30. Further, A sealing film 11 is provided thereon.

The element substrate 30 including the above-mentioned organic light-emitting element has a thin film transistor (TFT) 2 as a driving element arranged on the substrate 1 in a manner corresponding to each sub-pixel, a sealing film 3 thereon, and further a TFT 2 on the sealing film 3. The electrode 4 (anode) corresponding to each sub-pixel and the partition wall 5 dividing each sub-pixel are arranged in this block, and organic light-emitting elements (6R, 6G, 6B) constituting the three-color sub-pixels of R, G, and B are arranged. This organic light-emitting element (6R, 6G, 6B) is further provided with an electrode 7 (cathode). The element substrate 30 provided with the organic light-emitting element further includes a sealing layer 8 covering the organic light-emitting element.

The sealing layer 8 on the organic EL elements (6R, 6G, 6B) in the element substrate 30 is provided with an external light anti-reflection film 20, which includes 3 layers corresponding to each organic EL element formed using a photocurable colored resin composition. The color-colored cured film (9R, 9G, 9B) and the light-shielding portion 10 further include a sealing film 11 on the above-mentioned anti-reflection film 20 for external light.

The display device 100 of the present invention in FIG. 1 further includes a covering material 13 on the sealing film 11 with a transparent adhesive layer 12 interposed therebetween.

Although not shown in the figures, the display device 100 of the present invention may further include a touch sensor layer including an insulating film and a transparent electrode layer on the sealing film 11 , and may further appropriately include a well-known hard coat layer on the touch sensor layer. constitute.

As described above, the colored cured films (9R, 9G, 9B) and the layer of the light shielding portion 10 provided on the element substrate 30 having the above-mentioned organic light-emitting element serve as the external light anti-reflection film 20. Therefore, the external light used in the present invention The anti-light reflection film does not include externally mounted circular polarizing plates or externally mounted color filter substrates, and can improve thinness and flexibility.

In the display device of the present invention, it is preferable to use the color of the sub-pixels (6R, 6G, 6B) of the organic light-emitting element and the colored cured film (9R, 9G, 9G, 9B) The colors are adjusted to the same color. Through the colored cured film provided on the organic light-emitting element, external light is blocked except for the color originally emitted by the organic light-emitting element, and the light emitted by the organic light-emitting element is not reduced. Therefore, it is possible to use light without reducing the light utilization efficiency. Suppress external light reflection.

The cured film of the photocurable green resin composition of the present invention may be the green cured film (9G) among the three-color colored cured films (9R, 9G, 9B).

The substrate 1 used in the display device of the present invention, a thin film transistor (TFT) 2 as a driving element, a sealing film 3, an electrode 4 (anode), a partition wall 5 dividing each sub-pixel, and an organic light-emitting element constituting the sub-pixel (6R, 6G, 6B), the electrode 7 (cathode), etc. can be appropriately selected from known structures and used.

In addition to the light-emitting layer, the organic light-emitting element may also have known structures such as a hole injection layer, a hole transport layer, and an electron injection layer.

The sealing layer 8 on the organic EL element used in the display device of the present invention includes an inorganic film, an organic film, and a multilayer film in which these are laminated. It is preferable to use a multilayer film in view of the high effect of inhibiting the penetration of moisture and oxygen.

Specific examples include metal films, metal oxide films, multilayer films in which inorganic films such as SiOx and SiNx and organic films are laminated.

At least one of the colored cured films used in the display device of the present invention is a cured film of the photocurable green resin composition of the present invention.

The colored cured film is usually formed on the opening of the light-shielding portion described below on the sealing layer 8 on the organic light-emitting element, and usually consists of a colored pattern of three or more colors. These may be the same coloring patterns as (6R, 6G, 6B) of the sub-pixels of the organic light-emitting element.

The arrangement of the colored cured films (9R, 9G, 9B) may be, for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. In addition, the width, area, etc. of the colored layer can be appropriately set to suit the sub-pixels (6R, 6G, 6B) of the organic light-emitting element.

The thickness of the colored cured film is appropriately controlled by adjusting the coating method, solid content concentration or viscosity of the photocurable green resin composition, but is usually in the range of 1 μm to 5 μm.

The light-shielding portion 10 used in the display device of the present invention is usually formed in a pattern on the sealing layer 8 on the organic light-emitting element, and can be used as a light-shielding portion in a normal color filter.

The pattern shape of the light shielding portion may be appropriately selected according to the shape of the colored cured film, and examples thereof include striped shapes, matrix shapes, and the like. The light-shielding part may be a metal thin film such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there is a method of patterning using a photosensitive resist through development, a method of patterning using an inkjet ink containing light-shielding particles, and a method of thermally treating the photosensitive resist. Transfer methods, etc.

The film thickness of the light-shielding portion is set to approximately 0.2 μm to 0.4 μm in the case of a metal thin film, and is set to 0.5 μm to 0.5 μm in the case of a black pigment dispersed or dissolved in a binder resin. About 2μm.

As the sealing film 11 provided on the colored cured film (9R, 9G, 9B) and the light shielding part 10, a known material can be appropriately selected and used.

In addition, as the transparent adhesive layer 12 and the covering material 13 provided on the sealing film 11, known materials may be appropriately selected and used. In the present invention, even when glass is used as the covering material, the weather resistance of the green cured film is good and the decrease in transmittance is suppressed. From this point of view, glass can be used as the covering material.

It should be noted that the display device of the present invention is not limited to the configuration shown in FIG. 1 , and may further include a display device having a known organic light-emitting element.

III. Method for manufacturing a laminate of an organic light-emitting element and an anti-reflection film for external light

The manufacturing method of a laminate of an organic light-emitting element and an external light anti-reflection film of the present invention includes the step of forming a cured film of the photocurable green resin composition of the present invention on the organic light-emitting element by including the following steps:

The process of forming a coating film by coating the above-mentioned photocurable green resin composition of the present invention on an organic light-emitting element;

The process of illuminating the above-mentioned coating film;

The above-mentioned illuminated film is subjected to a heating post-baking process; and

The step of developing the film after the above-mentioned irradiation.

Each process is explained below.

In the process of applying the photocurable green resin composition of the present invention to the organic light-emitting element, the application may not be adjacent to the organic light-emitting element, but may be applied with at least one layer interposed therebetween. As shown in FIG. 1 , in an element substrate 30 including an organic light-emitting element, electrodes 7 are usually further provided on the sub-pixels (6R, 6G, 6B) of the organic light-emitting element for suppressing penetration of moisture or oxygen. The sealing layer 8 can be coated on the organic light-emitting element through these electrodes and sealing layers.

For example, the light-shielding part 10 may be provided in advance on the sealing layer 8 by a known method as exemplified above, and the colored cured film (9R, 9G, 9B) may be formed by coating the opening of the light-shielding part 10.

For example, a coating method such as spray coating, dip coating, rod coating, roll coating, spin coating, or die coating is used to apply the photocurable green resin composition of the present invention to on the above-mentioned organic light-emitting element. As the coating method, spin coating method and die coating method can be preferably used.

Then, the wet coating film is dried using a hot plate, an oven, etc. to form a coating film.

The obtained coating film is exposed to light (exposure) through a mask of a specific pattern, and the photopolymerizable compound and, if necessary, an alkali-soluble resin and the like are subjected to a photopolymerization reaction. Examples of light sources used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, and electron beams. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, etc.

Then, in order to promote the polymerization reaction after exposure, a post-baking process of heating the film after the above-mentioned irradiation may be performed. Heating conditions may be appropriately selected depending on the mixing ratio of each component in the photocurable green resin composition used, the thickness of the coating film, and the like.

The post-baking process can be performed on the film after the above-mentioned irradiation before the development process described below, after the development process, or before and after the development process.

In the present invention, since the colored cured film is directly formed on the element substrate provided with the organic light-emitting element, the heating temperature in the above-mentioned post-baking step is preferably 130° C. or lower. The heating temperature is more preferably 100°C or lower, further preferably 90°C or lower. In addition, the heating temperature may be 30°C or higher, 35°C or higher, or 40°C or higher.

Next, the film after the above light exposure is developed. The developed film after light exposure may also be a post-baked film.

In the development process, a developing solution is used to perform a development process to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As a developer, a solution in which an alkali is dissolved in water or a water-soluble solvent can usually be used. An appropriate amount of surfactant or the like may be added to this alkaline solution. In addition, a common method can be used as a development method.

After the development process, the developer is usually washed and the cured film of the photocurable green resin composition is dried to form a colored cured film. In addition, after the development process, in order to fully cure the coating film, you may also perform a heat process.

In the present invention, the colored cured film is directly formed on the element substrate provided with the organic light-emitting element, so the heating temperature in the post-baking step is also preferably 130°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower. In addition, the heating temperature may be 30°C or higher, 35°C or higher, or 40°C or higher.

In addition, in order to further solidify the film after the development process and post-baking, light (exposure) may be additionally performed.

Example

Hereinafter, an Example is shown and this invention is demonstrated concretely. These descriptions do not limit the present invention.

The mass average molecular weight (Mw) of the copolymer before salt formation is determined in terms of standard polystyrene by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.

(Synthesis Example 1: Synthesis of Block Copolymer 1)

250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-neck detachable flask equipped with a condenser tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the nitrogen gas was fully replaced. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) and 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA) as monomers for the B block were added dropwise over 60 minutes. ) 29.1 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass, n-butyl methacrylate (BMA) 13.7 parts by mass, benzyl methacrylate (BzMA) 9.5 parts by mass, methyl methacrylate 17.5 parts by mass of ester (MMA). After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) as the monomer for block A was added dropwise over 20 minutes. After the reaction was carried out for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a solution with a solid content of 30% by mass. Add 32.5 parts by mass of water, raise the temperature to 100°C, and react for 7 hours. The structural unit derived from EEMA is deprotected to form a structural unit derived from methacrylic acid (MAA). The structural unit derived from TMSMA is deprotected to form a structural unit derived from methacrylic acid (MAA). Structural unit of 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain block copolymer 1 (amine value 95 mgKOH) containing the structural unit represented by the above general formula (I). /g, acid value 8mgKOH/g, Tg38℃). The mass average molecular weight Mw is 7730.

(Synthesis Example 2: Synthesis of oxime ester-based photoinitiator represented by formula (A-2))

The oxime ester photoinitiator represented by the above formula (A-2) was synthesized in the same manner as in the production of compound No. 73 in paragraphs 0114 to 0117 of International Publication No. 2015/152153.

(Preparation Example 1: Preparation of alkali-soluble resin A)

300 parts by mass of PGMEA was added to the polymerization tank, and after the temperature was raised to 100°C in a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methyl group were continuously added dropwise over 1.5 hours. 36 parts by mass of acrylic acid (MAA), 6 parts by mass of PERBUTYLO (manufactured by NOF Co., Ltd.), and 2 parts by mass of a chain transfer agent (n-dodecylmercaptan). Thereafter, the reaction was continued while maintaining 100°C. Two hours after the dropwise addition of the main chain forming mixture was completed, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.

Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and after the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the process was carried out at 110°C. The addition reaction was carried out for 15 hours to obtain an alkali-soluble resin A solution (mass average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).

It should be noted that in the above-described mass average molecular weight measurement method, polystyrene is used as a standard material, THF is used as an eluent, and the mass average molecular weight is measured using Shodex GPC System-21H. In addition, the acid value measurement method is based on JIS K 0070.

(Example 1: Production of photocurable green resin composition G-1)

(1) Production of Color Dispersion B (1)

In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40 mass %) of Preparation Example 1, and the PGMEA solution of block copolymer 1 of Synthesis Example 1 (solid content 35 mass %) were added. %) 9.2 parts by mass and stirred. Thereto, 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 30 minutes.

12.0 parts by mass of C.I. Pigment Blue 15:4 (B 15:4) as a blue pigment and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were added thereto and pre-crushed using a paint oscillator (manufactured by Asada Iron Works Co., Ltd. ) was shaken for 1 hour, then changed to 200 parts of zirconium oxide beads with a particle size of 0.1 mm, and dispersed using a paint shaker for 4 hours as a formal crushing to obtain a color dispersion B (1). In addition, the block copolymer 1 forms a salt using phenylphosphonic acid, and becomes the salt type block copolymer 1.

(2) Production of color dispersion liquid Y (1)

In the production of color material dispersion B (1), except that C.I. Pigment Blue 15:4 (B 15:4) is changed to C.I. Pigment Yellow 139 (Y139), it is the same as the production of color material dispersion B (1). In the same manner, color material dispersion liquid Y(1) is obtained.

(3) Production of color dispersion liquid Y (2)

In the production of color material dispersion B (1), the same process as the production of color material dispersion B (1) was used except that C.I. Pigment Blue 15:4 (B 15:4) was changed to C.I. Pigment Yellow 150 (Y150). In the same manner, color material dispersion liquid Y(2) is obtained.

(4) Production of color dispersion liquid Y (3)

In the production of color material dispersion B (1), except that C.I. Pigment Blue 15:4 (B 15:4) is changed to C.I. Pigment Yellow 138 (Y138), it is the same as the production of color material dispersion B (1). In the same manner, color material dispersion liquid Y (3) is obtained.

(5) Production of photocurable green resin composition G-1

Add 6.4 parts by mass of color material dispersion B(1), 5.2 parts by mass of color material dispersion Y(1), 9.0 parts by mass of color material dispersion Y(2), and color material dispersion Y(3) obtained above. 15.0 parts by mass, 3.5 parts by mass of the alkali-soluble resin A solution obtained in Preparation Example 1, 5.6 parts by mass of a polyfunctional monomer (trade name ARONIXM-305, manufactured by Toagosei Co., Ltd.), represented by the above formula (A-2) 0.5 parts by mass of oxime ester photoinitiator, 0.03 parts by mass of fluorine surfactant (trade name MEGAFACR-08MH, manufactured by DIC Co., Ltd.), and 54.6 parts by mass of PGMEA were used to obtain a photocurable green resin composition G-1.

(Examples 2 to 5: Production of photocurable green resin compositions G-2 to G-5)

In Example 1, except as shown in Table 1, the types and/or mass ratios of the blue pigment, yellow pigment and green pigment were changed, and the alkali-soluble resin A solution, the multifunctional monomer, and the above formula (A -2) The ratio of the oxime ester-based photoinitiator is the same as in Example 1, except that the pigment concentration is changed to the value shown in Table 1. The ratio is the same as that of the photocurable green resin composition G-1. In the same manner, photocurable green resin compositions G-2 to G-5 were obtained.

It should be noted that regarding the color dispersion of C.I. Pigment Blue 15:6 (B15:6), C.I. Pigment Green 59 (G59) or C.I. Pigment Green 7 (G7), except for the color dispersion B (1) respectively During the production, C.I. Pigment Blue 15:4 (B15:4) was changed to other than C.I. Pigment Blue 15:6 (B15:6), C.I. Pigment Green 59 (G59) or C.I. Pigment Green 7 (G7) to match the color The color dispersion liquid B (1) is produced in the same manner as the color material dispersion liquid B (2), the color material dispersion liquid G (1), or the color material dispersion liquid G (2).

(Comparative Examples 1 to 2: Production of comparative photocurable green resin compositions CG-1 to CG-2)

In Examples 4 and 5, as shown in Table 1, except that the green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10% by mass in the total amount of colorants, the same as the photocurable green pigment was used. In the same manner as resin composition G-4 or G-5, comparative photocurable green resin compositions CG-1 to CG-2 were obtained.

(Comparative Examples 3 to 4: Production of comparative photocurable green resin compositions CG-3 to CG-4)

In Example 1, in the same manner as Examples 1 and 2 of Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-242568), except as shown in Table 1, the types and/or types of the blue pigment and the yellow pigment were changed. The mass ratio, the type of initiator (Irgacure 907 (907, manufactured by BASF) and Kayacure DETX-S (DETX, manufactured by Nippon Kayaku) mass ratio 2:1), and the pigment was changed so that the pigment concentration was as shown in Table 1 Comparative photocurable green resin compositions CG-3 to CG-4 were obtained in the same manner as the photocurable green resin composition G-1 except for the other component amounts.

In addition, regarding the color material dispersion liquid of C.I. Pigment Blue 16 (B 16) or C.I. Pigment Blue 15:3 (B15:3), except for the production of the color material dispersion B (1), the C.I. Pigment Blue 15:4 (B15:4) is changed to C.I. Pigment Blue 16 (B16) or C.I. Pigment Blue 15:3 (B15:3), in the same manner as the production of color material dispersion B (1), as Color material dispersion liquid B (3) or color material dispersion liquid B (4) is obtained.

(Comparative Examples 5 to 7: Production of comparative photocurable green resin compositions CG-5 to CG-7)

In Example 1, except as shown in Table 1, in the same manner as Examples 2, 5, and 1 of Patent Document 3 (International Publication No. 2020/196393), the types and values of the blue pigment and the yellow pigment were changed. / Or the mass ratio, the type of initiator (Irgacure OXE02 (OXE02, manufactured by BASF)), and the amount of components other than pigments were changed so as to achieve the pigment concentration shown in Table 1, so as to be consistent with the photocurable green resin composition In the same manner as G-1, comparative photocurable green resin compositions CG-5 to CG-7 were obtained.

(Comparative Example 8: Production of comparative photocurable green resin composition CG-8)

In Example 1, except as shown in Table 1, the types and/or mass ratios of the yellow pigment, green pigment, and black pigment were changed to the same types and/or mass ratios as Example 1 of Patent Document 1 (Japanese Patent Application Laid-Open No. 2017-182067). , the type of initiator (Irgacure907 (907, manufactured by BASF Corporation) and Irgacure OXE01 (OXE01, manufactured by BASF Corporation)), and the amount of components other than pigments was changed to achieve the pigment concentration shown in Table 1, in order to match the photocuring Comparative photocurable green resin composition CG-8 was obtained in the same manner as the green resin composition G-1.

In addition, regarding the color dispersion of black pigment (carbon black), except for the production of color dispersion B (1), C.I. Pigment Blue 15:4 (B15:4) was changed to carbon black (Mitsubishi Except for chemical production, MA77), it was obtained as the color material dispersion liquid BK (1) in the same manner as the production of the color material dispersion liquid B (1).

[Evaluation method]

The photocurable green resin composition obtained in each Example and each Comparative Example was applied to a glass substrate (manufactured by NHTECHNO GLASS Co., Ltd.) using a spin coater so that the thickness of the finally obtained cured film would be 3.0 μm. , "NA35"), and then dried using a hot plate at 80° C. for 3 minutes to form a coating film on the substrate. On this coating film, a photomask (chromium mask) having a pattern with an opening size of 2 μm to 100 μm for forming independent thin lines was interposed, and exposed to ultraviolet light of 70 mJ/cm ² using an ultrahigh-pressure mercury lamp, thereby A coating film is formed after exposure. Then, a 0.05 wt% potassium hydroxide aqueous solution was used as a developer for rotational development, and after being in contact with the developer for 60 seconds, the film was developed by washing with pure water to obtain an independent fine line pattern coating film. Thereafter, post-baking was performed for 30 minutes in a clean oven at 90° C. to form an independent thin line pattern-shaped cured film (green cured film).

Using the cured film obtained in the above manner, transmittance measurement, weather resistance evaluation, solvent resistance evaluation, and external light reflection suppression evaluation were performed.

＜Transmittance＞

The transmission spectrum of the cured film from 380 nm to 780 nm was measured using a microspectroscopy device (OSP-SP200 manufactured by Olympus), and the maximum transmittance from 380 nm to 480 nm, the maximum transmittance and minimum transmittance from 510 nm to 550 nm, and the maximum transmittance from 580 nm to 700 nm were calculated. The half-maximum width is determined by the difference between the wavelengths at two points where the transmittance is half of the maximum transmittance in the peak showing the maximum transmittance in the wavelength range of 380 nm to 700 nm.

＜Weather resistance evaluation＞

For a sample in which a glass substrate was attached to a cured film produced on a glass substrate via a transparent adhesive layer, a weather resistance testing machine (Ci4000 manufactured by ATLAS Corporation) was used, and the light intensity at 340 nm was 0.63 W/m ² . The weather resistance test was conducted for 48 hours under the conditions of internal temperature of 60°C and humidity of 50% RH.

For each cured film for weather resistance evaluation before and after the weather resistance test, the chromaticity (L ₀ , a ₀ , b ₀ ) before the weather resistance test and the chromaticity after the weather resistance test were measured using a microspectroscopy device OSP-SP200 manufactured by Olympus. Chroma (L ₁ , a ₁ , b ₁ ).

The chromaticity change of the cured film before and after the weather resistance test was evaluated by the following formula. The results are shown in the table.

ΔEab＝{(L ₁ -L ₀ )2+(a ₁ -a ₀ )2+(b ₁ -b ₀ ) ² } ^1/2

The smaller the value of ΔEab is, the more excellent the heat resistance is evaluated.

(Evaluation criteria for weather resistance evaluation)

A: The value of ΔEab is less than 3

B: The value of ΔEab is more than 3 and less than 5

C: The value of ΔEab is 5 or more

If the evaluation result is B, the weather resistance is good, and if the evaluation result is A, the weather resistance is excellent.

<Evaluation of solvent resistance (PGME resistance)>

After measuring the film thickness of the obtained cured film, it was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, and then air-dried, and the film thickness was measured again. In addition, the film thickness was measured using a stylus type step film thickness meter "P-15Tencor" (manufactured by Instruments). The film thickness after solvent immersion/film thickness before solvent immersion × 100 was calculated as the remaining film rate.

(Evaluation criteria for solvent resistance)

A: The residual film rate after solvent immersion is more than 98%

B: The residual film rate after solvent immersion is more than 96% and less than 98%

C: The residual film rate after solvent immersion is 94% or more and less than 96%

D: The residual film rate after solvent immersion is less than 94%

If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.

<Evaluation of external light reflection suppression of green cured film>

(brightness Y)

The transmission spectrum of the obtained cured film from 380 nm to 780 nm was measured using a microspectroscopic measuring device (OSP-SP200 manufactured by Olympus), the brightness Y was measured, and the transmittance of the green cured film was evaluated.

(Reflectivity)

When the transmittance of the obtained cured film at each wavelength of 380 nm to 780 nm is set to T(CF), the reflectance of the glass substrate is set to 50%, and the visual color matching function is set to y, Rn= T(CF)×0.5×T(CF)×y Calculate the reflectance Rn at each wavelength, and let the value obtained by integrating Rn at each wavelength be the reflectance of the green cured film of 380 nm to 780 nm.

If the brightness Y is 32 or more and the reflectance is less than 9%, it is judged that the transmittance of the green cured film is high. On the other hand, the reflectance is low and the external light reflection suppression effect is good.

[Table 1]

[Result summary]

It was shown that in Comparative Examples 1 and 2 that were modified so as to use a green pigment (halogenated phthalocyanine pigment) in an amount exceeding 10% by mass in the total amount of colorants, although the spectrum in the wavelength range of 380 nm to 480 nm The transmittance is set to 20% or less, the spectral transmittance in the wavelength range of 580nm to 700nm is set to 30% or less, and the spectral transmittance in the wavelength range of 510nm to 550nm is set to 40% or more and 80% or less. However, reflection The transmittance is lower but the transmittance is also lower, or the transmittance is higher but the reflectivity is also increased, and the external light reflection suppression effect is poor. In addition, the cured films of Comparative Examples 1 and 2 also had poor weather resistance.

It has been shown that Comparative Examples 3 and 4 in which the types and/or mass ratios of the blue pigment and the yellow pigment are the same as those in Examples 1 and 2 of Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-242568) are shown to have the same wavelength at the above-mentioned specific wavelengths. The specific spectral transmittance is not satisfied in the area, and although the reflectivity is low, the transmittance is also reduced, or although the reflectivity is slightly high, the transmittance is reduced, and the external light reflection suppression effect is poor. In addition, the cured films of Comparative Examples 3 and 4 also had poor solvent resistance.

In addition, it was shown that Comparative Examples 5, 6 and 7 were the same as Examples 2, 5 and 1 of Patent Document 3 (International Publication No. 2020/196393), and the types and/or mass ratios of the blue pigment and the yellow pigment were the same. The specific spectral transmittance is also not satisfied in the above-mentioned specific wavelength regions. Although the reflectivity is low, the transmittance is also reduced, and the external light reflection suppression effect is poor. In addition, the cured films of Comparative Examples 5 to 7 also had poor solvent resistance.

In addition, it was shown that the types and/or mass ratios of the yellow pigment, the green pigment and the black pigment, and the type of the initiator were changed to the same comparative example as Example 1 of Patent Document 1 (Japanese Patent Application Laid-Open No. 2017-182067). Although the transmittance of the cured film of 8 is high, the reflectivity is also increased, and the external light reflection suppression effect is poor. In addition, the cured film of Comparative Example 8 was poor in weather resistance and solvent resistance.

In contrast, regarding Examples 1 to 5 of the photocurable green resin compositions of the present invention, it was found that when formed on an organic light-emitting element, a cured film was formed by post-baking at a preferable low temperature (90° C.) , however, when the cured film is formed with a film thickness of 3.0 μm, the spectral transmittance in the wavelength range of 380 nm to 480 nm becomes 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm becomes 30% or less, and the spectral transmittance in the wavelength range of 510 nm to 550 nm becomes 30% or less. The spectral transmittance in the wavelength range is 40% or more and 80% or less. The transmittance is high. On the other hand, the reflectance is low and the external light reflection suppression effect is good. It is also shown that a transparent adhesive can be formed even if there is an interlayer The cured film has excellent weather resistance even when glass is bonded to the layer, and has good solvent resistance even if it is heat-treated at low temperature. Therefore, it is shown that the photocurable green resin composition of the present invention is suitable for use in a cured film formed on an organic light-emitting element, and the cured film is a thin film that can suppress external light reflection and can produce a thin film with improved flexibility. Luminous display device.

Explanation of reference signs

1:Substrate;

2: Thin film transistor (TFT);

3:Sealing film;

4:Electrode;

5: partition wall;

6B: Organic light-emitting components;

6G: organic light-emitting components;

6R: organic light-emitting components;

7: Electrode;

8:Sealing layer;

9B: Colored cured film;

9G: Colored cured film;

9R: Colored cured film;

10: Shading part;

11:Sealing film;

12: Transparent adhesive layer;

13: Covering material;

20: Anti-reflection film for external light;

30: Component substrate with organic light-emitting components;

100: Display device.

Claims (8)

1. A photocurable green resin composition for a cured film formed on an organic light-emitting element,

the photocurable green resin composition contains a coloring material, a photopolymerizable compound and a photoinitiator,

the colorant comprises a blue pigment and a yellow pigment, wherein the content of halogenated metal phthalocyanine pigment is 10% by mass or less relative to the total amount of the colorant,

when a cured film is formed with a film thickness of 3.0 [ mu ] m, the spectral transmittance in the wavelength range of 380nm to 480nm is 20% or less, the spectral transmittance in the wavelength range of 580nm to 700nm is 30% or less, and the spectral transmittance in the wavelength range of 510nm to 550nm is 40% or more and 80% or less.

2. The photocurable green resin composition according to claim 1, wherein the blue pigment comprises a pigment selected from c.i. pigment blue 15: 3. c.i. pigment blue 15: 4. and at least one of c.i. pigment blue 16, the yellow pigment comprises c.i. pigment yellow 139, optionally further comprising at least one selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and c.i. pigment yellow 185.

3. The photocurable green resin composition according to claim 1 or 2, wherein the photoinitiator comprises at least one of compounds represented by the following general formula (a),

general formula (A)

Wherein R is ¹ R is R ² Each independently represents R ¹¹ 、OR ¹¹ 、COR ¹¹ 、SR ¹¹ 、CONR ¹² R ¹³ Or the CN of the two-dimensional network,

R ¹¹ 、R ¹² r is R ¹³ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R ¹¹ 、R ¹² r is R ¹³ The hydrogen atom of the radicals represented being optionally further substituted by R ²¹ 、OR ²¹ 、COR ²¹ 、SR ²¹ 、NR ²² R ²³ 、CONR ²² R ²³ 、-NR ²² -OR ²³ 、-NCOR ²² -OCOR ²³ 、NR ²² COR ²¹ 、OCOR ²¹ 、COOR ²¹ 、SCOR ²¹ 、OCSR ²¹ 、COSR ²¹ 、CSOR ²¹ A hydroxyl group, a nitro group, CN, or a halogen atom,

R ²¹ 、R ²² r is R ²³ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R ²¹ 、R ²² r is R ²³ The hydrogen atom of the represented group is optionally further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxyl group,

R ¹¹ 、R ¹² 、R ¹³ 、R ²¹ 、R ²² R is R ²³ The alkylene portion of the radicals represented optionally contains 1 to 5-O-, optionally under conditions in which the oxygen atoms are not adjacent-S-, -COO-, -OCO-, -NR ²⁴ -、-NR ²⁴ CO-、-NR ²⁴ COO-、-OCONR ²⁴ -, -SCO-, -COS-; OCS-or-CSO-,

R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

R ¹¹ 、R ¹² 、R ¹³ 、R ²¹ 、R ²² 、R ²³ r is R ²⁴ Represented byThe alkyl portion of the group may have a branched side chain, or may be a cyclic alkyl group,

R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, R ³ The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group, and R ³ And R is R ⁷ And R is ³ And R is R ⁸ The rings may be formed separately and together with each other,

R ³ the hydrogen atom of the radicals represented being optionally further substituted by R ²¹ 、OR ²¹ 、COR ²¹ 、SR ²¹ 、NR ²² R ²³ 、CONR ²² R ²³ 、-NR ²² -OR ²³ 、-NCOR ²² -OCOR ²³ 、NR ²² COR ²¹ 、OCOR ²¹ 、COOR ²¹ 、SCOR ²¹ 、OCSR ²¹ 、COSR ²¹ 、CSOR ²¹ A hydroxyl group, a nitro group, CN, or a halogen atom,

R ⁴ 、R ⁵ 、R ⁶ r is R ⁷ Each independently represents R ¹¹ 、OR ¹¹ 、SR ¹¹ 、COR ¹⁴ 、CONR ¹⁵ R ¹⁶ 、NR ¹² COR ¹¹ 、OCOR ¹¹ 、COOR ¹⁴ 、SCOR ¹¹ 、OCSR ¹¹ 、COSR ¹⁴ 、CSOR ¹¹ A hydroxyl group, CN or halogen atom, R ⁴ And R is R ⁵ 、R ⁵ And R is R ⁶ And R is ⁶ And R is R ⁷ The rings may be formed separately and together with each other,

R ¹⁴ 、R ¹⁵ r is R ¹⁶ Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ¹⁴ 、R ¹⁵ R is R ¹⁶ The alkyl portion of the group represented may have a branched side chain or may be a cyclic alkyl group, R ⁸ R represents ¹¹ 、OR ¹¹ 、SR ¹¹ 、COR ¹¹ 、CONR ¹² R ¹³ 、NR ¹² COR ¹¹ 、OCOR ¹¹ 、COOR ¹¹ 、SCOR ¹¹ 、OCSR ¹¹ 、COSR ¹¹ 、CSOR ¹¹ A hydroxyl group, a CN or a halogen atom,

k represents 0 or 1.

4. The photocurable green resin composition according to any one of claims 1-3, wherein the half-width of a peak exhibiting a maximum transmittance in a wavelength range of 380nm to 700nm of the transmission spectrum is 70nm or less when a cured film is formed at a film thickness of 3.0 μm.

5. The photocurable green resin composition according to any one of claims 1-4, wherein the wavelength exhibiting the maximum transmittance in the wavelength range of 380nm to 700nm of the transmission spectrum is in the range of 525nm to 545nm when a cured film is formed at a film thickness of 3.0 μm.

6. A display device having the cured film of the photocurable green resin composition according to any one of claims 1 to 5 on an organic light-emitting element.

7. A method for producing a laminate of an organic light-emitting element and an external light reflection preventing film, comprising the step of forming a cured film of the photocurable green resin composition according to any one of claims 1 to 4 on the organic light-emitting element by comprising the steps of:

a step of forming a coating film by applying the photocurable green resin composition according to any one of claims 1 to 5 onto an organic light-emitting element;

a step of irradiating the coating film with light;

A post-baking step of heating the irradiated film; and

And developing the film after the irradiation.

8. The method for producing a laminate of an organic light-emitting element and an external light reflection preventing film according to claim 7, wherein a heating temperature in the post-baking step is 130 ℃ or lower.