TW202035525A - Resin composition, black resin film, layered body and display device - Google Patents

Abstract

Provided is a resin composition containing: a resin including a repeating unit represented by chemical formula (1) or (2) as a main component; a solvent; and a pigment. In chemical formulas (1) and (2), X is a tetravalent tetracarboxylic acid residue having at least two carbon atoms, and Y is a divalent diamine residue having at least two carbon atoms. The tetracarboxylic acid of X and/or the diamine of Y has maximum light absorbance at a wavelength within a range from 380-580 nm. R' and R" are each independently a hydrogen atom, a C1-C10 hydrocarbon group, a C1-C10 alkyl silyl group, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion. With this resin composition, a black resin film having excellent light-blocking properties can be obtained.

Description

Resin composition, black resin film, laminate and display device

The invention relates to a resin composition, a black resin film, a laminate, and a display device.

Organic light-emitting display devices (Electroluminescence (EL) displays) are self-luminous display devices that exhibit characteristics such as light weight and thinness, wide viewing angle, low power consumption, and high contrast.

Organic light-emitting display devices are classified into a bottom emission method that emits light to the substrate side and a top emission method that emits light to the opposite surface of the substrate according to their light emission method. Organic light-emitting display devices have thin film transistors (TFT) and electrodes, but these have high reflectivity and reflect indoor and outdoor light, so the visibility of images is reduced.

As a method of preventing a decrease in visibility caused by reflection of indoor and outdoor light, there are methods such as suppression of reflection on the TFT surface, suppression of reflection of electrodes, use of a polarizing plate, and improvement of the brightness of the image itself. However, since other layers are provided in order to prevent reflection, there is a problem that the number of steps increases, the thickness of the organic light-emitting display device becomes thick, and the like. In addition, there are also problems in that the flexibility of the display device is reduced, or afterglow occurs when the brightness is increased.

Therefore, a technique for improving visibility by blackening the base material of the display device has been proposed. For example, Patent Document 1 discloses a method of using a substrate containing a black pigment. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Korean Patent Application Publication No. 2018-0021342

[The problem to be solved by the invention] However, in the method described in Patent Document 1, there is a problem that the light shielding property is insufficient, and sufficient visibility cannot be obtained.

The present invention was invented in view of the disadvantages of the aforementioned prior art, and its object is to provide a resin composition that can obtain a black resin film with good light-shielding properties. [Means to solve the problem]

The present invention is a resin composition containing a resin having a repeating unit represented by any one of chemical formula (1) and chemical formula (2) as main components, a solvent, and a pigment.

[化1]

In the chemical formula (1) and the chemical formula (2), X represents a tetravalent tetracarboxylic acid residue having a carbon number of 2 or more. Y represents a divalent diamine residue having 2 or more carbon atoms. Among them, at least one of the X-providing tetracarboxylic acid or the Y-providing diamine has a maximum light absorption in a wavelength range of 380 nm or more and 580 nm or less. R'and R" each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbons, an alkylsilyl group having 1 to 10 carbons, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

Furthermore, another aspect of the present invention is a black resin film, which is a resin film containing a resin mainly composed of a repeating unit represented by the chemical formula (1) and a pigment, and the resin film When the thickness is 5 μm, the light transmittance in the range of 380 nm or more and 780 nm or less has a wavelength of 5% or less.

Moreover, another aspect of the present invention is a laminate in which the black resin film and a resin film containing a resin mainly composed of a repeating unit represented by the chemical formula (3) are laminated.

[化2]

In the chemical formula (3), U is at least one selected from the structure represented by the chemical formula (5) to the chemical formula (7). V represents a divalent diamine residue having 2 or more carbon atoms.

[化3]

Furthermore, another aspect of the present invention is a display device including the black resin film or the laminate. [Effects of the invention]

By using the resin composition of the present invention, a black resin film with good light-shielding properties can be obtained.

The black resin film of the present invention can be preferably used as a substrate for an organic light-emitting display device, a substrate for a liquid crystal display, a substrate for a micro light emitting diode (Light Emitting Diode, LED) display, a substrate for a flexible color filter, Substrates for display devices, such as flexible electronic paper substrates and flexible touch panel substrates. In particular, it is preferably used as a substrate for an organic light emitting display device. By using the black resin film of the present invention as a substrate, a display device with high contrast and small color shift can be obtained.

Hereinafter, preferred embodiments of the resin composition, black resin film, laminate, and organic light emitting display device of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various changes depending on the purpose or application.

＜Resin composition＞ The resin composition of the present invention is a resin composition containing a resin having a repeating unit represented by any one of the chemical formula (1) and the chemical formula (2) as a main component, and a pigment. Here, the main component means that the repeating unit represented by any one of the chemical formula (1) and the chemical formula (2) accounts for 50 mol% or more of all the repeating units of the resin, preferably 80 mol%, more preferably 90 mol%.

[化4]

In the chemical formula (1) and the chemical formula (2), X represents a tetravalent tetracarboxylic acid residue having a carbon number of 2 or more. Y represents a divalent diamine residue having 2 or more carbon atoms. Among them, at least one of the X-providing tetracarboxylic acid or the Y-providing diamine has a maximum light absorption in a wavelength range of 380 nm or more and 580 nm or less. In addition, the tetracarboxylic acid mentioned here also includes tetracarboxylic dianhydride. R'and R" each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbons, an alkylsilyl group having 1 to 10 carbons, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

(Resin) The chemical formula (1) represents the chemical structure of polyimide. The chemical formula (2) represents the chemical structure of polyamide acid. Polyamide acid is obtained by reacting a tetracarboxylic acid and a diamine compound as described later. Furthermore, polyimide can be converted into polyimide by heat treatment or chemical treatment.

In the chemical formula (1) and chemical formula (2), X is preferably a tetravalent organic group with a carbon number of 2 to 80, which has a hydrogen atom and a carbon atom as essential components, and more preferably a tetravalent organic group with a carbon number of 2 to 80 Hydrocarbyl. X may include one or more atoms selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen. The number of each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen in X is independently preferably 20 or less, and more preferably 10 or less.

When the resin film obtained by using the resin composition of the present invention is used as a substrate for an organic light-emitting display device, since heat resistance and insulation are required, as X, an aromatic tetracarboxylic acid can be preferably used Residues.

The tetracarboxylic acid that provides X is not particularly limited, and known ones can be used. Examples include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2' ,3,3'-Biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3 ,3',4,4'-Diphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-p-diphenyltetracarboxylic dianhydride Acid dianhydride, 3,3',4,4'-m-triphenyltetracarboxylic dianhydride, etc.

From the viewpoint of reactivity, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride or homo Pyromellitic dianhydride. One or more of these aromatic tetracarboxylic dianhydrides can be used.

In the chemical formula (1) and chemical formula (2), Y is preferably a divalent organic group with a hydrogen atom and a carbon atom as essential components and a carbon number of 2 to 80, more preferably a divalent organic group with a carbon number of 2 to 80 Hydrocarbyl. Y may include more than one atom selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen. The number of each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen in Y is each independently preferably 20 or less, more preferably 10 or less.

As Y, aromatic diamine residues can be preferably used. There are no particular restrictions on the diamine providing Y, and known ones can be used. As an example, a group selected from p-phenylenediamine, m-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamine can be used Diphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminobenzene) One or more of oxy)benzene, 2,2-bis(trifluoromethyl)benzidine, 9,9'-bis(4-aminophenyl)fluorene, perylene diamine, and the like.

From the viewpoint of reactivity, it is more preferable that at least a part of the diamine component is selected from p-phenylenediamine, m-phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 9,9'- One or more of bis(4-aminophenyl)fluorene and perylene diamine.

Among them, at least one of X-providing tetracarboxylic acid and Y-providing diamine is a compound having a maximum absorption in a wavelength range of 380 nm or more and 580 nm or less. This allows the resin with high heat resistance to efficiently absorb light having a wavelength of 380 nm or more and 580 nm or less.

The compound having a maximum absorption in a wavelength range of 380 nm or more and 580 nm or less is not particularly limited. From the viewpoint of light resistance, heat resistance, and chemical resistance, for example, those containing any of the following chemical structures can be cited.

[化5]

Here, R ¹ to R ³⁰ may be the same or different, and are selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl, cycloalkyl, heterocyclyl, alkenyl, and cycloalkene Group, alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl sulfide group, aryl group, heteroaryl group, cyano group, carbonyl group, carboxyl group, oxycarbonyl group, aminomethanyl group, amino group, alkyl group At least one of an amine group, a nitro group, and a silyl group may form a ring by bonding adjacent substituents to each other.

From the viewpoint of further improving insulation, it is preferable that at least one of X and Y includes a perylene structure.

The tetracarboxylic acid and diamine having a maximum absorption in the range of 380 nm or more and 580 nm or less are not particularly limited, and specific examples include the following.

[化6]

[化7]

[化8]

Here, R ¹⁷ to R ^{20 are} as described above.

By containing residues of tetracarboxylic acid or diamine having maximum light absorption in the wavelength range of 380 nm or more and 580 nm or less, the repeating unit represented by either of chemical formula (1) and chemical formula (2) is The resin of the main component preferably has a maximum light absorption in the range of a wavelength of 380 nm or more and 580 nm or less.

The resin composition preferably further contains a resin having a repeating unit represented by any one of the chemical formula (3) and the chemical formula (4) as a main component. Here, the main component means that the repeating unit represented by the chemical formula (3) or the chemical formula (4) accounts for 50 mol% or more of all the repeating units of the resin, preferably 80 mol%, and more preferably 90 mol%.

[化9]

In the chemical formula (3) and the chemical formula (4), U is at least one structure selected from the structures represented by the chemical formula (5) to the chemical formula (7). V represents a divalent diamine residue having 2 or more carbon atoms. As the diamine providing V, those exemplified as the diamine providing Y can be preferably used. R'and R" each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbons, an alkylsilyl group having 1 to 10 carbons, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

[化10]

If the resin composition contains a resin whose main component is a repeating unit represented by any one of the chemical formula (3) and the chemical formula (4), the heat resistance and mechanical properties of the obtained resin film become good. A resin containing a resin whose main component is a repeating unit represented by any one of the chemical formula (3) and the chemical formula (4) is preferably relative to the resin represented by either one of the chemical formula (1) and the chemical formula (2) The repeating unit of is 100 parts by mass of the resin as the main component, and contains 10 parts by mass to 1000 parts by mass. Furthermore, a resin having a repeating unit represented by any one of chemical formula (3) and chemical formula (4) as a main component may be repeated with a resin represented by any one of chemical formula (1) and chemical formula (2) The resin of the unit as the main component is copolymerized and used as the resin of the present invention. When the resin composition is further processed into a resin film for use, as described later, a resin containing a repeating unit represented by either of the chemical formula (3) and the chemical formula (4) as the main component can also be prepared separately A resin composition and a resin composition containing a resin whose main component is a repeating unit represented by either of the chemical formula (1) and the chemical formula (2), and a resin film obtained from each resin composition is laminated.

(Hardening accelerator) The resin composition of the present invention preferably contains a hardening accelerator. The hardening accelerator is not particularly limited, and examples thereof include acid anhydride hardeners, amine hardeners, and phenol hardeners. The role of the hardening accelerator is to perform the imidization of the polyimide precursor at 200°C or lower. By containing a curing accelerator in the resin composition, part or all of the resin contained in the resin composition can be imidized. Moreover, by containing a curing accelerator in the step of forming a resin film using a resin composition, the resin film is formed by heating and curing at a low temperature. Therefore, the sublimation of the pigment can be prevented and a uniform light-shielding polymer can be obtained. Imide film. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.

Examples of acid anhydride hardeners include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, maleic anhydride, and partial benzene. Tricarboxylic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc.

Examples of the amine curing agent include imidazole curing accelerators, tertiary amine curing accelerators, and the like. Among them, in terms of easy control of the reaction system for adjusting the curing rate, the physical properties of the cured product, etc., an imidazole-based curing accelerator is preferred. Examples of imidazole-based hardening accelerators include 2-phenyl-4-methyl-5-hydroxymethylimidazole, 6-[2-(2-ethyl-4-methyl-1H-imidazol-1-yl )Ethyl)-1,3,5-triazine-2,4-diamine, 1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 6-2- (2-Methyl-1H-imidazol-1-yl)-1,3,5-triazine-2,4-diamine, 1-(2-cyanoethyl)-2-undecylimidazole, etc. .

The hardening accelerator is preferably contained at 1 part by mass or more with respect to 100 parts by mass of the resin, and is preferably contained at 20 parts by mass or less. Here, "with respect to 100 parts by mass of the resin" means combining a resin having a repeating unit represented by any one of the chemical formula (1) and the chemical formula (2) as the main component and the resin having the chemical formula (3) and the chemical formula (4) The total content of all the resins whose repeating units represented by any of them are the main component is set to 100 parts by mass, and the content is calculated. The following is the same.

(Sensitizer) The resin composition of the present invention can form a photosensitive resin composition by containing a photosensitive agent. A resin composition containing a photoacid generator as a photosensitizer becomes a positive photosensitive resin composition. In the case of using a positive photosensitive resin composition, acid is generated in the light-irradiated part to increase the solubility of the light-irradiated part with respect to the alkaline aqueous solution, and a positive relief pattern in which the light-irradiated part is dissolved can be obtained. . On the other hand, a resin composition containing a photopolymerization initiator as a photosensitive agent becomes a negative photosensitive resin composition. In the case of using a negative photosensitive resin composition, the light-irradiated portion undergoes polymerization of unsaturated bonds, so that the solubility of the light-irradiated portion with respect to the alkaline aqueous solution is reduced, and a negative concave-convex pattern in which the light-irradiated portion is insoluble can be obtained.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, quinonediazide compounds can be preferably used.

Examples of the quinone diazide compound include: quinone diazide sulfonic acid ester-bonded to a polyhydroxy compound, quinone diazide sulfonic acid ester-bonded to a polyamine compound, quinone Diazide sulfonic acid is formed by bonding an ester bond and/or a sulfonamide to a polyhydroxypolyamine compound. Preferably, more than 50 mol% of the total functional groups of the polyhydroxy compounds or polyamine compounds are substituted with quinonediazide.

In the present invention, as the quinonediazide compound, any one having a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group can be preferably used. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazidesulfonyl ester compound extends to the g-ray region of the mercury lamp, and is suitable for g-ray exposure. It is preferable to select any one of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength of exposure. Moreover, it may contain both 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound, and it may also contain 4-naphthoquinone diazide sulfonyl ester compound in the same molecule. Naphthoquinone diazide sulfonyl ester compound of 5-naphthoquinone diazide sulfonyl group.

As the photopolymerization initiator, for example, benzophenone, Michelone, 4,4-bis(diethylamino)benzophenone, 3,3,4,4-tetra(third Benzophenones such as butylperoxycarbonyl) benzophenone; 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis (Diethylaminobenzylidene)-N-ethyl-4-piperidone and other benzylidene groups; 7-diethylamino-3-nonylcoumarin, 4,6-dimethyl -3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylmethylbenzimidazole) Base) coumarin, 3-(2-benzothiazolyl)-7-diethylaminocoumarin and other coumarins; 2-tert-butylanthraquinone, 2-ethylanthraquinone, 1 ,2-Benzoanthraquinone and other anthraquinones; benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; ethylene glycol bis(3-mercaptopropionate), 2-mercaptobenzothiazole, 2-mercapto Mercapto groups such as benzoxazole and 2-mercaptobenzimidazole; N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine Glycine such as amino acid and N-(4-cyanophenyl)glycine; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl- 1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1, 2-Propanedione-2-(o-benzoyl) oxime, bis(α-isonitrosopropiophenone oxime) isophthalic acid, 1,2-octanedione-1-[4-(benzene Sulfuryl)phenyl]-2-(ortho-benzyl oxime), IRGACURE (registered trademark, same below) OXE01, IRGACURE OXE02 (above, trade name, BASF) (Stock) Manufacturing), N-1818, N-1919, NCI-831 (above, trade name, manufactured by ADEKA (Stock)) and other oxime esters; 2-benzyl-2-dimethylamine -1-(4-morpholinylphenyl)-butane-1-2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one etc.α- Amino alkyl phenones; 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc. Among these, oxime esters are preferable in terms of enabling pattern processing with higher sensitivity. The photopolymerization initiator can also be used in combination of two or more types.

The content of the photosensitizer is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more. Moreover, the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. By setting the content of the photosensitizer to 0.5 parts by mass or more, the film thinning of the exposed portion during development can be reduced. By setting the content of the photosensitizer to 50 parts by mass or less, the heat resistance of the cured film can be improved. If necessary, a sensitizer may be further contained.

(pigment) The pigment used in the present invention is not particularly limited, and a pigment selected from black pigments, blue pigments, and purple pigments can be cited. Among these pigments, one kind may be used alone, or two or more kinds may be used in combination.

As black pigments, carbon black, perylene black, aniline black, and the like can be cited.

Examples of blue pigments include CI Pigment Blue 1, CI Pigment Blue 1:2, CI Pigment Blue 9, CI Pigment Blue 14, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15: 2, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 17, CI Pigment Blue 19, CI Pigment Blue 25, CI Pigment Blue 27, CI Pigment Blue 28, CI Pigment Blue 29, CI Pigment Blue 33, CI Pigment Blue 35, CI Pigment Blue 36, CI Pigment Blue 56, CI Pigment Blue 56:1, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 61:1, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 66, CI Pigment Blue 67, CI Pigment Blue 68, CI Pigment Blue 71, CI Pigment Blue 72, CI Pigment Blue 73, CI Pigment Blue 74, CI Pigment Blue 75, CI Pigment Blue 76, CI Pigment Blue 78 or CI Pigment Blue 79. From the viewpoint of compatibility of heat resistance and light absorption in the range of 580 nm to 780 nm, a phthalocyanine derivative can be preferably used. As specific examples, preferred are CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, or CI Pigment Blue 60, more preferably CI Pigment Blue 15:6.

Examples of purple pigments include CI Pigment Violet 1, CI Pigment Violet 1:1, CI Pigment Violet 2, CI Pigment Violet 2:2, CI Pigment Violet 3, CI Pigment Violet 3:1, CI Pigment Violet 3:3, CI Pigment Violet 5, CI Pigment Violet 5:1, CI Pigment Violet 14, CI Pigment Violet 15, CI Pigment Violet 16, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 25, CI Pigment Violet 27, CI Pigment Violet 29. CI Pigment Violet 31, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 39, CI Pigment Violet 42, CI Pigment Violet 44, CI Pigment Violet 47, CI Pigment Violet 49 or CI Pigment Violet 50. Preferably it is C.I. Pigment Violet 19 or C.I. Pigment Violet 23, more preferably C.I. Pigment Violet 23.

The pigment used in the present invention preferably has a maximum light absorption in a wavelength range of 580 nm or more and 780 nm or less. By having the maximum light absorption in this range, the resin composition obtained by mixing with the resin containing the repeating unit represented by either of the chemical formula (1) and the chemical formula (2) as the main component can be more effective black.

In addition, pigments that have absorption in the wavelength range of 380 nm or more and less than 580 nm lack heat resistance, and may decompose or sublime above 350° C., which may degrade the performance of the organic light-emitting display device. From the said viewpoint, it is also preferable that it is a pigment which has the maximum light absorption in the wavelength range of 580 nm or more and 780 nm or less.

The phthalocyanine derivative has a large absorption coefficient, so it is better to control the light absorption in the wavelength range of 580 nm to 780 nm by adding a smaller amount.

The pigment preferably contains 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin.

(Photopolymerizable compound) The negative photosensitive resin composition may contain a photopolymerizable compound. The photopolymerizable compound has an unsaturated bond in the molecule, and is polymerized by the action of the photopolymerization initiator contained in the negative photosensitive resin composition. This reduces the solubility of the light-irradiated portion with respect to the alkaline aqueous solution, and can obtain a negative concavo-convex pattern in which the light-irradiated portion is insoluble. Examples of the unsaturated bond include unsaturated double bonds such as vinyl, allyl, acryloyl, and methacryloyl, and unsaturated triple bonds such as propargyl. Among these, an acryloyl group or a methacryloyl group is preferable in terms of polymerizability.

Examples of polyfunctional monomers containing acrylic or methacrylic groups that can be preferably used as photopolymerizable compounds include: bisphenol A diglycidyl ether (meth)acrylate, poly(methyl) )Acrylic urethane, modified bisphenol A epoxy (meth)acrylate, 1,6-hexanediol (meth)acrylate adipic acid, phthalic anhydride propylene oxide (methyl) )Acrylate, diethylene glycol trimellitate (meth)acrylate, rosin modified epoxy di(meth)acrylate, alkyd modified (meth)acrylate, fluorene diacrylate oligomer Compounds, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate Base) acrylate, pentaerythritol tri(meth)acrylate, triacryl formal (triacryl formal), pentaerythritol tetra(meth)acrylate or its acid modification, dipentaerythritol hexa(meth)acrylate or its Acid-modified substance, dipentaerythritol penta(meth)acrylate and its acid-modified substance, 2,2-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]propane, double [4-(3-propenyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl] chrysene, bis[4 -(3-propenyloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]cyclohexane Alkyl, 9,9-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-propenyloxy) -2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-chloro-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]fluorene, bisphenoxyethanol Fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, or biscresol fluorene dimethacrylate.

By appropriately selecting and combining oligomers or monofunctional monomers on the basis of these polyfunctional monomers, it is possible to adjust the characteristics such as sensitivity and processability of the obtained negative colored photosensitive resin composition. Among them, in order to increase sensitivity, a compound having 3 or more functional groups is preferred, a compound having 5 or more functional groups is more preferred, and dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylic acid is more preferred Esters or these acid modifiers.

Moreover, in order to improve the developability and processability, it is also preferable to use an unsaturated compound obtained by reacting a reaction product of an epoxy compound with two glycidyl ether groups and methacrylic acid with a polybasic acid carboxylic acid or its anhydride. Base soluble monomer. Furthermore, in order to control the pattern shape at the time of development, it is preferable to use together the (meth)acrylate which has a some aromatic ring in a molecule|numerator, and has a fluorene ring with high water repellency.

With respect to 100 parts by mass of the resin, the content of the photopolymerizable compound is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. The content is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less. By setting the content of the photopolymerizable compound to 10 parts by mass or more, the film thinning of the exposed portion during development can be reduced. By setting the content of the photopolymerizable compound to 150 parts by mass or less, the heat resistance of the cured film obtained can be improved.

(Interface active agent) The resin composition of the present invention may contain a surfactant for the purpose of improving the coating properties and the uniformity of the surface of the film obtained, or for the purpose of improving the dispersibility of the pigment. Examples of surfactants include: "Fluorad" (registered trademark) manufactured by Sumitomo 3M (Stock), "Megafac" (registered trademark) manufactured by DIC (Stock), Fluorine-based surfactants such as "Surflon" (registered trademark) manufactured by Asahi Glass Co., Ltd.; KP341 manufactured by Shin-Etsu Chemical Co., Ltd., DBE manufactured by Chisso Co., Ltd., Kyoeisha "Polyflow" (registered trademark), "Glanol" (registered trademark) manufactured by Chemical Co., Ltd., BYK manufactured by BYK-Chemie (Stock), etc. Alkane surfactants; acrylic polymer surfactants such as Polyflow manufactured by Kyoeisha Chemical Co., Ltd., etc. The content of the surfactant is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin.

(Adhesion improver) The resin composition of the present invention may contain an adhesion improving agent for the purpose of improving adhesion to inorganic substances such as glass substrates and silicon wafers. As the adhesion improving agent, a silane coupling agent, a titanium coupling agent, etc. can be used. The content of the adhesion improving agent is preferably 0.01 parts by mass or more and 10 parts by mass relative to 100 parts by mass of the resin.

(Thermal crosslinking agent) The resin composition of the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule. As a thermally reactive functional group, an alkoxymethyl group, a hydroxymethyl group, an epoxy group, an oxetanyl group etc. are mentioned, for example. Two or more of these may be contained. By including a thermal crosslinking agent, other added components are crosslinked, and the heat resistance, chemical resistance and hardness of the cured film can be improved. Moreover, the amount of outgassing from the cured film can be reduced, and the reliability of the organic light emitting display device can be improved.

(Solvent) The resin composition of the present invention may also contain a solvent. As the solvent, an amide-based polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide can be preferably used.

The preferred content of the solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and more preferably 100 parts by mass of the resin mainly composed of the repeating unit represented by the chemical formula (1) or (2) It is 2000 parts by mass or less, more preferably 1500 parts by mass or less. If it is a range that satisfies this condition, the viscosity becomes suitable for coating, and the film thickness after coating can be easily adjusted. Furthermore, as described later, by reacting tetracarboxylic acid and diamine in a solvent to produce a resin containing a repeating unit represented by the chemical formula (1) or (2) as the main component, it can be used as a resin without separating the resin. Composition.

(Dispersion method) The resin composition of the present invention is produced by a method of directly dispersing the pigment in a resin solution using a dispersing machine, or dispersing the pigment in water or an organic solvent by using a dispersing machine to prepare a pigment dispersion, and then The method of mixing the pigment dispersion with the resin solution, etc. The pigment dispersion method is not particularly limited, and various methods such as a bead mill, a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill can be used. In terms of dispersion efficiency and microdispersion, a bead mill is preferred. As the bead mill, a double cone ball mill (Co-ball mill), basket mill (basket mill), pin mill, or DYNO-MILL (DYNO-MILL) can be used. As the beads of the bead mill, it is preferable to use titania beads, zirconia beads, or zircon beads.

The solid content concentration of the resin composition of the present invention is preferably 5 mass% or more and 40 mass% or less, and more preferably 10 mass% or more and 25 mass% or less from the viewpoints of coating properties and drying properties. . In addition, the solid content in the present invention is a component other than the solvent in the resin composition.

(Black resin film) The black resin film of the present invention is a resin film containing a resin mainly composed of a repeating unit represented by the chemical formula (1) and a pigment. When the film thickness is set to 5 μm, the wavelength ranges from 380 nm to 780 nm. The light transmittance is 5% or less.

[化11]

The detailed description of the resin having the repeating unit represented by the chemical formula (1) as the main component and the pigment is the same as the description of the resin composition.

In the present invention, black means that the light transmittance in the range of 380 nm or more and 780 nm or less when the thickness of the resin film is 5 μm is 5% or less. In addition, when the film thickness of the resin film is not 5 μm, the transmittance when the film thickness is set to 5 μm can be calculated from the film thickness and transmittance of the actual resin film by the following formula. T _C =(T _R /100)^(5/F _R )×100 where T _C is the transmittance [%] when the film thickness is 5 μm, and F _R is the actual resin film thickness [μm] , _TR is the actual transmittance of the resin film [%].

From the viewpoint of further improving the performance of the organic light-emitting display device, the breakdown voltage of the black resin film of the present invention is preferably 2.70 MV/cm or more.

The black resin film of the present invention preferably has heat resistance. As such a black resin film, the 1% weight loss temperature is preferably 350°C or higher, more preferably 380°C or higher.

＜Laminated body＞ The laminate of the present invention is a laminate in which the black resin film and a resin film containing a resin mainly composed of a repeating unit represented by the chemical formula (3) are laminated. The black resin film has high light-shielding properties, and a resin film containing a resin whose main component is the repeating unit represented by the chemical formula (3) has good mechanical properties. When these resin films are laminated, it is easier to improve both light-shielding properties and mechanical properties than a film obtained by mixing these resins.

＜Display device＞ The black resin film of the present invention and the laminate of the present invention are preferably used as a substrate for an organic light-emitting display device, a substrate for a liquid crystal display, a substrate for a micro LED display, a substrate for a flexible color filter, and a flexible electronic paper Substrates for display devices such as substrates and flexible touch panel substrates. In particular, it is preferably used as a substrate for an organic light emitting display device.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of an organic light-emitting display device. The organic light-emitting display device has a black resin film 2 on a glass substrate 1, and includes a first electrode 3 corresponding to a unit of each light-emitting color, light-emitting layers 5R, 5G and 5B of different light-emitting colors, and a pair of The insulating layer 4 and the second electrode 6 separated by the light-emitting layer. By peeling the glass substrate 1 from the black resin film 2 in the above configuration, a flexible organic light-emitting display device can also be produced.

＜Method of manufacturing resin composition＞ The resin composition of the present invention (hereinafter, referred to as the resin composition of the present invention) can be obtained by dissolving the resin, and optionally the pigment, curing accelerator, photosensitizer, thermal crosslinking agent, adhesion improver, and surfactant, etc. in a solvent For varnish). The dissolution method may include stirring or heating. Furthermore, the order of dissolving each component is not particularly limited. For example, there is a method of sequentially dissolving from a compound with low solubility. In addition, with regard to components that are likely to generate bubbles during stirring and dissolution, such as surfactants, it is possible to prevent poor dissolution of other components caused by bubbles by dissolving other components and adding them last.

In addition, the resin can be polymerized by a known method. For example, polyamide acid can be obtained by polymerizing tetracarboxylic acid and diamine in a reaction solvent. The polyamide acid may be a salt formed with a carboxyl group and an alkali metal ion, ammonium ion or imidazolium ion, or may be esterified by a hydrocarbon group having 1 to 10 carbons or an alkylsilyl group having 1 to 10 carbons. On the other hand, polyamide is obtained by imidizing polyamide by the method described later.

As the reaction solvent, an amide-based polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide can be preferably used.

The amount of the reaction solvent used is preferably adjusted so that the total amount of the tetracarboxylic acid and the diamine compound becomes 0.1% by mass to 50% by mass of the entire reaction solution. Furthermore, the reaction temperature is preferably -20°C to 200°C, more preferably 0°C to 160°C. Furthermore, the reaction time is preferably from 0.1 hour to 24 hours, more preferably from 0.5 hour to 12 hours. Furthermore, if the mole number of the diamine compound used in the reaction is equal to the mole number of the tetracarboxylic acid, it is easy to obtain a resin film with high mechanical properties, which is preferable.

The obtained polyamide acid solution can also be used directly as the resin composition of the present invention without separating the resin. In this case, by using the same solvent as the resin composition used as the reaction solvent, or adding the solvent after the completion of the reaction, the target resin composition can be obtained without separating the resin.

Furthermore, regarding the obtained polyamide, a part or all of the repeating units of the polyamide may be further imidized. In this case, the polyamic acid solution obtained by the polymerization of polyamic acid may be directly used for the imidization reaction, or it may be used for the imidization reaction after the polyamic acid is separated.

As a method of imidizing the polyamide, a method of heating the polyamide or a method of adding a dehydrating agent to the polyamide and optionally heating is preferred. In the case of the latter method, a step of removing the reaction product of the dehydrating agent or the imidization catalyst, etc. is required, so the former method is more preferable.

<Method of manufacturing black resin film> An example of the manufacturing method of the black resin film of this invention is demonstrated. In addition, the manufacturing method of a black resin film is not limited to the following content.

First, the varnish obtained as described above is applied to the support. Examples of the support include wafer substrates such as silicon and gallium arsenide; glass substrates such as sapphire glass, soda lime glass, and alkali-free glass; metal substrates or metal foils such as stainless steel and copper; and ceramic substrates. Among them, from the viewpoint of surface smoothness and dimensional stability during heating, an alkali-free glass substrate is preferred.

As the coating method of the varnish, spin coating method, slit coating method, dip coating method, spray coating method, printing method, etc. are mentioned. These can be used in combination. When the resin film is used as a substrate of an organic light-emitting display device, it needs to be coated on a large-sized support, so in particular, a slit coating method can be preferably used.

After coating, the coating film of the varnish is usually dried. As a drying method, reduced-pressure drying, heat drying, or a combination of these methods can be used. As a method of drying under reduced pressure, for example, it is performed by placing a support on which a coating film is formed in a vacuum chamber, and reducing the pressure in the vacuum chamber. In addition, heat drying is performed using a hot plate, oven, infrared rays, and the like. In the case of using a hot plate, the coating film is directly held on the plate, or the coating film is held on a jig such as a proximity pin (proximity pin) provided on the plate and heated and dried.

Finally, heat treatment is performed in the range of 180° C. or higher and 500° C. or lower, and the coating film is sintered, thereby producing a black resin film.

In order to improve the adhesion between the support and the black resin film, it is effective to make the temperature during the heat treatment higher than the Tg of the resin. Therefore, the heat treatment temperature in the production step of the black resin film is preferably 380°C or higher. By making the temperature during the heat treatment higher than the Tg of the resin, as the internal stress decreases, the adhesiveness can be improved.

When the black resin film obtained through the above steps is used as a substrate of an organic light-emitting display device, it is usually used in the next step without peeling from the support. However, it is also possible to peel the resin film from the support body using the peeling method mentioned later, and proceed to the next step.

<Method of manufacturing display device> With regard to the manufacturing method of the display device of the present invention, the case of an organic light-emitting display device will be described as an example.

Preferably, an inorganic film is provided on the black resin film. This prevents moisture or oxygen from penetrating through the black resin film from the outside of the substrate and causing deterioration of the pixel driving element or the light emitting element. Examples of the inorganic film include silicate (SiOx), silicon nitride (SiNy), and silicate nitride (SiOxNy). These can be used in a single layer or stacked in multiple layers. In addition, these inorganic films may be alternately laminated and used with organic films such as polyvinyl alcohol. Regarding the film forming method of these inorganic films, it is preferable to use a vapor deposition method such as chemical vapor deposition (Chemical Vapor Deposition, CVD).

By further forming a resin film or further forming an inorganic film on the inorganic film as necessary, a substrate of an organic light-emitting display device including a multilayer inorganic film or a resin film can be manufactured. In addition, from the viewpoint of simplification of the manufacturing process, the resin composition used in the production of each resin film is preferably the same resin composition.

The respective constituent elements of the display device are formed on the obtained resin film (in the case where there is an inorganic film or the like thereon, further on). As the constituent element, for example, in the case of an organic EL display, TFT as an image driving element, a first electrode, an organic EL light-emitting element (light-emitting layer), a second electrode, a sealing film, etc. can be cited. These are sequentially formed to form an image display element. In the case of a color filter substrate, after forming a black matrix as necessary, colored pixels such as red pixels, green pixels, and blue pixels are formed. In the case of a substrate for a touch panel, a wiring layer and an insulating layer are formed.

Finally, at the interface between the support and the black resin film, both are peeled off, thereby removing the support. As a method of peeling, a laser peeling, a mechanical peeling method, a method of etching a support, etc. are mentioned. In the case of laser peeling, a support such as a glass substrate is irradiated with the laser from the side opposite to the side where the black resin film and the element are formed. Thereby, peeling can be performed without damaging the element.

As the laser light, laser light in the wavelength range from ultraviolet light to infrared light can be used, but ultraviolet light is particularly preferable. More preferably, an excimer laser of 308 nm is suitable. The peeling energy is preferably 250 mJ/cm ² or less, more preferably 200 mJ/cm ² or less. Example

Hereinafter, the present invention will be described with reference to Examples and the like. First, the evaluation method will be explained.

＜Filtration of varnish＞ A PTFE filter (filter pore size 10 μm) made by ADVANTEC was used to filter the varnish. The case where the filter can be filtered is regarded as the filterability "good", and the case where the filtering cannot be performed is regarded as the filterability "bad".

＜Measurement of film thickness＞ The thickness of the resin film in each of the Examples and Comparative Examples was measured using a surface roughness measuring machine (SURFCOM 1400D; manufactured by Tokyo Precision Co., Ltd.).

＜Insulation breakdown voltage＞ Use a spin coater (1H-DX2 manufactured by Mikasa Co., Ltd.) to spin coat varnish on a 5 cm×5 cm aluminum substrate, and then use a heating plate (manufactured by ASONE Co., Ltd.) HPD-3000BZN) dried at 110°C for 10 minutes. Then, using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), in a nitrogen atmosphere (oxygen concentration below 20 ppm), the heating rate was 4℃/min from 50℃ Warm up to 400°C. It was heated at 400°C for 30 minutes to form a polyimide film with a thickness of 10 μm on the aluminum substrate.

The insulation breakdown voltage of the polyimide film was measured using an insulation resistance tester (TOS9202 manufactured by Kikusui Electronics Co., Ltd.).

<Evaluation of shading> Use a spin coater (1H-DX2 manufactured by Mikasa Co., Ltd.) to spin coat varnish on a 10 cm×10 cm alkali-free glass substrate, and then use a hot plate (ASONE Co., Ltd.) HPD-3000BZN manufactured by the company) was dried at 110°C for 10 minutes. Then, using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), in a nitrogen atmosphere (oxygen concentration below 20 ppm), the heating rate was 4℃/min from 50℃ Warm up to 400°C. It was heated at 400°C for 30 minutes to form a polyimide film with a thickness of 5 μm on the glass substrate.

Using a spectrophotometer (U-4100; manufactured by Hitachi High-Technologies Corporation), measure the transmittance of the polyimide film at a wavelength of 380 nm or more and 780 nm or less. If both the maximum transmittance in the range of wavelength 380 nm or more and less than 580 nm and the maximum transmittance in the wavelength range of 580 nm or more and 780 nm or less are both 5% or less, it is set as A evaluation, if at least one If it exceeds 5% and is 10% or less, it is evaluated as B, and if both exceed 10%, it is evaluated as C.

＜Dark brightness evaluation of organic light emitting display device＞ FIG. 2 shows a schematic diagram of the dark brightness evaluation environment of the organic light emitting display device. The organic light-emitting display device 7 obtained by each of the examples and comparative examples was placed 2.4 m directly below the fluorescent lamp 8 in an unlit state, and an illuminance of 500 lx was placed at an angle of 45 relative to the horizontal. ° Make settings. Secondly, for the spectroradiometer 9 (CS-1000; manufactured by Konica Minolta (stock)), the organic light-emitting display device 7 is used as a reflecting surface and the fluorescent lamp 8 and the spectroradiometer 9 Configure in a positive way. Using the spectroradiometer 9, the brightness of the surface 7 of the organic light emitting display device in this environment was measured, and the obtained brightness was regarded as dark brightness.

<Brightness and chromaticity evaluation of organic light emitting display devices> Under the same environment as the dark brightness evaluation (the configuration of FIG. 2), the organic light-emitting display device 7 obtained by each of the Examples and Comparative Examples was made to emit light by a DC drive of 0.625 mA, and a spectroradiometer was used 9. Measure the brightness and chromaticity of the surface of the organic light-emitting display device 7. Based on the chromaticity (x, y=0.350, 0.600) of the luminous color, the color shift is determined based on the difference between the standard and the measured value. Regarding the judgment of color shift, if x and y are both within ±0.01, it is considered as good chromaticity (A), and if both x and y are both ±0.02 or more, it is considered as poor chromaticity (C), otherwise Set the chroma to be good (B).

<Contrast evaluation of organic light emitting display devices> The ratio of the brightness to the dark brightness measured by the above method is calculated by setting the dark brightness to 1. The larger the ratio, the higher the contrast, and the better. When the contrast is 1.8 or more, it is set to "good", and when the contrast is less than 1.8, it is set to "poor".

<Reliability Evaluation of Organic Light-Emitting Display Device> For the organic light-emitting display device obtained in each of the Examples and Comparative Examples, the light-emitting surface was placed on a hot plate heated to 80°C, and the irradiation wavelength was 365 nm and the illuminance was 0.6 mW/cm ² ultraviolet (ultraviolet, UV) light. Immediately after irradiation (0 hours), after 250 hours, 500 hours, and 1000 hours, the organic light-emitting display device was driven to emit light by a 0.625 mA DC drive, and the area ratio of the light-emitting portion relative to the area of the light-emitting pixel was measured. (Pixel luminous area rate).

<Evaluation of pattern workability> The photosensitive resin composition obtained in the example was coated on an alkali-free glass substrate by a spin coating method, and prebaked on a hot plate at 110°C for 2 minutes to obtain a film thickness of 2.0 μm film. Secondly, an exposure device (mask aligner PEM-6M; manufactured by Union Optical (Stock)) is used to form a mask for line and space pattern formation at a distance of 100 μm ，Using the i-ray (wavelength 365 nm), h-ray (wavelength 405 nm) and g-ray (wavelength 436 nm) of the ultra-high pressure mercury lamp and exposure with 100 mJ/cm ² exposure. Thereafter, an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.) was used, and a 2.38% by mass tetramethylammonium hydroxide aqueous solution was used to perform spray development for 60 seconds, and then rinse with pure water for 30 seconds. In the case of a positive photosensitive resin composition, the film in the exposed part was completely dissolved by development and the film remained in the unexposed part was judged to have good pattern processability. On the other hand, in the case of a negative photosensitive resin composition, the film in the unexposed part was completely dissolved by development and the film remained in the exposed part was judged to have good pattern processability.

Hereinafter, the abbreviations of the compounds used in the examples are described. Furthermore, the maximum absorption wavelength of the compound is described in parentheses. Here, "<380 nm" means a wavelength shorter than 380 nm where the maximum absorption wavelength is the lower limit of the measurement range. PyDA: 1,6-diaminopyrene (440 nm) PMDA: Pyromellitic dianhydride (<380 nm) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (<380 nm) PTCDA: 3,4,9,10-perylenetetracarboxylic dianhydride (520 nm) ODPA: 4,4'-oxydiphthalic anhydride (<380 nm) PDA: 1,4-diaminobenzene (<380 nm) BIS-A-AF: 2,2'-bis(4-aminophenyl)hexafluoropropane (<380 nm) BIS-AT-AF: 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane (<380 nm) TFDB: 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (<380 nm) 4,4'-DDS: 4,4'-diaminodiphenyl sulfide (<380 nm) 3,3'-DDS: 3,3'-diaminodiphenyl sulfide (<380 nm) BIS-A-AP-AF: 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane (<380 nm) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone APMDS: 1,3-bis(3-aminopropyl)tetramethyldisiloxane PMA: Polymethacrylate Photopolymerization initiator A: "ADEKA ARKLS" (registered trademark) NCI-831 (made by ADEKA (stock)) Photopolymerizable compound B: "KAYARAD" (registered trademark) DPHA dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) C11Z-CN: 1-(2-cyanoethyl)-2-undecylimidazole.

Preparation Example 1 Preparation of blue pigment dispersion (BD-1) CI Pigment Blue 15:6 (EP193 manufactured by DIC, a phthalocyanine derivative with maximum light absorption in the wavelength range from 580 nm to 780 nm) 120 g, polymer dispersant (completed "BYK" 6919 manufactured by BYK-Chemie, solid content concentration 60% by mass) 86.7 g, alkali-soluble resin (daicel-allnex (stock) manufacturing, "Sycroma ( Cyclomer)" (registered trademark) P (ACA) Z250 (solid content concentration 45% by mass) 88.9 g and PMA 704.4 g were mixed to prepare a slurry. Use a tube to connect the beaker containing the slurry to the Dyno mill, use zirconia beads with a diameter of 0.5 mm as the medium, and perform a dispersion treatment for 8 hours at a circumferential speed of 14 m/s to produce a blue pigment dispersion. (BD-1).

Preparation Example 2 Preparation of carbon black dispersant (CB-1) According to the method described in the literature (Japanese Patent No. 3120476; Example 1), after synthesizing a methyl methacrylate/methacrylic acid/styrene copolymer (weight ratio 30/40/30), methacrylic acid was added 40 parts by weight of glycidyl ester. The obtained polymer was precipitated again with purified water, filtered, and dried to obtain acrylic polymer (P-1) powder with an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH/g).

400 g of carbon black (TPX1291; manufactured by CABOT), 187.5 g of propylene glycol monomethyl ether acetate 40% by mass solution of acrylic resin (P-1), and polymer dispersant (BYK21116; BYK Chemical ( BYK-Chemie) 62.5 g and 890 g of propylene glycol monoethyl ether acetate were put into the tank, and stirred with a homomixer (manufactured by special machine) for 1 hour to obtain a pre-dispersion liquid 2. After that, pre-dispersion 2 was supplied to a high-performance grinding and dispersing machine (Ultra Apex Mill) (manufactured by Kotobukiya) with a centrifugal separator filled with 70% of 0.10 mmϕ zirconia beads (manufactured by Toray) to Dispersion was performed for 2 hours at a rotation speed of 8 m/s to obtain a carbon black pigment dispersion CB-1 with a solid content concentration of 35% by mass and a pigment/resin (weight ratio)=80/20.

Preparation Example 3 Preparation of red pigment dispersion (RED-1) Pigment Red 254 (manufactured by TCI, a dihydropyrrolopyrrole derivative with maximum light absorption in the wavelength range from 380 nm to less than 580 nm) 105 g, polymer dispersant (BYK- "BYK" 6919 manufactured by Chemie, solid content concentration 60% by mass) 80.7 g, alkali-soluble resin (made by Daicel-allnex (stock), "Cyclomer" (registered) Trademark) P (ACA) Z250 (solid content concentration 45% by mass) 85.6 g and PMA 690.4 g were mixed to prepare a slurry. Use a tube to connect the beaker containing the slurry to the Deynold mill, use zirconia beads with a diameter of 0.5 mm as the medium, and perform a dispersion treatment for 8 hours at a circumferential speed of 14 m/s to produce a red pigment dispersion (RED-1 ).

Preparation Example 4 Preparation of blue pigment dispersion (BD-2) Manufactured from Pigment Blue (SIGMA-ALDRICH), indigo, with maximum light absorption in the wavelength range above 580 nm and below 780 nm) 110 g, polymer dispersant (BYK -"BYK" 6919 manufactured by Chemie, solid content concentration 60% by mass) 84.3 g, alkali-soluble resin (made by Daicel-allnex (stock), "Cyclomer" ( Registered trademark) P (ACA) Z250 (solid content concentration 45% by mass) 86.9 g and PMA 700.5 g are mixed to prepare a slurry. Use a tube to connect the beaker containing the slurry to the Deynold mill, use zirconia beads with a diameter of 0.5 mm as the medium, and perform a dispersion treatment for 8 hours at a circumferential speed of 14 m/s to produce a blue pigment dispersion (BD- 2). Preparation Example 5 Synthesis of Photoacid Generator C Under a stream of dry nitrogen, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazidesulfonyl chloride were dissolved in 450 g In 1,4-dioxane, set to room temperature. Among them, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the system did not become 35°C or higher. After dropping, it was stirred at 30°C for 2 hours. After removing the triethylamine salt by filtration, the filtrate was poured into water. The precipitated precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a photoacid generator A represented by the following chemical formula.

[化12]

Synthesis example 1: A thermometer and a stirring rod with a stirring blade are set in a 300 mL four-necked flask. In this flask, 120 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After the temperature was raised, 21.48 g (92.48 mmol) of PyDA was added while stirring, and washed with 20 g of NMP. Confirm that PyDA is dissolved, put in 28.05 g (95.33 mmol) of BPDA, and wash with 20 g of NMP. The reaction was carried out at 60°C for 3 hours to obtain a polyimide precursor solution 1.

Synthesis Example 2: A thermometer and a stirring rod with a stirring blade are set in a 500 mL four-neck flask. In this flask, 113.77 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After heating, add BIS-A-AF 3.40 g (10.17 mmol) and PTCDA 2.54 g (6.47 mmol) while stirring, and wash with 60 g of NMP. The temperature was increased to 180°C, and after 8.0 hours, the temperature was decreased to 60°C. Add 1.09 g (3.70 mmol) of BPDA, wash with 20 g of NMP, and stir for 0.5 hour. Then, 10.00 g (92.47 mmol) of PDA was put in, washed with 20 g of NMP, and stirred for 5 minutes. Furthermore, 27.21 g (92.47 mmol) of BPDA was put into it, and after washing with 20 g of NMP, it was made to react at 60 degreeC for 3 hours, and the polyimide precursor solution 2 was obtained.

Synthesis Example 3: A thermometer and a stirring rod with a stirring blade are set in a 500 mL four-neck flask. In this flask, 113.77 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After heating, add BIS-A-AF 3.40 g (10.17 mmol) and PTCDA 2.54 g (6.47 mmol) while stirring, and wash with 40 g of NMP. After stirring for 0.5 hour, 0.48 g of C11Z-CN as a hardening accelerator was added, and after washing with 20 g of NMP, the temperature was raised to 160°C. After 2.5 hours, the temperature was lowered to 60°C. Add 1.09 g (3.70 mmol) of BPDA, wash with 20 g of NMP, and stir for 0.5 hour. Then, 10.00 g (92.47 mmol) of PDA was put in, washed with 20 g of NMP, and stirred for 5 minutes. Furthermore, 27.21 g (92.47 mmol) of BPDA was put into it, and after washing with 20 g of NMP, it was made to react at 60 degreeC for 3 hours, and the polyimide precursor solution 3 was obtained.

Synthesis Example 4: In Synthesis Example 3, except that 3.69 g (10.17 mmol) of BIS-AT-AF was used instead of BIS-A-AF, synthesis was performed in the same manner, and a polyimide precursor solution 4 was obtained.

Synthesis Example 5: In Synthesis Example 3, except that TFDB 3.26 g (10.17 mmol) was used instead of BIS-A-AF, synthesis was carried out in the same manner, and polyimide precursor solution 5 was obtained.

Synthesis Example 6: In Synthesis Example 3, except that 4,4'-DDS 2.53 g (10.17 mmol) was used instead of BIS-A-AF, synthesis was performed in the same manner, and a polyimide precursor solution 6 was obtained.

Synthesis Example 7: In Synthesis Example 3, except that 2.53 g (10.17 mmol) of 3,3'-DDS was used instead of BIS-A-AF, synthesis was performed in the same manner, and a polyimide precursor solution 7 was obtained.

Synthesis Example 8: A thermometer and a stirring rod with a stirring blade are set in a 500 mL four-neck flask. In this flask, 113.77 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After heating, add BIS-A-AF 3.40 g (10.17 mmol) and PTCDA 2.54 g (6.47 mmol) while stirring, and wash with 40 g of NMP. After stirring for 0.5 hour, 0.48 g of C11Z-CN as a hardening accelerator was added, and after washing with 20 g of NMP, the temperature was raised to 160°C. After 2.5 hours, the temperature was lowered to 60°C. Add 1.09 g (3.70 mmol) of BPDA, wash with 20 g of NMP, and stir for 0.5 hour. Then, 10.00 g (92.47 mmol) of PDA was put in, washed with 20 g of NMP, and stirred for 5 minutes. Furthermore, 13.60 g (46.23 mmol) of BPDA and 10.09 g (46.23 mmol) of PMDA were added, and the mixture was washed with 20 g of NMP, and then reacted at 60° C. for 3 hours to obtain a polyimide precursor solution 8.

Synthesis Example 9: A thermometer and a stirring rod with a stirring blade are set in a 500 mL four-neck flask. In this flask, 113.77 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After heating, add BIS-A-AF 3.40 g (10.17 mmol) and PTCDA 2.54 g (6.47 mmol) while stirring, and wash with 40 g of NMP. After stirring for 0.5 hour, 0.48 g of C11Z-CN as a hardening accelerator was added, and after washing with 20 g of NMP, the temperature was raised to 160°C. After 2.5 hours, the temperature was lowered to 60°C. Add 1.15 g (3.70 mmol) of ODPA, wash with 20 g of NMP, and stir for 0.5 hour. Then, 55.90 g (92.47 mmol) of BIS-A-AP-AF was added, washed with 20 g of NMP, and stirred for 5 minutes. Furthermore, 28.68 g (92.47 mmol) of ODPA was added, and after washing with 20 g of NMP, the reaction was carried out at 60° C. for 3 hours. After that, a solution obtained by diluting 23.83 g (200.0 mmol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 2 L of water to precipitate resin. The resin was collected by filtration, washed with water 3 times, and dried using a vacuum dryer at 80°C for 24 hours. 20 g of the obtained resin was dissolved in 80 g of GBL to obtain a polyimide precursor solution 9.

Synthesis Example 10: In Synthesis Example 3, except that APMDS 2.53 g (10.17 mmol) was used instead of BIS-A-AF, the synthesis was performed in the same manner, and a polyimide precursor solution 10 was obtained.

Synthesis Example 11: A thermometer and a stirring rod with a stirring blade are set in a 300 mL four-necked flask. In this flask, 120 g of NMP was put under a stream of dry nitrogen, and the temperature was raised to 60°C. After the temperature was raised, 10.00 g (92.47 mmol) of PDA was added while stirring, and washed with 20 g of NMP. Confirm that the PDA is dissolved, put in 28.05 g (95.33 mmol) of BPDA, and wash with 20 g of NMP. The reaction was carried out at 60°C for 3 hours to obtain a polyimide precursor solution 11.

In Synthesis Example 3 to Synthesis Example 8 using a hardening accelerator, the reaction temperature of PTCDA and various diamines can be lowered to 180°C to 160°C compared to Synthesis Example 2 not using it, so that the reaction time can be reduced From 8 hours to 2.5 hours.

Example 1 to Example 12, Comparative Example 1 to Comparative Example 3 With respect to the polyimide precursor solution 1 to the polyimide precursor solution 11 obtained in Synthesis Example 1 to Synthesis Example 11, the filterability was evaluated by the method described above. The polyimide precursor solution 10 could not be filtered, and therefore the subsequent evaluation (Comparative Example 1) was not performed. To 50 g of the filtered polyimide precursor solution described in Table 1, 6 g of the pigment dispersion liquid described in Table 1 was added and mixed to obtain varnish 1 to varnish 14. However, in Comparative Example 2, no pigment dispersion liquid was added. In Example 11, 3.5 g of photoacid generator C was added and mixed. In Example 12, 0.5 g of the photopolymerization initiator A and 2.5 g of the photopolymerizable compound B were added and mixed. Using these varnishes, a resin film was formed on a glass substrate and an aluminum substrate by the method described above. With respect to the obtained resin film, the light-shielding property and the breakdown voltage were measured by the method described above. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative example 1 Comparative example 2 Comparative example 3 Varnish Varnish 1 Varnish 2 Varnish 3 Varnish 4 Varnish 5 Varnish 6 Varnish 7 Varnish 8 Varnish 9 Varnish 10 Varnish 11 Varnish 12 - Varnish 13 Varnish 14 Polyimide precursor solution Solution 1 Solution 1 Solution 2 Solution 3 Solution 4 Solution 5 Solution 6 Solution 7 Solution 8 Solution 9 Solution 9 Solution 9 Solution 10 Solution 11 Solution 11 Resin concentration 23.6% 23.6% 15.9% 15.9% 16.0% 15.8% 15.6% 15.6% 14.8% 20.0% 20.0% 20.0% 15.9% 19.2% 19.2% Resin composition [mol%] Diamine PyDA 48.5 48.5 PDA 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 48.5 48.5 BIS-A-AF 5.0 5.0 5.0 5.0 5.0 5.0 BIS-AT-AF 5.0 TFDB 5.0 4,4'-DDS 5.0 3,3'-DDS 5.0 BIS-A-AP-AF 45.0 45.0 45.0 APMDS 5.0 Acid dianhydride PTCDA 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 BPDA 50.0 50.0 46.8 46.8 46.8 46.8 46.8 46.8 24.3 46.8 50.0 50.0 ODPA 46.8 46.8 46.8 PMDA 22.5 Hardening accelerator C11Z-C [parts by weight]※ 1.1 1.1 1.1 1.1 1.2 0.5 0.5 0.5 1.1 Filterability good good good good good good good good good good good good bad good good Additive [parts by weight]※ pigment RED-1 5.5 CB-1 13.2 BD-1 9.1 9.1 9.0 9.1 9.2 9.2 9.7 7.2 7.2 7.2 BD-2 7.0 Photopolymerization initiator A 5.0 Photo acid generator C 35 Photopolymerizable compound B 25 Evaluation results Shading Transmittance of wavelength above 380 nm and less than 580 nm ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% - >5% >5% Transmittance with wavelength above 580 nm and below 780 nm >5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% ≦5% - >5% >5% Evaluation results B A A A A A A A A A A A - C C Insulation breakdown voltage (MV/cm) 2.61 0.05 3.22 3.25 2.92 3.11 2.72 2.79 3.11 3.09 2.92 2.78 - 5.41 4.62 ※: The resin is set to 100 parts by weight.

Examples 1 to 12 have good filterability. The light-shielding properties of Examples 2 to 12 are A evaluation. The dielectric breakdown voltage of Examples 3 to 12 was 2.70 MV/cm or more.

As described above, the black resin film produced using the resin composition of the present invention has good light-shielding properties. Furthermore, as a preferable aspect, Examples 3 to 12 using the blue pigment containing a phthalocyanine derivative have a high dielectric breakdown voltage.

＜Production of organic EL devices＞ Example 101 to Example 107, Comparative Example 101 As an organic light-emitting display device, an organic EL element was produced and evaluated by the following process.

Using a spin coater (1H-DX2 manufactured by Mikasa Co., Ltd.), Example 2, Example 4 to Example 9 and comparison were respectively spin-coated on a 38 mm×46 mm alkali-free glass substrate 1 The varnish 2, varnish 4 to varnish 9, and varnish 13 obtained in Example 2 were then dried at 110° C. for 10 minutes using a hot plate (HPD-3000BZN manufactured by ASONE Co., Ltd.). Then, using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from 50°C at a heating rate of 4°C/min under a nitrogen atmosphere (oxygen concentration below 20 ppm) To 400°C. By heating at 400° C. for 30 minutes, a polyimide film (black resin film) 2 having a film thickness of 10 μm was formed on the glass substrate 1.

On the obtained polyimide film, a gas barrier film including a stack of SiO ₂ film and Si ₃ N ₄ film is formed by CVD. Then, a TFT is formed thereon, and an insulating film containing Si ₃ N ₄ is further formed so as to cover the TFT. Next, a contact hole is formed in the insulating film on the upper portion of the TFT, and a wiring connected to the TFT is formed through the contact hole.

Furthermore, a flattening film is formed on top of it in order to flatten the unevenness due to the formation of wiring. Next, the wiring is connected to the obtained planarization film to form an indium tin oxide (Indium Tin Oxide, ITO) film. After that, a resist is coated on the ITO film. After the resist is pre-baked, exposure is performed through a mask of a desired pattern, and development is performed, thereby obtaining a desired resist pattern. Using the obtained resist pattern as a mask, pattern processing of the ITO film was performed by wet etching using an ITO etchant, and the first electrode 3 was obtained. After that, a resist stripping solution (a mixed liquid of monoethanolamine and diethylene glycol monobutyl ether) was used to strip the resist pattern. The peeled substrate is washed with water and heated and dehydrated to obtain an electrode substrate with a flattened film. Next, an insulating film 4 in a shape covering the periphery of the first electrode 3 is formed.

Next, on the first electrode 3, 100 nm of aluminum was evaporated by a vacuum evaporation method to form an anode. On the aluminum anode, 50 nm containing N,N'-di-1-naphthyl-N,N'-diphenylbenzidine (NPD) and tetrafluorotetracyanoquinodimethane (F4-TCNQ ) Co-evaporated film (weight ratio 97:3) as the hole injection layer. Then, 80 nm N,N'-di-1-naphthyl-N,N'-diphenylbenzidine (NPD) was deposited as a hole transport layer. Furthermore, the formation of 20 nm 4,4',4"-tris(diphenylamino)triphenylamine (GH) and tris(2-phenylpyridinato)iridium(III) (Tris(2-phenylpyridinato) The co-evaporated film layer of iridium (III)) (GD) (weight ratio 97:3) is used as the green light-emitting layer. Then, 30 nm aluminum trihydroxyquinoline (Alq ₃ ) was evaporated as the electron transport layer, and 1 nm LiF was evaporated as the electron injection layer, and then 15 nm MgAg (weight ratio 10:1) was evaporated as the half Through the cathode. Furthermore, CPL (2,5-bis(4-(N-biphenyl-4-yl-3-pyridylamino)phenyl)thiophene) was vapor-deposited at 60 nm as a capping layer.

[化13]

Using a laser oscillator with a wavelength of 308 nm (manufactured by Coherent, Inc.), the glass substrate 1 on which the polyimide film 2 is formed, from the side where the polyimide film 2 is not formed The laser is irradiated to peel off the glass substrate 1 and the polyimide film 2 to obtain a flexible organic EL device. The frequency of the laser is set to 300 Hz. With respect to the obtained organic EL element, evaluations of dark brightness, brightness, chromaticity, contrast, and reliability were performed by the method described above. The evaluation results are shown in Table 2.

Example 201, Comparative Example 201 The varnish 7 and the varnish 13 were used to fabricate the same element as in Example 101, and the circular polarizing plate was superimposed on the front surface side of the organic light emitting display device to be mounted, and evaluation was performed in the same manner as in Example 101. The evaluation results are shown in Table 2.

[Table 2] Varnish Circular polarizer Dark brightness (cd/m2) Brightness (cd/m2) Chromaticity x, y (color shift judgment) Contrast (dark: bright judgment) reliability(%) number Polyimide precursor solution Pigment dispersion 0 h 250 h 500 h 1000 h Example 101 Varnish 2 Solution 1 CB-1 no 1661 3523 0.344,0.607(A) 1:2.12 (good) 100 94 90 88 Example 102 Varnish 4 Solution 3 BD-1 no 1892 3884 0.345,0.605(A) 1:2.05 (good) 100 97 95 90 Example 103 Varnish 5 Solution 4 BD-1 no 1904 3899 0.357,0.601(A) 1:2.05 (good) 100 97 94 89 Example 104 Varnish 6 Solution 5 BD-1 no 1943 3909 0.356,0.609(A) 1:2.01 (good) 100 98 96 89 Example 105 Varnish 7 Solution 6 BD-1 no 1847 3862 0.352,0.606(A) 1:2.09 (good) 100 97 95 90 Example 106 Varnish 8 Solution 7 BD-1 no 1698 3701 0.341,0.594(A) 1:2.18 (good) 100 96 94 90 Example 107 Varnish 9 Solution 8 BD-1 no 1508 3516 0.349,0.602(A) 1:2.33 (good) 100 98 96 90 Example 201 Varnish 7 Solution 6 BD-1 Have 883 1685 0.346,0.598(A) 1:1.91 (good) 100 99 97 95 Comparative Example 101 Varnish 10 Solution 10 - no 3278 4311 0.362,0.560(C) 1:1.41 (bad) 100 96 84 78 Comparative Example 201 Varnish 10 Solution 10 - Have 915 1288 0.348,0.585(B) 1:1.32 (bad) 100 91 89 83

In Example 101 to Example 107 and Example 201, organic light emitting display devices with high contrast and small color shift were obtained. On the other hand, the organic light-emitting display devices of Comparative Example 101 and Comparative Example 201 had poor contrast and large color shift.

Furthermore, according to the comparison between Comparative Example 101 and Comparative Example 201, it can be seen that in the organic light emitting display device of the prior art, the color shift can be reduced by overlapping the circular polarizing plate on the front surface side of the organic light emitting display device. On the other hand, according to the comparison between Example 105 and Example 201, it can be seen that in the organic light emitting display device of the present invention, the color shift can be reduced equally regardless of whether there is a circular polarizer.

As described above, if the black resin film produced using the resin composition of the present invention is used, an organic light emitting display device with excellent contrast, small color shift, and good visibility can be obtained.

Example 301 Using the varnish 11 used in Example 11, the pattern processability evaluation was performed by the said method. As a result, it was confirmed that the exposed part did not generate residues and was dissolved by development, on the other hand, the resin film remained in the unexposed part, and a good positive concave-convex pattern was obtained.

Example 302 Using the varnish 12 used in Example 12, the pattern processability evaluation was performed by the method described above. As a result, it was confirmed that the unexposed part did not generate residues and dissolved by development, but on the other hand, the resin film remained in the exposed part, and a good negative concavo-convex pattern was obtained.

1: glass substrate 2: Black resin film 3: The first electrode 4: insulating layer 5R, 5G, 5B: light-emitting layer 6: second electrode 7: Organic light emitting display device 8: Fluorescent light 9: Spectroradiometer

FIG. 1 is a schematic cross-sectional view showing an example of an organic light-emitting display device. FIG. 2 is a schematic diagram of the dark brightness, brightness, and chromaticity evaluation environment of the organic light emitting display device in the example.

no.

Claims (16)

A resin composition containing a resin mainly composed of a repeating unit represented by any one of chemical formula (1) and chemical formula (2), and a pigment;

In chemical formula (1) and chemical formula (2), X represents a tetravalent tetracarboxylic acid residue with a carbon number of 2 or more; Y represents a divalent diamine residue with a carbon number of 2 or more; wherein, the tetracarboxylic acid that provides X Or at least one of the diamines providing Y has a maximum light absorption in the wavelength range of 380 nm or more and 580 nm or less; R'and R'' each independently represent a hydrogen atom, a hydrocarbon group with 1 to 10 carbons, and a carbon number 1-10 alkylsilyl group, alkali metal ion, ammonium ion, imidazolium ion or pyridinium ion. The resin composition according to claim 1, wherein in the chemical formula (1) and the chemical formula (2), at least one of X and Y includes a perylene structure. The resin composition according to Claim 1 or Claim 2, which further contains a hardening accelerator. The resin composition according to any one of claims 1 to 3, which further contains a photosensitive agent. The resin composition according to claim 4, wherein the photosensitizer is a quinonediazide compound. The resin composition according to claim 4, wherein the photosensitizer is a photopolymerization initiator. The resin composition according to any one of claims 1 to 6, which further comprises a resin having a repeating unit represented by any one of chemical formula (3) and chemical formula (4) as a main component;

In chemical formula (3) and chemical formula (4), U is at least one structure selected from the structures represented by chemical formula (5) to chemical formula (7); V represents a divalent diamine residue with a carbon number of 2 or more;

. The resin composition according to any one of claims 1 to 7, wherein the pigment has a maximum light absorption in a wavelength range of 580 nm or more and 780 nm or less. The resin composition according to any one of claims 1 to 8, wherein the pigment contains one or more pigments selected from black pigments, blue pigments, and purple pigments. The resin composition according to claim 9, wherein the blue pigment is a phthalocyanine derivative. A black resin film comprising a resin mainly composed of a repeating unit represented by the chemical formula (1) and a pigment. The resin film has a wavelength of 380 nm or more when the film thickness is 5 μm and The light transmittance in the range below 780 nm is 5% or less;

In the chemical formula (1), X represents a tetravalent tetracarboxylic acid residue with a carbon number of 2 or more; Y represents a divalent diamine residue with a carbon number of 2 or more; wherein, the tetracarboxylic acid that provides X or the two that provides Y At least one of the amines has maximum light absorption in the range of wavelengths of 380 nm or more and 580 nm or less. The black resin film according to claim 11, wherein the breakdown voltage is 2.7 MV/cm or more. The black resin film according to claim 11 or claim 12, wherein at least one of X and Y in the chemical formula (1) includes a perylene structure. The black resin film according to any one of claims 11 to 13, wherein the pigment has a maximum light absorption in a wavelength range of 580 nm or more and 780 nm or less. A laminated body comprising the black resin film as described in any one of claim 11 to claim 14, and a resin film containing a resin mainly composed of a repeating unit represented by chemical formula (3);

In the chemical formula (3), U is at least one selected from the structures represented by the chemical formulas (5) to (7); V represents a divalent diamine residue with a carbon number of 2 or more;

. A display device includes the black resin film according to any one of claims 11 to 14, or the laminate according to claim 15.

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