TW202349036A - Photosensitive resin composition, cured film thereof, and display component and display device with that film - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured film that has high light-shielding properties and low reflectivity and has low brightness. The solution of the present invention is a photosensitive composition, which contains: (A) a resin ingredient, including an unsaturated group-containing alkali-soluble resin (A1), a photopolymerizable compound having at least two unsaturated bonds (A2), and a thermosetting epoxy compound (A3); (B) a light-shielding ingredient, including a black pigment (B1), and magnesium fluoride and/or cryolite fine particles (B2); and (C) a photopolymerizable initiator.

Description

Photosensitive resin composition, cured film, display components and display device

The present invention relates to a photosensitive resin composition, a cured film, a display component, and a display device.

In recent years, organic EL display elements (OLED), which are thinner, more flexible and have higher light utilization efficiency than conventional liquid crystal display elements, have attracted much attention and have been put into practical use.

In order to prevent the reduction of visual visibility caused by external light reflection, OLED has a circular polarizing plate as an anti-reflection film. However, if a circular polarizing plate is provided, not only the external light will be blocked, but also the light emitted by the organic EL will be blocked, so the light utilization efficiency will be greatly reduced. Therefore, there is a need to develop an OLED that has good visual visibility without using a circular polarizing plate and can be used with low power consumption.

Here, the resonance effect of the color filter (CF) and light not only does not block the light emitted by the organic EL, but also makes the spectrum sharp and high-intensity, and improves the brightness and color purity. This can be expected to increase the transmittance of OLED and improve power consumption. In addition, compared with circular polarizing plates, the film thickness of CF is thinner, allowing the device to be thinner. So try to replace the circular polarizer with CF. On the other hand, the anti-reflective function of the black matrix in CF is hardly sufficient, and there is a strong demand for a better low-reflective effect.

Until now, as an example of imparting better low-reflection characteristics to photosensitive resin compositions such as black photoresists, Patent Document 1 discloses a composition containing hydrophobic silica fine particles and a specific dispersant (urethane dispersant). ) black photosensitive resin composition. Next, by using hydrophobic silica particles and a specific dispersant, a black matrix with both high light-shielding properties and low reflectivity can be formed.

[Prior technical literature]

[Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2015-161815.

However, when a silica filler is added as described in Patent Document 1, the isolation layer of silica becomes a light diffusion source, reducing the blackness of the coating film and possibly deteriorating the appearance.

Therefore, there is a demand for a photosensitive resin composition for black photoresist that has both low reflectivity (especially low reflectivity obtained by the SCI method) and jet blackness, a light-shielding film formed by curing the same, and a color filter. piece.

The present invention was made in view of this point, and it is an object of the present invention to provide a photosensitive resin composition capable of obtaining a cured film having high light-shielding properties, low reflectivity and low brightness, a cured film formed by curing the photosensitive resin composition, and a photosensitive resin composition having the cured film. A display component, and a display device having the display component.

The present invention was developed in view of the above-mentioned problems. As the added filler, a magnesium fluoride filler with a lower refractive index is added. This can provide a better low-reflection effect and obtain a light-shielding film with high pitch blackness. In addition, the pitch blackness is related to the lightness, and the higher the pitch blackness, the lower the lightness of the light-shielding film.

That is, the gist of this invention is as follows.

[1] A photosensitive resin composition containing:

(A) The resin component includes an alkali-soluble resin (A1) containing an unsaturated group, a photopolymerizable compound (A2) having at least two unsaturated bonds, and a thermosetting epoxy compound (A3);

(B) The light-shielding component contains black pigment (B1), magnesium fluoride and/or cryolite particles (B2); and

(C) Photopolymerization initiator.

[2] The photosensitive resin composition according to [1], wherein the black pigment (B1) contains a transmittance of 80% or more at 850 nm when a coating film with unit OD: 1 [/μm] and film thickness of 1 μm is produced. Black pigment (B1a).

[3] The photosensitive resin composition according to [2], wherein the black pigment (B1a) is an organic black pigment.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the ratio of magnesium fluoride and/or cryolite fine particles (B2) to the total mass of the light-shielding component (B) 1 to 30% by mass.

[5] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [4].

[6] A display component having the cured film according to [5].

[7] A display device having the display components described in [6].

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a cured film with high light-shielding properties, low reflectivity and low brightness, a cured film formed by curing the composition, a color filter and a touch panel having the cured film, A display device having the color filter and the touch panel.

The present invention will be described in detail below.

The unsaturated group-containing alkali-soluble resin of component (A1) of this embodiment contains both a polymerizable unsaturated group and a carboxyl group in one molecule. It is not particularly limited as long as it is the above-mentioned resin and can be widely used.

Examples of the above-mentioned photosensitive resin containing an unsaturated group include an epoxy compound having two glycidyl ether groups derived from bisphenols (hereinafter also referred to as "bisphenol type represented by general formula (1)"). The epoxy (meth)acrylate acid adduct obtained by reacting an epoxy compound") with (meth)acrylic acid, and reacting the obtained compound with a hydroxyl group with a polycarboxylic acid or its anhydride. Epoxy compounds derived from bisphenols refer to epoxy compounds obtained by reacting bisphenols with epihalopropane or their equivalents. Moreover, "(meth)acrylic acid" is a collective name for acrylic acid and methacrylic acid, and represents one or both of them.

The unsaturated group-containing photosensitive resin belonging to the component (A1) is preferably a bisphenol-type epoxy compound represented by the general formula (1). Good development characteristics can be obtained by using a bisphenol type epoxy compound represented by general formula (1).

In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and X is -CO-, -SO ₂ - , -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 茀-9,9- represented by the general formula (2) Diradical or single bond, l is an integer from 0 to 10.

The bisphenol type epoxy compound represented by the general formula (1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols and epichlorohydrin. This reaction is usually accompanied by the oligomerization of the diepoxypropyl ether compound, so it may include epoxy compounds containing two or more bisphenol skeletons.

Examples of bisphenols used in this reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, and bis(4-hydroxy-3,5-dimethylphenyl)ketone. Chlorophenyl)ketone, bis(4-hydroxyphenyl)terine, bis(4-hydroxy-3,5-dimethylphenyl)terine, bis(4-hydroxy-3,5-dichlorophenyl)terine , bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane Propane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl) )dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5- Dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxybenzene) base) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) ) fluorine, 9,9-bis(4-hydroxy-3-methylphenyl) fluorine, 9,9-bis(4-hydroxy-3-chlorophenyl) fluorine, 9,9-bis(4-hydroxy- 3-bromophenyl)fluorine, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorine, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorine, 9,9- Bis(4-hydroxy-3,5-dimethylphenyl)fluoride, 9,9-bis(4-hydroxy-3,5- Dichlorophenyl) fluorine, 9,9-bis(4-hydroxy-3,5-dibromophenyl) fluorine, 4,4’-biphenol, 3,3’-biphenol, etc. Among them, bisphenols having a fluorine-9,9-diyl group are preferred.

In addition, examples of (a) dicarboxylic acid or tricarboxylic acid monoanhydride for reacting the hydroxyl group in the epoxy (meth)acrylate molecule obtained by reacting such an epoxy compound with (meth)acrylic acid include Acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids, acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids, etc. Here, examples of acid monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, Acid monoanhydrides of malonic acid, glutaric acid, citric acid, tartaric acid, oxyglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc. Furthermore, acid monoanhydrides of dicarboxylic acid or tricarboxylic acid into which optional substituents are introduced are also included. Furthermore, examples of acid monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norcamphene Acid monoanhydrides such as alkanedicarboxylic acids. Furthermore, acid monoanhydrides of dicarboxylic acid or tricarboxylic acid into which optional substituents are introduced are also included. Examples of the acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like. Furthermore, acid monoanhydrides of dicarboxylic acid or tricarboxylic acid into which optional substituents are introduced are also included.

烷四羧酸等的酸二酐。又，也包括導入有任意取代基之四羧酸的酸二酐等。又，芳香族四羧酸的酸二酐之例係包括焦蜜石酸、二苯基酮四羧酸、聯苯基四羧 酸、聯苯基醚四羧酸等的酸二酐。又，也包括導入有任意取代基之四羧酸的酸二酐等。 Furthermore, (b) the acid dianhydride of tetracarboxylic acid used to react with epoxy (meth)acrylate is an acid dianhydride of chain hydrocarbon tetracarboxylic acid, an acid dianhydride of alicyclic tetracarboxylic acid or an aromatic acid dianhydride. Dianhydrides of tetracarboxylic acids. Here, examples of acid dianhydrides of chain hydrocarbon tetracarboxylic acids include acid dianhydrides of butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and the like. In addition, acid dianhydrides of tetracarboxylic acid with optional substituents introduced therein are also included. Furthermore, examples of acid dianhydrides of alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and

Acid dianhydrides such as alkane tetracarboxylic acids. In addition, acid dianhydrides of tetracarboxylic acid with optional substituents introduced therein are also included. Examples of the acid dianhydride of aromatic tetracarboxylic acid include acid dianhydrides such as pyromelite acid, diphenylketonetetracarboxylic acid, diphenyltetracarboxylic acid, and diphenylethertetracarboxylic acid. In addition, acid dianhydrides of tetracarboxylic acid with optional substituents introduced therein are also included.

The preferred molar ratio (a)/(b) of (a) acid monoanhydride of dicarboxylic acid or tricarboxylic acid and (b) acid dianhydride of tetracarboxylic acid for reaction with epoxy (meth)acrylate It is 0.01 or more and 10.0 or less, and it is more preferable that it is 0.02 or more and less than 3.0. If the molar ratio (a)/(b) exceeds the above range, the optimum molecular weight for forming a photosensitive resin composition having good photopatterning properties cannot be obtained, which is undesirable. In addition, the smaller the molar ratio (a)/(b) is, the larger the molecular weight is and the alkali solubility tends to be reduced.

In addition, the reaction between the epoxy compound and (meth)acrylic acid and the reaction between the epoxy (meth)acrylate obtained by the reaction and the polycarboxylic acid or its anhydride are not particularly limited, and known methods can be used. In addition, the weight average molecular weight (Mw) of the unsaturated group-containing photosensitive resin synthesized by the above reaction is preferably 2,000 to 10,000, and the acid value is preferably 30 to 200 mg/KOH. Moreover, the weight average molecular weight (Mw) can be measured using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd.), for example. In addition, the acid value can be titrated with a 1/10N-KOH aqueous solution using, for example, a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

Other preferred examples of the unsaturated group-containing photosensitive resin as the component (A1) include copolymers of (meth)acrylic acid, (meth)acrylate, etc. and having a (meth)acrylyl group and Carboxyl resin. Examples of the above-mentioned resin include: copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent, reacting the resulting copolymer with (meth)acrylic acid, and finally reacting it with dicarboxylic acid or tricarboxylic acid. Alkali-soluble resin containing polymerizable unsaturated groups obtained by reacting anhydride of carboxylic acid. Examples of the above-mentioned copolymer include the copolymer shown in Japanese Patent Application Publication No. 2014-111722, which has repeating units of 20 to 90 derived from diester glycerol in which both terminal hydroxyl groups are esterified with (meth)acrylic acid. It consists of 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds that can be copolymerized with it. The average molecular weight (Mn) is 2000 to 20000 and the acid value is 35 to 120 mgKOH/g; and an alkali-soluble resin containing a polymerizable unsaturated group as shown in Japanese Patent Application Laid-Open No. 2018-141968, which is derived from (methyl ) Units of acrylate compounds and polymers having (meth)acrylyl groups and di- or tricarboxylic acid residues, with a weight average molecular weight (Mw) of 3,000 to 50,000, and an acid value of 30 to 200 mg/KOH.

The unsaturated group-containing photosensitive resin of component (A1) may be used alone or in combination of two or more types.

Examples of the photopolymerizable compound having at least two unsaturated bonds in the component (A2) of this embodiment include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, tripropylene glycol diacrylate, glycerin (meth)acrylic acid Ester, glyceryl di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentylerythritol di(meth)acrylate, Neopenterythritol tri(meth)acrylate, neopenterythritol tetra(meth)acrylate, dineopenterythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate Alkylene oxide modification of meth)acrylate, dipenterythritol penta(meth)acrylate, dipenterythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and phosphine nitrene (Meth)acrylates such as hexa(meth)acrylate and caprolactone-modified dineopenterythritol hexa(meth)acrylate; 2-hydroxyethyl (meth)acrylate, (meth)acrylate 2-Hydroxypropyl acrylate and other (meth)acrylates with hydroxyl groups; bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol F type Epoxy (meth)acrylate, diphenyl fluorine type epoxy (meth)acrylate, phenol novolak type epoxy (meth)acrylate, cresol phenolic acid varnish type epoxy (meth)acrylate Epoxy (meth)acrylates such as ethyl)acrylate and phenol aralkyl type epoxy (meth)acrylate; dendrimers having (meth)acrylyl groups which are compounds with vinyl double bonds Polymers etc. Only one type of these photopolymerizable compounds may be used alone, or two or more types may be used in combination. In addition, the ethylenic resin must have at least 2 The photopolymerizable compound with a saturated bond serves to cross-link the molecules of the alkali-soluble resin containing a polymerizable unsaturated group. In order to exert this function, it is preferable to use one having three or more unsaturated bonds. Furthermore, the acrylic acid equivalent, which is the molecular weight of the photopolymerizable compound divided by the number of (meth)acrylyl groups in 1 molecule, is preferably 50 to 300, and more preferably 80 to 200 acrylic acid equivalent. In addition, component (A2) does not have free carboxyl groups.

The photopolymerizable compound of (A2) component may be used individually by 1 type or in combination of 2 or more types.

烷(例如Araldite CY175：Huntsman公司製，「Araldite」為同公司之註冊商標)、雙(3,4-環氧環己基甲基)己二酸酯(例如CYRACURE UVR-6128：陶氏化學公司製)、包含3’,4’-環氧環己基甲基3,4-環氧環己烷羧酸酯之脂環式環氧化合物(例如Celloxide 2021P：Daicel股份有限公司製，「Celloxide」為同公司 之註冊商標)、丁烷四羧酸四(3,4-環氧環己基甲基)酯修飾ε-己內酯(例如Epolead GT401：Daicel股份有限公司製，「Epolead」為同公司之註冊商標)、具有環氧環己基之環氧化合物(例如HiREM-1：四國化成工業股份有限公司製)、具有二環戊二烯骨架之多官能環氧化合物(例如HP7200系列：DIC股份有限公司製)、2,2-雙(羥基甲基)-1-丁醇之1,2-環氧基-4-(2-環氧乙烷基)環己烷加成物(例如EHPE3150：Daicel股份有限公司製)等脂環式環氧化合物、環氧化聚丁二烯(例如NISSO-PB JP-100：日本曹達股份有限公司製，「NISSO-PB」為同公司之註冊商標)、具有聚矽氧骨架之環氧化合物等。又，該等熱硬化性環氧化合物可僅單獨使用1種或併用2種以上。 As the thermosetting epoxy compound in the component (A3), a known epoxy compound can be used without any particular limitation. Examples include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol-type epoxy compounds, bis-naphthol-type epoxy compounds, diphenyl-type epoxy compounds, and phenolic novolac-type epoxy compounds. Compounds, (o-, m-, p-)cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, biphenyl type epoxy compounds (such as jER YX4000: Mitsubishi Chemical Co., Ltd., "jER ” is a registered trademark of the same company), phenolic novolac compounds containing a naphthalene skeleton (such as NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds ( For example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compound, glycidyl ether of polyol, glycidyl ester of polycarboxylic acid, including methacrylic acid and methacrylic acid Copolymers of glycidyl ester, copolymers of monomers containing glycidyl (meth)acrylate as units and having (meth)acrylyl groups, hydrogenated bisphenol A diepoxypropyl ether (such as RIKARESIN HBE -100: Made by Shin Nippon Rika Co., Ltd., "RIKARESIN" is a registered trademark of the same company) and other epoxy compounds with epoxypropyl group, 1,4-cyclohexanedimethanol-bis-3,4-epoxy ring Hexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-di

Alkanes (such as Araldite CY175: manufactured by Huntsman Co., Ltd., "Araldite" is a registered trademark of the same company), bis(3,4-epoxycyclohexylmethyl) adipate (such as CYRACURE UVR-6128: manufactured by The Dow Chemical Company ), alicyclic epoxy compounds containing 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (such as Celloxide 2021P: manufactured by Daicel Co., Ltd., "Celloxide" is the same The company's registered trademark), butane tetracarboxylic acid tetrakis (3,4-epoxycyclohexylmethyl) ester modified ε-caprolactone (such as Epolead GT401: manufactured by Daicel Co., Ltd., "Epolead" is registered by the same company Trademark), epoxy compounds with an epoxycyclohexyl group (such as HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), multifunctional epoxy compounds with a dicyclopentadiene skeleton (such as HP7200 series: DIC Co., Ltd. System), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (such as EHPE3150: Daicel shares Co., Ltd.) and other alicyclic epoxy compounds, epoxidized polybutadiene (such as NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the same company), polysilicon Oxygen skeleton epoxy compounds, etc. Moreover, only one type of these thermosetting epoxy compounds may be used alone, or two or more types may be used in combination.

The content of component (A1) is preferably not less than 5% by mass and not more than 30% by mass, more preferably not less than 12% by mass and not more than 30% by mass, relative to the total solid mass. If the content of the component (A1) is 5% by mass or more, a high-resolution pattern can be formed.

The blending ratio of component (A1) and component (A2) is preferably 40/60 to 90/10, more preferably 50/50 to 80/20 in terms of weight ratio (A1)/(A2). If the blending ratio of component (A1) is 40/60 or more, the cured product after photocuring will not be easily broken, and the acid value of the coating film in the unexposed portion will not be easily reduced, so the solubility in the alkali developer can be suppressed. reduce. Therefore, it is less likely to cause problems such as jagged pattern edges or insufficient sharpness. Furthermore, if the blending ratio of component (A1) is 90/10 or less, the proportion of photoreactive functional groups in the resin is sufficient, so that the desired cross-linked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility to the alkali developer in the exposed portion is not easily increased, thereby suppressing the formed pattern from being thinner than the target line width or pattern defects.

The (A3) component is preferably 1 to 15% by mass, more preferably 2 to 9% by mass relative to the solid content in the photosensitive resin composition. If the component (A3) is 1% by mass or more, the cured product after thermal hardening Not easily broken. Therefore, even during low-temperature curing such as a post-baking temperature of 85°C, it is unlikely that the cured film will peel off from the substrate due to exposure to chemicals. In addition, if the solid content of the component (A3) is 15% or less, the blending amount of the alkali-soluble resin as the original other binder resin will not increase, and the developability can be ensured.

Furthermore, the photosensitive resin composition of the present invention may contain resins other than the component (A1) to the component (A3). Resins other than components (A1) to (A3) include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

If the light-shielding components such as black pigments, mixed-color organic pigments, and light-shielding materials belonging to the component (B) in this embodiment have an average secondary particle diameter of 1 to 1000 nm (measured by laser diffraction scattering particle size distribution or dynamic light If the average particle size measured by a scattering particle size distribution meter) is dispersed, well-known light-shielding components can be used without particular limitations. More preferably, the average secondary particle size is 10 to 300 nm.

Examples of black pigments belonging to component (B1) include perylene black, indigo black, aniline black, lactamine black, carbon black, titanium black, mixed color organic pigments, etc.

顏料、還原顏料、苝顏料、紫環酮顏料、喹啉黃顏料、二酮吡咯并吡咯顏料、硫靛藍顏料等有機顏料的至少2色混合並擬黑色化的顏料。 Examples of mixed-color organic pigments belonging to the component (B1) include those selected from the group consisting of azo pigments, condensed azo pigments, methine azo pigments, phthalocyanin pigments, quinacridone pigments, isoindolinone pigments, and isoindolinone pigments. Indoline pigment, 2

A pigment that is mixed with at least two colors of organic pigments such as pigments, reduced pigments, perylene pigments, iconone pigments, quinoline yellow pigments, diketopyrrolopyrrole pigments, and thioindigo pigments to produce a pseudo-black color.

The above-mentioned component (B1) may be used alone or in combination of two or more types according to the intended function of the photosensitive resin composition.

Furthermore, when using a mixed-color organic pigment as the component (B1), examples of the organic pigments that can be used include those with the following pigment index names, but are not limited thereto.

Pigment Red (Pigment Red) A16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;

Pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.;

Pigment green 7, 36, 58, etc.;

Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.;

Pigments purple 19, 23, 37, etc.

As the component (B1), in order to have IR transmittance, it is preferable to contain a black pigment (B1a) whose transmittance at 850 nm becomes 80% or more when a coating film with a unit OD of 1 [/μm] and a film thickness of 1 μm is produced.

顏料、還原顏料、苝顏料、紫環酮顏料、喹啉黃顏料、二酮吡咯并吡咯顏料、硫靛藍顏料等有機顏料的至少2色混合之擬黑色顏料等。 Examples of the component (B1a) include perylene black, indigo black, aniline black, and lactamide black which are organic black pigments, bismuth sulfide which is an inorganic black pigment, and azo which is a mixed-color organic pigment. Pigments, condensed azo pigments, methine azo pigments, phthalocyanin pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments,

Pseudo-black pigments mixed with at least two colors of organic pigments such as pigments, reduced pigments, perylene pigments, ionone pigments, quinoline yellow pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

The component (B1a) is preferably organic black pigments such as perylene black, indigo black, aniline black, and lactone black. By using organic black pigments, light can be blocked without using heavy metals, so a highly safe cured film can be formed.

The blending ratio of the black pigment of component (B1) can be arbitrarily determined according to the required opacity, but it is preferably 20 to 70 mass %, more preferably 30 to 60 mass % based on the solid content in the photosensitive resin composition. %. When an organic pigment such as aniline black, indigo black, lactide black or a carbon-based light-shielding component such as carbon black is used as part of the black pigment of the component (B1), the solid content in the photosensitive resin composition is preferably 25 to 60 mass%, preferably 30 to 50%. If the black pigment is 25% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. If the black pigment is 60% by mass or less relative to the solid content in the photosensitive resin composition, the content of the photosensitive resin ((A1) + (A2)) that originally forms the binder will not be reduced and the desired development can be obtained properties and film-forming capabilities.

When component (B1a) and component (B1) other than (B1a) are used together, the ratio (component (B1a))/(component (B1) other than (B1a)) is preferably 50/50 to 99/1. Better is 80/20 to 95/5. If the blending ratio of component (B1a) is 50/50 to 99/1, it can have both transmittance in the IR region and high opacity.

The above-mentioned component (B1) is generally mixed with other blending components as a black pigment dispersion dispersed in a solvent. In this case, a dispersant may be added. The dispersant can be any known compound (compounds sold under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) used for dispersing pigments (black pigments), etc., and is not particularly limited.

Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing aids). In particular, the dispersant preferably has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amine group as an adsorption point for the colorant, and the amine value is 1 to 100 mgKOH/g. , a cationic polymer dispersant with a number average molecular weight (Mn) in the range of 1,000 to 100,000. The blending amount of the dispersant is preferably 1 to 40 parts by mass, more preferably 2 to 25 parts by mass relative to the component (B1). Also, such as resin High-viscosity substances generally have the effect of stabilizing dispersion, and those that do not have the ability to promote dispersion are not used as dispersants. However, its use for stabilizing dispersion is not limited.

(B2) The component is magnesium fluoride microparticles and/or cryolite microparticles. The refractive index of the atmosphere is about 1.0. On the other hand, the refractive index of lactam black or carbon black that becomes the black pigment is about 1.7 to 2.0. Therefore, by using fine particles with a refractive index lower than that of the black pigment, that is The refractive index of the cured film containing the microparticles can be lowered. The refractive index of magnesium fluoride fine particles is 1.38 (documentary value), and the refractive index of cryolite is 1.34 (documentary value). Both refractive indexes are located near the middle between the (B1) component and (B3) component in the atmosphere. , it is thought that by using these fine particles, the refractive index difference between the atmosphere and the cured film can be reduced, thereby reducing the reflectivity. In addition, magnesium fluoride particles and/or cryolite particles will agglomerate to some extent in the cured film. However, unlike silica and the like, the refractive index difference between the agglomerated particles and the surrounding resin is low, so the brightness caused by agglomeration is not easily produced. Rising, the effect of reducing the brightness of the hardened film is higher.

The average primary particle size of component (B2) used in the present invention is preferably 10 to 100 nm. If it is 10 nm or more, the surface energy will not be too high, so it will be difficult to aggregate in the film, and it will be less likely to cause an increase in brightness due to the aggregation of the (B2) component becoming a light diffusion source. If it is 100 nm or less, the average primary particle diameter is suitably low, and therefore it is less likely to cause an increase in brightness caused by single particles becoming a diffusion source.

The average primary particle size of component (B2) used in the present invention is determined by observing the particle size using a transmission electron microscope, randomly selecting 100 particles, and measuring the major axis length and minor axis length of the particles. The value obtained by adding the average of . Furthermore, when the component (B2) forms aggregates or aggregates, the primary particles constitute the particles.

The magnesium fluoride particles and/or cryolite particles used in the present invention are not particularly limited in terms of the production method such as gas phase reaction or liquid phase reaction or the shape (spherical, non-spherical).

Ratio The blending ratio of the (B2) component is preferably 1 to 30 mass%, more preferably 2 to 25 mass%, and still more preferably 12 to 25 mass% relative to the total mass of the (B) light-shielding component. If the content of the component (B2) is 1 mass % or more, the refractive index of the cured film will be sufficiently reduced, and the reflectance reducing effect will be enhanced. If the content of component (B2) is 30% by mass or less, increasing the relative content of component (B1) can increase the optical density of the cured film. If the content of the component (B2) is 25% by mass or less, the adhesion decrease caused by the component (B2) is less likely to occur. In addition, even if the relative amount of the component (B2) is lower than the above-mentioned level, the reflectance reducing effect of the component (B2) can be fully exerted.

In addition, (B3) other organic pigment components may be added, which can compensate for the absorptivity of wavelengths in which the black pigment of the component (B1) has a low absorptivity in the visible light band, or can supplement the light-shielding property. In particular, when the above-mentioned component (B1a) is used as the component (B1), especially when an organic black pigment is used, the absorptive filling of the component (B3) creates a low-reflective effect or a light-shielding improvement effect, while maintaining low reflectivity or It has a remarkable effect of improving IR transmittance while blocking light.

As the component (B3), organic pigments other than black exemplified in (B1) can be added. By adding the (B3) component that can absorb light in the visible light band that cannot be completely blocked and transmitted by black pigments, the opacity OD of the cured film can be increased, and the high reflectivity of the transmission area can be suppressed and the reflectivity can be reduced.

When component (B1) and component (B3) are used together, the ratio ((B1) component)/((B3) component) is preferably 50/50 to 90/10. If the blending ratio is 50/50 to 90/10, the low-reflection effect and light-shielding improvement effect will be good. When using component (B1a) as component (B1), ((B1a) component)/((B3) component) is preferably 50/50 to 90/10.

In addition, the component (B2) and the component (B3) may be mixed with other blending components as a dispersion of a light-shielding component dispersed in a solvent. As a dispersant for dispersing these components, those exemplified as component (B1) can be appropriately used. Moreover, the blending quantity of a dispersing agent may be the same as the blending quantity of a dispersing agent with respect to (B1) component.

The blending ratio of component (B) is preferably 20 to 80% by mass, more preferably 40 to 60% by mass relative to the solid content in the photosensitive resin composition. If the content of the component (B) is 20% by mass or more, the light-shielding properties of the cured film can be further improved. If the content of component (B) is 80% by mass or less, a high-definition pattern can be formed.

二唑、2-三氯甲基-5-(對氰基苯乙烯基)-1,3,4-

二唑、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-

二唑等鹵甲基噻唑化合物類；2,4,6-三(三氯甲基)-1,3,5-三

、2-甲基-4,6-雙(三氯甲基)-1,3,5-三

、2-苯基-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-氯苯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(3,4,5-三甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

、2-(4-甲硫基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三

等鹵甲基-S-三

系化合物類；1,2-辛二酮、1-[4-(苯基硫基)苯基]-,2-(O-苯甲醯基肟)、1-(4-苯基氫硫基苯基)丁烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-甲氫硫基苯基)丁烷-1,2-二酮-2-肟-O-乙酸酯、1-(4-甲氫硫基苯基)丁烷-1-酮肟-O-乙酸酯、4-乙氧基-2-甲基苯基-9-乙基-6-硝基-9H-咔唑并-3-基-O-乙醯基肟等O-醯基肟系化合物類；二苯乙二酮二甲基縮酮、 噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等硫化合物；2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌等蒽醌類；偶氮雙異丁腈、過氧化苯甲醯、過氧化異丙苯等有機過氧化物；2-統基苯并咪唑、2-巰基苯并

唑、2-巰基苯并噻唑等硫醇化合物、三乙醇胺、三乙胺等三級胺等。該等光聚合起始劑可僅單獨使用其1種或併用2種類以上。 Examples of photopolymerization initiators belonging to component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and dichlorobenzene Acetophenones such as ethyl ketone, trichloroacetophenone, p-tert-butyl acetophenone, diphenyl ketone, 2-chlorodiphenyl ketone, p,p'-bisdimethylaminodiphenyl ketone Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; 2-(o-chlorophenyl)-4,5-phenylbiimidazole , 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methyl Oxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-styryl-1,3, 4-

Oxidazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-

Oxidazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-

Halomethylthiazole compounds such as oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-tris

, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-tri

Isohalomethyl-S-tri

Compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylhydrogenthio) Phenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylhydrosulfanyl)butane-1,2-dione-2-oxime- O-acetate, 1-(4-methylhydrothiophenyl)butane-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl- 6-nitro-9H-carbazolo-3-yl-O-acetyl oxime and other O-acetyl oxime compounds; benzoethylene glycol dimethyl ketal, thioxanthone, 2-chlorothiol Sulfur compounds such as xanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethylanthraquinone, octamethylanthraquinone, 1,2 - Anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; 2-benzyl Imidazole, 2-mercaptobenzo

Thiol compounds such as azoles and 2-mercaptobenzothiazole, tertiary amines such as triethanolamine and triethylamine, etc. Only one type of these photopolymerization initiators may be used alone or two or more types may be used in combination.

Examples of O-acyl oxime compounds that can be preferably used include O-acyl oxime photopolymerization initiators represented by general formula (3) and general formula (4). Among these compounds, when using a light-shielding component at a high concentration, it is preferable to use an O-acyl oxime-based photopolymerization initiator with a molar absorption coefficient at 365 nm of 10,000 or more. In addition, the "photopolymerization initiator" in the present invention is used in the sense of including a sensitizer.

In formula (3), R ₅ and R ₆ are each independently an alkyl group from C1 to C15, an aryl group from C6 to C18, an arylalkyl group from C7 to C20, or a heterocyclic group from C4 to C12, and R ₇ is C1 to C15 alkyl group, C6 to C18 aryl group or C7 to C20 arylalkyl group. Here, the alkyl and aryl groups may be substituted by C1 to C10 alkyl groups, C1 to C10 alkoxy groups, C1 to C10 alkyl groups, or halogens, and the alkylene group may contain unsaturated bonds, ether bonds, or sulfur bonds. Ether bond, ester bond. In addition, the alkyl group may be any linear, branched or cyclic alkyl group.

In formula (4), R ₈ and R ₉ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms; or a cycloalkyl group, cycloalkylalkyl group or alkyl group having 4 to 10 carbon atoms. Cycloalkyl; or phenyl which may be substituted by an alkyl group having 1 to 6 carbon atoms. R ₁₀ is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted by an -O- group. In addition, part of the hydrogen atoms in the R ₈ to R ₁₀ groups may be substituted with halogen atoms.

The usage amount of the photopolymerization initiator of component (C) is preferably 2 to 35 parts by mass, more preferably 5 to 20 parts by mass relative to the total amount of component (A1) and component (A2). When the blending ratio of component (C) is 2 parts by mass or more, the sensitivity is good and a sufficient photopolymerization speed can be obtained. When the blending ratio of component (C) is 25 parts by mass or less, moderate sensitivity can be achieved, so the desired pattern line width and desired pattern edge can be obtained.

In the photosensitive resin composition of the present invention, it is preferable to use a solvent belonging to the component (D) in addition to the components (A) to (C). Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, Ketones such as N-methyl-2-pyrrolidinone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellulosine, methylcellulose, ethylcellulose, carbitol, and Carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, cellulose acetate, ethyl cellulose acetate, butyl cellulose acetate, carboxyl Acetate esters such as ethanol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. the etc. can be used alone, or two or more types can be used in combination and dissolved and mixed to form a uniform solution-like composition.

In addition, the photosensitive resin composition of the present invention may be blended with a hardener, a hardening accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a surfactant, and a coupling agent as necessary. agents and other additives.

Examples of the hardener include amine compounds that harden thermosetting epoxy compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complexes, and the like. From the viewpoint of improving the adhesion between the cured film and the substrate, dicyandiamide is preferred among these.

Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles, etc. that accelerate the hardening of thermosetting epoxy compounds. .

、受阻酚系化合物等。塑化劑之例係包括鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、磷酸三甲苯酯等。填充劑之例係包括玻璃纖維、二氧化矽、雲母、氧化鋁等。調平劑或消泡劑之例係包括聚矽氧系、氟系、丙烯酸系之化合物。界面活性劑之例係包括月桂基硫酸銨、聚氧伸乙基烷基醚硫酸三乙醇胺等陰離子界面活性劑、硬脂基胺乙酸酯、月桂基三甲基銨氯化物等陽離子界面活性劑、月桂基二甲胺氧化物、月桂基羧甲基羥基乙基咪唑啉鎓甜菜鹼等兩性界面活性劑、聚氧伸乙基月桂基醚、聚氧伸乙基硬脂基醚、山梨醇酐單硬脂酸酯等非離子界面活性劑、以聚二甲基矽氧烷等為主骨架之聚矽氧系界面活性劑、氟系界面活性劑等。耦合劑之例係包括3-(環氧丙基氧基)丙基三甲氧基矽烷、3- 丙烯醯氧基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷等。 Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylquinone, and phenothiophene

, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of leveling agents or defoaming agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, and cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride. , lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethylimidazolinium betaine and other amphoteric surfactants, polyoxyethylene lauryl ether, polyoxyethylene ethyl stearyl ether, sorbitan anhydride Nonionic surfactants such as monostearate, polysiloxy surfactants with polydimethylsiloxane as the main skeleton, fluorine surfactants, etc. Examples of coupling agents include 3-(epoxypropyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-urea Propyltriethoxysilane, etc.

The photosensitive resin composition of the present invention removes the solid content of the solvent that is the component (D) (the solid content includes a photopolymerizable compound that becomes a solid content after hardening), and the resin component that is the component (A) and the component that is the component (B) ) component and the photopolymerization initiator belonging to (C) component preferably contain 80 mass% or more, more preferably 90 mass% or more. The amount of solvent belonging to component (D) will vary depending on the target viscosity, but relative to the total amount, it is preferably 40 to 90% by mass.

Furthermore, for example, the photosensitive resin composition of the present invention can be cured by applying a solution of the photosensitive resin composition to a substrate, drying the solvent, and curing it by irradiating light (including ultraviolet rays, radiation, etc.) Hardened film. The desired pattern can be obtained by setting the illuminated and non-illuminated parts using a mask, etc., hardening only the illuminated parts, and dissolving the other parts with an alkali solution. Can also be used without patterning.

Moreover, the light shielding degree OD [μm ^-1 ] of the cured film formed by curing the photosensitive resin composition of the present invention with a film thickness of 1 μm is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. . Moreover, when the cured film formed by curing the photosensitive resin composition of the present invention contains the component (B1a), the reflectance obtained by the SCI method is preferably less than 6.5%, more preferably less than 6.0%, and still more preferably Less than 5.5%. Moreover, when the cured film formed by curing the photosensitive resin composition of the present invention does not require IR transmittance and does not contain the (B1a) component, the reflectance obtained by the SCI method is preferably less than 6.0%, more preferably less than 6.0%. reaches 5.5%, and preferably less than 5.0%. Furthermore, the brightness of the cured film obtained by curing the photosensitive resin composition of the present invention by SCE is preferably less than 6.9, more preferably less than 6.0, and still more preferably less than 3.0. By suppressing brightness, a display device can be obtained with a cured film (light-shielding film) that has extremely excellent visual visibility and high pitch blackness.

The cured film (light-shielding film) of the present invention can be used for color filters or black matrices used in touch panels, or electric field light-emitting devices including organic EL elements, color liquid crystal display devices, and image sensors. In various multi-color displays such as monitors, display components such as partition materials for color differentiation or light shielding, pixel definition layers, and frames surrounding the display portion of the display. According to the present invention, the external light reflection at the interface between the colored layer (including the black photoresist layer) and the substrate can be reduced, or the reflection of the light emitted by the element, for example, when used in an organic EL element. That is, by reducing external light reflection, visual confirmation can be improved, or light extraction efficiency on the light emitting side can be improved, thereby achieving low power consumption.

In addition, for example, a cured film with a film thickness of 1.0 to 2.0 μm can be formed on a transparent substrate, and red, blue, and green pixels are formed by photolithography after the light-shielding film is formed, thereby producing the cured film of the present invention ( Light-shielding film) is used as a black matrix color filter or touch panel. In addition, it can also be produced by injecting red, blue and green inks into the light-shielding film using an inkjet process.

Furthermore, a cured film (light-shielding film) obtained by curing the photosensitive resin composition of the present invention can be used as a black column spacer in a liquid crystal display device. For example, a single black photoresist can be used to produce multiple parts with different film thicknesses, so that one can function as a spacer and the other can function as a black matrix.

Each step of the film-forming method of forming a cured film by coating and drying a photosensitive resin composition is specifically illustrated.

The photosensitive resin composition can be coated on the substrate by any method such as a known solution dipping method, a spray method, a method using a roll coater, a land coater, a slit coater, or a rotary machine. After coating to a desired thickness by these methods, the solvent is removed (prebaking) to form a coating. Prebaking can be performed by heating in an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in prebaking can be appropriately selected according to the solvent used, but for example, it is preferably 60 to 120° C. for 1 to 10 minutes.

The radiation used for exposure can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., but the wavelength range of the radiation is preferably 250 to 450 nm. In addition, as a developing solution suitable for this alkali development, for example, aqueous solutions such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide can be used. The developer can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The development temperature is preferably 20 to 35°C, and a commercially available developing machine or ultrasonic cleaning machine can be used to accurately form fine images. In addition, water washing is usually performed after alkali development. As the development treatment method, spray development method, spray development method, immersion development method, puddle development method, etc. can be applied.

After development using the above method, heat treatment (post-baking) is performed at 80 to 150°C for 20 to 100 minutes. The purpose of this post-baking is to improve the adhesion between the patterned cured film (light-shielding film) and the substrate. This is performed by heating with an oven, a hot plate, etc., like prebaking. The patterned cured film (light-shielding film) of the present invention is formed through various steps of photolithography. Then, polymerization or curing by heat is completed (the two are collectively referred to as curing), and a light-shielding film having a desired pattern can be obtained.

As mentioned above, the photosensitive resin composition of the present invention is not only suitable for forming fine patterns through operations such as exposure and alkali development, but also can obtain the same light-shielding properties, adhesion, and electrical insulation properties as conventional patterns formed by screen printing. , a light-shielding film with excellent heat resistance and drug resistance.

(Example)

The embodiments of the present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these.

First, a synthesis example of the alkali-soluble resin containing a polymerizable unsaturated group that is the component (A1) will be described. Unless otherwise specified, the evaluation of the resin in these synthesis examples is performed in the following manner.

[Solid content concentration]

Impregnate 1 g of the resin solution obtained in the synthesis example into a glass filter [weight: W0 (g)] and weigh [W1 (g)]. From the weight [W2 (g)] after heating at 160°C for 2 hours, the following formula is used And seek for it.

Solid concentration (weight%)=100×(W2-W0)/(W1-W0).

[acid price]

烷，使用電位差滴定裝置「COM-1600」(平沼產業股份有限公司製)以1/10N-KOH水溶液滴定而求得。 Dissolve the resin solution in two

Alkane was obtained by titrating a 1/10N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Molecular weight]

Gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 pieces) + TSKgelSuper H-3000 (1 piece) + TSKgelSuper H- 4000 (1 piece) + TSKgelSuper H-5000 (1 piece) (manufactured by TOSOH Co., Ltd.), temperature: 40°C, speed: 0.6ml/min), measured as standard polystyrene (PS-Oligomer, produced by TOSOH Co., Ltd. Kit) to obtain the weight average molecular weight (Mw).

[Measurement of primary particle size]

The solution containing the particles was diluted with a solvent to a particle concentration of about 0.1wt%, and the resulting dispersion was dropped into a metal mesh with a carbon support film to prepare a sample for measurement, which was analyzed by transmission electron microscopy (TEM; JEOL Ltd. The sample for measurement was observed using JEM-2000EX (manufactured by the company), and the obtained particle size was regarded as the primary particle size.

[Measurement of average secondary particle size]

The average secondary particle size of the dispersion containing the light-shielding component was measured by the cumulative volume method using a dynamic light scattering particle size distribution meter (Particle Size Analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). The dispersion liquid containing component (B1) or (B3) is diluted so that the concentration of particles dispersed in propylene glycol monomethyl ether acetate (PGMEA) becomes 0.1 to 0.5% by mass to form a sample for measurement. Also, those containing component (B2) The dispersion was diluted with methanol to a particle concentration of 1 to 10% by mass such that the scattering intensity could be measured, and used as a sample for measurement.

The abbreviations used in the synthesis examples are as follows.

BPFE: The reaction product of bisphenol fluoride type epoxy compound (9,9-bis(4-hydroxyphenyl) fluorine and chloromethyl ethylene oxide. In the compound of general formula (1), X is fluorine-9,9 -Diyl, compounds in which R ₁ to R ₄ are hydrogen).

AA: Acrylic.

BPDA: 3,3’,4,4’-biphenyltetracarboxylic dianhydride.

THPA: Tetrahydrophthalic anhydride.

TEAB: tetraethylammonium bromide.

PGMEA: propylene glycol monomethyl ether acetate.

PTMA: neopentylerythritol tetrakis[thioglycolate].

DPHA: dipenterythritol hexaacrylate (mixture with dipenterythritol pentaacrylate).

HQ: hydroquinone.

BzDMA: Benzyldimethylamine.

[Synthesis example 1]

Add BPFE (50.0g, 0.10 mol), AA (14.1g, 0.20 mol), PGMEA (67g) and TPP (0.26g) into a 500ml four-necked flask with a reflux cooler, and stir at 100 to 105°C for 12 hours and react. Then, BPDA (14.4 g, 0.05 mol) and THPA (7.4 g, 0.05 mol) were added to the flask, and the mixture was stirred at 120 to 125° C. for 6 hours to obtain an alkali-soluble resin (A1)-1 containing unsaturated groups. The solid content concentration of the obtained resin solution was 56% by mass, the acid value (in terms of solid content) was 96 mgKOH/g, and the Mw analyzed by GPC was 3600.

[Synthesis example 2]

Add BPFE (50.0g, 0.1 mol), AA (14.1g, 0.2 mol), PGMEA (67g) and TPP (0.26g) into a 500ml four-necked flask with a reflux cooler, and stir at 100 to 105°C for 12 hour response. Next, BPDA (20.9g, 0.07 mol) and THPA (0.23g, 0.015 mol) were added to the flask, and stirred at 120 to 125° C. for 6 hours to obtain alkali-soluble resin (A1)-2 containing unsaturated groups. . The solid content concentration of the obtained resin solution was 56% by mass, the acid value (in terms of solid content) was 102 mgKOH/g, and the Mw analyzed by GPC was 7000.

[Synthesis example 3]

Add PTMA (20g, 0.19 mole of mercapto group), DPHA (212g (2.12 mole of acrylyl group)), PGMEA (58g), HQ (0.1g), and BzDMA (0.01g) into a 1L four-necked flask. The reaction was carried out at 60° C. for 12 hours to obtain a dendritic polymer solution (A2)-3. The solid content concentration of the dendrimer solution was 80% by mass, and the Mw analyzed by GPC was 10,000. In addition, the obtained dendrimer was confirmed to have lost thiol groups by iodine titration.

[Synthesis Example 4]

Add BPFE (114.4g, 0.23mol), AA (33.2g, 0.46mol), PGMEA (156g) and TEAB (0.48g) into a 500ml four-necked flask with a reflux cooler, and stir for 20 seconds under heating at 100 to 105°C. hour response. Then add BPDA (44.1g, 0.15mol) and THPA (0.76g, 0.005mol) into the flask, and stir under heating at 120 to 125°C for 6 hours to obtain alkali-soluble resin (A1)-3 containing unsaturated groups. . The solid content concentration of the obtained resin solution was 55.6% by mass, the acid value (in terms of solid content) was 93 mgKOH/g, and the Mw analyzed by GPC was 8300.

Moreover, carbon black whose surface was coated with dye was prepared by the following method.

[Preparation example 1]

1000 g of carbon black (TPX-1099: Cabot Co., Ltd.) was mixed with water to prepare 10 L of slurry, and the mixture was stirred at 95° C. for 1 hour, allowed to cool, and then washed with water. Mix it with water again to prepare 10L of slurry, add 70% of 42.9g of nitric acid, stirred at 40°C for 4 hours. This was cooled, washed with water, and mixed with water again to prepare 10 L of slurry. 769.2 g of 13% sodium hypochlorite aqueous solution was added, and the mixture was stirred at 40° C. for 6 hours. Let it cool, wash it with water, mix it with water again to prepare 10L of slurry, add 38.1g of dye (Direct Deep BLACK) with a purity of 38.4%, stir at 40°C for 1 hour, and then add 10.1g of aluminum sulfate and stir at 40°C. Stir for 1 hour. After cooling, the mixture is washed with water, filtered and dried to obtain dye-coated carbon black.

The above dye-coated carbon black, polymer dispersant, and PGMEA are mixed and dispersed with a bead mill to obtain carbon black with a concentration of 25.0 mass% of the dye-coated carbon black and a concentration of 10.0 mass% of the polymer dispersant. Dispersion (B1b).

Experiments 1 to 3 were conducted using the components prepared in Synthesis Examples 1 to 3 and Adjustment Example 1 and the following components.

(Alkali-soluble resin containing polymerizable unsaturated groups)

(A1)-1: The alkali-soluble resin solution obtained in Synthesis Example 1 above.

(A1)-2: The alkali-soluble resin solution obtained in Synthesis Example 2 above.

(Photopolymerizable compound having at least 2 unsaturated bonds)

(A2)-1: A mixture of neopentylerythritol triacrylate and neopentylerythritol tetraacrylate (Aronix M-450, manufactured by Toagosei Co., Ltd.).

(A2)-2: A mixture of dipenterythritol pentaacrylate and hexaacrylate (DPHA (acrylic acid equivalent: 96 to 115), manufactured by Nippon Kayaku Co., Ltd.).

(A2)-3: The resinous polymer obtained in Synthesis Example 3 above.

(epoxy compound)

(A3)-1: Celloxide 2021P (manufactured by Daicel Co., Ltd.).

(A3)-2: EHPE3150P (made by Daicel Co., Ltd.).

(black pigment dispersion)

(B1a): PGMEA dispersion of 15.0% by mass of black pigment (lactam black Irgaphor S100CF manufactured by BASF) and 4.5% by mass of polymer dispersant (solid content: 19.5%, average secondary particle size of black pigment: 240 nm).

(B1b): The dye-coated carbon black dispersion obtained in Preparation Example 1 above.

(Magnesium fluoride and/or cryolite particles)

(B2): Magnesium fluoride dispersion (20.0 mass% MgF ₂ , 6.2 mass% polymer dispersant (26.2 mass% solid content), average secondary particle size 47 nm).

(SiO2 fine particles)

(B2'): Silica dispersion "YA010C" (MgF ₂ : 20.0 mass% (solid content: 20.0 mass%), manufactured by Admatechs Co., Ltd., average primary particle size: 10 nm).

(blue pigment dispersion)

(B3): Pigment blue 15:6 (PGMEA dispersion liquid (solid content: 17.6 mass%) with 13.0 mass% organic pigment component and 4.6 mass% polymer dispersant, average primary particle size 90nm).

(Photopolymerization initiator)

(C)-1: ADEKA ARKLS NCI-831, manufactured by ADEKA Co., Ltd., "ADEKA ARKLS" is a registered trademark of the same company).

(solvent)

(D)-1: Propylene glycol monomethyl ether acetate (PGMEA).

(D)-2: Ethyl lactate (EL).

(D)-3: Diethylene glycol ethyl methyl ether (EDM).

(hardener)

(Other ingredients)-1: Trimellitic anhydride.

(Other ingredients)-2: Dicyanodiamide.

(Experiment 1)

Use the following procedure to measure the transmittance of component (B1) at 850 nm.

[Assessment]

A cured film (light-shielding film) in which the photosensitive resin composition used for evaluation is cured is prepared in the following manner.

(Preparation of cured film (coating film) for evaluation of transmittance of component (B1) at 850nm)

A PGMEA solution with a solid content of 13.5% was prepared using the resin obtained in Synthesis Example 1 and the pigment belonging to the component (B1). Adjust the amount of component (B1) so that the coating film after heat hardening treatment has unit OD=1[/μm] and a film thickness of 1μm. The obtained PGMEA solution was coated using a spin coater so that the film thickness after heat hardening became 1 μm on a 125 mm × 125 mm glass substrate that had been previously irradiated with ultraviolet light at a wavelength of 254 nm and an illumination of 1000 mJ/cm ² using a low-pressure mercury lamp and the surface was cleaned. "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate"), prebaked at 85° C. for 1 minute using a hot plate to produce a cured film (coating film). Without covering the negative photomask, use an ultra-high pressure mercury lamp with i-ray illumination of 30mW/ ^cm2 to irradiate ultraviolet light of 40mJ/ ^cm2 for photohardening.

Then, the above-mentioned cured film (shielding film) was exposed at 23°C, 0.05% potassium hydroxide solution and a spray pressure of 1kgf/cm ² for 20 seconds from the development time (Break Time=BT) for pattern development. After the development process, spray water at 5kgf/ ^cm2 is performed to remove the unexposed part of the above-mentioned cured film (shielding film) to form a cured film pattern on the glass substrate. Use a hot air dryer to perform main curing (post-baking) at 85°C for 60 minutes to obtain a cured film (light-shielding film).

[Evaluation of 850nm transmittance]

(evaluation method)

Use the ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Co., Ltd.) with a C light source, an incident angle of 2°, and a wavelength range of 380 to 1000nm for the substrate with a cured film (shielding film) produced above. Measure the transmittance of the cured film (shielding film) side under the conditions.

(Evaluation standard for 850nm transmittance)

When (B1a) and (B1b) were respectively used as the pigment of the (B1) component, the evaluation results were shown in Table 1 to determine whether the transmittance of the cured film produced was 80% or more at 850 nm.

[Table 1]

(Experiment 2)

Various characteristics were evaluated for the composition using (B1a) as the black pigment (B1). The compositions prepared in this experiment are shown in Table 2 (units are parts by mass). In addition, in Table 2, except for (D) component, only the solid content is described.

[Table 2]

[Assessment]

A cured film (light-shielding film) in which the photosensitive resin composition used for evaluation is cured is prepared in the following manner.

(Preparation of cured film (coating film) for optical density (OD) evaluation)

The photosensitive resin composition shown in Table 2 was applied using a spin coater so that the film thickness after heat hardening became 1.2 μm, and was irradiated with ultraviolet rays with a wavelength of 254 nm and an illumination of 1000 mJ/cm ² in advance using a low-pressure mercury lamp, and then washed. On the surface of the 125mm×125mm glass substrate "#1737" (manufactured by Corning Corporation) ("Glass Substrate"), a hot plate was used to pre-bake it at 85°C for 1 minute to produce a cured film (coating film). Without covering the negative photomask, use an ultra-high pressure mercury lamp with an i-ray illumination of 30mW/ ^cm2 to irradiate ultraviolet light of 40mJ/ ^cm2 to perform a photohardening reaction.

Then, the above-mentioned cured film (shielding film) was exposed at 23°C, 0.05% potassium hydroxide solution and a spray pressure of 1kgf/cm ² for 20 seconds from the development time (Break Time=BT) for pattern development. After the development process, spray water at 5kgf/ ^cm2 is performed to remove the unexposed part of the above-mentioned cured film (shielding film) to form a cured film pattern on the glass substrate. Use a hot air dryer to perform main curing (post-baking) at 85°C for 60 minutes, and the cured films (light-shielding films) of Examples 11 to 17 and Comparative Examples 11 to 12 were obtained.

[Film thickness measurement]

(evaluation method)

The step gauge ("TENCOR P-17" manufactured by KLA-Tencor) was used to measure the step difference between the glass substrate surface and the cured film surface under the conditions of a measuring range of 500 μm, a scanning speed of 50 μm/second, and a sampling rate of 20 Hz, and the average value was used as the hardened film. The average thickness of the film.

[Optical density (OD) evaluation]

(evaluation method)

The optical density (OD) was measured using a transmission density meter "X-rite 361T (V)" manufactured by X-rite Corporation. The optical density (OD) per 1 μm of film thickness was calculated from the film thickness and optical density (OD) measured above.

The optical density (OD) is calculated by the following formula (5).

Optical concentration (OD)=-log ₁₀ T Formula (5)

(T stands for transmittance).

[SCI method reflectivity evaluation]

(evaluation method)

A substrate with a cured film (light-shielding film) was produced in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, and the ultraviolet-visible-infrared-spectrophotometer "UH4150" (Hitachi High-Tech Science Co., Ltd. Co., Ltd.) The reflectance of each cured film (light-shielding film) side was measured under the conditions of C light source, incident angle of 2°, and wavelength range of 380 to 780 nm.

(Evaluation criteria for reflectivity characteristics)

○: The reflectivity of SCI method does not reach 5.5%.

△: The reflectivity of SCI method is more than 5.5% and less than 6.5%.

×: The reflectivity of SCI method is above 6.5%.

[SCE method of brightness evaluation]

(evaluation method)

For producing a substrate with a cured film (light-shielding film) in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, an ultraviolet-visible-infrared spectrophotometer "UH4150" (Hitachi High-Tech Science Co., Ltd.) measured the brightness of the cured film (light-shielding film) side using the SCE method under the conditions of C light source, incident angle 2°, and wavelength range 380 to 780nm.

(Evaluation criteria for brightness in SCE method)

○: The brightness of SCE method does not reach 6.0.

△: The brightness of the SCE method is 6.0 or more and less than 6.9.

×: The brightness of the SCE method is 6.9 or more.

(Preparation of cured film (shielding film) for evaluation of development adhesion)

The photosensitive resin composition shown in Table 2 was applied using a spin coater so that the film thickness after heat hardening became 1.2 μm, and the surface was previously irradiated with ultraviolet rays with a wavelength of 254 nm and an illumination of 1000 mJ/cm ² using a low-pressure mercury lamp, and the surface was cleaned. On the 125mm×125mm glass substrate "#1737" (manufactured by Corning Incorporated) ("Glass Substrate"), use a hot plate to pre-bake at 85°C for 1 minute to produce a cured film (light-shielding film). Then, cover the dry cured film with a negative photomask with a line width of 1 to 20 μm without an exposure gap, and use an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm ² to irradiate ultraviolet rays of 40 mJ/cm ² for Photohardening reaction of the photosensitive part.

Then, the exposed cured film (shielding film) is treated with a 0.04% potassium hydroxide solution at 25°C and a spray pressure of 1kgf/cm ² for 20 seconds starting from the development time (Break Time=BT) for pattern development. After the development treatment, perform spray water washing at 5kgf/ ^cm2 to remove the unexposed portion of the above-mentioned cured film (shielding film), and form a cured film pattern on the glass substrate. Use a hot air dryer to perform main curing (post-baking) at 85°C. ) for 60 minutes, and the cured films (light-shielding films) of Examples 11 to 17 and Comparative Examples 11 to 12 were obtained.

The following items were evaluated about the cured films (light-shielding films) obtained by curing the photosensitive resin compositions of Examples 11 to 17 and Comparative Examples 11 to 12 obtained above.

[Development adhesion evaluation]

(evaluation method)

The above-obtained patterns formed using negative masks of various widths were observed using an optical microscope to see whether the pattern remained. Also, △ or above is a passing grade.

(Evaluation criteria for development adhesion)

◎: The minimum line width of the remaining pattern is less than 5μm.

○: The minimum line width of the remaining pattern is 5 μm or more and less than 10 μm.

△: The minimum line width of the remaining pattern is 10 μm or more and less than 20 μm.

×: The minimum line width of the residual pattern is only 20μm.

[Evaluation of 850nm (IR) transmittance]

(evaluation method)

A substrate with a cured film (light-shielding film) was produced in the same manner as the cured film (light-shielding film) for optical density (OD) evaluation, and an ultraviolet-visible-infrared spectrophotometer "UH4150" (Hitachi High-Tech Science Co., Ltd. (manufactured by our company), measure the transmittance of the cured film (light-shielding film) side under the conditions of C light source, incident angle 2°, and wavelength range 380 to 1000 nm.

(Evaluation criteria for IR transmittance)

○: The transmittance at 850 nm is 80% or more.

△: The transmittance at 850 nm is 20% or more and less than 80%.

×: The transmittance at 850nm is less than 20%.

The above evaluation results are presented in Table 3.

[table 3]

Compared with the system using silica particles (Comparative Example 11) or the additive-free system (Comparative Example 12), it was confirmed that the photosensitive resin compositions of Examples 11 to 17 can reduce the coating film surface at high light shielding rate. The reflectivity of SCI method and the brightness of SCE method. Moreover, it was confirmed that the cured films (light-shielding films) obtained by curing the photosensitive resin compositions of Examples 11 to 17 all had good development adhesion.

(Experiment 3)

Various characteristics were evaluated for the composition using only (B1b) as the black pigment (B1) without using (B1a). The compositions prepared in this experiment are shown in Table 4 (units are parts by mass). In addition, in Table 4, except for (D) component, only the solid content is described.

[Table 4]

[Assessment]

A cured film (light-shielding film) in which the photosensitive resin composition used for evaluation is cured is prepared in the following manner.

(Preparation of cured film (coating film) for optical density (OD) evaluation)

A 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) coated with a protective layer (OC) agent was irradiated with ultraviolet light at a wavelength of 254 nm and an illumination of 1000 mJ/cm ² in advance with a low-pressure mercury lamp, and the surface was cleaned, and then The photosensitive resin composition shown in Table 1 was applied using a spin coater so that the film thickness after heat curing treatment became 1.2 μm, and was prebaked at 85° C. for 1 minute using a hot plate to produce a cured film (coating film). Without covering the negative photomask, use an ultra-high pressure mercury lamp with an i-ray illumination of 30mW/ ^cm2 to irradiate ultraviolet light of 40mJ/ ^cm2 to perform a photohardening reaction.

(Preparation of protective layer agent)

The protective layer agent is a resin composition containing an alkali-soluble resin containing a polymerizable unsaturated group, a photopolymerizable compound having at least two unsaturated bonds, a photoinitiator, a solvent, and other components in any ratio. The composition system used in this experiment is as follows.

(Alkali-soluble resin containing polymerizable unsaturated groups)

(A1)-3: The alkali-soluble resin solution obtained in Synthesis Example 4 above.

(Photopolymerizable compound having at least 2 unsaturated bonds)

(A2)-2: A mixture of dipenterythritol pentaacrylate and hexaacrylate (DPHA (acrylic acid equivalent: 96 to 115), manufactured by Nippon Kayaku Co., Ltd.).

(Photopolymerization initiator)

(C)-2: 1-[4-(phenylhydrothio)phenyl]octane-1,2-dione 2-O-benzoyl oxime (IRGACURE OXE01, manufactured by BASF).

(solvent)

(D)-1: Propylene glycol monomethyl ether acetate (PGMEA).

(D)-3: Diethylene glycol ethyl methyl ether (EDM).

(silica coupling agent)

(Other ingredients) -3:3-glycidoxypropyltrimethoxysilane.

(surfactant)

(Other ingredients)-4: BYK-302 (1 mass % PGMEA solution) (manufactured by BYK Corporation).

[table 5]

(Production of substrate coated with protective layer agent)

The protective layer agent composition shown in Table 5 is applied using a spin coater so that the film thickness after heat hardening becomes 0.3 μm. The surface is previously irradiated with ultraviolet rays with a wavelength of 254 nm and an illumination of 1000 mJ/cm ² using a low-pressure mercury lamp and the surface is cleaned. On the 125mm×125mm glass substrate "#1737" (manufactured by Corning Incorporated) ("Glass Substrate"), a hot plate was used to pre-bake at 90°C for 1 minute to produce a cured film (coating film). Then, a hot air dryer was used for main curing (post-baking) at 230° C. for 30 minutes to obtain the underlying substrates used in Examples 21 to 24 and Comparative Example 21.

[Film thickness measurement]

(evaluation method)

Using a step gauge ("TENCOR P-17" manufactured by KLA-Tencor Corporation), the step difference between the surface of the glass substrate and the surface of the protective layer agent cured film was measured under the conditions of a measurement range of 500 μm, a scanning speed of 50 μm/second, and a sampling rate of 20 Hz, and averaged the steps. The value is taken as the average thickness of the protective layer agent cured film. Furthermore, the step difference between the glass substrate surface and the light-shielding film surface was measured under the same conditions, and the average value was taken as the average thickness of the cured film including the protective layer agent cured film and the light-shielding film. The average thickness of the protective layer agent cured film and the light-shielding film is subtracted from the average thickness of the cured film including the protective layer agent cured film and the light-shielding film, thereby obtaining the average thickness of the light-shielding film (= including the protective layer agent cured film and the light-shielding film The average thickness of the cured film - the average thickness of the protective layer agent cured film).

[Optical density (OD) evaluation]

(evaluation method)

The evaluation was performed in the same manner as in Experiment 2, except that a glass substrate (underlying substrate) coated with an OC agent was used instead of the glass substrate.

[SCI method reflectivity evaluation]

(evaluation method)

Evaluate in the same way as Experiment 2.

(Evaluation criteria for reflectivity characteristics)

○: The reflectance of SCI method does not reach 5.0%.

△: The reflectivity of SCI method is 5.0% or more and less than 6.0%.

×: The reflectivity of SCI method is above 6.0%.

[SCE method of brightness evaluation]

(evaluation method)

Evaluate in the same way as Experiment 2.

(Evaluation criteria for brightness in SCE method)

○: The brightness of SCE method does not reach 3.0.

×: The brightness of the SCE method is 3.0 or more.

(Preparation of cured film (shielding film) for evaluation of development adhesion)

It was produced in the same manner as Experiment 2 except that a glass substrate (base substrate) coated with an OC agent was used instead of the glass substrate.

The following items were evaluated for the cured films (light-shielding films) obtained by curing the photosensitive resin compositions of Examples 21 to 24 and Comparative Example 21 obtained above.

[Development adhesion evaluation]

(evaluation method)

Evaluate in the same way as Experiment 2. Also, △ or above is a passing grade.

(Evaluation criteria for development adhesion)

◎: The minimum line width of the remaining pattern is less than 5μm.

○: The minimum line width of the remaining pattern is 5 μm or more and less than 10 μm.

△: The minimum line width of the remaining pattern is 10 μm or more and less than 20 μm.

×: The minimum line width of the residual pattern is only 20μm.

The above evaluation results are shown in Table 6.

[Table 6]

Compared with the additive-free system (Comparative Example 21), it was confirmed that the photosensitive resin compositions of Examples 21 to 24 can reduce the reflectivity of the SCI method and the brightness of the SCE method of the coating surface even at high light shielding rates. Moreover, it was confirmed that the cured films (light-shielding films) obtained by curing the photosensitive resin compositions of Examples 21 to 24 all had good development adhesion.

(industrial applicability)

According to the photosensitive resin composition of the present invention, a photosensitive resin composition having both low reflectivity and low brightness, a cured film using the photosensitive resin composition, a color filter, and a touch panel can be provided. In addition, according to the color filter and the touch panel, various display devices with excellent visual confirmation can be provided.

Claims (7)

A photosensitive resin composition containing: (A) The resin component includes an alkali-soluble resin (A1) containing an unsaturated group, a photopolymerizable compound (A2) having at least two unsaturated bonds, and a thermosetting epoxy compound (A3); (B) The light-shielding component contains black pigment (B1), magnesium fluoride and/or cryolite particles (B2); and (C) Photopolymerization initiator. The photosensitive resin composition according to Claim 1, wherein the black pigment (B1) contains a black pigment ( B1a). The photosensitive resin composition according to claim 2, wherein the black pigment (B1a) is an organic black pigment. The photosensitive resin composition according to any one of claims 1 to 3, wherein the ratio of the magnesium fluoride and/or cryolite particles (B2) to the total mass of the light-shielding component (B) is 1 to 30 mass. %. A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 4. A display component having the cured film according to claim 5. A display device having the display components described in claim 6.