TWI667534B - Photosensitive composition for forming a shading screen, a light shielding screen, and a display device - Google Patents

Abstract

An object of the present invention is to provide a photosensitive composition suitable for forming a white light-shielding screen having high design properties and excellent solvent resistance.

The solution of the present invention is a photosensitive composition for forming a light-shielding screen comprising (A) a white pigment, (B) a binder resin, (C) a polymerizable compound, and (D) a photopolymerization initiator, wherein (D) The photopolymerization initiator contains an O-fluorene-based photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, a fluorenylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator. At least one photopolymerization initiator.

Description

Photosensitive composition for forming a shading screen, a light shielding screen, and a display device

The present invention relates to a photosensitive composition for forming a light-shield screen, a light-shielding screen, and a display device, and more particularly to a photosensitive composition for forming a light-shield screen used in a portable digital terminal or the like, and using the photosensitive composition The formed shading screen and a display device having the shading screen.

In recent years, in various portable digital display devices such as smart phones and tablet terminals, the touch panel has been rapidly popularized as a position input device, and is mainly a capacitive multi-touch capable of performing multiple multi-touch operations. The display has become mainstream. In the capacitive touch panel, in order to prevent the lead wires from being seen from the user side, a technique of hiding the lead wires behind the light shielding layer has been studied (for example, refer to Patent Document 1).

However, recently, miniaturization and weight reduction of a display have been desired, and therefore it has been studied to narrow the width of a light shielding layer (also referred to as a light shielding screen). Now, the light shielding layer is mainly formed by screen printing, but it is difficult to form a high-definition pattern for the following reasons. In other words, in the screen printing method, there is a problem that the wiring may be easily bleed, rubbed, or the like, or bubbles may be formed between the lines when the wiring is formed, which may cause the display screen to be eroded or corroded.

Therefore, it has been studied to form a light shielding layer by photolithography using a photosensitive composition. For example, in Patent Documents 2 to 3, a technique of forming a black light-shielding layer using a photosensitive composition in which a black pigment is dispersed has been proposed.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent No. 5199913

Patent Document 2 Japanese Patent Laid-Open Publication No. 2012-145699

Patent Document 3 Japanese Patent Laid-Open Publication No. 2013-205474

Conventionally, the light-shielding layer is usually made black from the viewpoint of light-shielding property, but in recent years, a white light-shielding layer may be desired as the design changes. In order to exhibit white color, for example, in Patent Documents 2 to 3, a white pigment is used instead of a black pigment to prepare a photosensitive composition, but when the photosensitive composition is used to form a white light-shielding layer, yellowing of the resin component due to heat causes whiteness. (whiteness) drops. In recent years, in order to integrate the touch panel assembly, a transparent electrode or a protective film for a touch panel may be formed on the upper layer of the light shielding layer. However, when the transparent electrode is formed, heat treatment at 250 ° C or higher causes a yellow component of the resin component. Therefore, it is becoming more and more difficult to make a white shade layer with a high whiteness.

Further, after the light shielding layer is formed, it is necessary to etch the metal film or the like, and therefore the material of the light shielding layer is required to have chemical resistance.

It is strongly desired to provide a photosensitive composition that satisfies all of the above-mentioned required characteristics.

Therefore, an object of the present invention is to provide a photosensitive composition suitable for forming a light-shield screen having high whiteness and excellent chemical resistance and light-shielding properties. Further, an object of the present invention is to provide a light shielding screen formed using the photosensitive composition and a display device including the same.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific photopolymerization initiator.

That is, the present invention provides a photosensitive composition for forming a light-shielding screen comprising (A) a white pigment, (B) a binder resin, (C) a polymerizable compound, and (D) a photopolymerization initiator, wherein (D) The photopolymerization initiator contains an O-fluorene-based photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, a fluorenylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator. At least one photopolymerization initiator.

Moreover, the present invention provides a light shielding screen formed using the photosensitive composition and a display device including the same.

When the photosensitive composition of the present invention is used, it is possible to form a light-shielding screen having high whiteness and excellent chemical resistance and light-shielding properties.

Therefore, the photosensitive composition of the present invention is very suitable for use in producing a display device typified by a portable digital display device such as a smart phone or a tablet terminal.

[Formation for implementing the invention]

First, the main terms used in the present invention will be described.

(shading layer (shading screen))

The light shielding layer has a function of hiding wirings, control circuits, and the like on the outer peripheral portion of the position detection area (touch panel portion) in the center of the display device so as not to be seen, so that the appearance of the display device is not impaired. Therefore, the shading layer is required to hide the shading property of the unnecessary components.

(white)

In the present invention, white is defined as a color in which CIELAB (L ^* a ^* b ^* color system) has a lightness index (L ^* ) of 80 or more and a color index (a ^* , b ^* ) of more than -5 and less than 5, respectively. The above three attributes of the L ^* a ^* b ^* color system can be measured using a commercially available spectrophotometer, spectrophotometer or the like.

(yellow)

Yellowing means that an object absorbs a large amount of light having a wavelength of 380 to 550 nm, particularly a wavelength of 400 to 450 nm, in a substantially visible light region, and as a result, a yellow component as a complementary color thereof is contained in a large amount in the color of the object. In the L ^* a ^* b ^* color system, if b ^* is 5 or more, yellowing can be recognized by visual observation. Also, a ^* indicates that the object is reddish or greenish, regardless of the degree of yellowing.

Next, the present invention will be described in detail.

Photosensitive composition for forming a shading screen - (A) white pigment -

The white pigment used as the photosensitive composition of the present invention can be, for example, oxidized from calcium carbonate, lead carbonate, cesium carbonate, barium sulfate, lead sulfate, lead phosphate, zinc phosphate, titanium oxide, aluminum oxide, cerium oxide, or the like. Zinc, cerium oxide, zirconia, tin oxide, zinc sulfide, barium sulfide, barium titanate, barium tungstate, lead metasilicate, talc, kaolin, clay, bismuth oxychloride, calcium hydroxide, hollow cerium oxide, etc. select.

The white pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a compound having the following color index (C.I.) number.

CI pigment white 1, CI pigment white 2, CI pigment white 3, CI pigment white 4, CI pigment white 5, CI pigment white 6, CI pigment white 6: 1, CI pigment white 7, CI pigment white 8, CI pigment white 10. CI Pigment White 11, CI Pigment White 12, CI Pigment White 13, CI Pigment White 14, CI Pigment White 15, CI Pigment White 16, CI Pigment White 17, CI Pigment White 18, CI Pigment White 18:1, CI Pigment white 19, CI pigment white 20, CI pigment white 21, CI pigment white 22, CI pigment white 23, CI pigment white 24, CI pigment white 25, CI pigment white 26, CI pigment white 27, CI pigment white 28, CI Pigment white 30, CI pigment white 32, CI pigment white 33.

These white pigments may also be treated with other metals such as alumina or decane.

Among these white pigments, at least one selected from the group consisting of titanium oxide and barium titanate is preferably contained from the viewpoint of obtaining a light-shielding layer having a high light-shielding property. The crystal form of titanium oxide is preferably rutile.

The average particle diameter of the white pigment is usually from 100 to 700 nm, and from the viewpoint of light-shielding property and storage stability of the photosensitive composition, it is preferably from 180 to 500 nm, more preferably from 200 to 400 nm, still more preferably from 250 to 400 nm. Here, the "average particle diameter" refers to a value obtained by measuring the long diameters of 100 primary particles existing in the observation field of the transmission electron microscope and calculating the average value thereof.

The photosensitive composition of the present invention may be used in combination with other coloring agents other than the white pigment, within the scope of the gist of the present invention. Examples of such other coloring agents include red pigments, yellow pigments, blue pigments, green pigments, violet pigments, and black pigments.

In the present invention, the white pigment and any other pigments which are optionally mixed may be used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating or a combination thereof. Further, these pigments may be used by modifying the surface of the particles with a resin as needed. For example, the carrier resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is used as the resin for modifying the surface of the pigment particles. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, a well-known dispersing agent and a dispersing aid may be further contained together with a white pigment and other pigments which are arbitrarily mixed.

Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polydispersant. An ethylene glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, a (meth)acrylic dispersing agent, a phosphate ester dispersing agent, and the like. As a commercial item, for example, Disperbyk-2000, Disperbyk-2001, Disperbyk-182, Disperbyk-184, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above (Methyl) acrylic dispersant such as BYK-Chemie (BYK), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (The above is BYK-Chemie (BYK) )), a urethane-based dispersant such as Solsperse 76500 (manufactured by Lubrizol Co., Ltd.); a polyethyleneimine-based dispersant such as Solsperse 24000 (manufactured by Lubrizol Co., Ltd.); Adisper PB821, Adisper PB822, and Adisper PB880 A polyester dispersant such as Adisper PB881 (above, Ajinomoto Fine-Techno Co., Ltd.); a phosphate ester dispersant such as Disperbyk-110 or Disperbyk-180.

In particular, the dispersing agent is preferably selected from the group consisting of a (meth)acrylic dispersing agent, a phosphate ester dispersing agent, an urethane dispersing agent, and a polyester dispersing agent from the viewpoint of improving storage stability. At least one of the group is more preferably at least one selected from the group consisting of a (meth)acrylic dispersant and a phosphate dispersant.

Further, from the viewpoint of improving storage stability, the dispersant is preferably a dispersant having an acid value of 10 to 200 mgKOH/g or a dispersant having an amine value of 20 to 200 mgKOH/g. The acid value is more preferably from 50 to 180 mgKOH/g, still more preferably from 60 to 180 mgKOH/g, still more preferably from 80 to 150 mgKOH/g. The amine value is more preferably from 40 to 200 mgKOH/g, still more preferably from 60 to 180 mgKOH/g, still more preferably from 70 to 150 mgKOH/g, from the viewpoint of storage stability of the pigment dispersion liquid and the curable composition. On the other hand, from the viewpoint of forming a light-shielding screen having a high whiteness, the amine value is preferably from 20 to 150 mgKOH/g, more preferably from 20 to 80 mgKOH/g. Here, the "acid value" in the present invention means that 1 g of the dispersant solid content is required for neutralization. The number of mg of KOH, "amine value" means the number of mg of HCl and equivalent KOH required to neutralize 1 g of the dispersant solid content.

In the present invention, the dispersing agent may be used singly or in combination of two or more. When it is used in combination of two or more kinds, it is preferred to contain at least a (meth)acrylic dispersant, and the content of the (meth)acrylic dispersant is preferably 50% by mass or more, and more preferably 70% by mass based on the total amount of the dispersing agent. %the above. By such an aspect, it is easy to obtain a photosensitive composition which is more excellent in storage stability.

In the present invention, the content of the dispersant is usually 0.5 to 50 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass based on 100 parts by mass of the total of the white pigment and any other coloring agent used arbitrarily. Share. By such an aspect, a photosensitive composition excellent in storage stability can be formed.

Further, examples of the dispersing aid include a pigment derivative and the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

The total content of the white pigment and any other colorant to be used is usually 10 to 80% by mass, preferably 30 to 75% by mass, based on the solid content of the photosensitive composition, from the viewpoint of forming a light-shielding screen having excellent light-shielding properties. More preferably, it is 40 to 70% by mass, and particularly preferably 50 to 70% by mass. Here, the solid content means a component other than the solvent described later.

When the other coloring agent is used in combination with the white pigment, the content ratio of the other coloring agent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less based on 100 parts by mass of the white pigment.

- (B) Adhesive Resin -

The (B) binder resin in the present invention is not particularly limited, and is preferably a resin having at least one functional group selected from the group consisting of an acidic functional group and a cyclic ether group. Examples of the acidic functional group include a sulfo group, a carboxyl group, a phosphoric acid group, and a phenolic hydroxyl group. In addition, as the cyclic ether group, a saturated heterocyclic group having an oxygen atom as a hetero atom constituting a hetero atom of a hetero ring and a saturated heterocyclic group having 3 to 7 atoms in the ring is preferable, and examples thereof include an epoxy group. Ethyl, oxetane, alicyclic epoxy, tetrahydrofuranyl and the like. Here, the "alicyclic epoxy group" refers to an epoxy group formed by bonding one oxygen atom between two adjacent carbon atoms in a carbon atom constituting the alicyclic structure, and examples thereof include 3, 4 - Epoxycyclohexyl, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9- Base.

Among them, the (B) binder resin is preferably a polymer having a carboxyl group or a polymer having a carboxyl group and a cyclic ether group.

Examples of the polymer having a carboxyl group include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (b1)") and other copolymerizable ethylenically unsaturated monomers. (hereinafter, also referred to as a copolymer of "unsaturated monomer (b2)"), a polymer obtained by reacting a polymer containing an ethylenically unsaturated monomer having a hydroxyl group as a monomer unit, and a polybasic acid anhydride, comprising A hydrolysis condensate of a decane compound of a decane monomer of a carboxyl group.

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene oxy oxyethyl] ester, and ω-carboxy condensate. Lactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

The unsaturated monomer (b1) may be used singly or in combination of two or more.

Further, examples of the unsaturated monomer (b2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; An aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, terpene; such as methyl (meth)acrylate or (meth)acrylic acid An alkyl (meth)acrylate such as n-butyl ester or 2-ethylhexyl (meth)acrylate; such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate a hydroxyalkyl (meth) acrylate such as a (meth) acrylate of an unsaturated alcohol such as (meth) acrylate or allyl (meth) acrylate; such as (meth) acrylate An aryl (meth)acrylate such as phenyl ester or benzyl (meth)acrylate; such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo(methyl)acrylate [5.2. 1.0 ^2,6 ]decane-8-yl ester, (meth) acrylate having an alicyclic hydrocarbon group such as dicyclopentenyl (meth)acrylate; such as polyethylene glycol (degree of polymerization 2 to 10) Methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~1) 0) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, glycerol single (Meth) acrylate of a polyol such as (meth) acrylate; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ]decane-8-ylethylene Vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether such as 3-(vinyloxymethyl)-3-ethyloxetane; such as 4-hydroxybenzene (meth)acrylate (meth) acrylate of an aromatic alcohol such as an ethylene oxide-modified (meth) acrylate of p-cumylphenol; such as polystyrene, poly(methyl) methacrylate, poly A macromonomer having a mono(meth)acrylinyl group at the end of the polymer molecular chain such as n-butyl (meth)acrylate or polyoxyalkylene oxide.

Further, examples of the polybasic acid anhydride include maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and simicarbic anhydride. An acid anhydride of a dibasic acid; a monoanhydride of a polybasic acid having a tribasic acid or higher such as trimellitic anhydride; a dianhydride of a polybasic acid having a tetrabasic acid or higher such as cyclohexanetetracarboxylic dianhydride or pyromellitic dianhydride.

Among them, as the polymer having a carboxyl group, a copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2) is preferred, and in this case, as the unsaturated monomer (b2), it is preferred to contain (A) Alkyl acrylate. Further, the unsaturated monomer (b2) may be used singly or in combination of two or more.

In addition, examples of the polymer having a carboxyl group and a cyclic ether group include an unsaturated monomer (b1) and an ethylenically unsaturated monomer having a cyclic ether group (hereinafter, also referred to as "unsaturated monomer". (b3)") a copolymer as a monomer unit; a part of an epoxy group of the copolymer having an ethylenically unsaturated monomer having an epoxy group as a monomer unit and an unsaturated group a copolymer obtained by reacting a monomer (b1) with a polybasic acid anhydride; a hydrolysis condensate comprising a decane monomer having a carboxyl group and a decane monomer having a cyclic ether group, the copolymer may be further One step has an unsaturated monomer (b2) as a monomer unit. The cyclic ether group is preferably an epoxy group, an oxetanyl group or an alicyclic epoxy group, more preferably an epoxy group or an oxetanyl group.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, and (meth)acrylic acid-2- Hydroxypropyl ester glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, (meth)acrylic acid-4-hydroxybutyl ester glycidyl ether, polyethylene glycol-polypropylene glycol (meth) acrylate A (meth) acrylate having a glycidyl group such as glycidyl ether; or an aromatic vinyl compound having a glycidyl group such as vinylbenzyl glycidyl ether.

Examples of the ethylenically unsaturated monomer having an alicyclic epoxy group include a compound represented by the following formula (1), a compound represented by the following formula (2), and the following formula (3). A (meth) acrylate having an alicyclic epoxy group, such as a compound represented by the formula.

Examples of the ethylenically unsaturated monomer having an oxetane group include 3-[(meth)acryloxymethyl]oxetane and 3-[(meth)acrylofluorene. (Meth) acrylate having an oxetanyl group such as methylmethyl-3-ethene oxide.

The ethylenically unsaturated monomer having a tetrahydrofuranyl group may, for example, be a (meth) acrylate having a tetrahydrofuranyl group such as a tetrahydrofurfuryl group (meth)acrylate.

The unsaturated monomer (b3) may be used singly or in combination of two or more.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may contain a hetero atom. ]

In the formulae (2) and (3), R ² independently represents a hydrogen atom or a methyl group, and X ² independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms which may contain a hetero atom. ]

The alkanediyl group having 1 to 6 carbon atoms in X ¹ and X ² may be linear or branched. Specific examples include methylene, ethyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, and propane-1,3-. Diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-di Base, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl and the like. Among them, an alkanediyl group having 1 to 4 carbon atoms is preferred, and an alkanediyl group having 1 or 2 carbon atoms is more preferred.

The above alkanediyl group having 1 to 6 carbon atoms may contain a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the alkanediyl group containing such a hetero atom include (*)-CH ₂ CH ₂ —O—, (*)-CH _{2 .} -O-CH ₂ -, (*)-CH ₂ CH ₂ -S-, (*)-CH ₂ -S-CH ₂ -, (*)-CH ₂ CH ₂ -NH-, (*)-CH ₂ -NH-CH ₂ -etc. Where (*) indicates a connection key to -COO-.

The compound represented by the formula (1) includes 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M100, manufactured by DAICEL Chemical Industry Co., Ltd.; and R ¹ is a formula (1) a compound in which X ¹ is a methylene group), and 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, manufactured by DAICEL Chemical Industry Co., Ltd.; in the formula (1), R ¹ is a hydrogen atom, X ¹ is a methylene compound).

Examples of the compound represented by the formula (2) include a compound represented by the formula (2-1) to (2-8).

The compound represented by the formula (3) may, for example, be a compound represented by the formula (3-1) to (3-8).

In particular, the unsaturated monomer (b3) is preferably a (meth) acrylate having a glycidyl group or a (meth) acrylate having an alicyclic epoxy group, from the viewpoint of chemical resistance. The (meth) acrylate of oxetanyl group is more preferably glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or the formula (2-1) The compound represented by the formula (3-1).

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 50% by mass, more preferably 10%. ~40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a photosensitive composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-10. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The disclosed copolymer.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. As the binder resin, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain can also be used as disclosed in Japanese Laid-Open Patent Publication No. 2008-181095.

Further, in the copolymer having the unsaturated monomer (b1) and the unsaturated monomer (b3) as a monomer unit, the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 40. The mass %, more preferably 10 to 25% by mass, and the copolymerization ratio (b1/b3) of the unsaturated monomer (b1) and the unsaturated monomer (b3) is preferably 1/9 to 7/3 by mass ratio. More preferably 3/7~6/4. By copolymerizing the unsaturated monomer (b1) and the unsaturated monomer (b3) in such a ratio, in addition to improvement in alkali developability and storage stability, light blocking properties and chemical resistance can be improved.

In the present invention, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC) (eluent solvent: tetrahydrofuran) is usually 1,000 to 100,000. It is preferably 3,000 to 50,000. By becoming like this In the aspect, the residual film ratio, the pattern shape, the heat resistance, the electrical properties, and the resolution of the film can be further improved, and the generation of dry foreign matter at the time of coating can be suppressed at a high level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (B) binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Further, Mn referred to herein means a polystyrene-equivalent number average molecular weight measured by GPC (solution solvent: tetrahydrofuran).

The (B) binder resin in the present invention can be produced by a known method. For example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 2007/029871 can be used. The disclosed method controls its structure, Mw, Mw/Mn.

In the present invention, the (B) binder resin may be used singly or in combination of two or more.

In the present invention, the content of the (B) binder resin is usually 5 to 300 parts by mass, preferably 10 to 200 parts by mass, more preferably 20 parts by mass based on 100 parts by mass of the total of the white pigment and any other coloring agent used. ~100 parts by mass. By such an aspect, it is possible to form a light-shielding screen excellent in light-shielding property, heat resistance, and chemical resistance.

- (C) Polymeric Compound -

The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Among them, (B) binder resin is not included. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as a polymerization The compound is preferably a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylonitrile groups include polyfunctional (meth) acrylates and caprolactones obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Modified polyfunctional (meth) acrylate, polyalkyl (meth) acrylate modified by alkylene oxide, poly (meth) acrylate having hydroxyl group and polyfunctional amine based on polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting an acid ester (meth) acrylate, a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a two-membered aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; for example, glycerin or trimethylolpropane A trivalent or higher aliphatic polyhydroxy compound such as pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic acid and biphenyl tetra A tetrabasic acid dianhydride such as carboxylic acid dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified as the polyfunctional (meth) acrylate which is modified by the caprolactone. The above-mentioned alkylene oxide-modified polyfunctional (meth)acrylate may, for example, be at least one modified bisphenol A di(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide. And modifying at least one modified isocyanuric acid tris(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and at least one selected from the group consisting of ethylene oxide and propylene oxide a trimethylolpropane tri(meth)acrylate, at least one modified pentaerythritol tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide And at least one modified pentaerythritol tetra(meth)acrylate of propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, At least one modified dipentaerythritol hexa(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Further, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or three substituted by phenyl The chemical structure of the ring as a basic skeleton is also a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having 3 or more elements with (meth)acrylic acid, or a polyfunctional (methyl) modified by caprolactone is preferable. Acrylate, polyfunctional urethane (meth) acrylate, N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. In the polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the unexposed portion is Particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like, which are less likely to cause scum, film residue, and the like on the substrate and the light shielding layer. ester.

In the present invention, the (C) polymerizable compound may be used singly or in combination of two or more.

In the present invention, the content of the (C) polymerizable compound is usually from 3 to 200 parts by mass, preferably from 5 to 100 parts by mass, more preferably from 10 to 100 parts by mass, based on 100 parts by mass of the total of the white pigment and any other coloring agent used. ~50 parts by mass. Further, the content of the (C) polymerizable compound is usually 20 to 150 parts by mass, preferably 30 to 120 parts by mass, more preferably 40 to 90 parts by mass, per 100 parts by mass of the binder resin. By such an aspect, it is possible to form a light-shielding screen excellent in light-shielding property, heat resistance, and chemical resistance.

-(D) Photopolymerization Initiator -

In the colored composition of the present invention, as the (D) photopolymerization initiator, a photopolymerization agent selected from the group consisting of an O-fluorene photopolymerization initiator and an α-aminoalkylphenone is used. At least one of a combination initiator, a fluorenylphosphine oxide-based photopolymerization initiator, and a titanocene-based photopolymerization initiator. a photopolymerization initiator selected from the group consisting of an O-fluorene photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, a fluorenylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator Two or more types may be used in combination in any combination.

Examples of the O-fluorene-based photopolymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6 -(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-{2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-B Ketone 1-(O-acetamidine), 1-[4-[3-[4-[[2-(ethoxy)ethyl]sulfonyl]-2-methylbenzylidene]- 6-[1-[(Ethyloxy)imino]ethyl]-9H-carbazole]-9-yl]phenyl-1-octanone 1-(O-acetyl) and the like. As a commercial item of an O-oxime compound, NCI-700, NCI-730, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (the above is Daito chemix) can be used. Co., Ltd.), Irgacure OXE-03, Irgacure OXE-04 (above, BASF).

Among these O-fluorene-based photopolymerization initiators, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-ethanone 1- is preferred. (O-acetamidine), 1-[4-[3-[4-[[2-(ethoxy)ethyl]sulfonyl]-2-methylbenzhydryl]-6-[ 1-[(Ethyloxy)imino]ethyl]-9H-carbazole]-9-yl]phenyl-1-octanone 1-(O-acetamidine).

The O-fluorene-based photopolymerization initiator may be used singly or in combination of two or more.

The α-aminoalkylphenone photopolymerization initiator may, for example, be 2-methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N- Polinylphenyl)butan-1-one and the like.

Among these α-aminoalkylphenone photopolymerization initiators, 2-methyl-1-[4-(methylthio)phenyl]-2-N- is preferred. Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Polinylphenyl)butan-1-one.

The α-aminoalkylphenone-based photopolymerization initiator may be used singly or in combination of two or more.

Examples of the sulfonium phosphine-based photopolymerization initiator include methyl isobutyl decyl methyl phosphinate, methyl isobutyl nonyl phenyl phosphinate, and methyl trimethyl acetyl phenyl phosphinate. Methyl 2-ethylhexylphenylphosphinate, isopropyl trimethylglycidylphenylphosphinate, methyl p-tolylmethylphenylphosphinate, o-tolylmethylphenyl Methyl phosphinate, methyl 2,4-dimethylbenzimidylphosphonate, p-tert-butyl butyl benzhydrylphenylphosphinate, propylene nonylphenylphosphinic acid Methyl ester, butyl isobutylphosphonium diphenylphosphine, 2-ethylhexyldiphenylphosphine oxide, o-tolylmethyl phenyl diphenylphosphine oxide, oxidized p-tert-butyl benzhydryl diphenyl Phosphine, oxidized-3-pyridylcarboxydiphenylphosphine, propylene oxide decyldiphenylphosphine, benzamidine diphenylphosphine oxide, trimethylethenyl Vinyl phenylphosphinate, hexamethylenediphenylphosphine oxide, trimethylacetamidodiphenylphosphine oxide, p-tolylmethylphenyl diphenylphosphine oxide, oxidized-4-(tri-butyl) Benzopyridyl diphenylphosphine, oxidized p-xylylene bisdiphenylphosphine, -2-methylbenzhydryldiphenylphosphine oxide, neodecyl diphenylphosphine oxide, oxidation 2-methyl-2-ethylhexyl diphenylphosphine, oxy-1-methylcyclohexyl phenyl diphenylphosphine, methyl trimethyl ethinyl phenylphosphinate, trimethyl ethane Oxidized monodecylphosphine such as isopropyl nonylphenylphosphinate, oxidized-2,4,6-trimethylbenzhydryldiphenylphosphine; oxidized bis(2,6-dichlorobenzylidene) Phenylphosphine, bis(2,6-dichlorobenzylidene)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzylidene)-4-ethoxylated Phenylphosphine, bis(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzylidene)-2-naphthylphosphine oxide, oxidation Bis(2,6-dichlorobenzhydryl)-1-naphthylphosphine, bis(2,6-dichlorobenzylidene)-4-chlorophenylphosphine oxide, oxidized bis(2,6-di Chlorobenzylidene)-2,4-dimethoxyphenylphosphine, oxidized bis(2,6-dichlorobenzene Mercaptophosphine, bis(2,6-dichlorobenzylidene)-4-octylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzene) Mercapto)-2,5-dimethylphenylphosphine, bis(2,6-dichloro-3,4,5-trimethoxybenzylidene)-4-ethoxyphenylphosphine oxide, Bis(2-methyl-1-naphthomethyl)-2,5-dimethylphenylphosphine oxide, bis(2-methyl-1-naphthomethyl)-4-ethoxyphenyl oxide Phosphine, bis(2-methyl-1-naphthylmethyl)-2-naphthylphosphine oxide, bis(2-methyl-1-naphthylmethyl)-4-propylphenylphosphine oxide, oxidation double (2-methyl-1-naphthomethyl)-2,5-dimethylphenylphosphine, bis(2-methoxy-1-naphthomethyl)-4-ethoxyphenylphosphine oxide Oxidized bis(2-chloro-1-naphthoquinone) Oxidized bis-decylphosphine, etc., such as 2,5-dimethylphenylphosphine, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine .

In addition, the mercaptophosphine compound described in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei.

Among these phthalocyanine-based photopolymerization initiators, as the oxidized monodecylphosphine, oxidized-2,4,6-trimethylbenzimidyldiphenylphosphine (for example, Darocur TPO manufactured by BASF Corporation) is preferred. As the bis(indenylphosphine oxide), bis(2,4,6-trimethylbenzylidene)phenylphosphine (for example, Irgacure 819, manufactured by BASF Corporation) and oxidized double (2,6-di) are preferred. Methoxybenzylidene)-2,4,4-trimethylpentylphenylphosphine (for example, Irgacure 1700, manufactured by BASF Corporation), more preferably oxidized bis(2,4,6-trimethylbenzene) Mercapto) phenylphosphine.

The fluorenylphosphine oxide-based photopolymerization initiator may be used singly or in combination of two or more.

In addition, examples of the titanocene-based photopolymerization initiator include bis(cyclopentadienyl)titanium dichloride, bisphenylbis(cyclopentadienyl)titanium, and bis-2,3,4. 5,6-pentafluorophenyl bis(cyclopentadienyl)titanium, bis-2,3,5,6-tetrafluorophenylbis(cyclopentadienyl)titanium, bis-2,4,6- Trifluorophenyl bis(cyclopentadienyl)titanium, bis-2,6-difluorophenylbis(cyclopentadienyl)titanium, bis-2,4-difluorophenylbis(cyclopentadiene) Titanium, bis-2,3,4,5,6-pentafluorophenyl bis(methylcyclopentadienyl)titanium, bis-2,3,5,6-tetrafluorophenyl bis(methyl) Cyclopentadienyl)titanium, bis-2,6-difluorophenylbis(methylcyclopentadienyl)titanium (for example, Irgacure 727L, manufactured by BASF Corporation), bis(2,6-difluoro-3-() Pyrrol-1-yl)phenyl)bis(cyclopentadienyl)titanium (for example, manufactured by BASF Corporation, Irgacure 784), double (2,4,6-trifluoro-3-(pyrrol-1-yl)phenyl)bis(cyclopentadienyl)titanium, bis(2,4,6-trifluoro-3-(2-5-) Dimethylpyrrol-1-yl)phenyl)bis(cyclopentadienyl)titanium, and JP-A-59-152396, JP-A-61-151197, and JP-A-63-10602 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A compound described in, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

Among these titanocene-based photopolymerization initiators, bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)bis(cyclopentadienyl)titanium is preferred.

The titanocene-based photopolymerization initiator may be used singly or in combination of two or more.

In particular, the (D) photopolymerization initiator preferably contains at least one selected from the group consisting of a fluorenylphosphine-based photopolymerization initiator and a titanocene-based photopolymerization initiator, and more preferably contains a fluorenylphosphine oxide system. Photopolymerization initiator.

Further, other photopolymerization initiators may be used in combination in the photosensitive composition of the present invention, without departing from the gist of the present invention. Examples of such a photopolymerization initiator include a thioxanthone compound, an α-hydroxyalkylphenone compound, a biimidazole compound, and the like. Compounds, etc. Examples of such other photopolymerization initiators include photopolymerization initiators exemplified in paragraphs [0079] to [0095] of JP-A-2010-134419.

In the present invention, the content of the (D) photopolymerization initiator is usually 5 to 200 parts by mass, preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of the polymerizable compound. By such an aspect, it is possible to form a light-shielding screen having excellent light-shielding properties, heat resistance, chemical resistance, curability, and film properties.

Further, at least one selected from the group consisting of an O-fluorene photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, a fluorenylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator is used. When the photopolymerization initiator and the other photopolymerization initiator are used, the content ratio of the other photopolymerization initiator is preferably 50% by mass or less, and more preferably 30% by mass based on the total content of the (D) photopolymerization initiator. Hereinafter, it is more preferably 20% by mass or less.

- (E) Antioxidants -

The photosensitive composition of the present invention preferably contains an antioxidant from the viewpoint of forming a light-shielding screen having less yellowing. Examples of such an antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and a benzophenone-based antioxidant. The antioxidants may be used singly or in combination of two or more.

Examples of the phenolic antioxidant include 2,4,6-tris(3',5'-di-tertiarybutyl-4'-hydroxybenzyl)-1,3,5-trimethylbenzene. , 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylanilino)-1,3,5-three , pentaerythritol tetrakis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate (for example, Irganox 1010 manufactured by BASF Corporation), 2,6-di-tertiary butyl-4-anthracene Phenol, thiodiethyl bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] (for example, Irganox 1035 by BASF), 2,2'-Methylene Bis-(6-(1-methylcyclohexyl)p-cresol), N,N-hexamethylenebis(3,5-di-tri-tert-butyl-4-hydroxy-hydrocinnamylamine), 2,5-di-tert-butyl hydroquinone, 2,5-di-triamylpentyl hydroquinone, 2,4-dimethyl-6-(1-methylcyclohexyl)phenol, 6-tertiary butyl o-cresol, 6-tert-butyl-2,4-xylenol, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, 2,4 - bis (octyl thiomethyl) o-cresol, 2,4-bis(dodecylthiomethyl) o-cresol, exoethyl bis(oxyethyl) bis [3-(3- tertiary) Butyl-4-hydroxy-5-methylphenyl)propionate] (for example, Irganox 245, manufactured by BASF Corporation), 3,9-bis[2-[3-(tri-butyl-4-hydroxy-5) -Methylphenyl)propenyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (for example, Sumitomo Chemical Co., Ltd. System, SUMILIZER GA-80), triethylene glycol double [3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (for example, ADK STAB AO-70, manufactured by ADEKA Co., Ltd.), 2-tert-amylphenol, 2-tertiary Phenolic, 2,4-di-tertiary butyl phenol, 1,1,3-tris(2'-methyl-4'-hydroxy-5'-tertiary butylphenyl)butane, 4,4 '-Butyl-bis-(2-tert-butyl-5-methylphenol), and as a commercial product, ADK STAB AO-30, ADK STAB AO-40, GPA-5001 (above is ADEKA Co., Ltd.) System), SUMILIZER BBM, SUMILIZER GM (above is Sumitomo Chemical Co., Ltd.), and TOPANOL CA (manufactured by ICI).

Examples of the phosphorus-based antioxidant include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, and phenylphosphite. Bis(tridecyl)ester, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris(phosphite) Phenyl) ester, 4,4'-isopropylidene diphenol alkyl phosphite, tridecyl phenyl phosphite, Tri-didecylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetra (trimium) -4,4'-butylene bis(3-methyl-6-tertiary butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl -4-hydroxy-5-tris-butylphenyl)butane triphosphite, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphite, 1,3-double (two Phenoxyphosphonium oxy)benzene, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite. As a commercial item, ADK STAB 1500, ADK STAB 2112, ADK STAB C, ADK STAB 135A, ADEKA 1500 (above, ADEKA Co., Ltd.), SUMILIZER GP (manufactured by Sumitomo Chemical Co., Ltd.), or the like can be used.

Examples of the sulfur-based antioxidant include the compounds described in paragraph [0084] of JP-A-2009-122650.

The benzophenone-based antioxidant is, for example, a compound described in paragraph [0123] of JP-A-2014-026228.

In particular, the antioxidant is preferably at least one selected from the group consisting of a phenolic antioxidant and a phosphorus antioxidant, and more preferably contains at least one phenolic antioxidant, from the viewpoint of forming a light-shielding screen having excellent lightness and light-shielding properties. . Further, the phenolic antioxidant preferably has four or more phenolic hydroxyl groups, and more preferably has six or more phenolic hydroxyl groups.

In the present invention, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass per 100 parts by mass of the components other than the solvent of the photosensitive composition. Parts by mass. By such an aspect, it is possible to form a blackout screen with less yellowing.

When the phenolic antioxidant and the phosphorus-based antioxidant are contained, the content ratio of the phenolic antioxidant to the phosphorus-based antioxidant (phenolic antioxidant/phosphorus antioxidant) is preferably 1/2 to 49/1 by mass ratio, more preferably The best is 1/1~19/1, more preferably 2/1~9/1, and even better 5/1~9/1.

-(F) solvent -

The photosensitive composition of the present invention contains the above components (A) to (D) and optionally added other components, and is usually prepared by mixing an organic solvent to prepare a liquid composition.

The (F) solvent can be appropriately selected and used as long as it can disperse or dissolve the components (A) to (D) constituting the photosensitive composition and other components, and does not react with these components, and has appropriate volatility.

Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol single (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, and butyl a (cyclo)alkyl alcohol such as an alcohol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol or cyclohexanol; Keto alcohol such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acid ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, acetic acid-3-methoxybutyl ester, acetic acid-3-methyl-3- (poly)alkylene glycol monoalkyl ether acetate such as methoxybutyl ester; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Glycol ether; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetic acid Diacetate such as ester; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxylate An alkoxycarboxylate such as ethyl acetate or butyl 3-methyl-3-methoxypropionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, N-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, Fatty acid alkyl esters such as n-butyl acrylate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate; toluene, xylene An aromatic hydrocarbon; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; or an indoleamine.

Among these organic solvents, (poly)alkylene glycol monoalkyl ether, alkyl lactate, (poly)alkylene glycol monoalkyl ether acetate are preferred from the viewpoints of solubility, dispersibility of pigment, coating property and the like. Ester, glycol ether, ketone, diethyl Acid esters, alkoxy carboxylates, fatty acid alkyl esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, 3-methoxyacetic acid butyl ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1 , 3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-B Ethyl oxypropionate, butyl 3-methyl-3-methoxypropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the (F) solvent may be used singly or in combination of two or more.

The content of the solvent (F) is not particularly limited, and the total concentration of each component other than the solvent of the photosensitive composition is preferably from 10 to 70% by mass, more preferably from 30 to 60% by mass. By adopting such a phenomenon, a photosensitive composition excellent in coatability and storage stability can be obtained.

-additive-

The photosensitive composition of the present invention may contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or a lanthanoid surfactant; and ethylene. Trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl oxygen Baseline, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, An adhesion promoter such as 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2-(3-tertiary butyl- Ultraviolet absorbers such as 5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; antiflocculating agents such as sodium polyacrylate; malonic acid, adipic acid, and y Kang acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2- Residue improver such as propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2-(methyl) propylene oxiranyl] ester, o-benzene A developability improving agent such as mono[2-(methyl)acryloyloxyethyl]dicarboxylate or ω-carboxypolycaprolactone mono(meth)acrylate.

The colored composition of the present invention can be produced by an appropriate method, and as a preparation method thereof, for example, a component (A) to (D) can be prepared by mixing together a solvent (F) and any other component added arbitrarily. Among them, it is preferred to use a bead mill, a roll mill, or the like, in the presence of a dispersant in a solvent (F), a coloring agent containing a white pigment, and (B) a binder resin, as the case may be. A part is pulverized, mixed and dispersed to prepare a pigment dispersion liquid, and then (C) a polymerizable compound is added to the pigment dispersion liquid, and (B) a binder resin, (D) a photopolymerization initiator, and, if necessary, further The additional (F) solvent and other components are prepared and mixed.

Shading screen and manufacturing method thereof

The shading screen of the present invention is formed using the photosensitive composition of the present invention, and more specifically, has a white cured film formed using the photosensitive composition of the present invention.

Hereinafter, a method of forming a white cured film constituting a light shielding screen will be described. First, the liquid composition of the photosensitive composition for forming a shading screen of the present invention is applied onto the surface of the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, a white cured film was formed in a predetermined arrangement by post-baking.

Examples of the substrate used for forming the white cured film include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, if necessary, appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition using a decane coupling agent or the like may be performed on these substrates.

When a photosensitive composition for forming a light-shielding screen is applied to a substrate, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, or the like may be employed. The coating method is particularly preferably a spin coating method or a slit mold coating method.

Pre-baking is usually carried out in combination with vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Further, the conditions of heat drying are usually carried out at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually from 1 to 50 μm, preferably from 2 to 30 μm, more preferably from 5 to 20 μm, in terms of the film thickness after drying.

Examples of the light source used for forming the white cured film include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury lamp. , argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser sources. As the light source for exposure, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4. An aqueous solution of 0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkali developer in an appropriate amount. Further, after alkali development, it is usually washed with water.

As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping (liquid pool) development method, or the like can be employed. The developing conditions are preferably carried out at room temperature for 5 to 300 seconds.

The post-baking conditions are usually carried out at 180 to 300 ° C for about 10 to 90 minutes. The photosensitive composition of the present invention can form a white cured film having less yellowing even under the conditions of a post-baking temperature of 200 to 300 ° C, further 230 to 300 ° C, and further 250 to 300 ° C.

The film thickness of the white cured film thus formed is usually 1 to 50 μm, preferably 2 to 30 μm, more preferably 5 to 20 μm. Using the photosensitive composition of the present invention The white cured film formed of the object can be used as a light-shielding screen excellent in light-shielding property even if it is a film. In addition, when a thick film thickness is formed in order to further improve the light-shielding property, since the photosensitive composition is excellent in the hardenability, it is excellent in the chemical-resistance, and does not exhibit the effect of not wrinkling the surface of the cured film.

On the thus obtained white cured film, a transparent conductive film can be formed by sputtering or a protective film can be formed as needed. The photosensitive composition of the present invention is particularly suitable as a white light-shielding film because it undergoes heat treatment at 250 ° C or higher when the transparent electrode is formed, and has less yellowing.

The light-shielding screen having the white cured film of the present invention thus formed is extremely suitable for a display device requiring a white design because it has less yellowing. Specifically, by making the screen of the present invention in CIELAB (L ^* a ^* b ^* color system), the brightness index (L ^* ) is 80 or more and the color indexes (a ^* , b ^* ) are respectively greater than -5 and When the thickness is less than 5, the display device including the light shielding screen can be excellent in design.

Display device

The display device of the present invention includes the blackout panel of the present invention. As the display device, a portable digital display device such as a smart phone or a tablet terminal can be cited.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

Dispersant synthesis Synthesis Example 1

100 parts by mass of propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as "PGMEA") was placed in a flask equipped with a cooling tube and a stirrer, and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of PGMEA, 5 parts by mass of succinic acid-2-propenyloxyethyl ester, 35 parts by mass of methyl methacrylate, and butyl methacrylate 30 were added dropwise thereto at this temperature. Parts by mass, 20 parts by mass of 2-ethylhexyl methacrylate, 10 parts by mass of glyceryl monomethacrylate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) The solution was mixed and maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour. After cooling to room temperature, the solid content concentration was adjusted to 40% by mass using PGMEA. This was used as a dispersant (1) solution (solid content concentration = 40% by mass). The obtained dispersant (1) had Mw = 16,000, Mn = 8,100, and an acid value of 13 mgKOH/g.

Synthesis of binder resin Synthesis Example 2

100 parts by mass of PGMEA was placed in a flask equipped with a cooling tube and a stirrer, and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of PGMEA, 10 parts by mass of methacrylic acid, 5 parts by mass of -2-methylpropenyloxyethyl succinate, and 35 parts by mass of benzyl methacrylate were added dropwise at this temperature. A mixed solution of 8.0 parts by mass of 2,2'-azobisisobutyronitrile and 8.0 parts by mass of α-methylstyrene dimer was maintained at 80 ° C for 4 hours of polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. After cooling to room temperature, the solid content concentration was adjusted to 40% by mass using PGMEA. This was used as a binder resin (B-1) solution. The obtained binder resin (B-1) had Mw = 8,100 and Mn = 5,300.

Synthesis Example 3

100 parts by mass of PGMEA was placed in a flask equipped with a cooling tube and a stirrer, and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of PGMEA, 10 parts by mass of methacrylic acid, 5 parts by mass of -2-methylpropenyloxyethyl succinate, and 15 parts by mass of benzyl methacrylate were added dropwise at this temperature. 20 parts by mass of glycidyl methacrylate, 8.0 parts by mass of 2,2'-azobisisobutyronitrile and 8.0 parts by mass of α-methylstyrene dimer were mixed and maintained at 80 ° C for 4 hours of polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. After cooling to room temperature, the solid content concentration was adjusted to 40% by mass using PGMEA. This was used as a binder resin (B-2) solution. The obtained binder resin (B-2) had Mw = 10,600 and Mn = 4,900.

Synthesis Example 4

100 parts by mass of PGMEA was placed in a flask equipped with a cooling tube and a stirrer, and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of PGMEA, 10 parts by mass of methacrylic acid, 5 parts by mass of -2-methylpropenyloxyethyl succinate, and 15 parts by mass of benzyl methacrylate were added dropwise at this temperature. 20 parts by mass of 3-ethyl-3-oxetanylmethyl methacrylate, 8.0 parts by mass of 2,2'-azobisisobutyronitrile, and 8.0 parts by mass of α-methylstyrene dimer The mixed solution was maintained at 80 ° C for 4 hours of polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. After cooling to room temperature, the solid content concentration was adjusted to 40% by mass using PGMEA. This was used as a binder resin (B-3) solution. The obtained binder resin (B-3) had Mw = 6,900 and Mn = 4,200.

Synthesis Example 5

100 parts by mass of PGMEA was placed in a flask equipped with a cooling tube and a stirrer, and replaced with nitrogen. The mixture was heated to 80 ° C, and 100 parts by mass of PGMEA, 10 parts by mass of methacrylic acid, 5 parts by mass of -2-methylpropenyloxyethyl succinate, and 15 parts by mass of benzyl methacrylate were added dropwise at this temperature. 20 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 8.0 parts by mass of 2,2'-azobisisobutyronitrile and 8.0 parts by mass of α-methylstyrene dimer and maintained The polymerization was carried out at 80 ° C for 4 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. After cooling to room temperature, the solid content concentration was adjusted to 40% by mass using PGMEA. This was used as a binder resin (B-4) solution. The obtained binder resin (B-4) had Mw = 8,300 and Mn = 4,500.

Particle size distribution particle size evaluation

The pigment dispersion prepared below was diluted 10-fold with PGMEA, and the average particle diameter of the white pigment was determined using a particle size distribution meter (L-500 manufactured by HORIBA).

Preparation of pigment dispersion Preparation Example 1

60.0 parts by mass of barium titanate as a coloring agent (A) and 6.2 parts by mass of DISPERBYK-180 (a product of BYK-Chemie (BYK) Co., Ltd., a phosphate ester dispersing agent) was used as a solid content concentration of 65% by mass. The PGMEA as a solvent and the PGMEA as a solvent were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion liquid (A-1). The white pigment has an average particle diameter of 250 nm.

Preparation Example 2

60.0 parts by mass of a CI pigment white 6:1 (titanium oxide) modified with alumina as a (A) coloring agent and 12.5 parts by mass of a dispersing agent as a dispersing agent were used as a solid content concentration of 65% by mass ( 1) A solution (acid value: 5.2 mgKOH/g, solid content concentration: 40% by mass), propylene glycol monomethyl ether (hereinafter sometimes referred to as "PGME") as a solvent, and mixed and dispersed in a bead mill for 12 hours. Pigment dispersion (A-2). The average particle diameter of the white pigment was 480 nm.

Preparation Example 3

60.0 parts by mass of the CI pigment white 6:1, 9.6 parts by mass of the surface modified with alumina as the (A) coloring agent as the solid content concentration of 65% by mass, DISPERBYK-110 (BYK-Chemie) (BYK), a phosphate ester dispersant, an acid value of 53 mgKOH/g, a solid content concentration of 52% by mass, and a PGMEA as a solvent, which was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-3). ). The white pigment has an average particle diameter of 320 nm.

Preparation Example 4

60.0 parts by mass of BYK-LPN21116 (BYK- as a dispersing agent) as a dispersing agent of 6% by mass of a surface-modified CI pigment white as a (A) coloring agent as a coloring agent (A) as a coloring agent. A pigment dispersion liquid was prepared by mixing and dispersing PGMEA as a solvent in a bead mill for 12 hours by a Chemie (BYK) company, a (meth)acrylic dispersant, an amine value of 29 mgKOH/g, and a solid content of 40% by mass. (A-4). The white pigment has an average particle diameter of 280 nm.

Preparation Example 5

60.0 parts by mass of CI Pigment White 12 (zirconia) as a coloring agent (A) and 9.6 parts by mass of DISPERBYK-110 (BYK-Chemie (BYK)), which is a dispersing agent, were used as a solid content concentration of 65% by mass. Phosphate-based dispersant, acid value: 53 mgKOH/g, solid content concentration: 52% by mass), and PGME as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-5). The white pigment has an average particle diameter of 120 nm.

Preparation Example 6

60.0 parts by mass of CI pigment white 4 (zinc oxide) as a coloring agent (A) and 9.6 parts by mass of DISPERBYK-110 (BYK-Chemie (BYK)), which is a dispersing agent, were used as a solid content concentration of 65% by mass. A phosphate ester dispersant (acid value: 53 mgKOH/g, solid content: 52% by mass) and ethyl lactate as a solvent were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-6). The white pigment has an average particle diameter of 180 nm.

Preparation and evaluation of photosensitive compositions Example 1

275 parts by mass of the pigment dispersion liquid (A-1) as the coloring agent (A) and 275 parts by mass of the pigment dispersion liquid (A-3) were mixed as the (B) binder resin, so that the solid content concentration was 50% by mass. 250 parts by mass of the binder resin (B-1) solution, 50 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as (C) polymerizable compound, and DAROCUR TPO (BASF) as (D) photopolymerization initiator 20 parts by mass of GPA-5001 (made by Adeka) as (E) antioxidant, and 1 part by mass A photosensitive composition (S-1) was prepared by using ADK STAB 135A (manufactured by ADEKA) in an amount of 0.2 parts by mass of PGMEA as a solvent.

The white photosensitive composition (S-1) was applied onto a soda glass substrate by a spin coater, and then prebaked at 100 ° C for 1 minute using a hot plate to form a coating film having a film thickness of 12 μm. Next, using a high pressure mercury lamp, the radiation containing the wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the coating film at an exposure amount of 100 J/m ² without interposing a photomask. Thereafter, a 0.04% potassium hydroxide aqueous solution of 23 ° C was sprayed onto the coating film at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development, and then further baked at 270 ° C for 1 hour, and baked on the substrate. A white cured film having a film thickness of 10 μm was formed.

Color evaluation

The reflected light of the white cured film formed above was measured using a spectrophotometer (CM-2600d manufactured by KONICA MINOLTA Japan), and was quantified by CIELAB (L ^* a ^* b ^* color system).

Regarding the chromaticity, the case where b ^{* is} less than 2 is evaluated as "○", the case where b ^* is 2 or more and less than 5 is evaluated as "Δ", and the case where b ^* is 5 or more and less than 7, is evaluated as "△△", and the case where b ^* is 7 or more is evaluated as "x". The results are shown in Table 1.

Regarding the brightness, the case where L ^* is 85 or more is evaluated as "○", the case where L ^* is 80 or more and less than 85 is evaluated as "△", and the case where L ^* is 75 or more and less than 80 is evaluated as "". ΔΔ”, and the case where L ^{* is} less than 75 is evaluated as “×”. The results are shown in Table 1.

In Table 1, as long as the chromaticity and the lightness are both "○" or one of the "○" and the other is "△", it can be said that the cured film does not yellow. in case When at least one of chromaticity and lightness is "x", it is considered that the cured film is yellowed. In other cases, it is considered that the cured film has undergone some yellowing, which is a grade having no practical problem.

Shading evaluation

The optical density (OD) of the white cured film formed above was measured using an optical densitometer (TD-904 manufactured by Macbeth). The case where the OD was 0.8 or more was evaluated as "○", the case where the OD was 0.5 or more and less than 0.8 was evaluated as "Δ", and the case where the OD was less than 0.5 was evaluated as "x". The larger the OD, the better the opacity. The results are shown in Table 1.

Chemical resistance evaluation

The reflected light of the white cured film formed above was measured using a spectrophotometer (CM-2600d manufactured by KONICA MINOLTA Japan), and was quantified by CIELAB (L ^* a ^* b ^* color system).

Next, the white cured film was immersed in TOK106 (a resist stripping liquid made of a monoethanolamine/dimethyl sulfonium solution manufactured by Tokyo Ohka Chemical Co., Ltd.), and washed with ultrapure water at 100 minutes. Baking for 1 minute at °C. The reflected light of the cured film was measured and quantified by CIELAB (L ^* a ^* b ^* color system).

The amount of change in b ^* before and after immersion was determined, and the case where Δb ^{* was} less than 1 was evaluated as “○”, and the case where Δb ^* was 1 or more and less than 2 was evaluated as “Δ”, and Δb ^* was evaluated as The case of 2 or more is evaluated as "X". The smaller the Δb ^* , the better the chemical resistance. The results are shown in Table 1.

Examples 2 to 33 and Comparative Examples 1 to 4

In the same manner as in Example 1, except that the type and amount of each component were changed in Table 1, a photosensitive composition was prepared. (S-2)~(S-37). Next, evaluation was performed in the same manner as in Example 1 except that the photosensitive composition (S-2) to (S-37) was used instead of the photosensitive composition (S-1). The results are shown in Table 1. Among them, Examples 15 to 17 and 26 are reference examples.

In Table 1, each component is as follows.

(polymerizable compound)

C-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate).

C-2: ARONIX M-450 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate.)

C-3: ARONIX M-315 (manufactured by Toagosei Co., Ltd., a mixture of diacrylate and triacrylate modified by iso-cyanuric acid ethylene oxide).

C-4: KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd. Polyfunctional urethane acrylate.)

C-5: ARONIXTO-1382 (manufactured by Toagosei Co., Ltd.) a mixture of dipentaerythritol pentaacrylate and monoester of succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

(photopolymerization initiator)

D-1: Darocur TPO (manufactured by BASF. Oxidation-2,4,6-trimethylbenzhydryldiphenylphosphine. Oxidized monophosphorylphosphine-based photopolymerization initiator)

D-2: Irgacure 1700 (manufactured by BASF. Oxidized bis(2,6-dimethoxybenzylidene) (2,4,4-trimethylpentyl)phosphine. Oxidized bis-decylphosphine photopolymerization Agent)

D-3: Irgacure 819 (manufactured by BASF. Oxidized bis(2,4,6-trimethylbenzylidene)-phenylphosphine. Oxidized bis-decylphosphine-based photopolymerization initiator)

D-4: Irgacure 784 (manufactured by BASF. Bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]bis(2,4-cyclopentadienyl)titanium (IV). Titanocene Photopolymerization initiator)

D-5: Irgacure 907 (manufactured by BASF. 2-Methyl-1-[4-(methylthio)phenyl]-2-N- Lolinylpropan-1-one. α-Aminoalkylphenone photopolymerization initiator)

D-6: Irgacure 184 (manufactured by BASF. 1-Hydroxycyclohexyl phenyl ketone. Other photopolymerization initiator)

D-7: Irgacure 127 (manufactured by BASF. 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropan-1- Ketone. Other photopolymerization initiators)

D-8: Irgacure 369 (manufactured by BASF. 2-Benzyl-2-dimethylamino-1-(4-N-) Polinylphenyl)butan-1-one. α-Aminoalkylphenone photopolymerization initiator)

D-9: Irgacure OXE-02 (manufactured by BASF. 1-[9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-醯肟)). O-antimony photopolymerization initiator)

(phenolic antioxidants)

E-1: GPA-5001 (made by Adeka)

E-4: SUMILIZER GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)

E-5: Irganox 1010 (manufactured by BASF Corporation)

E-6: Irganox 1035 (manufactured by BASF Corporation)

E-8: 2,5-di-tertiary butyl hydroquinone

(phosphorus antioxidants)

E-2: ADK STAB135A (manufactured by Adeka. Alkyl allyl phosphite)

E-3: SUMILIZER GP (manufactured by Sumitomo Chemical Co., Ltd. 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10 - Tetra-tertiary butyl dibenzo[d,f][1,3,2] 6-[3-(3-t-Butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3 , 2]dioxaphosphepin))

E-7: ADEKA 1500 (. ADEKA manufactured by four -C _12-15 - alkyl-2,2-diyl-bis (4,1-phenylene)) bis (phosphite) Tetra-C _12-15 -alkylpropane-2,2-diylbis(4,1-phenylene))bis(phosphite))

(solvent)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

Claims (11)

A photosensitive composition for forming a light-shielding screen comprising (A) a white pigment, (B) a binder resin, (C) a polymerizable compound, (D) a photopolymerization initiator, and (E) an antioxidant, (C) The polymerizable compound contains a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and (D) a photopolymerization initiator contains a phthalocyanine-based photopolymerization initiator and a ferrocene. At least one photopolymerization initiator in the titanium-based photopolymerization initiator, and the (E) antioxidant contains at least one selected from the group consisting of a phenolic antioxidant having four or more phenolic hydroxyl groups and a phosphorus-based antioxidant. The photosensitive composition for forming a shading screen according to claim 1, wherein the (E) antioxidant contains a phenolic antioxidant and a phosphorus-based antioxidant, and a ratio of a phenolic antioxidant to a phosphorus-based antioxidant (phenolic antioxidant/phosphorus) It is an antioxidant) in a mass ratio of 2/1 to 9/1. The photosensitive composition for forming a shading screen according to claim 1, wherein the (B) binder resin is a resin having at least one functional group selected from the group consisting of an acidic functional group and a cyclic ether group. The photosensitive composition for forming a shading screen according to claim 3, wherein the cyclic ether group is an epoxyethyl group, an oxetane group or an alicyclic epoxy group. The photosensitive composition for forming a shading screen according to claim 1, wherein the (A) white pigment contains at least one selected from the group consisting of titanium oxide and barium titanate. The photosensitive composition for forming a shading screen according to claim 1, wherein the (A) white pigment has an average particle diameter of 200 to 400 nm. The photosensitive composition for forming a shading screen according to claim 1, further comprising a dispersing agent having an acid value of 10 to 200 mgKOH/g or a dispersing agent having an amine value of 20 to 200 mgKOH/g. A light-shielding screen formed using the photosensitive composition for forming a shading screen according to any one of claims 1 to 7. The shading screen of claim 8, wherein the film thickness is 1 to 50 μm. The shading screen of claim 8 or 9, wherein in the CIELAB (L ^* a ^* b ^* color system), the brightness index L ^* is 80 or more and the color indices (a ^* , b ^* ) are greater than -5 and less than 5, respectively. . A display device provided with a shading screen according to any one of claims 8 to 10.