KR20220040388A - Photosensitive resin composition for light shielding film, light shielding film using the same, and display device with that film - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition for forming a light-shielding film, capable of sufficiently reducing the light reflectance of a film when a light-shielding film is formed and sufficiently increasing patterning performance in alkali development at the time of production of the light-shielding film. There is provided a photosensitive resin composition for forming a light-shielding film, in which a film composed of a cured product of a photosensitive resin composition that contains an alkali-soluble resin as a component (A), a photopolymerizable compound having at least one ethylenically unsaturated bond as a component (B), a photopolymerization initiator as a component (C), a light-shielding agent as a component (D), and silica particles as a component (E) and has a specific average film thickness is formed on a glass substrate. When specific atomic ratios (X), (Y), and (Z) are determined by performing elemental analysis on the cross-section of the film by an energy dispersive X-ray analysis method using STEM-EDS, a value of the atomic ratio (Y) is 1.1-10 times a value of the atomic ratio (X), and a value of the atomic ratio (Z) is 0.5-2.8 times the value of the atomic ratio (X).

Description

A photosensitive resin composition for forming a light-shielding film, a light-shielding film, and a display device

The present invention relates to a photosensitive resin composition for forming a light-shielding film, a light-shielding film, and a display device.

In display devices such as liquid crystal displays, for the purpose of improving contrast or preventing light leakage, a light-shielding film such as a grid-like, stripe-like, or mosaic-like black matrix is formed at the boundary between each pixel such as red, green, and blue. there is. As such a light-shielding film, one formed on a transparent substrate using a photosensitive resin composition containing a light-shielding agent such as a black pigment is known. However, in a display device having a transparent substrate having such a light-shielding film disposed on the surface, light incident from the transparent substrate side is reflected on the surface (interface with the transparent substrate) of the light-shielding film, so that objects placed around it are reflected on the screen. had a problem. Therefore, in the field of such a light-shielding film, various studies are being conducted in order to reduce the reflectance.

For example, in International Publication No. 2015/159370 (Patent Document 1), (A) a color material and (B) an organic binder is included, and further, the following (1) and (2):

(1) the light-shielding material contains (C) fine particles having a refractive index of 1.2 or more and 1.8 or less;

(2) the concentration of the fine particles in the light shielding material is different in the thickness direction, and the side opposite to the transparent substrate is lower than the side opposite to the transparent substrate;

A light-shielding material satisfying the conditions described in is disclosed. However, even with the light-shielding material described in patent document 1, reflection of light could not necessarily be fully suppressed.

International Publication No. 2015/159370

The present invention has been made in view of the problems of the prior art, and when the light-shielding film is formed, it is possible to sufficiently reduce the light reflectance of the film, and the patterning performance in alkali development at the time of manufacturing the light-shielding film is sufficiently high. It aims at providing the photosensitive resin composition for light-shielding film formation which can do this, the light-shielding film obtained using the same, and the display apparatus provided with this light-shielding film.

As a result of the present inventors repeating earnest research in order to achieve the said objective, the photosensitive resin composition for light-shielding film formation shall contain the following components (A)-(E), Furthermore, the photosensitive resin composition is averaged on a glass substrate A film having a film thickness in the range of 0.5 to 2.5 µm and a film made of a cured product of the photosensitive resin composition is formed, and the cross section of the film is subjected to elemental analysis by energy dispersive X-ray analysis using STEM-EDS. When the ratios (X), (Y) and (Z) are obtained, the value of the atomic ratio (Y) is 1.1 to 10 times the value of the atomic ratio (X), and the atomic ratio ( By setting the value of Z) to be 0.5 to 2.8 times the value of the atomic ratio (X), when the light-shielding film is formed, it becomes possible to sufficiently reduce the light reflectance of the film, and the alkali at the time of production of the light-shielding film It found that it became possible to make the patterning performance (developability) in image development higher, and came to complete this invention.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition for forming a light-shielding film, the following components (A) to (E):

(A) alkali-soluble resin,

(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;

(C) a photoinitiator;

(D) a shading agent;

(E) silica particles,

contains, and

A film having an average film thickness in the range of 0.5 to 2.5 µm and made of a cured product of the photosensitive resin composition is formed on a glass substrate, and the cross section of the film is analyzed by energy dispersive X-ray analysis using STEM-EDS. By performing the following atomic ratios (X), (Y) and (Z):

[Atomic Ratio (X)] The atomic ratio of the Si element in the film to the total amount of C, O and Si elements present in the film;

[Atomic Ratio (Y)] Si in the region near the glass substrate of the film relative to the total amount of C, O and Si elements present in the region near the glass substrate of the film between the interface between the glass substrate and the film up to a thickness of 200 nm atomic ratio of elements,

[Atomic Ratio (Z)] The total amount of C, O and Si elements present in the region near the surface of the film from the surface of the film on the side not in contact with the glass substrate to the thickness of 200 nm relative to the surface vicinity of the film Atomic ratio of Si elements in the region,

is obtained, the value of the atomic ratio (Y) is 1.1 to 10 times the value of the atomic ratio (X), and the value of the atomic ratio (Z) is It is characterized in that the size is 0.5 to 2.8 times the value.

Moreover, as for the photosensitive resin composition of this invention, it is preferable that the said component (E) is a silica particle whose average particle diameter is 10-180 nm.

Moreover, as for the photosensitive resin composition of this invention, it is preferable that the said component (D) is carbon black whose average particle diameter is 50-180 nm.

The light-shielding film of the present invention is a film made of a cured product of the photosensitive resin composition of the present invention, and has an average thickness of 0.5 µm to 2.5 µm.

In addition, the display device of the present invention is characterized in that it includes the light-shielding film of the present invention.

According to the present invention, when the light-shielding film is formed, it is possible to sufficiently reduce the light reflectance of the film, and further, the photosensitive resin composition for forming a light-shielding film capable of sufficiently high patterning performance in alkali development at the time of production of the light-shielding film, It becomes possible to provide the light-shielding film obtained using the same, and a display device provided with the light-shielding film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment.

[Photosensitive resin composition (photosensitive resin composition for light-shielding film formation)]

The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a light-shielding film,

The following components (A) to (E):

(A) alkali-soluble resin;

(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;

(C) a photoinitiator;

(D) a shading agent;

(E) silica particles,

contains, and

A film having an average film thickness in the range of 0.5 to 2.5 µm and made of a cured product of the photosensitive resin composition is formed on a glass substrate, and the cross section of the film is analyzed by energy dispersive X-ray analysis using STEM-EDS. By performing the following atomic ratios (X), (Y) and (Z):

[Atomic Ratio (X)] The atomic ratio of the Si element in the film to the total amount of C, O and Si elements present in the film ([Amount of Si element in the film]/[C, O and Si present in the film] total amount of elements]),

[Atomic Ratio (Y)] Si in the region near the glass substrate of the film relative to the total amount of C, O and Si elements present in the region near the glass substrate of the film between the interface between the glass substrate and the film up to a thickness of 200 nm Atomic ratio of elements ([Amount of Si element in the region near the glass substrate of the film]/[Total amount of C, O and Si elements present in the region near the glass substrate of the film]),

[Atomic Ratio (Z)] The total amount of C, O and Si elements present in the region near the surface of the film from the surface of the film on the side not in contact with the glass substrate to the thickness of 200 nm relative to the surface vicinity of the film Atomic ratio of Si elements in the region ([Amount of Si element in the region near the surface of the film]/[Total amount of C, O and Si elements present in the region near the surface of the film]),

is obtained, the value of the atomic ratio (Y) is 1.1 to 10 times the value of the atomic ratio (X), and the value of the atomic ratio (Z) is 0.5 to 2.8 times the value,

is characterized by Hereinafter, first, the component (A) - (E) which the photosensitive resin composition contains is demonstrated.

[Component (A)]

Although it does not restrict|limit especially as an alkali-soluble resin used as such a component (A), A well-known resin (for example, those described in Unexamined-Japanese-Patent No. 2019-203963, etc.) which can be used for so-called alkali development can be used suitably. can Thus, as alkali-soluble resin, what melt|dissolves in what is called an alkali developing solution can be used suitably. Thus, "alkali solubility" as used in this invention should just be a property which can be dissolved using a well-known alkali developing solution. Among these alkali-soluble resins, a resin having a polymerizable unsaturated group and an acidic group for expressing alkali solubility in the resin molecule (in one molecule) is more preferable from the viewpoint of having higher curability and solubility in an alkali developer. As such a polymerizable unsaturated group, an acryl group and a methacryl group are mentioned, for example, Moreover, a carboxyl group is mentioned as said acidic group, for example.

In addition, although it does not restrict|limit especially as this alkali-soluble resin, For example, to the epoxy (meth)acrylate compound which has a hydroxyl group obtained by making the compound which has two or more epoxy groups react with (meth)acrylic acid, (a) dicarboxyl acid monoanhydrides of acids or tricarboxylic acids; And/or (b) tetracarboxylic dianhydride; epoxy (meth)acrylate acid adduct obtained by making it react is mentioned as a suitable thing. In addition, "(meth)acrylic acid" as used herein means "acrylic acid and/or methacrylic acid."

As a compound which has two or more of such epoxy groups, a bisphenol-type epoxy compound and a novolak-type epoxy compound can be used suitably. Moreover, as such a bisphenol-type epoxy compound and a novolak-type epoxy compound, a well-known thing (for example, the thing described in Unexamined-Japanese-Patent No. 2019-203963) can be used suitably. Moreover, a bisphenol fluorene type epoxy compound is especially preferable from a viewpoint that alkali solubility, sclerosis|hardenability, and heat resistance improve more among such a bisphenol type epoxy compound and a novolak type epoxy compound.

Further, as the acid monohydride of (a) dicarboxylic acid or tricarboxylic acid reacted with epoxy (meth)acrylate, the acid monohydride of chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic dicarboxylic acid, or Acid monoanhydride of tricarboxylic acid, acid monoanhydride of aromatic dicarboxylic acid or tricarboxylic acid, etc. are used. Here, examples of the acid monohydride of a chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, and acid monoanhydrides such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Also included are acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with optional substituents, and the like. Examples of the acid monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid include acids such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid. 1 Contains an anhydride. Also included are acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with optional substituents, and the like. Examples of the acid monoanhydride of aromatic dicarboxylic acid or tricarboxylic acid include acid monoanhydrides such as phthalic acid, isophthalic acid and trimellitic acid. Also included are acid monoanhydrides of dicarboxylic acids or tricarboxylic acids introduced with optional substituents.

In addition, as (b) tetracarboxylic dianhydride reacted with epoxy (meth)acrylate, acid dianhydride of chain hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, or acid 2 of aromatic tetracarboxylic acid Anhydrous is used. Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include acid dianhydrides such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid, and also optionally substituents are introduced. acid dianhydrides of tetracarboxylic acids. Further, examples of the acid dianhydride of alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid. acid dianhydride of , and also acid dianhydride of tetracarboxylic acid introduced with an optional substituent. Examples of the acid dianhydride of aromatic tetracarboxylic acid include acid dianhydrides such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and biphenylethertetracarboxylic acid, and optional acid dianhydride of tetracarboxylic acid introduced with a substituent of

The epoxy (meth)acrylate acid adduct can be produced by a known method, for example, by a method described in Japanese Patent Application Laid-Open No. Hei 8-278629 and Japanese Patent Application Laid-Open No. 2008-9401. First, in an example of a method of reacting (meth)acrylic acid with such an epoxy compound, (meth)acrylic acid of an epoxy group and equimolar (meth)acrylic acid of the epoxy compound is added to a solvent, and a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol) etc.), there is a method of reacting by heating and stirring at 90 to 120°C while blowing air. Next, as an example of a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound, which is the reaction product, predetermined amounts of the epoxy acrylate compound, acid dianhydride, and acid monoanhydride are added to a solvent, and a catalyst (tetraethylammonium bromide, tri There is a method of reacting by heating and stirring at 90 to 130°C in the presence of phenylphosphine, etc.).

In addition, as such alkali-soluble resin, from the viewpoint of further improving alkali solubility, curability and heat resistance, an anhydride of an alicyclic dicarboxylic acid (acid monoanhydride) and an aromatic tetracarboxylic acid in a reaction product of a bisphenol fluorene type epoxy compound and (meth)acrylic acid Cardo resin obtained by making an acid dianhydride react is more preferable.

Moreover, as alkali-soluble resin of a component (A), you may use suitably what is described in Unexamined-Japanese-Patent No. 2014-111722 and Unexamined-Japanese-Patent No. 2018-141968, for example. Moreover, as alkali-soluble resin of (A) component, you may use individually by 1 type, or may use 2 or more types together.

In addition, in such alkali-soluble resin, it is different depending on the skeleton of the resin, and although it cannot be said uniformly, it is preferable that the weight average molecular weight (Mw) is 1000 to 100000 (more preferably 2000 to 80000), and the acid value is preferably 30 to 120 mgKOH/g (more preferably 40 to 110 mgKOH/g). When these Mw and acid value exist in the said range, while developability at the time of alkali development improves more, there exists a tendency for the adhesiveness of the pattern at the time of alkali development to also improve more.

[Component (B)]

The photopolymerizable compound having at least one ethylenically unsaturated bond used as the component (B) is not particularly limited, but for example, a known photopolymerizable compound having an ethylenically unsaturated bond that can be used as a photopolymerizable monomer (e.g. For example, a photopolymerizable monomer having at least one ethylenically unsaturated bond described in Japanese Patent Laid-Open No. 2017-72760 (for example, (meth)acrylic acid esters having at least one ethylenically unsaturated bond), etc.) can be suitably used can As such a component (B), the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and ethylene glycol, for example. Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth)acrylic acid esters, such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol (meth)acrylate, are mentioned. These compounds may be used individually by 1 type, or may use 2 or more types together.

In addition, as the photopolymerizable compound having at least one ethylenically unsaturated bond, it becomes possible to play a role of crosslinking the molecules of the alkali-soluble resin contained therein. more preferably. Moreover, it is preferable that the acrylic equivalent obtained by dividing the molecular weight of this photopolymerizable compound by the number of (meth)acryl groups in one molecule is 50-20000, and, as for the acrylic equivalent, it is more preferable that it is 70-10000. Moreover, it is more preferable that component (B) does not have a free carboxy group.

[Component (C)]

It does not restrict|limit especially as a photoinitiator used as said component (C), A well-known photoinitiator (For example, the photoinitiator of Unexamined-Japanese-Patent No. 2017-72760, etc.) can be used suitably. Especially, as such a photoinitiator, also in a light shielding film, the reactivity with respect to an ultraviolet-ray is high, and an oxime ester type polymerization initiator is especially preferable from a viewpoint that a photocuring reaction can be accelerated|stimulated. Moreover, as such a photoinitiator, a commercial item can be used suitably. In addition, the "photoinitiator" as used in this invention is used by the meaning containing a sensitizer.

[Component (D)]

Although it does not restrict|limit especially as a light-shielding agent used as said component (D), It is preferable that it consists of at least 1 sort(s) of light-shielding component selected from the group which consists of an organic black pigment, an inorganic black pigment, and a mixed color pseudo black pigment. Perylene black, aniline black, cyanine black, lactam black etc. are mentioned as such an organic black pigment. Examples of the inorganic black pigment include carbon black, chromium oxide, iron oxide, and titanium black. Moreover, as said mixed color pseudo black pigment, what mixed 2 or more types of pigments, such as red, blue nucleus, green, purple, yellow, cyanine, magenta, and made it pseudo black is mentioned. As such a light-shielding agent, 1 type may be used individually among the said light-shielding components, or 2 or more types may be used together. Moreover, as such a light-shielding agent, carbon black is especially preferable from a viewpoint that light-shielding property, surface smoothness, dispersion stability, and compatibility with resin are favorable.

As such a light-shielding agent, it is preferable to consist of a light-shielding component (especially preferably carbon black) with an average particle diameter of 50-180 nm (more preferably 80-160). When the average particle diameter of such a light-shielding component (especially preferably carbon black) is less than the lower limit, the light-shielding property of the light-shielding film tends to decrease. On the other hand, when it exceeds the upper limit, the value of the atomic ratio (Y) is There is a tendency that the size cannot be set to 1.1 to 10 times the value of the atomic ratio (X). In addition, the average particle diameter of a light-shielding component can be calculated|required by the particle size distribution measurement using the dynamic light scattering method etc.

[ingredient (E)]

The silica particles used as the component (E) are not particularly limited, and well-known silica particles that can be used in a light-shielding film (for example, those described in Japanese Patent Application Laid-Open No. 2016-161926, etc.) can be suitably used. there is. As such silica particles, those prepared or surface-treated so as to be dispersible in an organic solvent from the viewpoint of dispersion stability in the photosensitive resin composition are more preferable. Fumed silica, colloidal silica, and organo silica sol are mentioned as silica particles prepared or surface-treated so as to be dispersible in such an organic solvent, for example, organo silica sol manufactured by Nissan Chemical Co., Ltd. Adomafine and Adomano from Adomatex, colloidal silica made by Fuso Chemical Co., Ltd., organo silica sol and silica no powder, and fumed silica made by Nippon Aerosil Co., Ltd. under trade names Among those on the market, those that can be dispersed in an organic solvent can be suitably used.

Moreover, as such a silica particle, it is preferable that an average particle diameter is 10-180 nm (preferably 20-150 nm). If the average particle diameter is less than the above lower limit, aggregation of particles tends to occur and dispersion stability is lowered. In order to ensure dispersion stability, it tends to be necessary to use a large amount of dispersing agent, on the other hand, if the upper limit is exceeded The linearity of the pattern tends to decrease. Moreover, it is preferable to use the thing of 1.10 - 1.47 (more preferably 1.40 - 1.47) of a refractive index as such a silica particle.

As mentioned above, although components (A) - (E) were divided and demonstrated, the component which can be contained in the photosensitive resin composition of this invention is not limited to the said component (A) - (E), The said composition is as needed as needed. , dispersants, polymerization initiators other than the above-mentioned photopolymerization initiator, chain transfer agents, sensitizers, non-photosensitive resins, curing agents, curing accelerators, antioxidants, plasticizers, fillers, coupling agents, surfactants, dyes and other additives may be blended.

Moreover, it is preferable that the photosensitive resin composition of this invention contains an organic solvent from a viewpoint that it becomes possible to employ|adopt a well-known coating method etc. and formation of a light-shielding film becomes easier (Hereinafter, the organic solvent which can be contained in such a composition) For convenience, in some cases, only "component (F)").

As such an organic solvent (component (F)), any one that can be used for making the photosensitive resin composition into a solution state is sufficient, and a well-known organic solvent (For example, the organic solvent described in Unexamined-Japanese-Patent No. 2017-72760, etc.) can be used suitably can Moreover, as such an organic solvent, For example, alcohol, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; ketones such as methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol ethers such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate; and the like.

In addition, in the manufacture of the photosensitive resin composition for photosensitive resin composition light-shielding film formation, the said component (D) and the said component (E) use the dispersion liquid which disperse|distributed each of these components in an organic solvent, respectively, with other components, such as a component (A) Mixing is preferred. In addition, when using such a dispersion, it is preferable to add a dispersing agent to the dispersion from the viewpoint of uniformly dispersing the component (D) or the component (E) in the organic solvent. Therefore, when such a dispersion liquid is used, the dispersing agent contained in a dispersion liquid will be contained in the photosensitive resin composition as it is. From such a viewpoint, the photosensitive resin composition of this invention may contain the dispersing agent. In addition, such a dispersing agent can be used without particular limitation, such as known compounds (compounds marketed under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) used for dispersing the component (D) or (E).

For example, as such a dispersing agent, a phosphoric acid ester type dispersing agent can be used suitably. In addition, as such a phosphoric acid ester-based dispersant, a known one can be suitably used, and a commercially available product (for example, Adecachol (TS-230E, CS-141E, CS-1361E, CS-279, PS-440E, PS-810E, PS) -807, PS-984: All made by ADEKA Corporation, "Adecacol" is a registered trademark of the company), Flysurf (A208B, A208F, A208N, A219B, DB-01, M208F: All made by Daiichi Kogyo Seiyaku Co., Ltd.) manufactured by Shiki Corporation, "Flysurf" is a registered trademark of the company), phosphanol (RS-710, RL-310, RB-410, RL-210, RS-610, RD-720N: all Toho Chemical Co., Ltd.) (registered trademark of “Phosphanol”)) may be used.

[About composition, etc.]

The photosensitive resin composition of the present invention comprises a component (A): alkali-soluble resin, component (B): a photopolymerizable compound having at least one ethylenically unsaturated bond, component (C): a photoinitiator, component (D): a light-shielding agent, and, component (E): one containing silica particles.

In such a composition, the mass ratio of component (A) and component (B) ([component (A)]/[component (B)] is 90/10 to 50/50 (especially preferably 85/15 to 55/45) In the case where the mass ratio (the blending ratio of the component (A) to the component (B)) is within the above range, the developing adhesiveness point by making the blending ratio of the (A) component more than the lower limit On the other hand, there exists a tendency for a higher effect to be acquired, and on the other hand, by making the compounding ratio of (A) component below the said upper limit, there exists a tendency for a higher effect to be acquired in the point of UV curability.

It is preferable that the total amount of a component (A) and a component (B) is 20-80 mass % with respect to the total amount of solid content (solid content includes the compound which becomes a solid content after hardening of the said composition) in the photosensitive resin composition, 25-75 It is more preferable that it is mass %. By setting the total amount of component (A) and component (B) to be equal to or greater than the lower limit, a higher effect tends to be obtained in that appropriate patterning can be performed by the photolithography process, and by setting it below the upper limit, the light-shielding degree is required In order to set it as a level, there exists a tendency for a higher effect to be acquired at the point which enables addition of a light-shielding component.

Moreover, content in particular of a component (C) is although it does not restrict|limit, It is preferable that it is 2-40 mass parts with respect to 100 mass parts of total amounts of a component (A) and a component (B), It is more preferable that it is 3-35 mass parts. When the content of the component (C) is within the above range, a higher effect tends to be obtained in terms of sensitivity by making the blending ratio of the component (C) equal to or higher than the lower limit, and on the other hand, when the content of the component (C) is below the upper limit, the patternability point tends to have a higher effect.

In addition, the content of the component (D) is not particularly limited, but is preferably 20 to 80 mass % with respect to the total amount of the solid content in the photosensitive resin composition (the solid content includes a compound that becomes a solid content after curing of the composition), 25 It is more preferable that it is -75 mass %. When the content of the component (D) falls within the above range, a higher effect tends to be obtained in terms of light-shielding properties by making the blending ratio of the component (D) equal to or more than the lower limit, and by setting the content of the component (D) to below the upper limit, the light-shielding layer In terms of the improvement of the surface smoothness of the light-shielding agent and the improvement of the dispersion stability of the light-shielding agent, a higher effect tends to be obtained.

In addition, the content of the component (E) is not particularly limited, but is preferably 1 to 20% by mass relative to the total amount of the solid content in the photosensitive resin composition (the solid content includes a compound that becomes a solid content after curing of the composition), It is more preferable that it is 1-10 mass %. When the content of the component (E) is within the above range, a higher effect in terms of reflectance tends to be obtained by making the blending ratio of the component (E) equal to or higher than the lower limit, and by setting it below the upper limit, the straight line of the pattern A higher effect tends to be obtained in terms of performance. In the present invention, even if the addition amount of the component (E) is the same, the component (E) is not uniformly dispersed when the film is formed and the cross section is observed. When the reflectance is measured from the glass surface side, the reflectance can be reduced. In addition, when the viewpoint that it is possible to form an appropriate pattern stably and more easily, such as the linearity of the pattern at the time of patterning, is also taken into consideration, content of component (E) is 1-7 mass % with respect to the total amount of solid content in the photosensitive resin composition. It is more preferable to set it as, and there exists a tendency which the effect of this invention can be achieved more efficiently by this.

Moreover, when the photosensitive resin composition of this invention contains an organic solvent (component (F)), although content of this component (F) can be suitably changed according to target viscosity etc., 50 with respect to the total amount in the photosensitive resin composition. It is preferable to set it as -90 mass %. Moreover, when the photosensitive resin composition of this invention contains a dispersing agent, Content in particular of the dispersing agent is although it does not restrict|limit, It is preferable that it is 3-12 mass % with respect to the total amount of solid content of the photosensitive resin composition.

In addition, the photosensitive resin composition of the present invention contains a component (A), a component (B), a component (C) in the solid content of the composition excluding the organic solvent of the component (F) (the solid content includes a compound that becomes a solid content after curing of the composition) ), a component (D), and a component (E) are contained in 80 mass % or more (more preferably 90 mass % or more, More preferably, 94 mass % or more) in total is contained.

Moreover, it is preferable to use the photosensitive resin composition of this invention in the state of the solution using the organic solvent of (F) component. Thereby, it becomes possible to form a uniform film|membrane more efficiently. Moreover, as such a solution composition, it is preferable to adjust the usage-amount of an organic solvent suitably, and to make the viscosity (B-type or E-type viscometer) into about 1-30 mPa*sec.

In addition, the photosensitive resin composition of the present invention has an average film thickness in the range of 0.5 to 2.5 µm on a glass substrate and forms a film made of a cured product of the photosensitive resin composition, and energy using STEM-EDS for the cross section of the film The following atomic ratios (X), (Y) and (Z) were obtained by conducting elemental analysis by dispersive X-ray analysis:

[Atomic Ratio (X)] The atomic ratio of the Si element in the film to the total amount of C, O and Si elements present in the film;

[Atomic Ratio (Y)] Si in the region near the glass substrate of the film relative to the total amount of C, O and Si elements present in the region near the glass substrate of the film between the interface between the glass substrate and the film up to a thickness of 200 nm atomic ratio of elements,

[Atomic Ratio (Z)] The total amount of C, O and Si elements present in the region near the surface of the film from the surface of the film on the side not in contact with the glass substrate to the thickness of 200 nm relative to the surface vicinity of the film Atomic ratio of Si elements in the region,

is obtained, the value of the atomic ratio (Y) is 1.1 to 10 times the value of the atomic ratio (X), and the value of the atomic ratio (Z) is It will be 0.5 to 2.8 times the value.

Thus, when the photosensitive resin composition of the present invention has an average film thickness in the range of 0.5 to 2.5 µm on a glass substrate and a film made of a cured product of the photosensitive resin composition is formed, the value of the atomic ratio (Y) is It is 1.1 to 10 times the value of the atomic ratio (X). When the value of the atomic ratio (Y) is less than 1.1 times the value of the atomic ratio (X), the reflectance cannot be sufficiently lowered. It becomes impossible to maintain patternability. Moreover, as a value of this atomic ratio (Y), it is more preferable that it becomes the magnitude|size set to 1.1-5 times (preferably 1.1-3 times) of the value of the said atomic ratio (X). In addition, when the value of the atomic ratio (Y) is within the range of the magnification with respect to the value of the atomic ratio (X), the concentration of silica particles dispersed in the film of the cured product of the photosensitive resin composition is in the vicinity of the glass substrate. In the region, it becomes darker than the concentration of silica particles in the entire film, and more silica particles exist in the region near the glass substrate. In this way, when the concentration of silica particles is different in the thickness direction and more silica particles exist in the region near the glass substrate, the refractive index difference between the interface between the glass and the photosensitive resin composition cured film becomes small, so the reflectance is reduced it becomes possible to

In addition, when the photosensitive resin composition of the present invention has an average film thickness in the range of 0.5 to 2.5 µm on a glass substrate and a film made of a cured product of the photosensitive resin composition is formed, the value of the atomic ratio (Z) is It becomes 0.5 to 2.8 times the value of the atomic ratio (X). If the value of the atomic ratio (Z) is less than 0.5 times the value of the atomic ratio (X), the effect of reducing the reflectance is not obtained. On the other hand, if it exceeds 2.8 times, the linearity of the pattern when patterned is lowered It is discarded, and sufficient patterning property is no longer obtained. Moreover, as a value of this atomic ratio (Y), it is more preferable that it becomes the magnitude|size of 0.7-2.5 times (preferably 0.8-2 times) of the value of the said atomic ratio (X). In addition, when the value of the atomic ratio (Z) is within the range of the magnification with respect to the value of the atomic ratio (X), aggregation of silica on the upper part of the coating film is prevented, so that the reflectance reduction effect and the linearity of the pattern are improved. compatibility becomes possible.

In addition, the photosensitive resin composition of the present invention has an average film thickness in the range of 0.5 to 2.5 µm on a glass substrate, and when a film made of a cured product of the photosensitive resin composition is formed into a film, the atomic ratio (X) , together with (Y) and (Z), the following atomic ratios (W):

[Atomic Ratio (W)] Other than the region near the glass substrate of the film (the region between the interface between the glass substrate and the film to a thickness of 200 nm) and the region near the surface of the film (the region from the surface to the thickness of 200 nm) The atomic ratio of the Si element in the intermediate region to the total amount of C, O and Si elements present in the intermediate region of

, it is more preferable that the value of the atomic ratio (W) is 0.1 to 1.1 times (more preferably 0.1 to 1.0 times) the value of the atomic ratio (X). In addition, when the value of the atomic ratio (W) is within the range of the magnification with respect to the value of the atomic ratio (X), since the concentration of silica particles is different in the thickness direction, it is possible to lower the reflectance becomes

In addition, as described above, the photosensitive resin composition of the present invention has an average film thickness in the range of 0.5 to 2.5 µm on a glass substrate, and when a film made of a cured product of the photosensitive resin composition is formed, the atomic ratio ( The value of Y) is 1.1 to 10 times the value of the atomic ratio (X), and the value of the atomic ratio (Z) is 0.5 to 2.8 times the value of the atomic ratio (X) The condition (hereinafter, for convenience, this condition is sometimes referred to as "distribution condition (I) of silica particles") is satisfied.

In addition, the distribution conditions (I) of these silica particles are, for example, silica particles having an average particle diameter of 10 to 170 nm as the silica particles (component (E) above) to be contained in the composition, and a light-shielding agent to be contained in the composition. It is also possible to achieve this by using (more preferably carbon black) having an average particle diameter of 50 to 180 nm as (the component (D)). In this way, it is possible to satisfy the distribution condition (I) of the silica particles by using them in combination while keeping the average particle diameters of the component (D) and the component (E) within the above range, and in this case, the component ( Cardo resin is used as alkali-soluble resin of A), (meth)acrylic acid ester is used as said component (B), and content of component (D) is 20-80 with respect to the total amount of the solid component in the photosensitive resin composition. It is set as mass %, and it is preferable to make content of component (E) into 1-10 mass % with respect to the total amount of the solid component in the photosensitive resin composition, and it is made to contain component (F) in a composition (the component (F) as Glycol ethers and glycol acetates are preferable) and it is preferable to make content of the component (F) into 50-90 mass % with respect to the total amount (total amount) of the photosensitive resin composition. Moreover, when a dispersing agent is further included, it is preferable to make the kind of dispersing agent into a urethane type or an acrylic type, and to make the content into 3-12 mass % with respect to the total amount of the solid component in the photosensitive resin composition). In this way, it is also possible to satisfy the distribution condition (I) of the silica particles by combining each component.

In the present invention, the following method is employed as a method for elemental analysis of a film when the values of the atomic ratios (X), (Y), (Z) and (W) are measured. That is, first, an ultra-thin section (measurement sample) for film analysis is prepared using an ultramicrotome (trade name: EM UC6, manufactured by Leica), and STEM-EDS (for example, STEM (scanning transmission electron microscope) manufactured by Hitachi High-Tech Corporation) as a measurement device. : Trade name "SU9000" and AMETEK company EDS (energy dispersive X-ray spectrometer): trade name "ApolloXTL") are used. In the measurement, an acceleration voltage of 30 kV and a magnification of about 50,000 times are adopted as measurement conditions, and the cross section of the film made of a cured product of the photosensitive composition in the ultra-thin section for analysis is observed, and elemental analysis is performed by energy dispersive X-ray analysis. In addition, in the element analysis by such cross-sectional observation, the measurement area of the cross-section (the area to be observed for the cross-section: the area to be analyzed for the element) is set vertically: the same size as the film thickness of the film to be measured, and horizontally: 2.5 µm or more (more preferably Preferably, it should be a region with a size of about 2.5 to 3 μm). In addition, in such elemental analysis, the ratio of each atom can be obtained by using the method of calculating the number of atoms (atom%) of C, O and Si with the software attached to EDS. In addition, the conditions of magnification at the time of measurement of the cross section by the measuring device include the interface of the upper surface side and the lower surface side (glass substrate side) of the film within the measurement field of the measuring device, and the measuring area of the cross section (vertical: It can be suitably changed so that it includes the same size as the film thickness of the film to be measured, width: a region having a size of 2.5 μm or more). For example, in the above measurement device, when measuring at a magnification of 50,000 times, the measurement field can be set to an area of 2 µm in length × 2.5 µm in width. By setting the magnification to 50,000, it becomes possible to include an area of the length of the cross section of the film: the same size as the film thickness to be measured, and the width: 2.5 μm in the measurement field, and the measurement of the measurement area of the same size as described above ( elemental analysis) can be performed. In this way, the magnification at the time of measurement may be appropriately set so that the measurement area having the size as described above can be observed. In addition, as a method of forming a film when measuring the atomic ratios (X), (Y), (Z), and (W), a photosensitive composition is applied on a glass substrate, the solvent is dried and photocured, and then further heat-cured. By (baking), the method of forming the film|membrane which consists of hardened|cured material of the photosensitive composition is employable. Moreover, the average film thickness of the film|membrane (measurement sample) which consists of a hardened|cured material of the photosensitive composition used for such a measurement should just be in the range of 0.5-2.5 micrometers, and it is preferable to set it as 1.2 micrometers. In addition, in the measurement, it is preferable to peel from the glass substrate to prepare an ultra-thin section (measurement sample) for analysis. In addition, as the "average film thickness" of the film to be subjected to such elemental analysis, an average value of the film thickness measured using a stylus-type step shape measuring device ("P-10" manufactured by KLA Tencol) can be adopted. In addition, as a method of elemental analysis of a film or a method of preparing a sample when measuring such atomic ratios (X), (Y), (Z), (W), "Elemental analysis of film (Si element Measurement of atomic ratio)" is preferably employed.

In addition, the method for producing the photosensitive resin composition of the present invention is not particularly limited, for example, a resin solution (solvent: component (F)) containing component (A), component (B), component (C) , a method of mixing the dispersion of the component (D) (solvent: component (F)) and the dispersion of the component (E) (solvent: component (F)) may be employed.

[Light-shielding film]

The light-shielding film of this invention is a film|membrane which consists of a photocured material of the said photosensitive resin composition of this invention, and is characterized by the average thickness of 0.5 micrometer - 2.5 micrometers.

In this way, the light-shielding film of the present invention has an average thickness of 0.5 µm to 2.5 µm (more preferably 0.8 to 2.0 µm). If the thickness is less than the lower limit, the light-shielding degree tends to be insufficient. On the other hand, when the thickness exceeds the upper limit, the patternability tends to decrease. As the average thickness (average film thickness) of such a light-shielding film, a value measured using a stylus-type step difference measuring device ("P-10" manufactured by KLA Tencol Corporation) can be adopted. Moreover, when forming a pattern shape on such a light shielding film, the shape is not restrict|limited in particular, According to a use, a component in a composition, etc., the design can be changed suitably into stripe shape, mosaic shape, etc.

Moreover, the light-shielding film of this invention is a film|membrane which consists of a photocured material of the said photosensitive resin composition of this invention. In addition, the "photocured material" referred to herein is a concept including what is cured by thermosetting (post-baking) after photocuring, as long as it is cured by light at any one stage during curing of the photosensitive resin composition. That is, the hardened|cured material hardened|cured only by photocuring may be sufficient as the photocured material mentioned here, or the hardened|cured material thermosetted after photocuring may be sufficient as it. In this way, the light-shielding film of the present invention is obtained by curing the photosensitive resin composition of the present invention with light (if necessary, after curing with light and further with heat). As such a light-shielding film, a method that can be employed when forming a light-shielding film having a specific pattern is not particularly limited, but, for example, as the photosensitive resin composition of the present invention, a solution (including the component (F)) After applying the solution-like photosensitive resin composition on a substrate using and exposure treatment, photocuring the photosensitive (photocurable) resin of the photosensitive portion (exposed portion), and then developing treatment to remove the photosensitive resin composition of the unexposed portion, further heat treatment as necessary A method of forming a light-shielding film (light-shielding film pattern) by (post-baking) can be suitably used. Hereinafter, a method that can be suitably used as a method for forming such a light-shielding film will be briefly described.

In this method of forming a light-shielding film, first, the solution-like photosensitive resin composition is applied onto a substrate. As a method of apply|coating such a solution-form photosensitive resin composition on a board|substrate, the method of using a roller coater, a land coater, a slit coater, a spin coater etc. other than the well-known solution immersion method and spray method is mentioned, for example. In addition, as such a substrate, it is sufficient as long as it is necessary to form a light-shielding film, and a well-known transparent substrate for display apparatuses (for example, a glass substrate) etc. can be illustrated as a suitable thing.

Moreover, in the formation method of such a light-shielding film, after apply|coating the said solution-form photosensitive resin composition on a board|substrate, in order to remove the organic solvent (component (F)) in the said composition, it heat-processes (pre-baking). The heating temperature and heating time in this pre-bake can be appropriately set depending on the type of organic solvent (component (F)) to be used, for example, the heating temperature is set to 60 to 110°C (the heat resistance temperature of the transparent substrate is While setting so as not to exceed), you may set the heating time to 1 to 3 minutes. A dry coating film of the photosensitive resin composition can be obtained by such heat treatment.

In addition, in this method of forming a light-shielding film, the pre-baked coating film (dry film of the photosensitive resin composition) is subjected to exposure treatment using a mask for forming a desired light-shielding film pattern, and a photosensitive portion (light irradiated portion) of the coating film. of the resin is photocured. Conditions employed at the time of such exposure treatment are not particularly limited, and well-known exposure conditions used when forming a light-shielding film using a photosensitive resin can be appropriately used, and the components (A), (B) and components to be used What is necessary is just to employ|adopt suitable conditions suitably according to the kind etc. of (C).

Moreover, in the formation method of such a light shielding film, the photosensitive resin composition of the unexposed part of the said coating film is removed by developing to the coating film after exposure. It does not restrict|limit especially as a method of such a developing process, A well-known developing method can be employ|adopted suitably. Moreover, since the said photosensitive resin composition uses alkali-soluble resin as a component (A), in such a developing process, it is preferable to perform a developing process (alkali developing process) using an alkali developing solution. As such an alkali developing solution, well-known alkali developing solutions, such as aqueous solutions of carbonates and hydroxides of alkali metals or alkaline earth metals, can be used. Moreover, a pattern-like light-shielding film (light-shielding film pattern: pixel pattern) can be formed by developing in this way and removing the resin composition of an unexposed part. Moreover, in order to fully harden the light-shielding film obtained, or to fully remove a developing solution, you may further heat-process (post-baking) with respect to the said light-shielding film (light-shielding film pattern).

In this way, the light-shielding film which consists of the photocured material of the said photosensitive resin composition of this invention can be formed. In addition, the method for forming such a light-shielding film is not limited to the above method, and as described above, in addition to forming a fine pattern by operations such as exposure and development, the light-shielding film is formed by, for example, forming a desired pattern by screen printing. A method of obtaining it can also be appropriately adopted.

The light-shielding film of the present invention formed in this way can have a reflectance of 5% or less when the OD value per 1 µm in thickness is less than 4/µm. In addition, such a light-shielding film can have a reflectance of 6% or less, more preferably 5% or less when the OD value per 1 µm of the film thickness is 4/µm or more.

[Display device]

The display device of the present invention is characterized in that it includes the light-shielding film of the present invention. It does not restrict|limit especially as a kind of such a display apparatus, For example, a liquid crystal display device, the organic electroluminescent device represented by organic ELED element, a touch panel, etc. are mentioned. In addition, the display device of the present invention may be provided with the light-shielding film, and other configurations are not particularly limited. In addition, as the display device of the present invention, the light-shielding film of the present invention is provided on the back surface of the transparent substrate on the display surface side of the display device (a device provided with a transparent substrate with a light-shielding film disposed so as to view the light-shielding film through the transparent substrate) It is preferable to be According to the display device of the present invention provided with the light-shielding film of the present invention, it is possible to sufficiently reduce the reflection of external light by the light-shielding film, so that visibility can be further improved.

(Example)

Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[About the evaluation method, etc. of the characteristics of a composition and a light-shielding film]

The average particle diameter of the silica particles and carbon black used in Examples and Comparative Examples, the properties of the compositions and films obtained in each Example, and the like were measured by the following methods.

<Measurement of average particle diameter of silica particles and carbon black>

The average particle diameter of a silica particle and carbon black was measured as follows, respectively. That is, first, the dispersion liquid in which the particle|grains of the measurement object were disperse|distributed so that the density|concentration of the particle|grains might become 0.1-0.5 mass % using propylene glycol monomethyl ether acetate (PGMEA) as a solvent was prepared as a measurement sample. Thereafter, the particle size distribution of the particles in the obtained dispersion (measurement sample) was measured by a dynamic light scattering method using a particle size distribution analyzer (“Particle Size Analyzer FPAR-1000” manufactured by Otsuka Denshi Co., Ltd.), and the obtained particle size distribution was calculated by the Quinland method. was analyzed to obtain an average particle diameter (average secondary particle diameter). The average particle diameter of the silica particle and the carbon black was respectively calculated|required by employ|adopting the value calculated|required in this way as the average particle diameter of the particle|grains (silica particle or carbon black) to be measured.

<Elemental Analysis of Film (Measurement of Atomic Ratio of Si Elements)>

The photosensitive resin composition prepared in each Example was coated on a glass substrate having a size of 125 mm in length and 125 mm in width using a spin coater so that the film thickness after post-baking was 1.2 μm, and then the obtained coating film was subjected to a temperature condition of 90 ° C. Minute heating treatment (pre-bake) is performed, followed by photocuring reaction under the conditions of irradiating 100mJ/m2 of ultraviolet rays with an ultra-high pressure mercury lamp with I-ray irradiance of 30mW/cm2, followed by 230 using a hot air dryer. The glass substrate on which the light-shielding film (average film thickness: 1.2 micrometers) was laminated|stacked by the process (post-baking) of 30 minutes at degreeC was manufactured. The light-shielding film thus obtained was peeled off from the glass substrate, and an ultra-thin section of the light-shielding film was produced using an ultra-microtome (trade name: EM UC6, manufactured by Leica), and STEM-EDS (STEM manufactured by Hitachi Hi-Tech Corporation: trade name "SU9000" and EDS manufactured by AMETEK Corporation) as a measuring device. : Observing the cross section of the light-shielding film using the trade name "Apollo XTL") The elements constituting the light-shielding film were analyzed. As the measurement conditions, the cross-section was observed at an accelerating voltage of 30 kV and a magnification of 50,000 times, and the conditions for calculating the number of atoms (atom%) of C, O, and Si were adopted with the software provided with EDS. In this way, the atomic ratio (X), the atomic ratio (Y), the atomic ratio (Z), and the atomic ratio (W) were respectively obtained, and the ratio (magnification) of each atomic ratio to the atomic ratio (X) was calculated. .

<Measurement of average film thickness of light-shielding film>

The average film thickness of the light-shielding film obtained in each Example, etc., using the photosensitive resin composition obtained in each Example, is similar to the method employed in each Example "Using a spin coater, on a glass substrate having a size of 125 mm in length and 125 mm in width. After applying the photosensitive resin composition obtained so that the film thickness after post-baking becomes 1.2 μm, and performing a treatment (pre-baking) of heating for 1 minute under a temperature condition of 90° C. to obtain a dry coating film”, I After the photocuring reaction is performed under the conditions of irradiating 100mJ/m2 of ultraviolet light with an ultra-high pressure mercury lamp with a linear roughness of 30mW/cm2, then a treatment (post-baking) is performed using a hot air dryer to heat at 230°C for 30 minutes, and a glass substrate The obtained film was used as a measurement sample, and the level difference between the film-forming portion of the measurement sample and the glass surface from which the film was removed was determined by measuring it with a stylus-type step difference measurement device ("P-10" manufactured by KLA Tenchol Corporation).

<Measurement of shading degree (OD value)>

The optical density (OD value) was measured for the light-shielding film (pixel pattern) obtained in each Example etc. using an optical densitometer ("X-Rite361T(V)" manufactured by Sakata Ink Engineering Co., Ltd.), and the OD per 1 µm in film thickness value was found.

<Measurement of reflectance>

Using the glass substrate on which the light-shielding film (pixel pattern) obtained in each Example was laminated, from the surface side of the glass substrate on which the light-shielding film pattern was not formed, a spectrophotometer ("UH4150" manufactured by Hitachi High-Tech Sciences, Ltd.) was used, The reflectance [%] was measured under the conditions of a C light source and a 2 degree field of view.

<Evaluation of developability>

About the glass substrate on which the light-shielding film (pixel pattern) obtained in each Example etc. was laminated|stacked, the pixel pattern was observed with the optical microscope, and the following evaluation criteria evaluated.

(Evaluation criteria for developability)

A: An appropriate pattern with good linearity is formed.

B: A sawtooth shape is seen in a part of the pattern edge, and the pattern has insufficient linearity.

C: The sawtooth shape of the pattern edge part is confirmed over the whole, and it is a pattern with very insufficient linearity.

[About the components used in Examples etc.]

The components used in each Example etc. are divided and demonstrated below. In addition, in the following, a compound is expressed using the abbreviation etc. described here as needed.

(1) Component (A): Alkali-soluble resin (alkali-soluble photocurable transparent resin)

In each Example etc., the cardo resin prepared in the following synthesis example 1 was used as alkali-soluble resin (component (A)). In addition, in preparation of the composition of each Example etc., the resin solution (solvent: PGMEA) obtained in Synthesis Example 1 was used as it was. The abbreviation of the raw material used by the synthesis example 1, etc. are shown below.

[Abbreviation of the raw material used in Synthesis Example 1, etc.]

BPFE: Bisphenol fluorene type epoxy compound (9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane reaction product (epoxy equivalent: 250 g/eq))

AA: acrylic acid

PGMEA: Propylene glycol monomethyl ether acetate

TEAB: tetraethylammonium bromide

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

• THPA: tetrahydrophthalic anhydride.

(Synthesis Example 1)

BPFE (114.4 g (0.23 mol)), AA (33.2 g (0.46 mol)), PGMEA (157 g) and TEAB (0.48 g) were put in a four-neck flask with a reflux condenser (capacity 500 ml), and at 100 to 105 ° C. The reaction was stirred for 20 hours. Next, BPDA (35.3 g (0.12 mol)) and THPA (18.3 g (0.12 mol)) were added to the reaction product in the flask, and stirred at 120 to 125° C. for 6 hours, whereby a photocurable Cardo resin (alkali soluble) A resin solution containing resin) was obtained. The obtained resin solution WHEREIN: The solid content concentration was 56.1 mass %, the acid value (solid content conversion) was 103 mgKOH/g, and Mw by GPC analysis was 3600.

(2) Component (B): Photopolymerizable monomer

-DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name "DPHA" manufactured by Nippon Kayaku Co., Ltd.).

(3) Component (C): Photoinitiator

OXE02: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name manufactured by BASF Japan Co., Ltd. " Ilgacure OXE02”).

(4) Ingredient (D): Light-shielding agent

Carbon black-A or B was used as a light-shielding agent (component (D)), and the following CB dispersion liquid (I) or (II) was used for the introduction.

· CB dispersion (I): A PGMEA dispersion (average particle size of 120 nm by the CB-A dispersion in the dispersion of CB-A of 120 nm) having a carbon black-A (CB-A) concentration of 25% by mass and a polymer dispersing agent of 5% by mass.

· CB dispersion (II): PGMEA dispersion with a carbon black-B (CB-B) concentration of 25% by mass and a polymer dispersing agent of 5% by mass (average particle diameter of 200 nm according to the CB-B dispersion by the Querland method).

(5) Component (E): Silica particles

The following silica-A or B was used as a silica particle (component (E)), and the following silica dispersion liquid (I) or (II) was used for the introduction.

-Silica dispersion liquid (I): A PGMEA dispersion liquid with a silica-A concentration of 30 mass %, and a dispersing agent 3 mass % (average particle diameter of 110 nm by the Querland method in the dispersion liquid of silica-A).

- Silica dispersion liquid (II): A PGMEA dispersion liquid with a silica-B concentration of 30 mass %, and a dispersing agent 3 mass % (average particle diameter of 185 nm by the Querland method in the dispersion liquid of silica-B).

(6) Component (F): Organic solvent

·PGMEA: Propylene glycol monomethyl ether acetate.

(Examples 1 to 12 and Comparative Examples 1 to 4)

First, the resin solution (containing photocurable cardo resin) obtained in Synthesis Example 1, DPHA, OXE02, carbon The photosensitive resin composition was obtained by mixing the dispersion liquid of black (CB dispersion liquid (I) or (II)), the dispersion liquid of silica particles (silica dispersion liquid (I) or (II)), and PGMEA, respectively. In addition, the quantity (mass part) of (A)-(E) component and dispersing agent shown in Table 1 is a ratio of the quantity of solid content (including the component used as solid content after hardening), and quantity of PGEMA of (F) component ( parts by mass) is an amount including PGMEA contained as a solvent in the resin solution, the carbon black dispersion, and the silica particle dispersion used for the preparation of the composition, and is a ratio of the total amount (total amount) of PGEMA contained in the composition.

Next, using the obtained photosensitive resin composition, respectively, the light-shielding film was manufactured as follows. That is, using a spin coater, the photosensitive resin composition obtained so that the film thickness after post-baking becomes 1.2 μm is applied on a glass substrate having a size of 125 mm in length and 125 mm in width by using a spin coater, and heating at a temperature of 80° C. for 1 minute (free of charge) Bake) to obtain a dry coating film. After that, a negative photomask (using a [line]/[space]=20 µm/20 µm thing) was put on the obtained dry coating film while adjusting the exposure gap to be 80 µm, and ultra-high pressure mercury with I-line roughness of 30 mW/cm 2 100 mJ/cm<2> of ultraviolet-ray was irradiated using the lamp, and the exposed part (photosensitive part) was photocured. Next, the photocured coating film (exposed coating film) was subjected to shower development at a pressure of 1 kgf/cm 2 under a temperature condition of 23° C. using 0.05 mass % aqueous potassium hydroxide solution as a developer, and the time the pattern was observed. was taken as the development drop-off time (BT seconds), and after the development cut-off time (BT seconds), after further development was continued for 20 seconds, spray water washing at a pressure of 5 kgf/cm 2 was performed to remove the unexposed portion of the coating film. After forming a patterned light-shielding film (pixel pattern) on the glass substrate in this way, the obtained light-shielding film was heated at 230°C for 30 minutes using a hot air dryer (post-baking) to obtain a light-shielding film (pixel pattern). In this way, the light-shielding film (pixel pattern) laminated|stacked on the glass substrate was obtained.

As is clear from the results shown in Tables 1 and 2, when a film made of a photocured of the photosensitive composition having an average film thickness of 1.2 µm is formed and subjected to elemental analysis, the atomic ratio (Y)/atomic ratio (X) is 1.1 to The photosensitive resin composition obtained in Examples 1 to 12 in the range of 10 (times), and the atomic ratio (Z)/atomic ratio (X) in the range of 0.5 to 2.8 (times), when the light-shielding film is formed , it was confirmed that the reflectance was 5.0% or less and exhibited excellent characteristics in developability. On the other hand, the photosensitive resin compositions obtained in Comparative Examples 1 to 3 having an atomic ratio (Y)/atomic ratio (X) outside the range of 1.1 to 10 (times) had a reflectance of 5.8% or more when a light-shielding film was formed. It turned out that reflectance cannot fully be reduced. Further, a comparative example in which the atomic ratio (Z)/atomic ratio (X) falls outside the range of 0.5 to 2.8 (times) even when the atomic ratio (Y)/atomic ratio (X) is within the range of 1.1 to 10 (times). It turned out that the photosensitive resin composition obtained in 4 has low developability at the time of light shielding film formation, and cannot form the favorable pattern of linearity. Moreover, in the comparative example 1 which does not use a silica particle, it originates in the high refractive index of an interface, and it is guessed that the reflectance could not be reduced.

From these results, while the photosensitive resin composition for light-shielding film formation shall contain components (A)-(E), the average film thickness forms a film into a film which consists of a hardened|cured material of the said photosensitive resin composition which is 1.2 micrometers on a glass substrate. Thus, when the atomic ratios (X), (Y) and (Z) are obtained by performing elemental analysis on the film, the value of the atomic ratio (Y) is 1.1 to 10 of the value of the atomic ratio (X). double the size, and the value of the atomic ratio (Z) is 0.5 to 2.8 times the value of the atomic ratio (X) It turned out that it becomes possible to make the patterning performance (developability) in alkali development at the time of manufacture of a light shielding film sufficiently high.

As described above, according to the present invention, when the light-shielding film is formed, it is possible to sufficiently reduce the light reflectance of the film, and it is possible to make the patterning performance in alkali development at the time of manufacturing the light-shielding film sufficiently high. It becomes possible to provide the photosensitive resin composition for formation, the light-shielding film obtained using the same, and the display apparatus provided with this light-shielding film. Therefore, the photosensitive resin composition (photosensitive resin composition for light-shielding film formation) of this invention is especially useful as a material etc. for forming the light-shielding film used for various display apparatuses (for example, a liquid crystal display device etc.).

Claims (5)

A photosensitive resin composition for forming a light-shielding film, comprising:
The following components (A) to (E):
(A) alkali-soluble resin;
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;
(C) a photoinitiator;
(D) a shading agent;
(E) silica particles,
contains, and
A film having an average film thickness in the range of 0.5 to 2.5 µm and made of a cured product of the photosensitive resin composition is formed on a glass substrate, and the cross section of the film is analyzed by energy dispersive X-ray analysis using STEM-EDS. By performing the following atomic ratios (X), (Y) and (Z):
[Atomic Ratio (X)] The atomic ratio of the Si element in the film to the total amount of C, O and Si elements present in the film;
[Atomic Ratio (Y)] Si in the region near the glass substrate of the film relative to the total amount of C, O and Si elements present in the region near the glass substrate of the film between the interface between the glass substrate and the film to a thickness of 200 nm atomic ratio of elements,
[Atomic Ratio (Z)] The total amount of C, O, and Si elements present in the region near the surface of the film from the surface of the film on the side not in contact with the glass substrate to the thickness of 200 nm relative to the surface vicinity of the film Atomic ratio of Si elements in the region,
is obtained, the value of the atomic ratio (Y) is 1.1 to 10 times the value of the atomic ratio (X), and the value of the atomic ratio (Z) is The photosensitive resin composition, characterized in that the size is 0.5 to 2.8 times the value. The method of claim 1,
The photosensitive resin composition, characterized in that the component (E) is silica particles having an average particle diameter of 10-180 nm. 3. The method according to claim 1 or 2,
The photosensitive resin composition, wherein the component (D) is carbon black having an average particle diameter of 50 to 180 nm. It is a film|membrane which consists of a photocured material of the photosensitive resin composition in any one of Claims 1-3, and is 0.5 micrometer - 2.5 micrometers in average thickness, The light-shielding film characterized by the above-mentioned. A display device comprising the light-shielding film according to claim 4.