KR20210146967A - A display device having a black photosensitive resin composition, a cured product thereof, and a hiding layer comprising the cured product - Google Patents

Abstract

[PROBLEMS] To provide a black photosensitive resin composition excellent in hardness and adhesiveness of a cured product while maintaining hiding properties and insulating properties. [Solution means] A black photosensitive resin composition comprising at least (A) a photosensitive resin, (B) a photoinitiator, (C) a black pigment, and (D) a filler, wherein the (A) photosensitive resin comprises a bonding portion and the bonding It is an acrylate compound in which at least two (meth)acryloyl groups are bonded to the part through a connection part, and the connection part is at least one selected from the group consisting of a caprolactone group, an ethylene oxide group and a propylene oxide group, and a carbon atom in one connection part and an acrylate compound having a total number of oxygen atoms of 3 to 15, wherein the (D) filler comprises calcium carbonate.

Description

A display device having a black photosensitive resin composition, a cured product thereof, and a hiding layer comprising the cured product

The present invention relates to a black photosensitive resin composition, and more particularly, to a black photosensitive resin composition that can be suitably used for hiding a glass substrate of a display device, a cured product thereof, and a display device having a hiding layer comprising the cured product will be.

In recent years, a display device having a liquid crystal element, a light emitting diode element, an organic electroluminescent element, etc. has adopted a display having a touch panel function, and in such a display device, an ITO wiring pattern is formed in the image display area, A metal wiring pattern is formed around it. For example, in the type (OGS type) in which a touch panel layer is directly formed in a cover glass, after forming a hiding layer around a cover glass so that a metal wiring pattern etc. may not be visually recognized, ITO and a metal wiring pattern are formed. Therefore, in order to prevent the high light-shielding property for concealing wiring and the panel malfunction by electricity supply between wiring, high insulation is calculated|required of the light-shielding layer. Moreover, in recent years, a higher optical density (OD) has come to be calculated|required as a hiding layer.

As for the hiding layer as described above, conventionally, a black film is affixed to a desired location on the cover glass surface, or black ink is repeatedly applied until the hiding property is obtained. It has come to be performed (for example, patent document 1).

In addition, carbon black has been used as a hiding material used for black ink. Since carbon black is a conductive material, in order to satisfy hiding and insulating properties, an inorganic filler such as talc or illite is used in combination with carbon black. is proposed (Patent Document 2).

Japanese Patent Laid-Open No. 2018-35219 Japanese Patent Laid-Open No. 10-316904

In the photosensitive resin as described above, when the blending amount of the hiding material is increased in order to improve the light-shielding property, light is difficult to transmit, so exposure failure occurs, and as a result, the adhesiveness of the cured product to the cover glass becomes insufficient. Therefore, it is the present situation that the photosensitive resin composition excellent also in insulation reliability and adhesiveness with glass has not yet implement|achieved, maintaining concealability.

Therefore, the objective of this invention is providing the black photosensitive resin composition excellent also in insulation reliability and adhesiveness with glass, maintaining concealability.

Moreover, another object of this invention is to provide the display apparatus provided with the concealing layer containing the hardened|cured material obtained by hardening|curing the black photosensitive resin composition, and this hardened|cured material.

The present inventors use an ethylenically unsaturated group-containing compound having a specific modified site as the photosensitive resin, and by using a specific inorganic filler in combination with a black pigment, insulation reliability and adhesion to glass can be improved while maintaining hiding properties. gained knowledge The present invention is based on this knowledge.

That is, the black photosensitive resin composition according to the present invention is a black photosensitive resin composition comprising at least (A) a photosensitive resin, (B) a photoinitiator, (C) a black pigment, and (D) a filler,

The (A) photosensitive resin is an acrylate compound in which a bonding portion and at least two (meth)acryloyl groups are bonded to the bonding portion through a connection portion, and the connection portion is a caprolactone group, an ethylene oxide group and a propylene oxide group. At least one selected from the group consisting of an acrylate compound in which the total number of carbon atoms and oxygen atoms in one connection portion is 3 to 15,

The (D) filler comprising calcium carbonate

is characterized by

In an embodiment of the present invention, the acrylate compound is preferably 6 to 165 in total number of carbon atoms and oxygen atoms in all the connecting portions.

In the embodiment of this invention, it is preferable that the said (D) filler contains talc further.

In the embodiment of this invention, it is preferable that 30-50 mass % of said (D) fillers are contained with respect to a resin component.

In the embodiment of this invention, it is preferable that the said (C) black pigment is carbon black.

Moreover, the hardened|cured material by another embodiment of this invention is obtained by hardening|curing a black photosensitive resin composition, It is characterized by the above-mentioned.

In addition, the display device according to another embodiment of the present invention,

glass substrate,

A hiding layer including the cured product, provided on at least a part of one surface of the glass substrate

It is characterized in that it comprises at least.

According to the present invention, an ethylenically unsaturated group-containing compound having a specific modified site is used as the photosensitive resin, and in addition to a black pigment, a specific inorganic filler is used in combination to maintain hiding properties, and the black color excellent in insulation reliability and adhesion to glass A photosensitive resin composition can be provided.

Furthermore, in another aspect of this invention, the hardened|cured material obtained by hardening|curing the black photosensitive resin composition, and the display apparatus provided with the concealing layer containing this hardened|cured material can be provided.

[Black photosensitive resin composition]

The black photosensitive resin composition of the present invention contains (A) photosensitive resin, (B) photoinitiator, (C) black pigment, and (D) filler as essential components, (A) photosensitive resin, It is an acrylate compound in which at least two (meth)acryloyl groups are bonded to the bonding portion through a connection portion, and the connection portion is at least one selected from the group consisting of a caprolactone group, an ethylene oxide group and a propylene oxide group, and in one connection portion An acrylate compound having a total number of carbon atoms and oxygen atoms of 3 to 15 is included, and (D) calcium carbonate is included as a filler. Hereinafter, each component which comprises the black photosensitive resin composition of this invention is demonstrated in detail.

<(A) photosensitive resin>

(A) photosensitive resin contained in the black photosensitive resin composition of the present invention is an acrylate compound in which a bonding portion and at least two (meth)acryloyl groups are bonded to the bonding portion through a connection portion, and the connection portion is a caprolactone group; It is at least 1 sort(s) selected from the group which consists of an ethylene oxide group and a propylene oxide group, and contains the acrylate compound whose total number of carbon atoms and oxygen atoms in one connection part is 3-15. By using such a specific acrylate compound as a photosensitive resin and using together with calcium carbonate to be described later as a filler, even in a black photosensitive resin composition containing carbon black, it is possible to improve insulation and adhesion to glass while maintaining hiding properties. . Although the reason for this is not clear, the black photosensitive resin composition tends to have insufficient adhesion to the glass substrate because light does not reach the deep part during exposure, but by using a specific acrylate compound as described above as the photosensitive resin, It is thought that adhesiveness can be improved.

As the specific acrylate compound described above, an acrylate compound in which at least two (meth)acryloyl groups are bonded to the bonding portion through any one or more types of connection portions selected from a caprolactone group, an ethylene oxide group and a propylene oxide group (that is, modified polyfunctional (meth)acrylate) can be suitably used, but it is necessary that the total number of carbon atoms and oxygen atoms in one connecting portion is 3 to 15. In a modified polyfunctional acrylate in which the total number of carbon atoms and oxygen atoms in one connection part is less than three, adhesiveness with a glass substrate becomes inadequate, on the other hand, when it exceeds 15, the hardness of a cured film becomes inadequate. A preferred range is 3 to 10. In addition, in this specification, let the (meth)acryloyl group be a term which collectively names an acryloyl group and a methacryloyl group, and (meth)acrylate is a term which generically names acrylate, methacrylate, and mixtures thereof. , and the same is true for other similar expressions.

Caprolactone-modified (meth)acrylate can be prepared, for example, by reacting a polyhydric alcohol, (meth)acrylic acid, and ε-caprolactone. In addition, in the present invention, caprolactone-modified urethane (meth)acrylate obtained by urethanating caprolactone-modified (meth)acrylate and a polyisocyanate compound, caprolactone-modified (meth)acrylate and polycarboxylic acid Caprolactone-modified polyester (meth)acrylate obtained by esterifying a compound, caprolactone-modified (meth) obtained by esterifying a compound in which some or all of the hydroxyl groups of a polyhydric alcohol are modified with caprolactone groups and (meth)acrylic acid An acrylate may be sufficient.

Examples of the polyhydric alcohol used for caprolactone denaturation include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, Although trimethylolmelamine etc. are mentioned, It is not limited to these.

In addition, as a polyisocyanate compound used for caprolactone-modified urethane (meth)acrylate, for example, tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylenebis (dimethylmethylene) diisocyanate aromatic diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1, Although aliphatic or alicyclic diisocyanate compounds, such as 5-diisocyanatocyclohexane, 4,4'- dicyclohexylmethane diisocyanate, and isophorone diisocyanate, are mentioned, It is not limited to these. Moreover, as a polyisocyanate compound, the prepolymer which has an isocyanate group obtained by making the above-mentioned diisocyanate compound addition-react with a polyhydric alcohol, The compound which has an isocyanurate ring obtained by cyclization trimerization of the above-mentioned diisocyanate compound, The above-mentioned diisocyanate compound A polyisocyanate compound having a urea bond or a biuret bond obtained by reacting a compound with water can also be used. These polyisocyanate compounds may be used individually by 1 type, and may be used as 2 or more types of mixture.

Moreover, as a polycarboxylic acid compound used for caprolactone-modified polyester (meth)acrylate, For example, aliphatic poly acids, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, maleic acid Although aromatic polycarboxylic acid compounds, such as a carboxylic acid compound, phthalic acid, and trimellitic acid, etc. are mentioned, It is not limited to these. Moreover, as a polycarboxylic acid compound, the prepolymer etc. which have a carboxy group obtained by making an above-mentioned polycarboxylic acid compound react with a polyhydric alcohol can also be used.

As (meth)acrylate, although both monofunctional and polyfunctional can be used, polyfunctional (meth)acrylate can be used suitably from a viewpoint of the hardness of hardened|cured material.

As monofunctional (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acryl Rate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylic Rate, benzyl (meth) acrylate, cresol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, di ethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, polyurethane mono (meth) acrylate, polyepoxy mono (meth) acrylate, polyester mono (meth) acrylate, and the like. It may be used individually by 1 type, and may be used as 2 or more types of mixture.

Specific examples of the bifunctional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol 1 ,3-di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, tricyclodecanediyldimethylene Di(meth)acrylate, bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, poly Carbonate di(meth)acrylate, or polyalkylene oxide adduct of these monomers, polycaprolactone adduct, polycarbonate adduct, polyurethane di(meth)acrylate, polyepoxydi(meth)acrylate, polyester Di(meth)acrylate etc. are mentioned, These may be used individually by 1 type, and may be used as a 2 or more type mixture.

Specific examples of the trifunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyurethane tri(meth)acrylate, polyepoxytri(meth)acrylate, poly Ester tri(meth)acrylate etc. are mentioned, These may be used individually by 1 type, and may be used as a 2 or more type mixture.

Specific examples of the tetrafunctional or higher (meth)acrylate include ditrimethylolpropanetetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, polyepoxytetra(meth)acrylate, polyester tetra(meth)acrylate , dipentaerythritol penta (meth) acrylate, penta (meth) acrylate such as tripentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) Hexa(meth)acrylate such as acrylate, hepta(meth)acrylate such as tripentaerythritol hepta(meth)acrylate, octa(meth)acrylate such as tripentaerythritol octa(meth)acrylate, 4 Polyurethane poly(meth)acrylate more than functional, polyepoxy poly(meth)acrylate more than tetrafunctional, polyester poly(meth)acrylate more than tetrafunctional, etc. are mentioned. In addition, modified products such as polyalkylene oxide modified product addition product, polycaprolactone modified product addition product, and polycarbonate modified product addition product of (meth)acrylate monomers having tetrafunctional or higher function, polyurethane poly(meth) having tetrafunctional or higher function acrylates, polyepoxy poly(meth) acrylates tetrafunctional or higher, polyester poly(meth) acrylates tetrafunctional or higher, and these may be used alone or as a mixture of two or more. .

As the caprolactone-modified polyfunctional (meth)acrylate, commercially available ones may be used, for example, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, etc. (all are Nippon Kayaku Co., Ltd.) Shiki geisha) can be mentioned.

In addition, as the acrylate modified with an ethylene oxide group or a propylene oxide group, for example, trimethylolmethane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytri(meth) ) acrylate, glycerin polyethoxytri(meth)acrylate, glycerin polypropoxytri(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, Dipentaerythritol polyethoxy hexa(meth)acrylate, dipentaerythritol polypropoxy hexa(meth)acrylate, etc. are mentioned.

The black photosensitive resin composition of this invention may contain photosensitive resins other than an above-described modified polyfunctional (meth)acrylate compound as (A) photosensitive resin. For example, (meth)acrylate that is not caprolactone-modified as described above may be used without limitation. Among these, from the viewpoint of insulation and hardness, bisphenol A type epoxy (meth)acrylate resin synthesized by reaction of bisphenol A, epichlorohydrin, and (meth)acrylic acid, bisphenol S, epichlorohydrin and (meth)acrylic acid Bisphenol S type epoxy (meth) acrylate resin synthesized by the reaction of bisphenol F type epoxy (meth) acrylate resin synthesized by reaction of bisphenol F with epichlorohydrin and (meth) acrylic acid and a phenol novolak-type epoxy (meth)acrylate resin synthesized by reaction of epichlorohydrin and (meth)acrylic acid, and these may be used alone or as a mixture of two or more. .

(A) When a photosensitive resin other than the above-mentioned modified polyfunctional (meth)acrylate is included as the photosensitive resin, the compounding amount of the modified polyfunctional (meth)acrylate is from the viewpoint of the curability of the cured product or adhesion to glass, the photosensitive resin It is preferable that it is 5-45 mass % with respect to a component, and it is more preferable that it is 15-35 mass %.

<(B) Photoinitiator>

Specific examples of the photoinitiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2). ,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2 bisacylphosphine oxides such as ,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, P monoacylphosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate, 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one , hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di thioxanthone such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned, These may be used individually by 1 type, or 2 or more types You may use it as a mixture.

As a commercial item of (alpha)-aminoacetophenone type|system|group photoinitiator, IGM Resins company Omnirad 907, 369, 369E, 379, etc. are mentioned. Moreover, as a commercial item of an acyl phosphine oxide type|system|group photoinitiator, IGM Resins company Omnirad TPO, 819, etc. are mentioned. As a commercial item of an oxime ester type photoinitiator, Irgacure OXE01, OXE02 made by BASF Japan Co., Ltd., N-1919 made by ADEKA Co., Ltd., ADEKA ACL's NCI-831, NCI-831E, Changzhou Chiangri Dianz New Chailao Co., Ltd. make TR-PBG-304 etc. are mentioned.

In addition, Japanese Patent Laid-Open No. 2004-359639, Japanese Patent Laid-Open No. 2005-097141, Japanese Patent Laid-Open No. 2005-220097, Japanese Patent Laid-Open No. 2006-160634, Japanese Patent Laid-Open No. 2008-094770 The carbazole oxime ester compound of Unexamined-Japanese-Patent No. 2008-509967, Unexamined-Japanese-Patent No. 2009-040762, and Unexamined-Japanese-Patent No. 2011-80036, etc. are mentioned.

It is preferable that it is 5-20 mass parts with respect to 100 mass parts of photosensitive resin (A) components in conversion of solid content, and, as for the compounding quantity of a photoinitiator, it is more preferable that it is 7-15 mass parts. The photocurability of a resin composition becomes favorable as it is 7 mass parts or more, and the hardness and adhesiveness of hardened|cured material become further favorable. Moreover, while the reduction effect of an outgas is acquired as it is 15 mass parts or less, deep-part sclerosis|hardenability falls easily.

It may use together with said (B) photoinitiator, and may use a photoinitiation adjuvant or a sensitizer. As a photoinitiation adjuvant or a sensitizer, a benzoin compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound, etc. are mentioned. In particular, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are used. It is preferable to use By containing a thioxanthone compound, deep part sclerosis|hardenability can be improved. Although these compounds can be used as a photoinitiator in some cases, it is preferable to use together with a photoinitiator. In addition, a photoinitiation adjuvant or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

Moreover, since these photoinitiators, a photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as a ultraviolet absorber. However, these are not used only for the purpose of improving the sensitivity of the resin composition. If necessary, it is possible to increase the photoreactivity of the surface by absorbing light of a specific wavelength, change the line shape and aperture of the resist pattern to vertical, tapered shape, or reverse tapered shape, and improve the precision of line width and aperture diameter. have.

<(C) Black pigment>

The black pigment may be an inorganic pigment or an organic pigment, for example, inorganic pigments such as carbon black, triferric oxide, black titanium oxide, copper manganese black, copper chromium black and cobalt black, and organic pigments such as cyanine black and aniline black and these may be used individually by 1 type, and may be used as 2 or more types of mixture. Moreover, the pigment mixture made black by mixing pigments, such as red, blue, green, and yellow, is also contained in a black pigment. Moreover, a black pigment may use together coloring agents, such as another pigment and dye, within the range which does not impair the effect of this invention.

Among the above, carbon black is preferable from a viewpoint of adhesiveness with glass. In addition, by using carbon black, it is possible to form a shielding layer with high smoothness in which stripes or citron shell-like patterns are not formed. Moreover, if it is carbon black, the OD value of a shielding part can be made into the range of 3-6 by addition of a small amount, and shielding property can be improved more while maintaining insulation. The OD value can be measured using, for example, a transmission densitometer (manufactured by Video Jet X-Rite Co., Ltd., X-Rite 361T(V)).

As carbon black, channel black, oil furnace black, gas furnace black, thermal black, acetylene black, bone black etc. are mentioned, for example. Among these, it is preferable to use together carbon black with a graphite structure undeveloped and a large electrical resistance value from an insulating viewpoint.

As the above-mentioned black pigment, commercially available ones may be used, for example, MA-100, MA-100R, MA-600, #25, #3230, 33250 (all manufactured by Mitsubishi Chemical Corporation), REGAL99R (manufactured by Cabot Corporation), Raven860U, Raven780ULTRA (all made by Colombian Chemicals), Prix 25 (made by Degussa), HTC#100 (made by Nittetsu Chemicals & Materials Co., Ltd.) etc. are mentioned.

It is preferable that the compounding quantity of a black pigment is 3.5-7.5 mass % with respect to the whole composition from a viewpoint of hiding property, the hardness of hardened|cured material, and adhesiveness with glass. By making the compounding quantity of a black pigment into 3.5 mass % or more, a high optical density can be maintained and hiding property can be made sufficient. Moreover, by setting it as 7.5 mass % or less, deep part exposure becomes a sufficient thing, and the hardened|cured material of sufficient adhesiveness and hardness can be obtained.

<(D) Filler>

The black photosensitive resin composition of the present invention contains calcium carbonate as a filler. As described above, the black photosensitive composition has a problem that deep hardening upon exposure is insufficient, but in the present invention, the modified polyfunctional (meth)acrylate compound is used as the photosensitive resin, and calcium carbonate is used as a filler. By using, the adhesiveness to glass and insulation reliability can be improved, maintaining concealability. Conventionally, silica, talc, barium sulfate, etc. have been added to the black photosensitive composition as a filler in some cases. However, when the above-described specific modified polyfunctional (meth)acrylate and calcium carbonate are used together, the insulation reliability and the glass substrate are unexpectedly improved. It turned out that adhesiveness is compatible. Although the reason is not clear, even when it is set as the resin composition which has an OD value sufficient to maintain hiding property by using together specific modified polyfunctional (meth)acrylate and calcium carbonate, insulation reliability and adhesiveness to glass is considered to be compatible with a higher level.

In this invention, in addition to calcium carbonate as a filler, it is preferable to contain talc further. By using two specific fillers, the effect of this invention can be made into a still more remarkable thing.

The mixing ratio of calcium carbonate and talc is preferably 1:9 to 9:1 in terms of mass, and 2:1 to 1:2 is more preferable from the viewpoint of utilizing both properties of calcium carbonate and talc, particularly advantageous From a viewpoint of adhesiveness with 1:1 - 1:2 is preferable.

The average particle diameter of calcium carbonate and talc is preferably 10 µm or less, and more preferably 0.1 to 5 µm. In addition, in this specification, let the average particle diameter measure the major axis diameter of 20 randomly selected inorganic fillers with an electron microscope, and let it be the number average particle diameter computed as the arithmetic mean value.

Moreover, as for the average primary particle diameter of calcium carbonate and a talc, a major axis diameter becomes like this. Preferably it is 10 micrometers or less, More preferably, it is 1-5 micrometers. On the other hand, the minor axis diameter is preferably 10 µm or less, and more preferably 0.1 to 1 µm. In addition, in this specification, let the average particle diameter be the number average particle diameter computed as each arithmetic mean value by measuring the major axis diameter and minor axis diameter of 20 randomly selected inorganic fillers with an electron microscope, respectively.

The total blending amount of the filler containing calcium carbonate is preferably 30 to 60 parts by mass, more preferably 40 to 50 parts by mass, based on 100 parts by mass of the photosensitive resin (A) component, in terms of solid content, from the viewpoint of insulation and adhesiveness. .

Moreover, in this invention, other fillers may be contained within the range which does not impair the effect of this invention other than said calcium carbonate and talc, For example, barium sulfate, barium titanate, silicon oxide powder, fine powder oxidation Well-known and usual fillers, such as silicon, amorphous silica, clay, magnesium carbonate, aluminum oxide, and mica powder, may be contained.

<Other ingredients>

Components, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and a dispersing agent, can be further mix|blended with the black photosensitive resin composition as needed. Those known in the field of black photosensitive ink can be used. In addition, at least any one of antifoaming agents and leveling agents such as silicone-based, fluorine-based, and polymer-based antifoaming agents, silane coupling agents such as imidazole-based, thiazole-based and triazole-based antifoaming agents, rust inhibitors, and optical brighteners, etc. You can mix 1 type.

In this invention, the organic solvent can be used for preparation of a black photosensitive resin composition, and viscosity adjustment. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, For example, Ketones, such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether glycol ethers such as; Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, diethylene glycol monoethyl ether acetate (carbitol acetate), diethylene glycol monobutyl ether esters such as acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents may be used individually by 1 type, and may be used as 2 or more types of mixture.

Machines, such as a triaxial roll and a blender, are used for each essential component mentioned above in the black photosensitive resin composition of this invention, and kneading|mixing and dispersion|distribution with an arbitrary component. Thus, the black photosensitive resin composition in which each component is disperse|distributed is apply|coated on glass substrates, such as a cover glass, by suitable application methods, such as a screen printing method, a bar coater, a blade coater, and can form hardened|cured material by exposure. Exposure can be performed using a conventionally well-known exposure apparatus (UV exposure apparatus etc.), For example, the black photosensitive resin composition can be hardened by irradiating an ultraviolet-ray with the exposure amount of 1000-1500 mJ/cm<2>.

It is preferable that OD value is the range of 3-6, and, as for the hardened|cured material formed using the black photosensitive resin composition of this invention from a concealable viewpoint, the range of 3-4 is more preferable. As conditions for measuring an OD value in this invention, it measures as hardened|cured material and a cured film with a film thickness of 10 micrometers. In addition, the OD value measures the amount of transmitted light using a transmission densitometer, and the following formula:

OD value=-log ₁₀ (T/100)

(wherein T represents transmittance (%))

can be calculated based on

Even if the hiding layer containing the hardened|cured material formed using the black photosensitive resin composition of this invention has sufficient hiding property as mentioned above, since it is excellent in insulation reliability and adhesiveness with a glass substrate, it hides in at least a part of one surface. A glass substrate provided with a layer can be suitably used as a cover glass of a display device.

Example

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following, what is referred to as "part" and "%" is a mass basis, unless otherwise stated.

<Preparation of black photosensitive resin composition>

Each black photosensitive resin composition of the same table was obtained by mix|blending each component of following Table 1 and kneading|mixing with a 3-axis roll mill.

In addition, *1 - *14 in a table|surface are as follows.

*1: DPCA-60: caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

*2: M-360: Trimethylolpropane EO (ethylene oxide) modified triacrylate (manufactured by Toagosei Corporation)

*3: SP4010-9: Novolak-type epoxy acrylate (manufactured by Showa Denko Co., Ltd.)

*4: DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

*5: VR-77-11: Bisphenol type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.)

*6: acrylic ester HO: 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation)

*7: Omnirad TPO: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by IGM Resins)

*8: MA-100: Carbon black (manufactured by Mitsubishi Chemical Corporation)

*9: Keishitsu CaCO ₃ : Calcium carbonate (Maruo Calcium Co., Ltd., average primary particle diameter (major axis diameter): 2 µm, (short axis diameter): 0.4 µm)

*10: LMP-100 talc/FG105: talc (manufactured by Fuji Talc Kogyo Co., Ltd.)

*11: FUSELEX WX: Silica (manufactured by Tatsumori, Ltd.)

*12: B-30: barium sulfate (manufactured by Sakai Chemical High School Co., Ltd.)

*13: KAYAMER PM-2: phosphate ester of caprolactone-modified 2-hydroxyethyl methacrylate (manufactured by Nippon Kayaku Co., Ltd.)

*14: BYK-9077: Dispersing agent (Big Chemie Japan Co., Ltd.)

<Evaluation>

(1) Glass adhesion evaluation

After degreasing the surface of one side of a glass substrate (made of soda glass, length 160 mm, width 110 mm, thickness about 2.0 mm) with alcohol, the entire degreasing surface was screen-printed (300 mesh) as above, Each obtained black photosensitive resin composition was apply|coated so that the thickness of the coating film after hardening might be set to 10 micrometers, and the coating film was formed. The coating film was cured by exposing the coating film to ultraviolet rays at an exposure amount of 1200 mJ/cm 2 with an exposure apparatus (UV conveyor furnace) to form a cured film on the glass substrate. In addition, the exposure amount was measured using UV-351 by ORC company.

Then, based on JISK5600-5-6:1999 (ISO2409:1992), the crosscut tape peeling test was implemented to the cured film formed on the glass substrate. The following evaluation criteria evaluated the adhesiveness of a glass substrate and a cured film.

(double-circle): Corresponds to classification 0 or 1 of Table 1 of JIS K5600-5-6: 1999 8.3.

○: JIS K5600-5-6: Corresponds to Class 2 of Table 1 of 1999 8.3.

△: JIS K5600-5-6: Corresponds to category 3 of Table 1 of 1999 8.3.

×: Corresponds to classification 4 or 5 of Table 1 of JIS K5600-5-6: 1999 8.3.

The evaluation results are as shown in Table 1 below.

Moreover, after performing the process (PCT process) of leaving the glass substrate on which the said cured film was formed in the environment of temperature 121 degreeC, and 97% of humidity for 82 hours, it carried out similarly to the above, and the adhesiveness of a glass substrate and a cured film was evaluated. The evaluation results are as shown in Table 1 below.

(2) Insulation reliability evaluation

Said (1) glass adhesive evaluation WHEREIN: Instead of a glass substrate, except having used the glass epoxy board|substrate with which the comb-tooth-shaped electrode of L/S=100 micrometer/100 micrometer was provided in one side, it carried out similarly, and formed the cured film. Next, using an insulation deterioration evaluation tester (MIG-8600B manufactured by IMV Corporation) for insulation reliability of the cured film, a voltage of 30 V is applied in an environment of 121°C temperature and 97% humidity, and the insulation resistance value is measured over time did. The elapsed time when an insulation resistance value became 1x10 ⁶ ohms or less was measured, and the following references|standards evaluated insulation reliability.

◎: Elapsed time until 1×10 ⁶ Ω or less is 70 hours or more

○: Elapsed time until 1×10 ⁶ Ω or less is 40 hours or more and less than 70 hours

△: Elapsed time until 1×10 ⁶ Ω or less is 15 hours or more and less than 40 hours

×: Elapsed time until 1 × 10 ⁶ Ω or less is less than 15 hours

The evaluation results are as shown in Table 1 below.

(3) Concealment evaluation

The OD value of the glass substrate on which the said cured film was formed was measured using the transmission densitometer (The Videojet X-light company make, X-Rite 361T(V)). The measurement results are as shown in Table 1 below. In addition, "-" in Table 1 shows non-measurement.

Moreover, when visually confirming the glass substrate on which the cured film was formed, the hiding property with respect to a base was favorable in all that used the black photosensitive resin composition of Examples 1-5.

As shown in Table 1, the black photosensitive resin composition of Examples 1 to 5 is a photosensitive resin, and the total number of carbon atoms and oxygen atoms in the connection portion is 3 to 15 modified polyfunctional (meth) acrylate compounds (that is, DPCA- 60, M-360) is contained, and since calcium carbonate is contained as a filler, it turns out that favorable adhesiveness and insulation with respect to a glass substrate are acquired, maintaining the outstanding hiding property.

On the other hand, as the photosensitive resin, even when a modified polyfunctional (meth) acrylate compound having a total number of 3 to 15 carbon atoms and oxygen atoms in the connecting portion is used, an inorganic filler such as talc, silica, barium sulfate, etc. is used as a filler alone. In this case, it turns out that coexistence of the adhesiveness with respect to a glass substrate and insulation reliability is difficult (Comparative Examples 1, 3, 4).

In addition, when an unmodified normal polyfunctional (meth)acrylate compound (ie, DPHA) is used as the photosensitive resin, even when calcium carbonate is used as a filler, for example, adhesion to a glass substrate and insulation reliability It can be seen that the coexistence of is difficult (Comparative Example 2).

Claims (7)

A black photosensitive resin composition comprising at least (A) photosensitive resin, (B) photoinitiator, (C) black pigment, and (D) filler,
The (A) photosensitive resin is an acrylate compound in which a bonding portion and at least two (meth)acryloyl groups are bonded to the bonding portion through a connection portion, and the connection portion is a caprolactone group, an ethylene oxide group and a propylene oxide group. At least one selected from the group consisting of an acrylate compound in which the total number of carbon atoms and oxygen atoms in one connection portion is 3 to 15,
The (D) filler comprising calcium carbonate
A black photosensitive resin composition, characterized in that. The black photosensitive resin composition according to claim 1, wherein in the acrylate compound, the total number of carbon atoms and oxygen atoms in all the connecting portions is 6 to 165. The black photosensitive resin composition according to claim 1 or 2, wherein the (D) filler further contains talc. The black photosensitive resin composition of any one of Claims 1-3 in which 30-50 mass % of said (D) fillers are contained with respect to a resin component. The black photosensitive resin composition according to any one of claims 1 to 4, wherein the (C) black pigment is carbon black. It is obtained by hardening|curing the black photosensitive resin composition in any one of Claims 1-5, The hardened|cured material characterized by the above-mentioned. glass substrate,
The hiding layer containing the hardened|cured material of Claim 6 provided in at least one part of one surface of the said glass substrate.
A display device comprising at least a.