CN106842816B

CN106842816B - Self-luminous photosensitive resin composition, color filter and image display device

Info

Publication number: CN106842816B
Application number: CN201610983623.4A
Authority: CN
Inventors: 王贤正; 金胄皓
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-12-03
Filing date: 2016-11-09
Publication date: 2022-03-25
Anticipated expiration: 2036-11-09
Also published as: TWI705297B; KR102054430B1; CN106842816A; TW201728996A; KR20170065280A

Abstract

The present invention relates to a self-luminous photosensitive resin, and more particularly, to a self-luminous photosensitive resin containing a photoluminescence quantum dot, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a UV absorber, and a solvent, and a color filter and an image display device manufactured using the same.

Description

Self-luminous photosensitive resin composition, color filter and image display device

Technical Field

The present invention relates to a self-luminous photosensitive resin, a color filter manufactured using the same, and an image display device.

Background

The color filter is a thin film type optical element that extracts 3 colors of red, green, and blue from white light and can support a minute pixel unit, and the size of one pixel is about several tens to several hundreds of micrometers. The color filter described above has the following structure: a black matrix layer formed in a predetermined pattern on a transparent substrate for blocking light at the boundary between pixels and a pixel portion formed by arranging 3 primary colors of a plurality of colors (usually red (R), green (G), and blue (B)) in a predetermined order for forming each pixel are sequentially stacked. Generally, a color filter is prepared by applying 3 or more colors to a transparent substrate by a dyeing method, an electrophoretic deposition method, a printing method, a pigment dispersion method, or the like. Recently, a pigment dispersion method using a pigment dispersion type photosensitive resin has become mainstream.

A pigment dispersion method, which is one of methods for realizing a color filter, is a method as follows: after a photosensitive resin composition containing an alkali-soluble resin including a colorant, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives is coated on a transparent substrate provided with a black matrix and a pattern of a form to be formed is exposed, a non-exposed portion is removed with the solvent and heat curing is performed, and the above series of processes is repeated to form a colored film. The pigment dispersion method is often applied to LCDs of mobile phones, notebook computers, displays, TVs, and the like. In recent years, there is a trend that, in addition to excellent pattern characteristics, higher performance such as high color reproduction rate and high brightness and high contrast is required for a photosensitive resin composition for a color filter using a pigment dispersion method having many advantages.

However, color reproduction is light that appears by light irradiated from a light source passing through a color filter, and in the process, a part of the light is absorbed by the color filter, so that light efficiency is lowered, and there is a fundamental limitation that perfect color reproduction cannot be achieved due to the characteristics of a pigment as the color filter.

Further, korean patent application laid-open No. 10-2013-0000506 discloses a display device including: a light source and a display panel on which light emitted from the light source is incident, the display panel including a plurality of color conversion portions, the color conversion portions including: a plurality of wavelength converting particles that convert a wavelength of the light; and a plurality of color filter particles that absorb light of a predetermined wavelength band from the light.

Although the above prior arts have similarities in terms of containing quantum dots, the content of the photosensitive resin composition is not specifically described, and only a display device having high color reproduction and brightness is disclosed, and thus further development of the photosensitive resin composition is required.

[ Prior art documents ]

[ patent document ]

Korean patent application laid-open No. 10-2013-0000506

Disclosure of Invention

Object of the Invention

An object of the present invention is to solve the above problems and to provide a self-luminous photosensitive resin which can produce a color filter having excellent brightness characteristics while avoiding problems of low luminous efficiency and poor photosensitive characteristics in a process of producing the color filter by including a UV absorber.

Another object of the present invention is to provide a color filter produced from the self-luminous photosensitive resin of the present invention and an image display device including the color filter.

Technical scheme

In order to achieve the above object, a self-luminous photosensitive resin according to an embodiment of the present invention includes a photoluminescent quantum dot, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a UV absorber, and a solvent.

The present invention is also characterized by a color filter produced from the self-luminous photosensitive resin and an image display device including the color filter.

Advantageous effects

The self-luminous photosensitive resin according to the present invention as described above includes the UV absorber, and thus the problems of low luminous efficiency and poor photosensitive characteristics do not occur in the post-baking process, and a high-quality color filter having excellent luminance characteristics can be provided.

Detailed Description

The self-luminous photosensitive resin comprises a photoluminescence quantum dot, a photopolymerization compound, a photopolymerization initiator, an alkali soluble resin, a UV absorbent and a solvent.

The self-luminous photosensitive resin is described in detail below.

Photoluminescent quantum dots

The self-luminous photosensitive resin comprises photoluminescence quantum dot particles.

Quantum Dots (QDs) are semiconductor substances of nanometer size. The atoms form molecules, which constitute small aggregates of molecules called molecular clusters, and thus form nanoparticles. In particular, when such nanoparticles have semiconductor properties, they are called quantum dots. When the quantum dot reaches an excited state by receiving energy from the outside, it spontaneously emits energy corresponding to the corresponding energy bandgap.

The photosensitive resin composition of the present invention contains the above-described photoluminescence quantum dot particles, and thus a color filter manufactured therefrom can emit light by color irradiation (photoluminescence). Further, since light having a color is emitted, color reproducibility is more excellent, and since light is emitted in all directions due to photoluminescence, a viewing angle can also be improved.

The quantum dot particle according to the present invention is not particularly limited as long as it emits light by stimulation of light, and may be selected from the group consisting of, for example, II-VI semiconductor compounds, III-V semiconductor compounds, IV-VI semiconductor compounds, group IV elements, compounds containing the same, and combinations thereof. They may be used alone or in a mixture of 2 or more.

The II-VI semiconductor compound may be selected from the group consisting of: a binary element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; a ternary compound selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS s, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and a quaternary element compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof. The group III-V semiconductor compound may be selected from the group consisting of: a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAsAlSb, InN, InP, InAs, InSb, and mixtures thereof; a ternary element compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and a quaternary element compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The group IV-VI semiconductor compound may be selected from the group consisting of: a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe and mixtures thereof; a ternary element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe and mixtures thereof; and four-element compounds of the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe and mixtures thereof. The group IV element or the compound containing the same may be selected from the group consisting of: an element selected from the group consisting of Si, Ge, and mixtures thereof; and a binary compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The quantum dot particles may be homogeneous (homogeneous) single structures; core-shell (core-shell), gradient (gradient) structures, and the like; or a hybrid structure thereof.

In the core-shell structure, the substances constituting the core (core) and the shell (shell), respectively, may be composed of the above-mentioned semiconductor compounds different from each other. For example, the core may be a material including one or more selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, aginnzns, and ZnO, but is not limited thereto. The shell may be one or more selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

As the colored photosensitive resin composition used in the conventional color filter manufacturing includes red, green, and blue colorants for the display of color, the photoluminescence quantum dot particles may also be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles, and the quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles, or blue quantum dot particles.

The quantum dot particles can be synthesized by a wet chemical method, an organic metal chemical vapor deposition method, or a molecular beam epitaxy method.

The wet chemical method is a method of adding a precursor substance to an organic solvent to grow particles. Since the organic solvent naturally coordinates to the surface of the quantum dot crystal and acts as a dispersant to regulate the growth of the crystal during the growth of the crystal, the growth of the nanoparticles can be controlled by a cheaper process than a vapor deposition method such as Metal Organic Chemical Vapor Deposition (MOCVD) or Molecular Beam Epitaxy (MBE).

The content of the photoluminescence quantum dot particles according to the present invention is not particularly limited, and for example, is preferably 3 to 80% by weight, more preferably 5 to 70% by weight, of the total weight of the solid components of the self-luminous photosensitive resin. If the content of the quantum dot particles is less than the above range, the luminous efficiency may be very slight; if it is larger than the above range, the content of other components is relatively insufficient, so that there is a problem that it is difficult to form a pixel pattern.

Photopolymerizable compound

The photopolymerizable compound contained in the self-luminous photosensitive resin of the present invention is a compound polymerizable by light or the action of a photopolymerization initiator described later, and examples thereof include a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like.

Specific examples of the bifunctional monomer may be 1,6-hexanediol dimethacrylate (1,6-hexanediol dimethacrylate), ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, triethylene glycol dimethacrylate, bisacryloxyethyl ether of bisphenol A (bis [2- (acryloyloxy) ethyl ] ether), 3-methylpentanediol dimethacrylate (3-methylpentanediol dimethacrylate), and the like.

Specific examples of the other polyfunctional monomer may be trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, polydipentaerythritol pentamethylacrylate, polydipentaerythritol hexamethacrylate, and the like. Among them, polyfunctional monomers having more than two functions are preferably used.

The content of the photopolymerizable compound is preferably in the range of 5 to 50 mass%, more preferably in the range of 7 to 45 mass%, with respect to the solid content in the self-luminous photosensitive resin. When the content of the photopolymerizable compound is within the above range, the strength or smoothness of the pixel portion can be improved.

Photopolymerization initiator

The photopolymerization initiator contained in the self-luminous photosensitive resin of the present invention is not particularly limited, and may be one or more compounds selected from the group consisting of triazine compounds, acetophenone compounds, bisimidazole compounds, and oxime compounds. The self-luminous photosensitive resin containing the photopolymerization initiator has high sensitivity, and the pixel part of the pixel formed by using the composition has good strength or pattern.

Further, it is preferable to use a photopolymerization initiator together with a photopolymerization initiator, and a self-luminous photosensitive resin containing these compounds has higher sensitivity, and when a color filter is formed using the composition, productivity can be improved.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -triazine 1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.

The acetophenone compounds may be, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethyl Ketal (Benzil Dimethyl Ketal), 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, oligomers of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and the like. Further, a compound represented by the following chemical formula 1 may be exemplified.

[ chemical formula 1]

In chemical formula 1, R1 to R4 are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having from C1 to C12, a benzyl group substituted or unsubstituted with an alkyl group having from C1 to C12, or a naphthyl group substituted or unsubstituted with an alkyl group having from C1 to C12.

The kind of the compound represented by the above chemical formula 1 is not particularly limited, and specific examples thereof include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propan-1-one 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, and the like.

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbiimidazole, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (trialkoxyphenyl) biimidazole, and imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by an alkoxycarbonyl group. Among them, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenylbenzimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenylbenzimidazole are preferably used.

The oxime compound may be exemplified by the compounds of the following chemical formula.

Further, other photopolymerization initiators and the like commonly used in the art may be further included without affecting the effect of the present invention. Examples of the other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. They may be used alone or in combination of 2 or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

The benzophenone compound may be exemplified by benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4,4' -bis (N, N ' -dimethylamino) -benzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the anthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene.

Further, other photopolymerization initiators may be exemplified by 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9, 10-phenanthrenequinone, camphorquinone, Methyl benzoylformate (Methyl phenylglyoylate), titanocene compound, and the like.

In the present invention, it is preferable to use one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds in combination with the photopolymerization initiator.

Specific examples of the amine compound in the photopolymerization initiation auxiliary agent include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aromatic amino compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (collectively referred to as michelson), and 4,4' -bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used.

Examples of the carboxylic acid compound include aromatic heteroacetic acids such as phenylthioacetic acid, methylphenylthioacetic acid, ethylthiophenoacetic acid, methylethylthiophenoacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid.

The content of the photopolymerization initiator in the self-luminous photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content. When the amount of the photopolymerization initiator is within the above range, the self-luminous photosensitive resin has high sensitivity, and the strength of the pixel portion or the smoothness of the surface of the pixel portion is excellent.

Further, the photopolymerization initiation auxiliary is used in an amount of preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the above. When the amount of the photopolymerization initiation assistant used is within the above range, the sensitivity efficiency of the self-luminous photosensitive resin is higher, and the productivity of a color filter formed using the composition can be improved.

Alkali soluble resin

The alkali-soluble resin is polymerized by including an ethylenically unsaturated monomer having a carboxyl group. This is a method of imparting a soluble component to an alkaline developer used in a developing process for forming a pattern.

The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, and monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate, and preferably acrylic acid and methacrylic acid. They may be used alone or in a mixture of 2 or more.

The alkali-soluble resin according to the present invention may be further polymerized with at least one other monomer copolymerizable with the above-mentioned monomer. Examples of the aromatic vinyl compound include aromatic vinyl compounds such as styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl ether, m-vinylbenzyl ether, p-vinylbenzyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate; alicyclic methacrylic acid esters such as cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, and isobornyl methacrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; unsaturated octane compounds such as 3- (methacryloyloxymethyl) octane, 3- (methacryloyloxymethyl) -3-ethyloctane, 3- (methacryloyloxymethyl) -2-trifluoromethyloctane, 3- (methacryloyloxymethyl) -2-phenyloctane, 2- (methacryloyloxymethyl) octane and 2- (methacryloyloxymethyl) -4-trifluoromethyloctane. They may be used alone or in a mixture of 2 or more.

Methacrylic acid in the present specification means acrylic acid or methacrylic acid.

The content of the alkali-soluble resin according to the present invention is not particularly limited, and is, for example, preferably 5 to 80% by weight, more preferably 10 to 70% by weight, based on the total weight of solid components of the photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in a developer is sufficient to facilitate the formation of a pattern, and the film of the pixel portion of the exposed portion is prevented from being reduced at the time of development, so that the omission of the non-pixel portion is good.

UV absorbers

The UV absorber in the present invention not only adjusts the size of the pattern, but also maintains the light maintenance of the quantum dots at a high level.

It is known that the UV absorber is generally used when a fine pattern cannot be formed due to an increase in the minimum line width deviation (CD bias) of the photosensitive resin composition. In this case, the CD refers to a positive-cut portion of the pattern, and the CD deviation refers to a degree that the size of the formed pattern is larger than the size of the mask pattern desired to be formed. When the UV absorber is added, a part of UV is absorbed to reduce CD deviation due to diffraction, and a desired pattern can be formed.

Meanwhile, quantum dots are difficult to maintain high emission intensity in a color filter manufacturing process due to their weak heat resistance. In this case, the UV absorber can maintain high emission intensity even after Post-baking (Post-bake) is performed a plurality of times.

The UV absorber according to the present invention may include one or more of benzotriazole, triazine, and benzophenone UV absorbers, and triazine compounds are preferably used.

As the benzotriazole-based UV absorber, a known compound can be used. Specifically, octyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2-ethylhexyl 3- (3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl) propionate, [3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-methylethyl) -4-hydroxyphenyl ] -1-oxopropyl ] -w- [3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-Dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] poly (oxy-1, 2-ethanediyl), (3- (3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl) -hydroxypoly (oxy-1, 2-ethanediyl), 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-amylphenol, 3- (2H-benzotriazol-yl) -5- (1, octyl 1-dimethylethyl) -4-hydroxy-phenoxypropionate, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, and the like.

Known compounds can be used as the triazine-based UV absorber. Specifically, the triazine derivative may be 2- (4, 6-dimethyl-1, 3, 5-triazin-2-yl) -5- ((hexyl) oxy) -phenol, 2- (4- (2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (4- (2-hydroxy-3-didecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4- (3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy) phenyl) -4 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2' - [6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine-2, 4-diyl ] bis (5-butoxyphenol), 6-methylheptyl 2- {4- [4, 6-bis (4-biphenyl) -1,3, 5-triazin-2-yl ] -3-hydroxyphenoxy } propionate, and the like.

The benzophenone UV absorber can use a known compound. Specifically, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like are mentioned.

The UV absorber is preferably present in an amount of 0.025 to 5% by weight, based on the total weight of the solids content of the composition. When the UV absorber content is within the above range, the absorber effect can be improved, and a good pattern can be formed without hindering the action of the photoinitiator.

Solvent(s)

The solvent contained in the self-luminous photosensitive resin of the present invention is not particularly limited, and may be an organic solvent generally used in the art.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methoxyethyl acetate and ethoxyethyl acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and the like; ketones such as methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ -butyrolactone. They may be used alone or in a mixture of 2 or more.

The above solvent has different viscosity according to the coating method or apparatus, and thus the content of the solvent is appropriately adjusted so that the concentration of the self-luminous photosensitive resin having the above composition is 10 to 50% by weight, preferably 10 to 30% by weight.

The content of the solvent according to the present invention is not particularly limited, and may be, for example, 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the self-luminous photosensitive resin. When the content of the solvent is within the above range, the coatability is good.

Color filter

In addition, the present invention provides a color filter manufactured using the self-luminous photosensitive resin.

When the color filter of the present invention is applied to an image display device, light from a light source of the image display device emits light, and therefore, more excellent light emission efficiency can be achieved. Further, since light having a color is emitted, color reproducibility is more excellent, and light is emitted in all directions due to photoluminescence, so that a viewing angle can be improved.

More specifically, in a typical image display device including a color filter, white light is transmitted through the color filter to represent a color, and in the process, a part of the light is absorbed by the color filter, thereby possibly reducing light emission efficiency. However, when a color filter manufactured using the self-luminous photosensitive resin according to the present invention is included, light of the light source causes the color filter to self-emit light, and thus excellent light emission efficiency can be achieved.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be a color filter substrate itself, or may be a portion of a display device or the like where a color filter is provided, without particular limitation. The substrate may be glass, silicon (Si), silicon oxide (SiO)_x) Or a polymer substrate, wherein the polymer substrate may be polyether sulfone (polyethe)rsulfone, PES), Polycarbonate (PC), or the like.

The pattern layer is a layer containing the self-luminous photosensitive resin of the present invention, and may be a layer formed by applying the self-luminous photosensitive resin and then exposing, developing, and thermally curing in a predetermined pattern.

The pattern layer formed of the self-luminous photosensitive resin may have a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. When light is irradiated, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

In this case, when it is applied to an image display device, the light emitted from the light source is not particularly limited, and a light source of blue light may be used in view of more excellent color reproducibility.

According to an embodiment of the present invention, the pattern layer may be provided with only 2 red color pattern layers of the red, green, and blue pattern layers. In this case, the pattern layer further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layers of 2 colors are provided, a light source that emits light of wavelengths of other colors not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. In this case, the red quantum dots emit red light, the green quantum dots emit green light, and the blue light directly transmits through the transparent pattern layer to represent blue.

The color filter including the substrate and the pattern layer may further include partition walls formed between the respective patterns, and may further include a black matrix. In addition, a protective film formed on the color filter pattern layer may be further included.

Image display device

In addition, the invention provides an image display device comprising the color filter.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

The image display device of the present invention may include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. At this time, when applied to an image display apparatus, the light emitted from the light source is not particularly limited, but a light source emitting blue light is preferably used in view of more excellent color reproducibility.

According to another embodiment of the present invention, the image display device of the present invention may be provided with a color filter including only pattern layers of 2 colors out of a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the color filter further includes a transparent pattern layer containing no quantum dot particles.

When only the pattern layers of 2 colors are provided, a light source that emits light of wavelengths of other colors not included may be used. For example, in the case of including a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, the red quantum dots emit red light, the green quantum dots emit green light, and the blue light directly transmits through the transparent pattern layer to appear blue.

The image display device of the present invention has excellent luminance with high brightness, excellent color reproducibility, and wide viewing angle.

The present invention will be described in detail below with reference to examples. However, the following examples are intended to illustrate the present invention more specifically, and the scope of the present invention is not limited by these examples. The following embodiments may be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production example 1: synthesis of photoluminescent Green Quantum dot particles A of CdSe (as core)/ZnS (as shell) Structure

CdO (0.4mmol), Zinc acetate (4mmol), Oleic acid (5.5mL) and 1-Octadecene (1-Octadecene) (20mL) were placed in a reactor and heated to 150 ℃ for reaction. The reaction was then placed under vacuum at 100mTorr for 20 minutes in order to remove acetic acid (acetic acid) formed by the replacement of oleic acid with zinc. However, the device is not suitable for use in a kitchenThereafter, the mixture was heated to 310 ℃ to obtain a clear mixture, which was maintained at 310 ℃ for 20 minutes, followed by charging with Cd (OA)₂And Zn (OA)₂A solution of Se and S obtained by dissolving 0.4mmol of Se powder and 2.3mmol of S powder in 3ml of tri-n-octylphosphine oxide (trioctylphosphine) was quickly charged into the reactor. After growth of the mixture thus obtained at 310 ℃ for 5 minutes, the growth was interrupted by means of an ice bath (ice bath). Then, the quantum dot particles a having a CdSe (core)/ZnS (shell) structure in which particles having a core particle diameter and a shell thickness and a value of 3 to 5nm were dispersed, stabilized with oleic acid, were finally obtained by precipitating with ethanol, separating the quantum dots using a centrifuge, and washing the remaining impurities with chloroform (chloroform) and ethanol.

Production example 2: synthesis of alkali-soluble resin (D)

A stirrer, a thermometer reflux condenser, a dropping liquid and a flask having a nitrogen inlet were prepared. A monomer dropping solution was prepared by adding 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butyl peroxide-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) and mixing them with stirring. After 6 parts by weight of n-dodecylmercaptan and 24 parts by weight of PGMEA were added, they were mixed by stirring to prepare a dropping solution of a chain transfer agent. Then, 395 parts by weight of PGMEA was introduced into the flask and the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ℃ while stirring. Subsequently, the monomer dropping liquid and the chain transfer agent dropping liquid are started to drop. Dropping was performed for 2 hours while maintaining 90 ℃, and after 1 hour, the temperature was increased to 110 ℃ and maintained for 3 hours, and then the mixture was introduced into a gas introduction tube, and bubbling of a mixed gas of 5/95(v/v) with oxygen/nitrogen was started. Then, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2' -methylenebis (4-methyl-6-tert-butylphenol) and 0.8 part by weight of triethylamine were put into a flask, and the reaction was continued at 110 ℃ for 8 hours, followed by cooling to room temperature to obtain an alkali-soluble resin having a solid content of 29.1% by weight, a medium-average molecular weight of 32000 and an acid value of 114 mgKOH/g.

Examples 1 to 10 sum ratioComparative example 1: preparation of self-luminous photosensitive resin

The respective components were mixed in the weight ratios described in the following table 1, diluted with propylene glycol monomethyl ether acetate so that the total solid content was 20% by weight, and sufficiently stirred to obtain a self-luminous photosensitive resin.

[ Table 1]

Example of production of color Filter (glass substrate)

A color filter was produced using the self-luminous photosensitive resins produced in examples 1 to 10 and comparative example 1. That is, each of the self-luminous photosensitive resins was coated on a glass substrate by a spin coating method, and placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a thin film. Then, a test photomask having a 20mm × 20mm square light-transmitting pattern and a line/space pattern of 1 μm to 100 μm was placed on the film, and the film was irradiated with ultraviolet rays with a distance of 100 μm from the test photomask.

In this case, an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Nikou electric company, Inc. (USHIO INC.) was used as the ultraviolet light source, and the lamp was set at 200mJ/cm in an atmosphere²The exposure amount (365nm) of (A) was determined, and no special optical filter was used. The film irradiated with ultraviolet light was immersed in a KOH aqueous solution developer having a pH of 10.5 for 80 seconds, and then developed. The film-coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ℃ for 10 minutes, thereby manufacturing a color filter pattern. The film thickness of the self-luminous color filter manufactured as described above was 3.0 μm.

Measurement of Pattern precision

The size of the pattern obtained by the line/space pattern mask designed to be 100 μm in the above color filter manufactured using the self-luminous photosensitive resin was measured using an OM (optical microscope) apparatus (ECLIPSE LV100POL, NIKON (NIKON) corporation). The width of the light-transmitting pattern formed in the pattern mask and the width of the color filter pattern (measured width of the pattern) were compared, and the pattern error was calculated. That is, the pattern error is obtained by the following equation.

Pattern error (Δ) ═ width of (light transmission pattern, 100 μm) - (width of measured pattern)

When the pattern error value is more than 20 μm, it is difficult to form a fine pattern, and thus it is difficult to realize a fine pixel, and a process failure may occur when the pattern error value has a negative value.

Determination of the luminescence Intensity (Intensity)

The pattern portions formed in a 20mm × 20mm square pattern in the color filter formed with the self-luminous pixels were measured for the light conversion region by a 365nm tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT corporation), and the light intensities in the 550nm region were measured by a spectroscope (manufactured by Ocean Optics corporation) in examples 1 to 10 and comparative example. A post-baking (hard cake) was performed at 230 ℃ for 60 minutes, and the intensities before and after the post-baking were measured, and the light emission maintenance ratios with respect to the comparative examples are shown in table 2.

[ Table 2]

Referring to table 2 above, since examples 1 to 5 and examples 8 to 10 use a UV absorber, a fine pattern can be realized, and also quantum dot oxidation can be suppressed after post-baking compared to comparative example 1, so that the emission intensity can be maintained higher, and particularly, examples 3,4, 8 and 10 including a triazine-based UV absorber can be confirmed to have more excellent emission intensity maintaining characteristics.

In examples 6 and 7, it was confirmed that the emission intensity maintenance ratio and the line width adjustment were not affected when the UV absorber content was 0.025 wt% or less based on the total weight of the solid content. It was also confirmed that when the content of the UV absorber is 5% or more, although the maintenance rate of the emission intensity is significantly effective, the problem of a significantly reduced line width was found.

Claims

1. A self-luminous photosensitive resin composition for a color filter pixel includes a photoluminescence quantum dot particle, a photopolymerization compound, a photopolymerization initiator, an alkali-soluble resin, a UV absorber, and a solvent,

comprising photoluminescence quantum dot particles in a range of 3 to 80% by weight, a photopolymerizable compound in a range of 5 to 50% by weight, a photopolymerization initiator in a range of 0.1 to 20% by weight, an alkali-soluble resin in a range of 5 to 80% by weight, a UV absorber in a range of 0.025 to 5% by weight, relative to the total weight of solid components of the self-luminous photosensitive resin composition,

the solvent is included in a range of 60 to 90% by weight with respect to the total weight of the self-luminous photosensitive resin composition.

2. The self-luminous photosensitive resin composition according to claim 1, wherein the UV absorber comprises one or more of benzotriazole, triazine, and benzophenone compounds.

3. The self-luminous photosensitive resin composition according to claim 1, wherein said UV absorber is a compound selected from octyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2-ethylhexyl 3- (3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl) propionate, [3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-methylethyl) -4-hydroxyphenyl ] -1-oxopropyl ] -w- [3- [3- (2H-benzotriazol-2-yl) -5- (1, 1-Dimethylethyl) -4-hydroxyphenyl ] -1-oxopropoxy ] poly (oxy-1, 2-ethanediyl), (3- (3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropyl) -hydroxypoly (oxy-1, 2-ethanediyl), 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-amylphenol, 3- (2H-benzotriazol-yl) -5- (1, octyl 1-dimethylethyl) -4-hydroxy-phenylpropionate, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2- (4, 6-dimethyl-1, 3, 5-triazin-2-yl) -5- ((hexyl) oxy) -phenol, 2- (4- (2-hydroxy-3-tridecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (4- (2-hydroxy-3-didecyloxypropyl) oxy) -2-hydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4- (3- (2-ethylhexyl-1-oxy) -2-hydroxypropoxy) phenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2' - [6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine-2, 4-diyl ] bis (5-butoxyphenol) 6-methylheptyl 2- {4- [4, 6-bis (4-biphenyl) -1,3, 5-triazine-2-yl ] -3-hydroxyphenoxy } propionate, 2-hydroxy-4-n-octoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.

4. The self-luminous photosensitive resin composition according to claim 1, wherein the UV absorber contains one or more triazine compounds.

5. The self-luminous photosensitive resin composition of claim 1, wherein the photoluminescence quantum dot particles are red quantum dot particles, green quantum dot particles, or blue quantum dot particles.

6. The self-luminous photosensitive resin composition according to claim 1, wherein the photoluminescence quantum dot particles comprise one or more selected from the group consisting of II-VI semiconductor compounds, III-V semiconductor compounds, IV elements, or compounds containing them, and combinations thereof.

7. A color filter produced from the self-luminous photosensitive resin composition according to any one of claims 1 to 6.

8. An image display device comprising the color filter according to claim 7.