KR102385884B1 - Photosensitive resin composition, photo-cured pattern fomeed forom the same and image display comprising the pattern - Google Patents

Abstract

The present invention includes heat-dissipating particles, colored particles, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent, wherein the binder resin has a dissolving property in an aqueous alkali solution, and a photosensitive resin composition comprising a thermosetting functional group, a light formed therefrom An image pattern and an image display device including the same are provided.

Description

A photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device comprising the same

The present invention relates to a photosensitive resin composition, a photocurable pattern formed of the composition, and an image display device having the photocurable pattern.

In the manufacture of display devices such as liquid crystal display materials, organic light emitting devices, and display panel materials, the photosensitive resin composition is used to form various photocurable patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. When manufacturing proceeds using the photosensitive resin composition, mass production is possible and the resolution that can be formed is very high. Such a photosensitive resin composition can generally be divided into a transparent photosensitive resin composition and a colored photosensitive resin composition. The colored photosensitive resin composition is a photosensitive composition having a color for a specific purpose, and the most representative colored photosensitive resin composition is a colored photosensitive resin composition for manufacturing a color filter and a black photosensitive resin composition. The colored photosensitive resin composition for manufacturing a color filter generally has red, green, and blue colors, and the black photosensitive resin composition is used at the boundary between the colored layers.

Recently, as the miniaturization and high performance of mobile products such as smartphones and tablet PCs are progressing, the heat generated from the mobile products has increased significantly. Accordingly, there is a growing interest in materials that dissipate the generated heat to the surroundings. In general, for heat dissipation, a graphite or ceramic heat dissipation composite sheet having high thermal conductivity is placed on the upper part of the heat generating part, or a method of attaching it to the heat generating part using an adhesive or an adhesive is used.

However, since the pressure-sensitive adhesive / adhesive used for attachment has relatively low thermal conductivity compared to the heat dissipation composite sheet, heat cannot be transferred quickly and the pressure-sensitive adhesive/adhesive is a bottleneck that collects heat.

On the other hand, heat dissipation particles are a general term for particles having heat dissipation properties, and are widely used in polymers or sheet films. However, in order to introduce heat dissipation particles into the photosensitive resin composition and perform patterning, it is necessary to study the binder resin for fixing the heat dissipation particles together with the study on the exposure process and the developing process, but there is no research on this.

As in Korean Patent Registration No. 10-1792755 (hereinafter referred to as 'Patent Document 1'), a resin composition and dry film solder resist having photocurability and thermosetting properties have been developed, but photosensitivity exhibiting improved heat dissipation performance and resolution characteristics There is still a need for a resin composition. In addition, in Patent Document 1 above, heat dissipation characteristics were not considered at all in selecting an oligomer or a monomer.

In Republic of Korea Patent No. 10-1687394 (hereinafter referred to as 'Patent Document 2'), a patent for a resin composition using coating particles having a surface coated with ceramic and complexing particle diameters of heat radiation particles has been proposed. However, even in Patent Document 2, the resin serving to fix the heat radiation particles has not been considered at all.

In Korean Patent Laid-Open Patent No. 10-2016-0078340 (hereinafter referred to as 'Patent Document 3'), the use of heat-dissipating particles and resin together as a heat-dissipating material has been proposed. This is a universal use, when including heat-dissipating particles together with a thermoplastic resin or a thermosetting resin, it is very difficult to form a pattern, and the application field is limited to simply manufacturing a coating film or film. In Patent Document 3, a composition is proposed for a lithography process for mass production and high resolution, and it is also used together with a cyan pigment, so that the flow of heat can be visually confirmed.

In Korean Patent Laid-Open Publication No. 10-2015-0075998 (hereinafter referred to as 'Patent Document 4'), a method for manufacturing a light blocking layer and a color filter using Zion pigment was developed. In Patent Document 4, it was attempted to form an excellent pattern after the process by discoloring the Zion pigment during the process. However, it can be seen that even in the above patent, the cyan pigment was used as a method to secure high properties due to heat during the process rather than being used for the purpose of confirming the flow of heat.

Republic of Korea Patent Registration No. 10-1792755 Republic of Korea Patent No. 10-1687394 Republic of Korea Patent Publication No. 10-2016-0078340 Republic of Korea Patent Publication No. 10-2015-0075998

An object of the present invention is to provide a photosensitive resin composition that is excellent in the realization of fine patterns upon curing, and is capable of realizing high-resolution patterns.

Another object of the present invention is to provide a photosensitive resin composition that has excellent thermal conductivity after curing and can form a photocurable pattern capable of displaying a color according to temperature.

Another object of the present invention is to provide a photocurable pattern formed of the above-described photosensitive resin composition and an image display device having the photocurable pattern.

The present invention includes heat dissipating particles, colored particles, binder resin, photopolymerizable monomer, photopolymerization initiator and solvent,

The binder resin provides a photosensitive resin composition, characterized in that it has a dissolving property in an aqueous alkali solution, it comprises a thermosetting functional group.

In addition, the present invention provides a photocurable pattern made of the photosensitive resin composition and an image display device including the same.

The photosensitive resin composition according to embodiments of the present invention has excellent heat transfer characteristics, excellent implementation of fine patterns, and high-resolution pattern implementation is possible.

In addition, the photosensitive resin composition of the present invention can display a color according to temperature, and has excellent thermal conductivity to form a photocurable pattern with improved heat dissipation characteristics.

Another object of the present invention is to provide an image display device for a photocurable pattern formed of the above-described photosensitive resin composition.

1 to 3 are photographs showing pattern formation characteristics of photocurable patterns formed using the photosensitive resin compositions of Examples and Comparative Examples.

The present invention includes heat dissipating particles, colored particles, binder resin, photopolymerizable monomer, photopolymerization initiator and solvent,

The binder resin has a dissolving property in an aqueous alkali solution, and provides a photosensitive resin composition comprising a thermosetting functional group, a photocurable pattern formed therefrom, and an image display device including the same.

Hereinafter, embodiments of the present invention will be described in detail. However, these are preferred examples, and the spirit and scope of the present invention are not necessarily limited thereto.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention includes heat dissipating particles, colored particles, binder resin, photopolymerizable monomer, photopolymerization initiator, and solvent.

heat dissipation particles

The heat dissipation particles used in the photosensitive resin composition of the present invention may exhibit high thermal conductivity properties to improve heat dissipation properties of the photocurable pattern.

The heat dissipation particle according to the present invention may be used without limitation as long as it is a thermally conductive material, for example, copper (Cu), aluminum (Al), aluminum oxide (Al ₂ O ₃ ), gold (Au) and silver (Ag) metals selected from the group consisting of; Carbon-based materials selected from the group consisting of graphite, carbon nanotubes (CNT) and graphene and graphene oxide; and silica, alumina (Al ₂ O ₃ ), boron nitride (BN), aluminum nitride (AlN), silicon carbide (SiC), magnesium oxide (MgO), zinc oxide (ZnO), and aluminum hydroxide (Al(OH) ₃ ) and ceramic compounds selected from the group consisting of These can be used individually or in mixture of 2 or more types, respectively.

The heat dissipation particles may be transparent particles having a transmittance of 90% or more in a visible light region. In this case, the visible light region may be in a wavelength range of 500 nm to 600 nm.

The particle size of the heat dissipation particles may be formed to be 2 to 50 nm based on the shortest length of the particles, and it is advantageous that the aspect ratio preferably has a value between 5 and 1000 in terms of improving heat dissipation characteristics. .

The aspect ratio (Aspect Ratio) means a ratio of the minimum length of the heat dissipating particle to the maximum length of the heat dissipating particle.

The content of the heat dissipation particles is not particularly limited, but may include, for example, 3 wt% to 30 wt% based on the total solid weight of the photosensitive resin composition. If the content of the heat-dissipating particles is less than 3% by weight, high thermal conductivity cannot be ensured, and when the content of 30% by weight or more is included, a problem occurs in that the viscosity increases due to the surface area of the particles, and the ratio increases compared to the content added There may be a problem in that the efficiency is lowered. In addition, agglomeration between particles may occur, which may be disadvantageous in the dispersion process.

colored particles

The colored particles include one or more pigments so that a pattern having a desired color can be prepared.

The pigment may be an organic pigment that is a compound classified as a pigment in the color color index (published by The Society of Dyers and Colorists), or an inorganic pigment that is an inorganic salt of a metal oxide, a metal complex, or barium sulfate.

Specifically, for example, C.I. Pigment White 6

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185 ;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264 and 279;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I Pigment Brown 28;

C.I Pigment Violet 23, 32 and 29;

C.I Pigment Black 1, 31, 32, and Organic Black 100 CF from Basf; and the like, but is not limited thereto.

The colorant may further include an additional Zion pigment in addition to the pigments exemplified above.

Zion pigments are pigments that change color when a certain temperature is reached, and are also called temperature-sensitive pigments. There are those that change color only once due to temperature, some that change color several times as the temperature rises, and some that do not, and some that become primary colors when the temperature decreases.

The principle of Zion pigment is to use the discoloration of the pigment based on physical and chemical changes such as crystal form transition, pH change, crystal water release, thermal decomposition reaction, and solid phase reaction by constant temperature.

The Zion pigment is divided into a reversible Zion pigment that returns to its primary color when the temperature rises and cools, and an irreversible Zion pigment that does not return even when the temperature goes down. Pigments may be used.

The Zion pigment is not particularly limited as long as it is a material that changes color in response to temperature, but, for example, CM Tech's Thermocromic 15 ℃ to Thermocromic 20 ℃, Thermocromic 25 ℃, Thermocromic 28 ℃, Thermocromic 31 ℃, Thermocromic 35 ℃, Thermocromic 60 ℃, Hali industrial's Thermochromic 31 ℃ Black, and the like.

When the photosensitive resin composition of the present invention includes the Zion pigment, it is possible to simultaneously check the heat flow or heat distribution according to heat conduction.

The content of the Zion pigment is not particularly limited, and for example, may be included in 10 to 40% by weight of the total weight of the colorant, and preferably to be included in 15 to 25% by weight in terms of recognizing heat flow and heat distribution. can

The colorant according to the present invention may further include organic pigments, inorganic pigments or mixtures thereof which are commonly used in the art within the limits that do not depart from the scope of the present invention in addition to the above pigments.

The content of the colored particles is not particularly limited, but may be included, for example, in an amount of 3 wt% to 20 wt% based on the total solid weight of the photosensitive resin composition. If the content of the colored particles is less than 3% by weight, it is difficult to have a desired color, and if the content of the colored particles is more than 20% by weight, the colored particles may interfere with the transfer of heat between the heat-dissipating particles, which may be disadvantageous.

binder resin

The photosensitive resin composition of the present invention includes a binder resin, wherein the binder resin has solubility in an alkali-soluble aqueous solution and includes a thermosetting functional group.

The binder resin used in the photosensitive resin composition of the present invention includes an acrylate group or an unsaturated double bond as a thermosetting functional group, and such a binder resin may be used without particular limitation as long as it can be used in the photosensitive resin composition, but with the following Chemical Formulas 1 to 3 It is preferable to include one or more of the compounds formed. The compounds of Chemical Formulas 1 to 3 may be included in an amount of 3 to 80 mol%, preferably 5 to 70 mol%, respectively, in mole fraction based on the total number of moles of the binder resin. When at least one of the compounds represented by Chemical Formulas 1 to 3 is included within the molar fraction range, the sensitivity and adhesion of the photosensitive resin composition are excellent, and the pattern peeling does not occur during the developing process.

[Formula 1]

[Formula 2]

[Formula 3]

In addition, the binder resin having one or more units selected from the group consisting of Chemical Formulas 4 to 5 in preparing the photosensitive resin composition by being included together with the heat dissipation particles has excellent heat dissipation properties to prepare a photosensitive resin composition including heat dissipation particles. Suitable.

[Formula 4]

[Formula 5]

The compound represented by Formula 4 is (Octahydro-4,7-methano-1H-indenyl)methyl acrylate, and the compound represented by Formula 5 is Vinylcarbazole.

The binder resin used in the photosensitive resin composition of the present invention may be one in which other monomers copolymerizable with Chemical Formulas 1 to 5 and Chemical Formulas 1 to 5 are copolymerized.

Specific examples of the unsaturated bond additionally copolymerizable with Formulas 1 to 5 include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o -Aromatic vinyls such as vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether compound; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; (meth)acrylamide; unsaturated amide compounds such as N,N-dimethyl (meth)acrylamide; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane; 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. of unsaturated oxetane compounds.

Each of the compounds exemplified above may be used alone or in combination of two or more.

The binder resin of the present invention may be used by further mixing with various other known binder resins generally used in the art, if necessary.

The binder resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin is out of the above range, the film is not prevented from being reduced during development, thereby causing a problem in that the pattern portion may be omitted.

The acid value of the binder resin is 50 to 150 (KOH mg/g), preferably 60 to 140 (KOH mg/g), more preferably 80 to 135 (KOH mg/g), and most preferably 80 to 130 (KOH mg/g). When the acid value of the binder resin is 50 to 150 (KOH mg/g), solubility in a developer is improved, and a residual film rate is improved.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution.

The binder resin comprises 20 to 80 wt%, preferably 20 to 70 wt%, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. In the above range, the solubility of the developer is sufficient, so that the pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission of the non-pixel portion is improved.

photopolymerizable monomer

The photopolymerizable monomer is a monomer that is polymerized by active radicals, acids, etc. generated from a photopolymerization initiator by light irradiation, and strengthens the strength of the pattern.

The photopolymerizable monomer used in the photosensitive resin composition of the present invention is not particularly limited, and for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol diacrylate Acrylate, neopentyl glycol diacrylate, pentaerythritol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol di Methacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The content of the photopolymerizable monomer is not particularly limited, but may be included, for example, in an amount of 20 to 70 wt%, preferably 30 to 50 wt%, based on the total solid weight of the photosensitive resin composition. When the content of the photopolymerizable monomer is within the above range, the strength of the prepared coating film and smoothness of the coating film may be good.

photopolymerization initiator

The photopolymerization initiator, which is one component of the photosensitive resin composition of the present invention, is an oxime-based photopolymerization initiator that generates methyl radicals after irradiation with light, and essentially includes an oxime ester-based compound.

The oxime ester compound is 1,2-octadione (1,2-Octanedione), 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)(1-[4-(phenylthio) ) phenyl]-,2-(O-benzoyloxime)) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) ( It is preferable to include at least one selected from the group consisting of 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime)). In addition, BASF's Irgacure® OXE01, Irgacure® OXE 02, Irgacure® OXE 03, etc. may be mentioned as products, and it is preferable to use a mixture of two or more types because each absorbance and the types of radicals generated vary.

As the oxime-based photopolymerization initiator used in the present invention, OXE 03 is preferably used in consideration of sensitivity and the shape of the pattern to be formed.

The oxime ester-based compound is included in an amount of 10 to 100 wt%, preferably 20 to 100 wt%, based on the total weight of the photopolymerization initiator.

When the oxime ester-based compound is included in an amount of less than 10% by weight, the problem of reduced sensitivity due to the additive cannot be solved, and a short circuit of the pattern is likely to occur during the developing process.

In addition, within the range that does not impair the effects of the present invention, in addition to the oxime ester-based compound, an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound One or more compounds selected from the group may be used.

Specifically, the acetophenone-based compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] propan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one; and the like.

The benzophenone-based compound is specifically, for example, benzophenone, 0-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'- and tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

The triazine-based compound is specifically, for example, 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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis( trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine;

The biimidazole compound is specifically, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group; can Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferred. used

The thioxanthone-based compound is specifically, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiok. Santon etc. are mentioned.

The photopolymerization initiator may be used alone or in combination of two or more.

In the present invention, the photopolymerization initiator is included in an amount of 2 to 10% by weight, preferably 3 to 7% by weight, based on the total solid weight of the photosensitive resin composition.

Within the range of 3 to 7% by weight, the photosensitive resin composition is highly sensitive and exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, pattern formation of the pixel portion formed by using the photosensitive resin composition may be improved.

In addition, the photopolymerization initiator may further include a photopolymerization initiator auxiliary in order to improve the sensitivity of the photosensitive resin composition of the present invention. The photosensitive resin composition according to the present invention contains a photopolymerization initiation adjuvant, thereby further increasing the sensitivity and improving productivity.

The photopolymerization initiation adjuvant may include, for example, at least one selected from the group consisting of an amine compound, a carboxylic acid compound, and a polyfunctional thiol compound.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4, 4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) and 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy and phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The polyfunctional thiol compound includes tris-[(3-mercaptopropionyloxy)-ethyl]-[0153] isocyanurate (Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate), trimethylopropane tris -3-mercaptopropionate (Trimethylolpropane tris-3-mercaptopropionate), pentaerythritol tetrakis-3-mercaptopropionate (Pentaerythritol tetrakis-3-mercaptopropionate) and dipentaerythritol hexa-3-mercaptopropionate and cypionate (Dipentaerythritol hexa-3-mercaptopropionate).

When the photopolymerization initiation adjuvant is used, the photopolymerization initiation adjuvant is included in an amount of 1 to 10 wt%, preferably 3 to 5 wt%, based on the total weight of the solid content in the photosensitive resin composition of the present invention.

When the photopolymerization initiation adjuvant is included in an amount of 3 to 5% by weight, the sensitivity of the photosensitive resin composition is increased.

solvent

The solvent included in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve the above components, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amides. These can be used individually or in mixture of 2 or more types.

For example, 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ethers such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Esters, such as 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned, Preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, It may be ethyl lactate, butalactate, 3-ethoxy ethyl propionate, 3-methoxymethyl propionate, and the like.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of coatability and drying properties. Specific examples include alkylene glycol alkyl ether acetates; ketones; esters such as 3-ethoxy ethyl propionate and 3-methoxy methyl propionate; and more preferred examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxy Ethyl propionate, 3-methoxymethyl propionate, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, and for example, may be included in an amount of 50 to 90% by weight, preferably 60 to 80% by weight, based on the total weight of the photosensitive resin composition. When the content of the solvent is within the above range, the applicability may be good.

additive

The photosensitive resin composition of the present invention may further include at least one additive selected from the group consisting of a dispersing agent, another high molecular compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent, if necessary.

The dispersing agent is added for deagglomeration and stability maintenance of pigments and dyes, and those generally used in the art may be used without limitation. Preferably, BMA (butyl methacrylate) or DMAEMA (N,N- dimethylaminoethyl methacrylate) containing an acrylate-based dispersant; polycarboxylic acid esters; unsaturated polyamides; polycarboxylic acids; (partial) amine salts of polycarboxylic acids; ammonium salts of polycarboxylic acids; alkylamine salts of polycarboxylic acids; polysiloxane; long-chain polyaminoamide phosphate salts; esters of hydroxyl group-containing polycarboxylic acids and modified products thereof; an amide or a salt thereof formed by the reaction of a polyester having a free carboxyl group and a poly (lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide; Phosphate ester etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Other high molecular compounds are not particularly limited, and for example, curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. A thermoplastic resin etc. are mentioned.

The curing agent is a component for enhancing deep hardening and mechanical strength, and the type thereof is not particularly limited, and examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

The epoxy compound is not particularly limited, and for example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins an epoxy resin, a glycidyl ester-based resin, a glycidylamine-based resin, or a brominated derivative of such an epoxy resin; aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; butadiene (co)polymer epoxides; isoprene (co)polymer epoxides; glycidyl (meth) acrylate (co) polymer; Triglycidyl isocyanurate etc. are mentioned.

The oxetane compound is not particularly limited, and examples thereof include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. .

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent.

The curing auxiliary compound is not particularly limited, and examples thereof include polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydrides, commercially available ones can be used as an epoxy resin curing agent.

A commercially available epoxy resin curing agent that can be used in the present invention is not particularly limited, and for example, a brand name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a brand name (Rikasiddo HH) (Shin Nippon Ewha) Manufactured by Co., Ltd.), and a brand name (MH-700) (manufactured by New Nippon Ewha Co., Ltd.).

The surfactant is a component that improves the film-forming property of the photosensitive resin composition, and the type thereof is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, or a mixture thereof.

The silicone-based surfactant is not particularly limited, and examples thereof include Dow Corning Toray Silicones DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc.; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 by GE Toshiba Silicon Corporation, etc. are mentioned.

The fluorine-based surfactant is not particularly limited, and examples of the commercially available product include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd.

The kind of adhesion promoter is not particularly limited, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The type of antioxidant is not particularly limited, and examples thereof include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. can

The kind of the ultraviolet absorber is not particularly limited, and examples thereof include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyrazole and alkoxybenzophenone.

The anti-aggregation agent is not particularly limited, and may be, for example, sodium polyacrylate.

The content of the additive is not particularly limited, but may be included, for example, in an amount of 0.1 to 5% by weight, preferably 0.2 to 1% by weight, based on the total solid weight of the photosensitive resin composition.

<Photocurable pattern and image display device>

An object of the present invention is to provide a photocurable pattern formed of the photosensitive resin composition and an image display device including the photocurable pattern.

The photocurable pattern made of the photosensitive resin composition realizes high resolution, displays a color according to temperature, and has excellent heat dissipation characteristics and heat resistance.

Accordingly, it can be used as various patterns in an image display device, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, etc., and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, etc. However, it is not limited thereto, and in particular, it is suitable for an insulating film pattern.

An image display device having such a photocurable pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, etc., but is not limited thereto, and all image display devices known in the art that can be applied can be exemplified.

The photocurable pattern may be prepared by coating the photosensitive resin composition of the present invention described above on a substrate and forming a photocurable pattern (after undergoing a developing process if necessary).

Hereinafter, experimental examples including specific examples and comparative examples are presented to help the understanding of the present invention, but these are merely illustrative of the present invention and do not limit the appended claims, the scope and description of the present invention It is apparent to those skilled in the art that various changes and modifications to the embodiments are possible within the scope of the spirit, and it is natural that such variations and modifications fall within the scope of the appended claims.

Synthesis Example: Preparation of binder resin

Synthesis Example 1

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared. As the monomer loading lot, (Octahydro-4,7-methano-1H-indenyl)methyl acrylate, 3,4-epoxytricyclodecan-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9- 80 g of a mixture of yl (meth) acrylate at 30:30:40, 10 g of methyl methacrylate, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added. to prepare agitation. As a chain transfer agent dropping tank, 6 g of n-dodecanthiol and 60 g of PGMEA were added to prepare stirring.

Thereafter, 200 g of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dripping was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and maintained for 5 hours to obtain a resin having a solid acid value of 85 mgKOH/g.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

[Analysis of binder resin of Synthesis Example 1]

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder resin was performed under the following conditions using the GPC method, and the ratio of the weight average molecular weight and the number average molecular weight obtained at this time was calculated as the molecular weight distribution (Mw / Mn).

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40 °C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Examples and Comparative Examples

With the composition and composition according to Table 1 below, the photosensitive resin composition was prepared by dispersing the heat dissipating particles and colored particles, the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the additive together with a solvent in a bead mill. In Table 1, the content unit of each component is g.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 heat radiation particle 1 15 - - 25 20 - 15 heat dissipation particle 2 - 20 - - - - - heat dissipation particle 3 - - 10 - - - - colored particles pigment 1 5 10 10 5 10 10 5 pigment 2 - 5 5 5 5 - - binder resin binder 1 35 30 35 30 25 45 - binder 2 - - - - - - 35 photopolymerizable monomer 40 30 35 30 35 40 40 Photoinitiator 1 4.8 4.5 4.5 4.5 4.5 4.5 4.8 Light polymerization initiator 2 - 0.3 0.3 0.3 0.3 0.3 - additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 solvent 350 400 400 400 500 500 350 Heat radiation particle 1: graphite flake Sigma-Aldrich
Heat radiation particle 2: graphite nanofiber Sigma-Aldrich
Heat radiation particle 3: Nano plate silver (Ag silver flake) Inframat
Pigment 1: DIC FASTOGEN SUPER RED 254 226-5254
Pigment 2: Hali industrial's Thermochromic 31℃
Binder 1: Binder of Synthesis Example 1
Binder 2: S-72B of Aekyung Corporation (molecular weight 14,800 g/mol)
Photopolymerizable monomer: dipentaerythritol hexaacrylate (Kayarad DPHA: Kayaku, Japan))
Photoinitiator 1: Irgacure OXE03 (Basf)
Photoinitiator 2: Irgacure OXE02 (Basf)
Additive: KBE-9007N (Shin-Etsu)
Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Experimental example

(1) Substrate fabrication

A 5cmХ5cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. On the prepared substrate, each of the photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 2 was spin-coated to have a final film thickness of 5.0 μm, pre-baked at 100° C., and dried for 2 minutes to remove the solvent. Then, it was exposed at an exposure rate of 100 mJ/cm ² to form a 2cmХ2cm pattern, and an aqueous alkali solution was used to remove the unexposed portion. Then, post-fired at 230°C for 20 minutes to prepare a pixel defining layer.

(2) Thermal conductivity evaluation

The thermal conductivity of the substrate was measured using Angstrom's Method using a thermal conductivity meter of Hantech, and the results are shown in Table 2.

(3) Check color change

One side of the substrate was placed on a plate heated to 70° C. and thermal movement was observed. If the heat transfer was observed with the eye, it was marked with a ◎. If it was not observed with the eye, it was marked with an X. The results are shown in Table 2.

(4) pattern formation characteristics

The pattern characteristics of the pattern formed through the exposure and development process were evaluated using an optical microscope. The standard was evaluated based on the patternability of the 50㎛ pattern and the 100㎛ pattern, and the evaluation was performed according to the following evaluation conditions. The results are shown in Table 2.

[Evaluation standard]

(double-circle): The pattern formation of 50 micrometers and 100 micrometers patterns is good as shown in FIG.

△: As shown in FIG. 2, patterns of 50 μm and 100 μm patterns can be formed.

X: It is impossible to form a pattern of 50 μm to 100 μm as shown in FIG. 3 .

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 thermal conductivity 14.3 25.3 43.6 42.5 35.5 0.04 9.3 Pattern forming characteristics ◎ ◎ ◎ ◎ △ ◎ △ color change check X ◎ ◎ ◎ ◎ X X

As can be seen in Table 2, it can be seen that Examples 1 to 5 exhibit high thermal conductivity compared to Comparative Examples 1 and 2.

In particular, when comparing Example 1 and Comparative Example 2, the difference in thermal conductivity according to the binder type can be confirmed.

Claims (12)

Contains heat dissipating particles, colored particles, binder resin, photopolymerizable monomer, photopolymerization initiator and solvent,
The heat dissipation particles may include metals selected from the group consisting of copper (Cu), aluminum (Al), aluminum oxide (Al ₂ O ₃ ), gold (Au), and silver (Ag); Carbon-based materials selected from the group consisting of graphite and carbon nanotubes (CNT); and silica, alumina (Al ₂ O ₃ ), boron nitride (BN), aluminum nitride (AlN), silicon carbide (SiC), magnesium oxide (MgO), zinc oxide (ZnO), and aluminum hydroxide (Al(OH) ₃ ) Including one or two selected from the ceramic-based compound selected from the group consisting of,
The binder resin has a dissolving property in an aqueous alkali solution, characterized in that it contains a thermosetting functional group, the photosensitive resin composition for manufacturing a color filter. The photosensitive resin composition of claim 1 , wherein the binder resin comprises at least one compound selected from the compounds represented by the following Chemical Formulas 4 to 5.
[Formula 4]

[Formula 5]

delete The photosensitive resin composition of claim 1, wherein the heat radiation particles are transparent particles having a transmittance of 90% or more in a range of 500 nm to 600 nm. The photosensitive resin composition of claim 1, wherein the heat dissipating particles have a particle size of 2 to 50 nm. The method according to claim 1, The heat dissipation particles have an aspect ratio (Aspect Ratio) of 5 to 1000, the photosensitive resin composition. The method according to claim 1,
With respect to the total weight of solids in the photosensitive resin composition,
3 to 30% by weight of heat dissipating particles; and
A photosensitive resin composition comprising; 3 to 20% by weight of colored particles. The photosensitive resin composition of claim 7 , wherein the colored particles include a Zion pigment. The photosensitive resin composition of claim 8, wherein the Zion pigment is included in an amount of 10 to 40 wt% based on the total weight of the colored particles. The photocurable pattern formed from the photosensitive resin composition in any one of 1, 2, and 4-9. The photocurable pattern of claim 10 , wherein the photocurable pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern. An image display device comprising the photocurable pattern of claim 11 .

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