KR20190110843A - Photosensitive resin composition, photo-cured pattern fomeed forom the same and image display comprising the pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, which comprises: heat dissipation particles; colored particles; a binder resin; a photopolymerizable monomer; a photopolymerization initiator; and a solvent, wherein the binder resin has dissolution characteristics in an aqueous alkali solution and contains a thermosetting functional group, to a photo-cured pattern formed therefrom, and to an image display device comprising the same.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTO-CURED PATTERN FOMEED FOROM THE SAME AND IMAGE DISPLAY COMPRISING THE PATTERN}

This invention relates to the photosensitive resin composition, the photocuring pattern formed from the said composition, and the image display apparatus provided with the said photocuring pattern.

In the production of display elements such as liquid crystal display materials, organic light emitting elements, and display panel materials, the photosensitive resin composition is used to form various photocuring patterns such as photoresists, insulating films, protective films, black matrices, column spacers, and the like. When manufacturing is performed using the photosensitive resin composition, mass production is possible and the resolution which can be formed is also very high. Such a photosensitive resin composition can be generally distinguished into a transparent photosensitive resin composition and a colored photosensitive resin composition. A colored photosensitive resin composition is a photosensitive composition which has color for a specific purpose, The most typical colored photosensitive resin composition is the colored photosensitive resin composition and black photosensitive resin composition for color filter manufacture. The colored photosensitive resin composition for color filter manufacture generally has red, green, blue color, and a black photosensitive resin composition is used for the boundary part between colored layers.

Recently, as miniaturization and high performance of mobile products such as smartphones and tablet PCs have progressed, the heat generated from mobile products has increased. Thus, there is a growing interest in materials that release heat generated to the environment. In general, a method of attaching graphite or ceramic heat dissipation composite sheet having high thermal conductivity to the upper part of the heat dissipating part or attaching to the heat dissipating part using a pressure-sensitive adhesive to the heat dissipating part is used.

However, since the adhesive / adhesive used for adhesion has a relatively low thermal conductivity compared to the heat dissipation composite sheet, there is a problem that the adhesive / adhesive becomes a bottleneck point that heat can be quickly transferred.

On the other hand, heat dissipation particles is a term that collectively refers to particles having heat dissipation characteristics, and is widely used in polymers or sheet films. However, in order to introduce the heat radiation particles into the photosensitive resin composition and to pattern the same, research on a binder resin for fixing the heat radiation particles is required along with a study on an exposure process and a development process, but there is no research on this.

As described in Korean Patent No. 10-1792755 (hereinafter referred to as 'Patent Document 1'), a resin composition and a 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. Moreover, in the said patent document 1, the heat dissipation characteristic was not considered at all in selecting an oligomer or a monomer.

In the Republic of Korea Patent No. 10-1687394 (hereinafter referred to as 'Patent Document 2') has been proposed a patent for a resin composition using a coating particle coated with a ceramic surface of the particle diameter of the radiation particles. However, in Patent Document 2, no consideration has been given to the resin that serves to fix the heat-dissipating particles.

Republic of Korea Patent Application Publication No. 10-2016-0078340 (hereinafter referred to as 'Patent Document 3') has been proposed to use as a heat radiation material using a heat radiation particles and a resin together. This is a universal use, if the thermoplastic resin to the thermosetting resin including the heat-dissipating particles, the formation of the pattern is very difficult and simply limited to the application of the coating film or film production. In Patent Document 3, a composition has been proposed for a lithography process for mass production and high resolution, and can also be used with cyan pigment to visually check the flow of heat.

Republic of Korea Patent Publication No. 10-2015-0075998 (hereinafter referred to as 'Patent Document 4') has been developed for a method for manufacturing a light shielding layer and a color filter using a Zion pigment. In Patent No. 4, the color of the Zion pigment was changed during the process to form an excellent pattern after the process. However, it can be seen that even in the above patent, cyan pigment was used as a method for securing a high characteristic by heat during the process, rather than being used for checking the flow of heat.

Republic of Korea Patent 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 implementation of a fine pattern upon curing and capable of implementing a high resolution pattern.

In addition, an object of the present invention is to provide a photosensitive resin composition which is excellent in thermal conductivity after curing and capable of forming a photocurable pattern capable of displaying color according to temperature.

Moreover, an object of this invention is to provide the photocuring pattern formed from the photosensitive resin composition mentioned above, and the image display apparatus provided with the said photocuring pattern.

The present invention includes heat-dissipating particles, colored particles, binder resins, photopolymerizable monomers, photopolymerization initiators and solvents,

The binder resin has a dissolving property in an aqueous alkali solution and provides a photosensitive resin composition comprising a thermosetting functional group.

 The present invention also provides a photocuring pattern made of the photosensitive resin composition and an image display device including the same.

The photosensitive resin composition according to the embodiments of the present invention is excellent in heat transfer characteristics, excellent in the implementation of fine patterns, it is possible to implement a high resolution pattern.

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

Moreover, an object of this invention is to provide the image display apparatus for the photocuring pattern formed from the photosensitive resin composition mentioned above.

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

The present invention includes heat-dissipating particles, colored particles, binder resins, photopolymerizable monomers, photopolymerization initiators and solvents,

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

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

<Photosensitive resin composition>

The photosensitive resin composition of this invention contains a heat radiating particle, colored particle, binder resin, a photopolymerizable monomer, a photoinitiator, and a solvent.

Heat resistant particles

The heat dissipation particle | grains used for the photosensitive resin composition of this invention can exhibit high thermal conductivity characteristic, and can improve the heat dissipation characteristic of a photocuring pattern.

The heat-dissipating particles according to the present invention can be used 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; Carbonaceous materials selected from the group consisting of graphite, carbon nanotubes (CNT), 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 radiating particles may be transparent particles having a transmittance of 90% or more in the visible light region. In this case, the visible light region may be in the wavelength range of 500nm to 600nm.

The particle size of the heat-dissipating particles may be formed to 2 to 50nm based on the shortest length of the particles, in terms of improving the heat dissipation characteristics, it is advantageous to have an aspect ratio of 5 to 1000. .

The aspect ratio refers to the ratio of the minimum length of the heat radiation particles to the maximum length of the heat radiation particles.

The content of the heat-dissipating particles is not particularly limited, but may include, for example, 3 wt% to 30 wt% with respect to the total weight of the solid content of the photosensitive resin composition. If the content of the heat-dissipating particles is less than 3% by weight, high thermal conductivity may not be secured, and when the content of 30% by weight or more is included, a problem of increasing the viscosity due to the surface area of the particles may occur, and the proportion of the heat-dispersing particles may increase. Lower efficiency may be a problem. Aggregation between the particles may also occur and may be disadvantageous in the dispersion process.

Colored particles

The colored particles include one or more pigments so as to produce a pattern having a desired color.

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 Colourists), or an inorganic pigment that is an inorganic salt of metal oxide, metal complex salt and 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;

CI Pigment Brown 28;

C.I pigment violet 23, 32 and 29;

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

The colorant may further comprise additional Zion pigments in addition to the pigments exemplified above.

Zion pigment is a pigment which changes color when it reaches a constant temperature, and is also called a thermosensitive pigment. There are only one color change caused by temperature and some color change as the temperature rises, and some things do not become the primary color when the temperature decreases.

The principle of Zion pigments is to use the discoloration of the pigments based on physical and chemical changes such as transition of crystalline form, change of pH, release of crystalline water, pyrolysis, solid phase reaction and the like at a constant temperature.

The Zion pigment is divided into a reversible Zion pigment which is returned to the primary color when the temperature is increased and cooled, and an irreversible Zion pigment which is not returned even when the temperature is lowered. The Zion pigment included in the photosensitive resin composition according to an embodiment of the present invention is a reversible Zion 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, for example, CM Tech's Thermocromic 15 ℃ to Thermocromic 20 ℃, Thermocromic 25 ℃, Thermocromic 28 ℃, Thermocromic 31 ℃, Thermocromic 35 ℃, Thermocromic 60 degreeC, Thermocromic 31 degreeC Black of Hali industrial company, etc. are mentioned.

When the photosensitive resin composition of this invention contains the said zion pigment, it is possible to confirm the heat flow and heat distribution according to heat conduction simultaneously.

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 included in 15 to 25% by weight in terms of recognizing the heat flow and heat distribution. Can be.

In addition to the pigment, the colorant according to the present invention may further include organic pigments, inorganic pigments or mixtures thereof commonly used in the art without departing from the scope of the present invention.

Although the content of the colored particles is not particularly limited, for example, it may be included in 3% by weight to 20% by weight relative to the total weight of the solid content of the photosensitive resin composition. When the content of the colored particles is less than 3% by weight, it is difficult to have a desired color, and when the content of the colored particles is more than 20% by weight, the colored particles may hinder the transfer of heat between the heat-dissipating particles.

Binder resin

The photosensitive resin composition of the present invention comprises a binder resin, the binder resin has a dissolution property 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 binder resin can be used without particular limitation as long as the binder resin can be used in the photosensitive resin composition. It is preferable to contain 1 or more types of the compound which consists of. The compounds of Formulas 1 to 3 may each be included in a mole fraction of 3 to 80 mol%, preferably 5 to 70 mol%, based on the total moles of binder resin. When at least one of the compounds of Formulas 1 to 3 is included in the mole fraction range, the sensitivity and adhesion of the photosensitive resin composition are excellent and no peeling of the pattern occurs during the developing process.

[Formula 1]

[Formula 2]

[Formula 3]

In addition, the binder resin having at least one unit selected from the group consisting of formulas (4) to (5) included in the production of the photosensitive resin composition with the heat radiation particles is excellent in the heat radiation characteristics to prepare a photosensitive resin composition comprising the heat radiation particles Suitable.

[Formula 4]

 [Formula 5]

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

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

Specific examples of the unsaturated bond that may be further copolymerized with Formulas 1 to 5 include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o Aromatic vinyls such as vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether 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 ] decane-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. And unsaturated oxetane compounds.

The compounds exemplified above may be used alone or in combination of two or more thereof.

The binder resin of the present invention may be used by further mixing various known binder resins generally used in the art as needed.

The binder resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, and preferably 5,000 to 50,000. If the weight average molecular weight of the binder resin is outside the above range, the film reduction is not prevented at the time of development, causing a problem in that a missing portion of the pattern may occur.

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), most preferably 80 to 130 (KOH mg / g). When the acid value of the said binder resin is 50-150 (KOHmg / g), solubility to a developing solution improves and a residual film rate improves.

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 determined by titration using an aqueous potassium hydroxide solution.

The binder resin includes 20 to 80% by weight, preferably 20 to 70% by weight based on the total weight of solids in the colored photosensitive resin composition of the present invention. In the above range, the solubility of the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the non-pixel portion has good omission.

Photopolymerizable monomer

The photopolymerizable monomer is a monomer polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator by light irradiation, and enhances the strength of the pattern.

The photopolymerizable monomer used for the photosensitive resin composition of this invention is not specifically limited, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 4- butanediol diacrylate, 1, 6- hexanediol di 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%, and preferably 30 to 50 wt%, based on the total weight of the solid content 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 the smoothness of the coating film may be good.

Photopolymerization initiator

The photoinitiator which is one component of the photosensitive resin composition of this invention is an oxime system photoinitiator which produces | generates methyl radical after light irradiation, and contains an oxime ester compound essentially.

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] ethanone1- (O-acetyloxime) ( 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime))) and preferably at least one member selected from the group consisting of. In addition, the products include BASF's Irgacure® OXE01, Irgacure® OXE 02, Irgacure® OXE 03, and the like. Since the absorbances and generated radicals vary, it is preferable to use two or more kinds in combination.

The oxime photoinitiator used in the present invention preferably uses OXE 03 in view of sensitivity and the shape of the pattern to be formed.

The oxime ester compound is contained in 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator.

When the oxime ester compound is included in less than 10% by weight does not solve the problem of sensitivity degradation by the additive, the short circuit of the pattern is likely to occur during the development process.

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

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 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, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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 and the like.

Specific examples of the biimidazole compound include 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) And imidazole compounds in which the phenyl group at the -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 4,4', 5,5 'position is substituted by a carboalkoxy group Can be. 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.

Specific examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothio xanthone and 1-chloro-4-propoxythiok. Santon etc. can be mentioned.

The said photoinitiator can be used individually or in mixture of 2 or more types.

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

Since the photosensitive resin composition becomes highly sensitive within the range of 3 to 7 wt%, the exposure time is shortened, productivity is improved and high resolution can be maintained. In addition, the pattern formation of the pixel portion formed using the photosensitive resin composition may be good.

In addition, the photopolymerization initiator may further include a photopolymerization initiator for improving the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition which concerns on this invention contains a photoinitiation start adjuvant, a sensitivity becomes high and productivity can be improved.

The photopolymerization initiation adjuvant may include, for example, one or more selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.

It is preferable to use an aromatic amine compound as said amine compound, Specifically, Aliphatic amine compounds, such as triethanolamine, methyl diethanolamine, 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), 4,4'-bis (diethylamino) benzophenone, etc. can be used.

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

Examples of the multifunctional thiol compound include tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate), trimethylpropane tris Trimethylolpropane tris-3-mercaptopropionate, Pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexa-3-mercaptoprop Cypionate (Dipentaerythritol hexa-3-mercaptopropionate) etc. are mentioned.

When using the photopolymerization start adjuvant, the photopolymerization start adjuvant is included in 1 to 10% by weight, preferably 3 to 5% by weight based on the total weight of solids in the photosensitive resin composition of the present invention.

When 3 to 5 weight% of photopolymerization start adjuvant is included, the sensitivity of the photosensitive resin composition will rise.

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, amides and the like. 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, 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, methoxy butyl acetate, and methoxy pentyl 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; Ester, such as 3-ethoxy ethyl propionate, methyl 3-methoxy propionate, (gamma) -butyrolactone, etc. are mentioned, Preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

It is preferable that a solvent is an organic solvent whose boiling point is 100 degreeC-200 degreeC from an applicability and drying property. Specific examples include alkylene glycol alkyl ether acetates; Ketones; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and the like, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxy. Ethyl propionate, methyl 3-methoxypropionate, and the like. 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 50 to 90% by weight of the total weight of the photosensitive resin composition, preferably may be included in 60 to 80% by weight. When the content of the solvent is within the above range, the applicability may be good.

additive

The photosensitive resin composition of this invention may further contain the at least 1 sort (s) of additive chosen from the group which consists of a dispersing agent, another high molecular compound, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor as needed.

Dispersants are added to maintain the stability and stability of the pigment and dye can be used without limitation to those commonly used in the art. An acrylate dispersant preferably comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate); Polycarboxylic acid esters; Unsaturated polyamides; Polycarboxylic acid; (Partial) amine salts of polycarboxylic acids; Ammonium salts of polycarboxylic acids; Alkylamine salts of polycarboxylic acids; Polysiloxanes; Long chain polyaminoamide phosphate salts; Esters of hydroxyl group containing polycarboxylic acids and modified products thereof; Amides or salts thereof formed by the reaction of a polyester having a free carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; Phosphate esters; and the like. These can be used individually or in mixture of 2 or more types.

The other high molecular compound is not particularly limited, and examples thereof include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Thermoplastic resins; and the like.

The hardening | curing agent is a component for improving core hardening and mechanical strength, The kind is not specifically limited, For example, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

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, noblock type epoxy resin, other aromatic epoxy resin, alicyclic type Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins; Aliphatic, cycloaliphatic or aromatic epoxy compounds other than the epoxy resin and its brominated derivatives; Butadiene (co) polymer epoxides; Isoprene (co) polymer epoxides; Glycidyl (meth) acrylate (co) polymers; Triglycidyl isocyanurate etc. are mentioned.

The oxetane compound is not particularly limited, and examples thereof include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane. .

A hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent.

The curing aid compound is not particularly limited, and examples thereof include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. As the polycarboxylic acid anhydride, a commercially available one can be used as the epoxy resin curing agent.

It is not specifically limited as a commercial epoxy resin hardener which can be used by this invention, For example, a brand name (Adekahadona EH-700) (made by Adeka Kogyo Co., Ltd.), a brand name (Rikasitdo HH) (New Japan Ewha The brand name (MH-700) (made by Nippon Ewha Co., Ltd.) etc. are mentioned.

Surfactant is a component which improves the film formability of the photosensitive resin composition, The kind is not specifically limited, For example, a fluorochemical surfactant, silicone type surfactant, or a mixture thereof is mentioned.

Silicone type surfactant is not specifically limited, For example, Dow Corning Toray Silicone Co., Ltd. DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc .; TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. of GE Toshiba Silicone Co., Ltd. are mentioned.

A fluorine-type surfactant is not specifically limited, For example, Megapieces F-470, F-471, F-475, F-482, F-489, etc. of Dainippon Ink & Chemical Co., Ltd. are mentioned as a commercial item.

The kind of adhesion promoter is not specifically limited, For example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (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 kind of antioxidant is not specifically limited, For example, 2,2'- thiobis (4-methyl-6-t-butylphenol), 2,6-di-t- butyl- 4-methylphenol, etc. are mentioned. Can be.

The kind of ultraviolet absorber is not specifically limited, For example, 2- (3-tert- butyl- 2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, an alkoxy benzophenone, etc. are mentioned.

The aggregation inhibitor 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, and preferably 0.2 to 1% by weight, based on the total weight of solids of the photosensitive resin composition.

<Photocurable pattern and image display device>

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

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

Accordingly, the image display device may be used in various patterns, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, or the like, or may be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, or the like. However, the present invention is not limited thereto, and is particularly suitable for an insulating film pattern.

An image display device having such a photocuring pattern or using the pattern during a manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like, but is not limited thereto. All image display devices known in the art may be applied. Can be illustrated.

A photocuring pattern can be manufactured by apply | coating the photosensitive resin composition of this invention mentioned above on a base material, and forming a photocuring pattern (after roughening a development process as needed).

Hereinafter, experimental examples including specific examples and comparative examples are provided to help understanding of the present invention, but these are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications to the embodiments can be made within the spirit and scope, and such variations and modifications are 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 condenser, a dropping lot, and a nitrogen inlet tube was prepared. As a monomer dropping lot, (Octahydro-4,7-methano-1H-indenyl) methyl acrylate, 3,4-epoxytricyclodecane-8-yl (meth) acrylate and 3,4-epoxytricyclodecane-9- 80 g of a mixture of mono (meth) acrylates 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. Stirring was prepared. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 60 g of PGMEA were added to prepare agitation.

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

The monomer and chain transfer agent were then started dropping from the dropping lot. The dropwise addition was performed 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 of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

[Binder Resin Analysis of Synthesis Example 1]

Measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was carried out using the GPC method under the following conditions, and the ratio of the weight average molecular weight and the number average molecular weight obtained at this time was determined by molecular weight distribution (Mw / Mn).

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Examples and Comparative Examples

The photosensitive resin composition was prepared by dispersing the heat-dissipating particles and the colored particles, the binder resin, the photopolymerizable monomer, the photopolymerization monomer, the photopolymerization initiator, and the additives together with the 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 Thermal Particle 1 15 - - 25 20 - 15 Heat dissipation particle 2 - 20 - - - - - Heat dissipation particle 3 - - 10 - - - - Colored particles Pigment1 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 Photopolymerization Initiator 1 4.8 4.5 4.5 4.5 4.5 4.5 4.8 Photopolymerization 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 Radiant Particles 1: Graphite flake Sigma-Aldrich
Radiant Particle 2: Graphite nanofiber Sigma-Aldrich
Heat dissipation particle 3: Nano silver flake inframat
Pigment 1: DIC FASTOGEN SUPER RED 254 226-5254
Pigment 2: Thermocromic 31 ° C from Hali industrial
Binder 1: Binder of Synthesis Example 1
Binder 2: S-72B (molecular weight 14,800 g / mol) of Aekyung
Photopolymerizable monomer: dipentaerythritol hexaacrylate (Kayarad DPHA: Nippon Kayaku)
Photopolymerization initiator 1: Irgacure OXE03 (Basf)
Photopolymerization initiator 2: Irgacure OXE02 (Basf)
Additive: KBE-9007N (Shin-Etsu)
Solvent: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

Experimental Example

(1) substrate fabrication

The glass substrate of 5 cm 5 cm (Corning) was washed with a neutral detergent and water and 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 so as to have a final film thickness of 5.0 μm, prebaked at 100 ° C., and dried for 2 minutes to remove a solvent. Thereafter, the sample was exposed at an exposure dose of 100 mJ / cm ² to form a ² cm Х ² cm pattern, and the non-exposed part was removed using an aqueous alkali solution. Subsequently, post-firing was carried out at 230 ° C. for 20 minutes to prepare a pixel definition film.

(2) thermal conductivity evaluation

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

(3) color change

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

(4) pattern formation characteristics

The pattern characteristics of the pattern formed through the exposure and development processes were evaluated using an optical microscope. The standard was evaluated based on the pattern of the 50㎛ pattern and 100㎛ pattern was evaluated 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 pattern is favorable like FIG.

(Triangle | delta): The pattern formation of a 50 micrometers and a 100 micrometers pattern is possible as shown in FIG.

X: As shown in FIG. 3, pattern formation of a 50 μm to 100 μm pattern is impossible.

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 Formation Characteristics ◎ ◎ ◎ ◎ △ ◎ △ Color change  X ◎ ◎ ◎ ◎ X X

As can be seen in Table 2, in the case of Examples 1 to 5 it can be confirmed that exhibits a high thermal conductivity compared to Comparative Examples 1 to 2.

In particular, the comparison of Example 1 and Comparative Example 2 can confirm the difference in thermal conductivity according to the type of binder.

Claims (12)

It includes heat dissipation particles, colored particles, binder resins, photopolymerizable monomers, photopolymerization initiators and solvents,
The binder resin has a dissolution property in an aqueous alkali solution, and comprises a thermosetting functional group, photosensitive resin composition. The photosensitive resin composition of claim 1, wherein the binder resin comprises at least one compound selected from compounds represented by Formulas 4 to 5.
[Formula 4]

[Formula 5]

The method of claim 1, wherein the heat-dissipating particles are 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, carbon nanotubes (CNT), 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 ) Photosensitive resin composition comprising one or two selected from a ceramic compound selected from the group consisting of. The photosensitive resin composition of claim 1, wherein the heat dissipating 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 in which the particle size of the said heat dissipation particle | grain has 2-50 nm. The photosensitive resin composition according to claim 1, wherein the heat dissipation particles have an aspect ratio of 5 to 1000. The method according to claim 1,
Regarding the total weight of solids in the photosensitive resin composition,
3 to 30% by weight of heat radiating particles; And
3 to 20% by weight of the colored particles; photosensitive resin composition comprising. The photosensitive resin composition of Claim 7 in which the said colored particle contains a cyan pigment further. The photosensitive resin composition according to claim 8, wherein the zion pigment is 10 to 40 parts by weight in the total weight of the colored particles. The photocuring pattern formed from the photosensitive resin composition in any one of Claims 1-9. The photocuring pattern of claim 10, wherein the photocuring pattern is selected from the group consisting of an array planarization film pattern, a protection film pattern, an insulation film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern. An image display device comprising the photocuring pattern of claim 11.

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