KR20150090497A - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition including: (1) a copolymer; (2) a pearl pigment; (3) a polymerizable unsaturated compound; and (4) a photopolymerization initiator. When a hardening film is produced by using the photosensitive resin composition of the present invention, the produced hardening film exhibits hiding power and aesthetics, has excellent film flatness, and can be thinned. When a bezel is produced by using the same from a display device of various portable devices such as a mobile phone, a tablet PC, and the like and a display device such as a TV, a monitor, and the like, repeat reproducibility of a bezel position is excellent, so that multiple bezel units can be formed on a large-area cover member, thereby being Accordingly, the composition can be usefully used.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition containing a pearl pigment that can be usefully used in the manufacture of a liquid crystal display (LCD) and a bezel of various portable displays.

Portable devices such as mobile phones and tablet PCs are composed of an upper plate on which a cover glass on which a colored ink is printed on a bezel and a touch sensor are cemented together, and a display device using an existing liquid crystal display device or an organic light emitting device. In recent years, a conductive film is deposited on a cover glass, patterned through etching, and then a conductive film is formed between the conductive film and the conductive film. Has developed into a form using a thermosetting overcoat for insulation.

Accordingly, since the layer corresponding to the bezel of the display portion becomes the first layer of the touch sensor, a high level of heat resistance and chemical resistance are required for the formation of the conductive pattern and the high temperature and etching required for forming the insulating layer.

Further, in order to realize a plurality of bezels corresponding to individual product sizes simultaneously at a precise position in a cover glass having a large area through conventional screen printing, problems are presented in the flatness of the film, repetitive reproducibility of the position of the bezel, Attempts have been made to use photosensitive resins.

On the other hand, in the case of a white bezel manufactured by applying a white photosensitive resin composition, it is not easy to obtain a sufficient light shielding effect (concealment ratio) even though it is a thin film.

Accordingly, an object of the present invention is to provide a photosensitive resin composition which can be made into a thin film of a cured film and which is excellent in light shielding property of a film.

In order to achieve the above object, the present invention relates to (1) a copolymer; (2) Pearl pigments; (3) a polymerizable unsaturated compound; And (4) a photopolymerization initiator.

The photosensitive resin composition of the present invention shows a hiding power and aesthetics when the cured film is produced by using the cured film, and it is possible to make the film thinner with excellent flatness of the film. By using the cured film, various photosensitive devices such as mobile phones and tablet PCs A bezel of a display device such as a display device, a TV, and a monitor is excellent in repetitive reproducibility of the position of the bezel, so that a large number of bezel portions can be formed on a large-area cover member.

The photosensitive resin composition according to the present invention comprises (1) a copolymer; (2) Pearl pigments; (3) a polymerizable unsaturated compound; And (4) a photopolymerization initiator and, if necessary, (5) a white pigment, (6) a silane coupling agent, (7) a surfactant, and / or (8) a solvent.

Hereinafter, the constituent components of the present invention will be described in detail.

(1) Copolymer

The copolymer includes (1-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (1-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound And (1-4) a structural unit derived from an unsaturated monomer containing a Si-O skeleton in the side chain (1-3) and / or (1-4) a structural unit derived from the structural unit (1-1) May contain constituent units derived from different ethylenically unsaturated compounds.

(1-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof

In the present invention, the constituent unit (1-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, wherein the ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, and anhydrides thereof; Unsaturated polycarboxylic acids of trivalent or more and their anhydrides; Mono [(meth) acryloyloxyalkyl] acrylate of a dicarboxylic or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] And esters. Among them, (meth) acrylic acid can be preferably used from the viewpoint of developability.

The content of the constituent unit (1-1) may be from 5 to 98 mol% of the total constituent units constituting the copolymer, and preferably from 15 to 50 mol% in order to maintain good developing properties.

In the present invention, the terms (meth) acrylate and (meth) acrylate refer to acrylic and / or methacrylic, and acrylate and / or methacrylate, respectively.

(1-2) a structural unit derived from an aromatic ring-containing ethylenically unsaturated compound

In the present invention, the structural unit (1-2) is derived from an aromatic ring-containing ethylenically unsaturated compound, and the aromatic ring-containing ethylenically unsaturated compound is selected from the group consisting of phenyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tribromophenyl (meth) Acrylate; Styrene; Styrene having alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; Styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, propoxystyrene; 4-hydroxystyrene, p-hydroxy-a-methylstyrene, acetyl styrene; Vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinylbenzyl glycidyl ether, and the like. Of these, styrene-based compounds are preferable in view of polymerizability.

The content of the constituent unit (1-2) may be from 2 to 95 mol% of the total constituent units constituting the copolymer, and preferably from 10 to 60 mol% from the viewpoint of the chemical resistance.

(1-3) a structural unit derived from an unsaturated monomer containing a Si-O skeleton in a side chain

In the present invention, the constituent unit (1-3) may be derived from an unsaturated monomer containing a Si-O skeleton in its side chain, and the unsaturated monomer containing a Si-O skeleton in the side chain may be represented by the following formula (1).

In Formula 1,

R 1 is hydrogen or a straight, branched or cyclic alkyl group having 1 to 8 carbon atoms, R ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms, R ₃ and R ₄ are each independently hydrogen, Branched or cyclic alkyl group having 6 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, R ₅ is hydrogen, a methyl group or an ethyl group, and n is an integer of 2 to 20.

(1-4) Structural unit derived from an ethylenically unsaturated compound which is different from the above-mentioned constituent units (1-1) to (1-3)

In the present invention, the structural unit (1-4) is derived from an ethylenically unsaturated compound which is different from the structural units (1-1) to (1-3), and specific examples thereof include methyl (meth) acrylate, ethyl Acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) (Meth) acrylate, methyl (meth) acrylate, ethyl (a-hydroxy) methyl acrylate, propyl? -Hydroxymethylacrylate, butyl? -Hydroxymethylacrylate , 2-methoxy (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethyleneglycol (meth) acrylate, (Ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobonyl ) Acrylates, unsaturated carboxylic acid esters including dicyclopentenyloxyethyl (meth) acrylate; N-vinyl tertiary amines including N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; Unsaturated ethers including vinyl methyl ether and vinyl ethyl ether; (Meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy (meth) acrylate, (Meth) acrylate,? -Ethylglycidyl acrylate,? -N-propylglycidyl (meth) acrylate, Acrylate,? -N-butylglycidyl acrylate, N- (4- (1,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, N- One or more epoxy groups such as hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, Unsaturated monomers including; Unsaturated imides including N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide. In particular, it may be an ethylenically unsaturated compound including an epoxy group in terms of copolymerization and strength improvement of an insulating film, and may preferably be glycidyl (meth) acrylate.

The content of the constituent unit (1-3) or the content of the constituent unit (1-4) may be 0 to 60 mol%, preferably 10 to 55 mol%, of the total constituent units constituting the copolymer . Within the above range, the storage stability of the photosensitive resin composition is maintained, and the heat resistance and residual film ratio of the coating film are improved.

The copolymer used in the present invention may be prepared by adding a molecular weight regulator, a polymerization initiator, a solvent, an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and an aromatic ring-containing ethylenically unsaturated compound, O skeleton, or other ethylenically unsaturated compound, into which nitrogen is added, followed by polymerization while slowly stirring. The weight average molecular weight (Mw) of the prepared copolymer in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) may be 3,000 to 50,000, preferably 5,000 to 40,000 . In the above range, adhesion with the substrate is excellent, physical and chemical properties are good, and viscosity is appropriate.

The molecular weight modifier is not particularly limited, but may be a mercaptan compound such as butylmercaptan, octylmercaptan or the like or? -Methylstyrene dimer.

The polymerization initiator is not particularly limited, Diazo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and benzoyl peroxide , Lauryl peroxide, t-butyl peroxypivalate or 1,1-bis (t-butylperoxy) cyclohexane.

The solvent may be any solvent used in the production of the copolymer, preferably propylene glycol monomethyl ether acetate (PGMEA).

The copolymer may be contained in the photosensitive resin composition alone or in combination of two or more. The copolymer may be an alkali-soluble resin that realizes developability in the development step, and may serve as a base for performing a base role of forming a coating film after coating and a final pattern.

The content of the copolymer used may be 0.5 to 60% by weight, preferably 2 to 50% by weight, based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above-mentioned range, pattern development after development is favorable, and properties such as heat resistance and chemical resistance are improved.

(2) Pearl pigment

The photosensitive resin composition of the present invention includes a pearl pigment to increase a concealment ratio when used as a bead to form a cured film and to increase optical density. The pearl pigment used in the present invention disperses the reflected light with a light-scattering substance to increase diffuse reflection, thereby increasing the concealment rate.

Examples of the pearl pigments such as ^{Magnapearl ® Exterior CFS 3103, MagnaPearl ®} Exterior CFS 1103, Glacier ™ Frost White EH 568 (S1303D), Mearlin ® Satin White 139F, Mearlin ® Bright Silver 1303Z, Mearlin ® Sparkle 139P, Firemist White Pearl, Mearlin ® Nu-Antique Silver and the like.

A dispersing agent may be used in combination in order to effectively disperse the pearl pigment. The dispersing agent is not particularly limited, and the dispersing agent described in the item of white pigment, which is a further component of the present invention, can be applied.

The content of the pearl pigment may be 5 to 60% by weight, preferably 10 to 40% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). In the above range, the concealment rate characteristic can be improved, and a high optical density can be realized.

(3) Polymerizable unsaturated compound

The polymerizable unsaturated compound is a compound which can be polymerized by the action of a polymerization initiator, and is a monomer, oligomer or polymer generally used in a photosensitive resin composition, and may be a copolymer of acrylic acid or methacrylic acid having at least one ethylenic unsaturated double bond Functional or multifunctional ester compound, but from the viewpoint of chemical resistance, it may preferably be a multifunctional compound having two or more functional groups.

Wherein the polymerizable unsaturated compound is at least one selected from the group consisting of ethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (Meth) acrylate, monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified di (Reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol But are not limited to, at least one selected from the group consisting of lithol octa (meth) acrylate, bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate.

When the polymerizable unsaturated compound is used as an oligomer or polymer, it may have a weight average molecular weight of 6,000 to 10,000.

The content of the polymerizable compound may be 5 to 60% by weight, preferably 10 to 55% by weight based on the total weight (solid content) of the photosensitive resin composition excluding the solvent. When the thickness is within the above range, the pattern is easily formed, the surface of the coated film is not roughened after formation of the coating film, the pattern outline is excellent, and the problem of the pattern shape such as scum is not generated at the lower end during development.

(4) Photopolymerization initiator

The photosensitive resin composition of the present invention includes a photopolymerization initiator and is not limited as long as it is a photopolymerization initiator used in the art.

Examples of the photopolymerization initiator include an acetophenone based compound, a nonimidazole based compound, a triazine based compound, an onium salt based compound, a benzoin based compound, a benzophenone based compound, a diketone based compound, an? - diketone based compound, a polynuclear quinone based compound, A photopolymerization initiator comprising an acid-tonide compound, a diazo compound, an imide sulfonate compound, an oxime compound, a carbazole compound, a sulfonium borate compound, and a mixture thereof.

In addition, in accordance with the present invention, there is provided a method for producing a compound of formula (I) as described in JP-A 2004-0007700, KR 2005-0084149, KR 2008-0083650, KR 2008-0080208, KR 2007-0044062, KR 2007-0091110, KR 2007-0044753, KR 2009-0009991, KR 2009-0093933, It is preferable to use at least one of the oxime compounds described in JP-A No. 0097658, KR 2011-0099542, KR 2011-0026467, KR 2011-0015683, WO 2010/102502, and WO 2010/133077 from the viewpoint of high sensitivity . Examples of these trade names include OXE-01 (BASF), OXE-02 (BASF), N-1919 (ADEKA), NCI-930 (ADEKA) and NCI-831 (ADEKA).

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.2 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). In this range, curing is sufficiently achieved by exposure, and it is easy to obtain excellent pattern margin characteristics and can be sufficiently adhered to the substrate.

(5) white pigment

The photosensitive resin composition of the present invention comprises a white pigment as a coloring agent for imparting light shielding property when forming a bezel.

As the white pigment, a pigment having high coloring property and high heat resistance is preferably used as the inorganic pigment.

Specific examples of the inorganic pigments include titanium oxide, barium sulfate, talc, barium carbonate, carbonated coal powder, silica, alkaline magnesium carbonate, alumina white, gross white, and the like. And satin white. Of these, titanium oxide is preferable in terms of optical density.

Meanwhile, a dispersant may be used to disperse the white pigment in the photosensitive resin composition of the present invention. The dispersant may be any of those known as pigment dispersants. Specific examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a silicone surfactant, and a fluorinated surfactant. have. Commercially available dispersing agents include Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-2000, Disperbyk-2150, Disperbyk-2155, Disperbyk-2163 and Disperbyk-2164 of BYK. These may be used alone or in combination of two or more.

The dispersing agent may be added to the white pigment in advance in a manner of surface-treating the white pigment, or may be used in the production of the photosensitive resin composition together with the white pigment.

After mixing the white pigment with the binder, it may be used in the production of a photosensitive resin composition. The binder used herein may be one or more materials selected from the above-mentioned (1) copolymer or a known copolymer as described in the present invention.

The content of the white pigment may be 5 to 75% by weight, preferably 10 to 65% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content).

When the content of the white pigment is within the above range, it is possible to prevent the optical density from becoming too low, achieve high optical density, and improve the processability such as developability.

(6) Surfactant

The photosensitive resin composition of the present invention may further contain a surfactant, if necessary, for improving coating properties and preventing defect formation. The kind of the surfactant is not particularly limited, but it may preferably be a fluorine-based surfactant or a silicon-based surfactant. Examples of commercial products of the above fluorine-based surfactants include Megafiz F-470, F-471, F-475, F-482 and F-489 manufactured by Dainippon Ink and Chemicals, Incorporated. Examples of commercially available silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicone Co., , BYK 333 manufactured by BYK, and the like. Of these, BYK 333 manufactured by BYK Corporation may be preferably used in terms of dispersibility. These may be used alone or in combination of two or more.

The surfactant may be used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above range, coating of the photosensitive resin composition is smooth.

(7) Silane coupling agent

The photosensitive resin composition of the present invention may further include a silane coupling agent to improve the adhesiveness with the substrate. Such a silane coupling agent may have at least one reactive substituent selected from the group consisting of a carboxyl group, a (meth) acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, an epoxy group and a combination thereof.

The type of the silane coupling agent is not particularly limited, and examples thereof include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltri Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, and preferably at least one selected from the group consisting of? -Glycidoxypropyltriethoxysilane and? -Glycidoxypropyltrimethoxysilane which have good adhesion to the substrate while improving the residual film ratio Or N-phenylaminopropyltrimethoxysilane can be used. To improve the chemical resistance,? -Isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) having an isocyanate group may also be used.

The content of the silane coupling agent may be 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above range, the adhesive property of the photosensitive resin composition can be improved.

(8) Solvent

The photosensitive resin composition of the present invention may be prepared by a conventional method, and preferably, a liquid composition in which the above-mentioned components are mixed with a solvent. The solvent is compatible with the above-described photosensitive resin composition components and does not react with the above photosensitive resin composition components, and any known solvent used in the photosensitive resin composition can be used.

Examples of such solvents include glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate. These solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited and may be an amount such that the total concentration of each component other than the solvent of the composition is usually from 5 to 70% by weight from the standpoint of coatability, stability and the like of the resulting photosensitive resin composition, By weight is 10 to 55% by weight.

In addition, the photosensitive resin composition of the present invention may contain other additives such as an antioxidant and a stabilizer within a range not lowering the physical properties.

As an example of the method for producing the photosensitive resin composition of the present invention, the following method can be exemplified.

First, the pearl pigment is mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the pearl pigment reaches a desired level. In this case, in addition to the pearlescent pigment, white pigments may be mixed and dispersed together if necessary. Alternatively, dispersions containing pearlescent pigments and dispersions containing white pigments may be respectively prepared and used in the production of photosensitive resin compositions.

Surfactants may be used together if necessary, and some or all of the copolymer may be blended. A copolymer, a polymerizable unsaturated compound and a photopolymerization initiator are added to the resulting dispersion, and if necessary, an additive such as a silane coupling agent or an additional solvent is further added so as to have a predetermined concentration, and the mixture is sufficiently stirred to obtain a photosensitive resin composition have.

As an example of a method for producing a cured film using the above photosensitive resin composition, the following method can be exemplified.

The photosensitive resin composition is coated on a predetermined pretreated substrate by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like to a desired thickness, for example, a thickness of 1 to 25 μm And then the solvent is removed by heating at a temperature of 70 to 90 DEG C for 1 to 10 minutes to form a coating film.

In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type is interposed, and an active line of 200 to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used. The exposure dose varies depending on the kind of each component of the composition, the blending amount and the dried film thickness, but may be 500 mJ / cm ² (at a wavelength of 365 nm) or less when a high-pressure mercury lamp is used.

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or the like as a developing solution, so that only the exposed portion can be left to form a pattern. After the image pattern obtained by the development is cooled to room temperature, it is post-baked at 180 ° C to 250 ° C for 10 to 60 minutes in a hot air circulation type drying furnace to obtain a cured film. The cured film exhibits a concealment ratio of 5% or more, more preferably 8% or more at a thickness of 1.5 탆, and can exhibit more efficient characteristics when a cured film including a white pigment is laminated.

That is, in the case of forming a cured film by using the photosensitive resin composition of the present invention, a photosensitive resin composition containing a white pigment may be prepared, if necessary, in place of the pearl pigment, And a white cured film is laminated through a series of processes including coating, light irradiation, development and curing, so that a composite film in which a cured film containing a pearl pigment and a cured film containing a white pigment are laminated can be manufactured.

Accordingly, the present invention provides a first cured film obtained from a photosensitive resin composition comprising (1) a copolymer, (2) a pearl pigment, (3) a polymerizable unsaturated compound, and (4) a photopolymerization initiator, and (1) , (3) a polymerizable unsaturated compound, (4) a photopolymerization initiator, and (5) a white pigment.

When the cured film is produced using the photosensitive resin composition of the present invention, the cured film produced exhibits a hiding power and aesthetics, and the film can be made thin, while the flatness of the film is excellent.

Further, the photosensitive resin composition can be applied to the formation of a bezel portion of a display device of a variety of portable devices such as a mobile phone, a tablet PC, and a display device such as a TV and a monitor. In this case, A plurality of bezel portions can be formed in a numerical stability in the cover member. In addition, not only is it possible to exhibit aesthetic sensation by including a pearl pigment, but also a cured film can be formed by further including a white pigment in the photosensitive resin composition, or a cured film formed from a photosensitive resin composition containing a pearl pigment, By constituting the composite form in which the cured film formed by the photosensitive resin composition is laminated, thinning can be achieved at the same time while the bezel exhibits a sufficient concealment ratio.

Accordingly, the present invention provides a bezel of the display device and a cover member including the bezel.

The display device of the present invention may include a configuration known to those skilled in the art, except for having a cover member for a display device of the present invention. That is, the bezel of the display device of the present invention and the display device to which the cover member including the bezel can be applied can all be included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

The weight average molecular weight described in the following Production Examples is a polystyrene reduced value measured by gel permeation chromatography (GPC).

Manufacturing example  1: Preparation of copolymer A

400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was introduced into a four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer and heated to 80 DEG C, A mixture of 2 parts by weight of 2,2'-azobisisobutyronitrile, 57 parts by weight of benzyl methacrylate, 13 parts by weight of methacrylic acid, and 30 parts by weight of methacryloxypolysiloxane (product name: silaplane TM0701, manufactured by Chisso Corporation) Was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic copolymer resin solution having a siloxane skeleton in the side chain having a weight average molecular weight (Mw) of 12,500. After cooling to room temperature, about 2 parts by weight of the resin solution was sampled, heated and dried at 180 DEG C for 20 minutes, and then the solid content was measured. Propylene glycol monomethyl ether acetate (PGMEA) was added to the resin solution so that the solid content was 20 wt% To obtain a copolymer A. < tb >< TABLE >

Manufacturing example  2: Preparation of pearl pigment dispersion

11.1 g of a polymer dispersant (DISPERBYK ^占 -2000), 17.7 g of pearl pigment (Glacier 占 Frost White EH 568 (S1303D), BASF) and 71.2 g of PGMEA were dispersed in a paint shaker at 25 to 60 占 폚 for 6 hours. Dispersion was carried out using 0.3 mm zirconia beads, and beads were added to the same weight as the dispersion. After dispersion was completed, the beads and the dispersion were separated by a filter to prepare a final pearl pigment dispersion.

Manufacturing example  3: Preparation of White Inorganic Pigment Dispersion

A polymer dispersant (DISPERBYK ^® -2000) 6 g, a TiO ₂ 120 g PGMEA and 74 g as a white inorganic pigment dispersion was treated for 6 hours at 25 to 60 ℃ in a paint shaker. Dispersion was carried out using 0.3 mm zirconia beads, and beads were added to the same weight as the dispersion. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a final white inorganic pigment dispersion.

Example  1: Preparation of photosensitive resin composition (1)

(DPHA, manufactured by Nippon Kayaku) 10.095 g, oxime-based photopolymerization initiator (OXE-02, manufactured by Ciba Specialty Chemicals Inc.) 0.6 0.131 g of Polymerizable unsaturated compound as a polymerizable unsaturated compound, 10.095 g of dipentaerythritol hexaacrylate g, a surfactant (product name DISPERBYK ^® -333, BYK Co., Ltd.) 0.06 g, a silane coupling agent (KBE-9007, Shin-Etsu Co., Ltd.) and 0.150 g of propylene glycol monomethyl the pearl pigment dispersion 31.250g produced in Production example 2, a solvent And 4.173 g of methyl ether acetate (PGMEA) was well stirred to prepare a photosensitive resin composition (1) containing a pearl pigment.

Example  2: Preparation of photosensitive resin composition (2)

23.557 g of the copolymer A prepared in Preparation Example 1, 4.476 g of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku) as the polymerizable unsaturated compound, 0.6 g of oxime-based photopolymerization initiator (OXE-02, manufactured by Ciba Specialty Chemicals) g, surface active agent (DISPERBYK ^® -333, BYK Co., Ltd.) 0.06 g, a silane coupling agent (KBE-9007, Shin-Etsu Co., Ltd.) and 0.150 g of propylene glycol monomethyl the white inorganic pigment dispersion 32.43 g prepared in Production example 3, the solvent And the mixture was well stirred with 38.723 g of methyl ether acetate (PGMEA) to prepare a photosensitive resin composition (2) containing a white inorganic pigment.

Example  3

The photosensitive resin composition (1) obtained in Example 1 was coated on a glass substrate with a thickness of 1.7 탆 using a spin coater and then dried at 90 캜 for 100 seconds to form a coating film. The obtained coating film was irradiated with light having a wavelength of 365 nm at a dose of 100 mJ / cm 2 using a pattern mask. Subsequently, the substrate was developed with an aqueous solution containing 1 wt% of potassium hydroxide at 25 DEG C for 60 seconds, and then washed with pure water for 1 minute to obtain a pattern in which unnecessary portions were removed. The pattern thus formed was heated in an oven at 230 캜 for 30 minutes to be cured, and finally a cured film containing a pearl pigment having a thickness of 1.5 탆 was obtained.

Example  4

A cured film containing a pearl pigment having a thickness of 2.5 占 퐉 was finally obtained by the same method as in Example 3 except that the coating thickness was changed to 2.9 占 퐉.

Example  5

A cured film containing a pearl pigment having a thickness of 4.0 mu m was finally obtained through the same method as in Example 3 except that the coating thickness was 4.5 mu m.

Example  6

Using the photosensitive resin composition (2) obtained in Example 2, a white cured film having a thickness of 4.0 占 퐉 was formed on the cured film of Example 3 in the same manner as in Example 3, and finally a 5.5 占 퐉 composite curing Film.

Example  7

Using the photosensitive resin composition (2) obtained in Example 2, a white cured film having a thickness of 4.0 탆 was formed on the cured film of Example 4 in the same manner as in Example 3, and finally a composite A cured film was obtained.

Example  8

Using the photosensitive resin composition (2) obtained in Example 2, a white cured film having a thickness of 4.0 탆 was formed on the cured film of Example 5 in the same manner as in Example 3, and finally a composite A cured film was obtained.

Example  9

Using the photosensitive resin composition (2) obtained in Example 2, a white cured film having a thickness of 9.0 mu m was formed on the cured film of Example 3 in the same manner as in Example 3, and finally a composite of 10.5 mu m in thickness A cured film was obtained.

Example  10

Using the photosensitive resin composition (2) obtained in Example 2, a white cured film having a thickness of 9.0 mu m was formed on the cured film of Example 4 in the same manner as in Example 3, and finally a composite of 11.5 mu m in thickness A cured film was obtained.

Example  11

Using the photosensitive resin composition (2) obtained in Example 2, a 9.0 탆 white cured film was formed on the cured film of Example 5 in the same manner as in Example 3 to finally obtain a composite cured film having a thickness of 13.0 탆 .

Test Example  1: Measurement of concealment rate

In the present invention, the concealment rate represents a measure indicating the degree of visibility of the rear surface of the cured film. For each of the cured films prepared in Examples 3 to 11, LENETA Form 2A-opacity (LENETA CO.) And NOVO Shade DUO (45/0 reflectometer, RHOPOINT Instrumentation Ltd.) And concealment rate was obtained.

Test Example  2: Optical density measurement

Each of the cured films prepared in Examples 6 to 11 was measured for transmittance using a UV-vis equipment (Cary 100 Conc, Varian), and the transmittance was substituted into the following equation 2 to obtain an optical density (OD) .

Test Example  3: Developable  Measure

The pattern developing properties were observed in the developing steps in Examples 3 to 11.

Curing membrane Evaluation items Thickness (㎛) Concealment rate
(%) Optical density pattern Developability A curing film comprising a pearl pigment
(Photosensitive resin
Composition (1)) White Curing membrane
(Photosensitive resin
Composition (2)) Total thickness Example 3 1.5 - 1.5 9.2 - Good Example 4 2.5 - 2.5 11.8 - Good Example 5 4.0 - 4.0 32.2 - Good Example 6 1.5 4.0 5.5 82.8 1.90 Good Example 7 2.5 4.0 6.5 85.0 1.99 Good Example 8 4.0 4.0 8.0 88.5 2.17 Good Example 9 1.5 9.0 10.5 91.3 2.11 Good Example 10 2.5 9.0 11.5 92.1 2.22 Good Example 11 4.0 9.0 13.0 93.8 2.38 Good

As can be seen from Examples 3 to 5, when the cured film is prepared using the photosensitive resin composition according to the present invention, the results of the experiment shown in Table 1 show that when the thickness is 1.5 탆, And as in Examples 6 to 11, when the cured film including a white pigment was laminated on the cured films of Examples 3 to 5 including the pearl pigment, the concealment rate was further improved. Therefore, a cured film having an optical density usable as a white bezel can be formed into a thin film having a thickness of several mu m to several tens of mu m.

Claims (7)

(1) a copolymer;
(2) Pearl pigments;
(3) a polymerizable unsaturated compound; And
(4) Photopolymerization initiator
Wherein the photosensitive resin composition is a photosensitive resin composition.
The method according to claim 1,
Wherein the cured film obtained from the photosensitive resin composition has a concealment ratio of 5% or more at a thickness of 1.5 占 퐉.
The method according to claim 1,
Wherein the photosensitive resin composition further comprises (5) a white pigment.
The method according to claim 1,
Wherein the copolymer (1) is derived from (1-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, and (1-2) an aromatic ring-containing ethylenically unsaturated compound Wherein the photosensitive resin composition is a photosensitive resin composition.
5. The method of claim 4,
The copolymer (1) contains the constituent units (1-1) and (1-2) in an amount of 5 to 98 mol% and 2 to 95 mol%, respectively, of the total constituent units constituting the copolymer, in
(1-3) a structural unit derived from an unsaturated monomer containing a Si-O skeleton in the side chain or (1-4) a structural unit derived from an ethylenically unsaturated compound different from the structural units (1-1) to (1-3) Wherein the photosensitive resin composition contains the derived constituent units in an amount of 0 to 60 mol%.
The method according to claim 1,
(1) a copolymer, (2) a pearl pigment, (3) a polymerizable unsaturated compound, and (4) a photopolymerization initiator, based on the total weight of the photosensitive resin composition (based on the solid content) %, 5 to 60 wt%, 5 to 60 wt%, and 0.01 to 10 wt%, based on the total weight of the photosensitive resin composition.
A first cured film obtained from a photosensitive resin composition comprising (1) a copolymer, (2) a pearl pigment, (3) a polymerizable unsaturated compound and (4) a photopolymerization initiator, and
A composite cured film comprising a second cured film obtained from a photosensitive resin composition comprising (1) a copolymer, (3) a polymerizable unsaturated compound, (4) a photopolymerization initiator, and (5) a white pigment.