Photosensitive resin composition, photosensitive resin layer using same, display device, and method for producing photosensitive resin layer

Abstract

Provided are a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, a display device including the photosensitive resin layer, and a method of manufacturing the photosensitive resin layer, the photosensitive resin composition including: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; (E) a solvent, wherein the binder resin includes at least one selected from structural units represented by Chemical Formula 1 and Chemical Formula 2, and at least two selected from structural units represented by Chemical Formula 3 to Chemical Formula 5. (In Chemical Formulae 1 to 5, the definition of each substituent is as described in the specification. > # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefits of Korean Patent Application No. 10-2023-0088564 filed in the Korean Intellectual Property Office on July 7, 2023, and Korean Patent Application No. 10-2024-0065960 filed in the Korean Intellectual Property Office on May 21, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the photosensitive resin composition, a display device, and a method for manufacturing the photosensitive resin layer. Background Art

[0004] Recently, there is an increasing interest in self-luminous (emissive) micro organic light emitting diode (OLED) display panels for use in virtual reality (VR) devices, augmented reality (AR) devices, and mixed reality (MR) devices.

[0005] In a micro OLED display panel with pixels 10 times smaller than a general OLED display panel, it is difficult to form a red (R) / green (G) / blue (B) light-emitting layer by using the conventional fine metal mask (FMM) technology. In other words, if a conventional liquid crystal display is applied to a device with functions such as VR and AR, the color filter may have a pattern size that is too large to improve the resolution.

[0006] Therefore, OLED on Silicon (OLEDoS) technology has recently been introduced to achieve a high resolution of about 4000 pixels per inch (ppi) or more. The corresponding technology uses an OLED deposited on a silicon wafer as a backlight to pattern the color filter thereon. Although conventional color filters for liquid crystal displays are formed by mounting a pattern of about 100 μm on glass and curing the pattern through an exposure process and a post-baking process at a high temperature of about 230°C or higher, the color filter mounted on OLEDoS may not be able to withstand high temperature processes due to OLED and must be cured at low temperatures, and in addition, micropatterning is important to improve resolution. Due to the small size of VR devices and AR devices, micropatterning is crucial to achieving the desired resolution.

[0007] However, low temperature (about 100° C. or lower) curing has the following problems: color filters made of conventional materials have weak adhesion and generate residues. Summary of the invention

[0008] Some embodiments provide a photosensitive resin composition that can be sufficiently cured even at low temperatures, thereby having excellent solvent resistance and coating appearance characteristics, and also having excellent color characteristics, thereby having high reliability and patterning capabilities.

[0009] Some embodiments provide a photosensitive resin layer, wherein the photosensitive resin layer is manufactured using the photosensitive resin composition.

[0010] Some embodiments provide a display device including the photosensitive resin layer.

[0011] Some embodiments provide a method for manufacturing a photosensitive resin layer.

[0012] Some embodiments provide a photosensitive resin composition, comprising: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; and (E) a solvent, wherein the binder resin comprises at least one of the structural units selected from Chemical Formula 1 and Chemical Formula 2, and at least two of the structural units selected from Chemical Formula 3 to Chemical Formula 5.

[0013] [Chemical formula 1]

[0014]

[0015] [Chemical formula 2]

[0016]

[0017] [Chemical formula 3]

[0018]

[0019] [Chemical formula 4]

[0020]

[0021] [Chemical formula 5]

[0022]

[0023] In Chemical Formula 1 to Chemical Formula 5,

[0024] R 1 to R 6 and R 8are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0025] R 7 and R 9 are each independently a substituted or unsubstituted C6 to C20 aryl group, and

[0026] L 1 To L 6 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0027] The binder resin may include structural units represented by Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5.

[0028] In Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5, R 1 , R 4 and R 6 may be independently a substituted or unsubstituted C1 to C20 alkyl group, R 2 , R 5 and R 8 may each independently be a hydrogen atom, and L 1 To L 6 Each independently may be a substituted or unsubstituted C1 to C20 alkylene group.

[0029] The binder resin may have a weight average molecular weight of about 5000 g / mol to about 8000 g / mol.

[0030] The binder resin may have a double bond equivalent of about 150 g / mol to about 500 g / mol.

[0031] The solid content constituting the photosensitive resin composition may be included in an amount of about 12 wt % to about 24 wt % based on the total amount of the photosensitive resin composition.

[0032] The polymerizable monomer may include one or more compounds including three or more functional groups.

[0033] The polymerizable monomer may be a mixture of two types of compounds, and the two types of compounds may each independently be a compound including three or more functional groups.

[0034] The two types of compounds may be a first polymerizable monomer including 3 to 5 functional groups and a second polymerizable monomer including 6 or more functional groups, and the first polymerizable monomer may be included in a smaller amount than the second polymerizable monomer.

[0035] The photosensitive resin composition may include, based on the total amount of the photosensitive resin composition: about 5 wt % to about 20 wt % of the (A) binder resin; about 70 wt % to about 90 wt % of the (B) colorant; about 1 wt % to about 10 wt % of the (C) polymerizable monomer; about 0.1 wt % to about 5 wt % of the (D) polymerization initiator; and the balance of the (E) solvent.

[0036] The photosensitive resin composition may further include an antioxidant.

[0037] The antioxidant may be included in an amount of about 0.01 wt % to about 1 wt % based on the total amount of the photosensitive resin composition.

[0038] The photosensitive resin composition may further include the following additives: malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, or a combination thereof.

[0039] The photosensitive resin composition may be a composition for a micro OLED display device.

[0040] Some embodiments provide a photosensitive resin layer manufactured using the photosensitive resin composition.

[0041] Some embodiments provide a display device including the photosensitive resin layer.

[0042] The display device may be a micro OLED display device, which includes an OLED substrate and a color filter layer, wherein the OLED substrate is deposited on a silicon wafer, and the color filter layer is stacked on the OLED substrate and converts white light generated from the OLED substrate into light of multiple colors, wherein the color filter layer includes a red filter, a green filter, and a blue filter.

[0043] Some embodiments provide a method of manufacturing a photosensitive resin layer, the method comprising: coating the photosensitive resin composition; performing pre-baking at a temperature of about 100° C. or less after the coating; and exposing to i-line after the pre-baking; and performing development.

[0044] Other embodiments of the invention are included in the detailed description that follows.

[0045] The photosensitive resin composition according to some embodiments can be cured at a low temperature of about 100° C. or less, can ensure high resolution by realizing fine patterns, and has excellent spectral characteristics, so that a wide color gamut can be ensured. In particular, even when pre-baking at about 100° C. or less is performed using only temperature and light curing (i-line exposure), it has excellent solvent resistance, excellent residue characteristics, and excellent coating appearance characteristics, making it suitable for micro OLED display devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 and Figure 4 is an optical microscope photograph of a photosensitive resin layer obtained by curing the photosensitive resin composition according to Example 1 at a low temperature.

[0047] Figure 2 and Figure 5 This is an optical microscope photograph of a photosensitive resin layer obtained by curing the photosensitive resin composition according to Comparative Example 1 at a low temperature.

[0048] Figure 3 and Figure 6 This is an optical microscope photograph of a photosensitive resin layer obtained by curing the photosensitive resin composition according to Comparative Example 2 at a low temperature. DETAILED DESCRIPTION

[0049] Embodiments of the present invention are described in detail below. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0050] As used herein, when a specific definition is not otherwise provided, “alkyl” refers to a C1 to C20 alkyl group, “alkenyl” refers to a C2 to C20 alkenyl group, “cycloalkenyl” refers to a C3 to C20 cycloalkenyl group, “heterocycloalkenyl” refers to a C3 to C20 heterocycloalkenyl group, “aryl” refers to a C6 to C20 aryl group, “arylalkyl” refers to a C6 to C20 arylalkyl group, “alkylene” refers to a C1 to C20 alkylene group, “arylene” refers to a C6 to C20 arylene group, “alkylarylene” refers to a C6 to C20 alkylarylene group, “heteroarylene” refers to a C3 to C20 heteroarylene group, and “alkyleneoxy” refers to a C1 to C20 alkyleneoxy group.

[0051] As used herein, when a specific definition is not otherwise provided, “substituted” means that at least one hydrogen of the compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Cl, Br or I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0052] As used herein, when a specific definition is not otherwise provided, "hetero" means including at least one heteroatom of N, O, S and P in a chemical formula.

[0053] As used herein, when a specific definition is not otherwise provided, “(meth)acrylate” refers to both “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.

[0054] As used herein, when no definition is otherwise provided, the term "combination" refers to mixing or copolymerization. In addition, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymer to random copolymer.

[0055] In the chemical formulae in the present specification, unless a specific definition is otherwise provided, when a chemical bond is not drawn where it should be given, a hydrogen bond is made at the position.

[0056] As used herein, when a definition is not otherwise provided, "*" refers to a connecting moiety between the same atom or different atoms or chemical formulas.

[0057] According to some embodiments, the photosensitive resin composition includes: (A) a binder resin; (B) a colorant; (C) a polymerizable monomer; (D) a polymerization initiator; and (E) a solvent, wherein the binder resin includes at least one of the structural units represented by Chemical Formula 1 and Chemical Formula 2, and at least two of the structural units represented by Chemical Formula 3 to Chemical Formula 5.

[0058] [Chemical formula 1]

[0059]

[0060] [Chemical formula 2]

[0061]

[0062] [Chemical formula 3]

[0063]

[0064] [Chemical formula 4]

[0065]

[0066] [Chemical formula 5]

[0067]

[0068] In Chemical Formula 1 to Chemical Formula 5,

[0069] R 1 to R 6 and R 8 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0070] R 7 and R 9 are each independently a substituted or unsubstituted C6 to C20 aryl group, and

[0071] L 1 To L 6 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0072] A liquid crystal display device is a display device having the advantages of being light, thin, low-cost, low-power and highly compatible with integrated circuits, and is therefore more widely used in laptop computers, monitors and television (TV) images. Such a liquid crystal display device has a color filter in which a unit pixel consisting of sub-pixels of red (R), green (G) and blue (B) corresponding to the three primary colors of light is repeatedly formed. If each sub-pixel is placed adjacently and a color signal is applied to each sub-pixel to control the brightness, the unit pixel displays a specific color by synthesizing the three primary colors. The color filter is made of red (R), green (G) and blue (B) dyes or pigments, and these color materials are used to convert the white light of the backlight unit into each corresponding color. The narrower the absorption band in the spectrum of these color materials without unnecessary wavelengths other than the required absorption wavelength, the better the color characteristics. In addition, the color filter should have excellent heat resistance, light resistance and chemical resistance so that the color filter can not fade or change color under ultraviolet, acid and alkali conditions exposed during the etching process of the color resist. A color filter formed of the photosensitive resin composition may be manufactured by coating three or more colors on a transparent substrate mainly by dyeing, electrodeposition, printing, pigment dispersion, or the like.

[0073] In addition to liquid crystal display (LCD) processes, photosensitive resin compositions can also be used for next-generation displays based on dye or pigment technology. Conventional LCD processes are designed to ensure durability in high-temperature processes, but since next-generation displays require low-temperature processes to minimize thermal deformation losses due to the material properties of the film, and in addition, materials for organic light-emitting diodes (OLEDs) also require low-temperature processes, the demand for low-temperature curable resin compositions is increasing. However, low-temperature curable resin compositions have problems of insufficient curing during low-temperature curing and unsatisfactory heat resistance and chemical resistance, and in order to improve this problem, if an excessive amount of hardening material is used to form a film, there is another problem of uneven surface properties and unfavorable residues.

[0074] Therefore, under the above background, the inventors finally completed the present invention after numerous trials and errors over several years, and developed a photosensitive resin composition having a high curing rate at low temperature and thus having excellent solvent resistance and uniform coating characteristics. Specifically, some embodiments relate to a photosensitive resin composition that can be cured at low temperature and form a color filter with excellent chemical resistance, and more specifically, to a photosensitive resin composition having high reliability and patterning ability when pre-baked and photocured (i-line (365nm) exposure) at about 100°C.

[0075] Meanwhile, conventional color photoresists are negative photosensitive liquid materials that realize color patterns of red, green, and blue, and technological development has been progressing in the direction of gradually changing the composition of the liquid material. For example, attempts have been made to improve color purity by changing the type or content of a pigment dispersion as a coloring material that realizes a color pattern, to improve patterning capability by changing the composition of a binder resin or a photopolymerization initiator, or to improve coating properties and color uniformity by using other additives such as a leveling agent.

[0076] However, unlike conventional color photoresists, some embodiments relate to a photosensitive resin composition applied to a color filter process used in a micro OLED display device.

[0077] In this article, micro OLED refers to a white OLED (White OLED, WOLED) deposited on a silicon wafer. In the inventors, it is also called an organic light emitting diode on silicon (OLEDoS). And, a micro OLED display device refers to a display device using a micro OLED.

[0078] With the advent of the fourth industrial revolution, due to the rapid growth of the metaverse market, the need to develop display devices that improve the realism and visibility of AR devices, VR devices, and MR devices but minimize dizziness is also increasing. For this purpose, several candidate technologies have been developed, such as Liquid Crystal on Silicon (LCoS), Light Emitting Diode on Silicon (LEDoS), Organic Light Emitting Diode on Silicon (OLEDoS), etc. Among these technologies, OLEDoS technology has the advantages of high contrast, fast response speed, and self-emission, which makes it possible to reduce the size and weight of the device into a relatively simple optical system and is rapidly developing in many fields.

[0079] OLEDoS has many difficulties in development because in order to realize a microdisplay with high resolution, pixels much smaller than conventional displays should be formed in units of several μm, and in order not to damage the lower OLED, color filters should be formed by a low-temperature process.

[0080] Against the above background, the present inventors have completed a photosensitive resin composition that can be cured at a low temperature of about 100° C. or lower, has excellent solvent resistance but leaves almost no residue, and achieves low temperature curing and fine patterns by limiting the type of binder resin and further ensures a uniform outer coating by controlling the molecular weight of the binder resin and the solid content of the photosensitive resin composition, wherein the photosensitive resin composition according to some embodiments can be applied to display devices for VR (virtual reality), AR (augmented reality) and MR (mixed reality) as next-generation displays (e.g., micro OLED display devices) due to these characteristics.

[0081] In the following, each component is described in detail.

[0082] (A) Binder resin

[0083] The binder resin may be an acrylic binder resin.

[0084] For example, the acrylic binder resin may be an epoxy-free acrylic binder resin that does not include an epoxy group.

[0085] The acrylic binder resin includes at least one selected from the structural units represented by Chemical Formula 1 and Chemical Formula 2, and includes at least two selected from the structural units represented by Chemical Formula 3 to Chemical Formula 5. Since the acrylic binder resin has such a structure, the photosensitive resin composition according to some embodiments may have superior solvent resistance and coating appearance characteristics compared to conventional photosensitive resin compositions.

[0086] For example, the binder resin may include structural units represented by Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5. In this case, R 1 , R 4 and R 6 may be independently a substituted or unsubstituted C1 to C20 alkyl group, R 2 , R 5 and R 8 may each independently be a hydrogen atom, and L 1 To L 6 Each may be independently a substituted or unsubstituted C1 to C20 alkylene group. In this case, the photosensitive resin composition according to some embodiments may have higher reliability and patterning capability only through low temperature curing and i-line exposure.

[0087] If the binder resin includes a cardo-based binder resin, an epoxy-based binder resin, a silsesquioxane-based binder resin and / or an epoxy-acrylic binder resin, curing does not occur well at a low temperature of about 100° C. or below, and thus it is difficult to improve reliability and patterning, and residue characteristics and coating uniformity may also be deteriorated.

[0088] That is, the photosensitive resin composition according to some embodiments has excellent residue characteristics and coating uniformity even at a low temperature of about 100° C. or less and using only i-line exposure, and in addition, since the structure within the binder resin, specifically the acrylic binder resin, is controlled as described above, the color characteristics can also be improved.

[0089] In addition, when the weight average molecular weight and double bond equivalent of the acrylic binder resin whose structure is controlled as described above are further controlled, the effects of improving residue characteristics, coating uniformity, and color properties can be further enhanced.

[0090] For example, the binder resin may have a weight average molecular weight of about 5000 g / mol to about 8000 g / mol.

[0091] For example, the binder resin may have a double bond equivalent of about 150 g / mol to about 500 g / mol.

[0092] When the weight average molecular weight and / or double bond equivalent of the acrylic binder resin is controlled as described above, the aforementioned improvement effect can be further doubled by low temperature of about 100° C. or less and i-line exposure.

[0093] Meanwhile, the photosensitive resin composition according to some embodiments can double the aforementioned effect even when the solid content constituting the composition is controlled. Specifically, the solid content constituting the photosensitive resin composition may be included in an amount of about 12 wt % to about 24 wt % based on the total amount of the photosensitive resin composition.

[0094] In the case of conventional photosensitive resin compositions for color filters, the solid content is generally greater than the above range. Since the photosensitive resin composition according to some embodiments is applied to a micro OLED display device including a WOLED deposited on a silicon wafer instead of a glass substrate or a polyimide substrate as a light source, low temperature curing is crucial, and therefore, controlling the solid content as described above can be more advantageous in improving patterning capabilities. Specifically, when the solid content satisfies about 12% by weight to about 24% by weight of the total amount of the photosensitive resin composition, during exposure in the low temperature pattern forming process, sufficient polymerization occurs with the photopolymerization initiator described later, and even at a low temperature process of about 100°C or less, a pattern with excellent heat resistance, light resistance and chemical resistance can be formed. The existing color filter for a liquid crystal display (LCD) uses a resist to form a pattern of about 100 μm, but the pattern is too large to be used for a micro OLED display device, and therefore the inventor controls the type of binder resin, the weight average molecular weight and the double bond equivalent as described above, and the solid content constituting the photosensitive resin composition to achieve a fine pattern and enable low temperature curing.

[0095] The binder resin may be included in an amount of about 5 wt % to about 20 wt %, such as about 5 wt % to about 15 wt %, such as about 7 wt % to about 12 wt %, based on the total amount of the photosensitive resin composition. If the binder resin is included within the above range, excellent sensitivity, developability, resolution and linearity of the pattern may be obtained.

[0096] (B) Colorants

[0097] The photosensitive resin composition according to some embodiments includes a colorant, and the colorant may be a green pigment, a blue pigment, a red pigment, a purple pigment, a yellow pigment, or the like.

[0098] The red pigment in the color index may be CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red pigment 89, etc. The red pigment may be used alone or in the form of a mixture of two or more thereof, but the present invention is not limited thereto.

[0099] The purple pigment in the color index may be CI purple pigment 23 (V.23), CI purple pigment 29, dioxazine purple, first purple B, methyl violet lake (Methyl Violet Lake), indanethrene Brilliant Violet (Indanethrene Brilliant Violet) and the like, and the purple pigment may be used alone or in the form of a mixture of two or more thereof, but the present invention is not limited thereto.

[0100] The green pigment in the color index may be CI green pigment 7, CI green pigment 36, CI green pigment 58, CI green pigment 59, etc. The green pigment may be used alone or in the form of a mixture of two or more, but the present invention is not limited thereto.

[0101] The blue pigment may be a copper phthalocyanine pigment, such as CI blue pigment 15, CI blue pigment 15:1, CI blue pigment 15:2, CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 15:6, and CI blue pigment 16 in the color index. The blue pigment may be used alone or in the form of a mixture of two or more thereof, but the present invention is not limited thereto.

[0102] The yellow pigment may be: an isoindoline pigment, such as CI yellow pigment 185, CI yellow pigment 139 and the like in the color index; a quinophthalone pigment, such as CI yellow pigment 138 in the color index; a nickel complex pigment, such as CI yellow pigment 150 in the color index. The yellow pigment may be used alone or in the form of a mixture of two or more thereof, but the present invention is not limited thereto.

[0103] The above pigments may be used alone or in admixture of two or more.

[0104] The pigment may be pretreated with a water-soluble inorganic salt and a wetting agent. When the pigment is pretreated, the average particle size of the pigment may become finer.

[0105] The pretreatment can be carried out by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

[0106] Kneading may be performed at a temperature of about 40° C. to about 100° C., and filtering and washing may be performed by filtering the pigment after washing away the inorganic salt with water or the like.

[0107] Examples of water-soluble inorganic salts may be materials such as sodium chloride and potassium chloride, but are not limited thereto. The wetting agent may allow the pigment and the water-soluble inorganic salt to be uniformly mixed and crushed. Examples of wetting agents include: alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc.; and alcohols, such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, etc. The materials may be used alone or in the form of a mixture of two or more thereof.

[0108] The kneaded pigment may have an average particle size ranging from about 5 nm to about 200 nm, for example, from about 5 nm to about 150 nm. If the average particle size of the pigment is within the above range, the stability of the pigment mill base (pigment dispersion) is excellent and pixel resolution may not be deteriorated.

[0109] The pigment may be used in the form of a pigment dispersion (eg, mill base) together with a dispersant and a solvent.

[0110] The dispersant helps the pigment to be uniformly dispersed in the dispersion, and each of a nonionic dispersant, an anionic dispersant, or a cationic dispersant can be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc. can be used, and the dispersant can be used alone or in combination of two or more.

[0111] Commercially available examples of dispersants may include: DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like materials made by BYK Co., Ltd.; Co.); Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc. made by AstraZeneka Co.; or PB711 or PB821 made by Ajinomoto Inc.

[0112] The dispersant may be included in an amount of about 0.1 wt % to about 15 wt % based on the total amount of the photosensitive resin composition. If the dispersant is included within the above range, the composition has excellent dispersibility, and thus when a photosensitive resin layer is manufactured, stability, developability, and patterning ability are excellent.

[0113] In addition to the pigment, dispersant and (dispersion) solvent, the pigment dispersion may further include a dispersing auxiliary, a dispersing resin, etc. The solid pigment may be included in an amount of about 5 wt % to about 20 wt %, for example, about 8 wt % to about 15 wt %, based on the total amount of the pigment dispersion.

[0114] The (dispersion) solvent of the pigment dispersion can be materials such as ethylene glycol acetate, ethyl celulose, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred.

[0115] As the dispersion resin, an acrylic resin including a carboxyl group may be used, which can improve the stability of the pigment dispersion and the patterning ability of pixels.

[0116] The colorant may include a pigment, and may also include a dye, and in this case, the photosensitive resin composition according to some embodiments may be a mixed composition. In addition, the dye is not particularly limited, but may include a metal complex dye.

[0117] The metal complex dye may be a compound having a maximum absorbance in the wavelength range of 200 nm to 650 nm, and metal complex dyes of all colors dissolved in an organic solvent may be used if the compound has an absorbance in the above range to match the color coordinates with the combination of dyes.

[0118] Specifically, the metal complex dye may be a green dye having a maximum absorbance in a wavelength range of 530 nm to 680 nm, a yellow dye having a maximum absorbance in a wavelength range of 200 nm to 400 nm, an orange dye having a maximum absorbance in a wavelength range of 300 nm to 500 nm, a red dye having a maximum absorbance in a wavelength range of 500 nm to 650 nm, or a combination thereof.

[0119] The metal complex dye can be a direct dye, an acid dye, a basic dye, an acid mordant dye, a sulfide dye, a vat dye, an ice dye, a disperse dye, a reactive dye, an oxidation dye, an oil-soluble dye, an azo dye, an anthraquinone dye, an indigo dye, a carbonium ion dye, a phthalocyanine dye, a nitro dye, a quinoline dye, a cyanine dye, a polymethine dye, or a combination thereof.

[0120] The metal complex dye may include at least one metal ion selected from Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd and Fe.

[0121] The metal complex dye may be a complex of at least one selected from the group consisting of: CI solvent dyes, such as CI Solvent Green 1, CI Solvent Green 3, CI Solvent Green 4, CI Solvent Green 5, CI Solvent Green 7, CI Solvent Green 28, CI Solvent Green 29, CI Solvent Green 32, CI Solvent Green 33, CI Solvent Green 34, CI Solvent Green 35 and the like; CI acid dyes, such as CI Acid Green 1, CI Acid Green 3, CI Acid Green 5, CI Acid Green 6, CI Acid Green 7, CI Acid Green 8, CI Acid Green 9, CI Acid Green 11, CI Acid Green 13, CI Acid Green 14, CI Acid Green 15, CI Acid Green 16, CI Acid Green 17, CI Acid Green 18, CI Acid Green 19, CI Acid Green 20, CI Acid Green 21, CI Acid Green 22, CI Acid Green 23, CI Acid Green 24, CI Acid Green 25 and the like; CI Acid Green 10, CI Acid Green 11, CI Acid Green 12, CI Acid Green 13, CI Acid Green 14, CI Acid Green 15 CI Acid Green 15, CI Acid Green 16, CI Acid Green 22, CI Acid Green 25, CI Acid Green 27, CI Acid Green 28, CI Acid Green 41, CI Acid Green 50, CI Acid Green 50:1, CI Acid Green 58, CI Acid Green 63, CI Acid Green 65, CI Acid Green 80, CI Acid Green 104, CI Acid Green 105, CI Acid Green 106, CI Acid Green 109 and other dyes; CI direct dyes, such as CI Direct Green 25, CI Direct Green 27, CI Direct Green 31, CI Direct Green 32, CI Direct Green 34, CI Direct Green 37, CI Direct Green CI direct green 63, CI direct green 65, CI direct green 66, CI direct green 67, CI direct green 68, CI direct green 69, CI direct green 72, CI direct green 77, CI direct green 79, CI direct green 82 and other dyes; CI basic dyes, such as CI basic green 1 and other dyes; CI mordant dyes, such as CI mordant green 1, CI mordant green 3, CI mordant green 4, CI mordant green 5, CI mordant green 10, CI mordant green 13, CI mordant green 15, CI mordant green 19, CI mordant green 21, CI mordant green 23, CI mordant green 26, CI mordant green 29, CI mordant green 31, CI Mordant Green 33, CI Mordant Green 34, CI Mordant Green 35, CI Mordant Green 41, CI Mordant Green 43, CI Mordant Green 53 and other dyes; CI green pigments, such as Pigment Green 7, Pigment Green 36, Pigment Green 58 and other pigments; Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent Orange 62, Solvent Orange 99, Solvent Red 8, Solvent Red 32, Solvent Red 109, Solvent Red 112, Solvent Red 119, Solvent Red 124, Solvent Red 160, Solvent Red 132 and Solvent Red 218, and metal ions.

[0122] In the solvent used in the photosensitive resin composition according to some embodiments (ie, a solvent to be described later), the metal complex dye may have a solubility greater than or equal to 5, specifically 5 to 10. The solubility can be obtained by the amount (g) of the dye dissolved in 100 g of the solvent. If the solubility of the metal complex dye is within the above range, compatibility with other components constituting the photosensitive resin composition according to some embodiments and tinting power can be ensured, and precipitation of the dye can be prevented.

[0123] The solvent may be, for example, propylene glycol monomethyl etheracetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol, or a combination thereof.

[0124] The metal complex dye may be included in an amount of about 0.01 wt % to about 1 wt %, for example, about 0.01 wt % to about 0.5 wt %, based on the total amount of the photosensitive resin composition. If a metal complex dye within the above range is used, high brightness and contrast may be expressed in desired color coordinates.

[0125] If the dye and the pigment are mixed and used, the dye and the pigment may be mixed in a weight ratio of about 0.1:99.9 to about 99.9:0.1, specifically, about 1:9 to about 9: 1. If mixed within the above weight ratio range, chemical resistance and maximum absorption wavelength may be controlled within appropriate ranges, and high brightness and contrast may be expressed in desired color coordinates.

[0126] The colorant may be included in an amount of about 70 wt % to about 90 wt %, for example, about 70 wt % to about 85 wt %, for example, about 75 wt % to about 80 wt %, based on the total amount of the photosensitive resin composition. If the colorant is included in a very high content as described above, in the micro OLED display device, the coloring effect and developability are excellent, making it easy to ensure high color gamut and viewing angle characteristics.

[0127] (C) polymerizable monomer

[0128] The polymerizable monomer in the photosensitive resin composition according to some embodiments may include one or more compounds including three or more functional groups, wherein the functional groups may be (meth)acrylate groups, epoxy groups, etc., but are not necessarily limited thereto.

[0129] According to some embodiments, the photosensitive resin composition has been developed for use in micro OLED display devices, and the low temperature curing process is crucial. In the case of a low temperature curing pattern process, the contribution of thermal curing is reduced, and the influence of photocuring is bound to increase. Therefore, maximizing the photocuring efficiency is conducive to ensuring excellent patterning capabilities under low temperature curing. According to some embodiments, the photocuring efficiency can be maximized by using a compound having at least three functional groups in a monomer as a polymerizable monomer. Specifically, the photocuring efficiency is greatly affected by the weight average molecular weight of the polymerizable monomer and the number of functional groups. The smaller the weight average molecular weight of the polymerizable monomer and the more the number of functional groups in the polymerizable monomer, the higher the photocuring efficiency. For example, a compound having at least three functional groups in a monomer has a small weight average molecular weight and a large number of functional groups, which is conducive to maximizing the photocuring efficiency.

[0130] For example, the polymerizable monomer is a mixture of two types of compounds, and the two types of compounds can each independently be a compound comprising three or more functional groups. For example, the polymerizable monomer can be a mixture of a first polymerizable monomer comprising 3 to 5 functional groups and a second polymerizable monomer comprising 6 or more functional groups. When the polymerizable monomer has the above mixed composition, the photocuring efficiency can be maximized while maintaining the aforementioned color characteristics, making it easy to form a low-temperature curing pattern.

[0131] For example, the first polymerizable monomer may be included in an amount smaller than the second polymerizable monomer.When the two types of compounds are mixed in the above weight ratio, low temperature curing patterning capability may be optimal.

[0132] For example, a polymerizable compound including three or four functional groups may be represented by Chemical Formula 1, but is not necessarily limited thereto.

[0133] [Chemical formula 1]

[0134]

[0135] In Chemical Formula 1,

[0136] L a To L d are each independently a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 oxyalkylene group, or a combination thereof, and

[0137] R a to R d Each is independently hydrogen, hydroxyl, epoxy or substituted or unsubstituted (meth)acrylate, with the proviso that R a to R d At least three of them are epoxy groups or substituted or unsubstituted (meth)acrylate groups.

[0138] For example, the compound including 5 to 6 functional groups may be pentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, but is not necessarily limited thereto.

[0139] The polymerizable monomer may be used after being treated with an acid anhydride to provide better developability.

[0140] The polymerizable monomer may be included in an amount of about 1 wt % to about 10 wt %, for example, about 1 wt % to about 5 wt %, based on the total amount of the photosensitive resin composition. If the polymerizable monomer is included within the above range, curing occurs sufficiently during exposure in a low-temperature pattern forming process, achieving excellent reliability of the pattern, excellent heat resistance, light resistance and chemical resistance, and excellent resolution and adhesion.

[0141] (D) Polymerization initiator

[0142] The photosensitive resin composition according to some embodiments includes a polymerization initiator. At this time, the polymerization initiator can be controlled to be about 0.1 wt % to about 5 wt %, for example, about 1 wt % to about 3 wt % based on the total amount of the photosensitive resin composition. When the amount of the polymerization initiator is controlled as described above, an optimal pattern and the composition of the aforementioned polymerizable monomer, binder resin and colorant can be formed in a low temperature curing process. If a polymerization initiator outside the above content range is used together with the composition of the aforementioned polymerizable monomer, binder resin and colorant, the patterning ability during the low temperature curing process can be greatly reduced.

[0143] The polymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or combinations thereof.

[0144] Examples of acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0145] Examples of benzophenone compounds include benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0146] Examples of the thioxanthone compounds may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0147] Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0148] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine. -triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxyphenylvinyl)-s-triazine, etc.

[0149] Examples of oxime compounds may be O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of O-acyl oxime compounds may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate, etc., but are not necessarily limited thereto.

[0150] In addition to the above compounds, the polymerization initiator may also be used together with, for example, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and the like.

[0151] (E) Solvent

[0152] The solvent may be a material that has compatibility with, but does not react with, the pigment dispersion including the colorant, the binder resin, the polymerizable monomer, and the polymerization initiator.

[0153] Examples of the solvent may include: alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, etc.; celulose acetates such as methyl celulose acetate, ethyl celulose acetate, diethyl celulose acetate, etc.; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates, For example, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid esters, such as methyl lactate, ethyl lactate, etc.; oxyacetic acid alkyl esters, such as oxymethyl acetate, oxyethyl acetate, oxybutyl acetate, etc.; alkoxyacetic acid alkyl esters, such as methoxyethyl acetate, 3-Oxypropionic acid alkyl esters, such as 3-oxymethyl propionate, 3-oxyethyl propionate, etc.; 3-alkoxypropionic acid alkyl esters, such as 3-methoxymethyl propionate, 3-methoxyethyl propionate, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, etc.; 2-Oxypropionic acid alkyl esters, such as 2-oxymethyl propionate, 2-oxyethyl propionate, propyl propionate, etc.; 2-alkoxypropionic acid alkyl esters, such as 2-methoxymethyl propionate, 2-methoxyethyl propionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc. ethyl ester, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionic acid esters, such as methyl 2-oxy-2-methylpropionic acid, ethyl 2-oxy-2-methylpropionic acid ester, etc.; monooxymonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters, such as methyl 2-methoxy-2-methylpropionic acid, ethyl 2-ethoxy-2-methylpropionic acid ester, etc.; esters, such as 2-hydroxyethyl propionic acid ester, 2-hydroxy-2-methylethyl propionic acid ester, hydroxyethyl acetate, 2-hydroxy-3-methylethyl butyrate, etc.; ketoesters, such as ethyl pyruvate, etc. In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celulose acetate, etc. can also be used.

[0154] Taking into account the miscibility and reactivity, the following can be used: glycol ethers, such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; ethylene glycol alkyl ether acetates, such as ethyl celulose acetate, etc.; esters, such as 2-hydroxyethyl propionate, etc.; carbitols, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0155] The solvent may be included in an amount of a balance, such as about 0.1 wt % to about 20 wt %, such as about 1 wt % to about 20 wt %, such as about 3 wt % to about 18 wt %, based on the total amount of the photosensitive resin composition. If the solvent is included within the above range, the photosensitive resin composition may have an appropriate viscosity and thus improve processability during production of the photosensitive resin layer.

[0156] (F) Other additives

[0157] Meanwhile, the photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, an antioxidant or a combination thereof.

[0158] The silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group to improve adhesion to the substrate.

[0159] Examples of silane coupling agents may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. The silane coupling agents may be used alone or in the form of a mixture of two or more.

[0160] The silane-based coupling agent may be included in an amount of about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. If the silane-based coupling agent is included within the above range, properties such as adhesion and storage capacity are improved.

[0161] In addition, if necessary, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant and / or a silicone-based surfactant, in order to improve coating properties and prevent defect formation.

[0162] Examples of fluorine-based surfactants include commercial fluorine-based surfactants such as BM Chemie Inc. etc.; MEGAFACE of Dainippon Ink Kagaku Kogyo Co., Ltd. Meijia method Meijia method Meijia method Meijia method etc.; FULORAD of SUMITOMO 3M Co., Ltd. Florard Florard Florard etc.; SURFLON of Asahi Glass Co., Ltd. Saffron Saffron Saffron S- Saffron etc.; Toray Silicone Co., Ltd. wait.

[0163] The silicone surfactant may be a commercial silicone surfactant, such as BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, etc. from BYK Chem.

[0164] The surfactant may be used in an amount of about 0.001 to about 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. If the surfactant is included within the range, coating uniformity may be ensured, stains may not be generated, and wettability on an indium zinc oxide (IZO) substrate or a glass substrate may be improved.

[0165] The antioxidant may include a hydroquinone compound, a catechol compound, or a combination thereof, but is not necessarily limited thereto. Since the photosensitive resin composition according to some embodiments further includes a hydroquinone compound, a catechol compound, or a combination thereof, room temperature crosslinking can be prevented during exposure after coating the photosensitive resin composition.

[0166] For example, the hydroquinone compound, the catechol compound, or a combination thereof may include hydroquinone, methyl hydroquinone, methoxy hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl) hydroquinone, catechol, tert-butyl catechol, 4-methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum, or a combination thereof, but is not necessarily limited thereto.

[0167] The hydroquinone compound, the catechol compound or the combination thereof may be used in the form of a dispersion, and the antioxidant in the form of a dispersion may be included in an amount of about 0.001 wt % to about 3 wt %, for example, about 0.01 wt % to about 1 wt %, based on the total amount of the photosensitive resin composition. If the antioxidant is included within the above range, the aging problem at room temperature can be solved, and the degradation of sensitivity and surface peeling can be prevented.

[0168] In addition, the photosensitive resin composition may include a predetermined amount of other additives (eg, additives such as stabilizers) unless the additives deteriorate the properties of the photosensitive resin composition.

[0169] The photosensitive resin composition according to some embodiments may be positive or negative, but should be negative to completely remove residues in a pattern-exposed region after exposing and developing the composition having a light-blocking property.

[0170] Some embodiments provide a photosensitive resin layer manufactured by low-temperature curing, exposure and development of the above-mentioned photosensitive resin composition. Compared with the traditional LCD process, the difference is that no post-curing (post-baking) process is required.

[0171] The method of producing the photosensitive resin layer is as follows.

[0172] (1) Coating and film formation (low temperature curing)

[0173] The photosensitive resin composition is coated on a substrate (e.g., a glass substrate or an ITO substrate) that has been pre-treated to a desired thickness using a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, etc., and heated at about 100° C. or less, for example, at about 85° C. for about 1 minute to 10 minutes to remove the solvent and thereby form a photosensitive resin layer. Through this step, image quality, etc. can be improved.

[0174] (2) Exposure

[0175] After a mask is set to form a necessary pattern on the obtained photosensitive resin layer, exposure is performed by irradiating actinic rays of i-line. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon laser, etc. can be used, and in some cases, a light source such as X-rays and electron beams can be used.

[0176] When a high pressure mercury lamp is used, the exposure process uses, for example, 500 mJ / cm 2 Or less than 500mJ / cm 2 The light dose is 500 mJ / cm2 (using a 365 nm sensor). However, the light dose may vary depending on the type of each component, its combination ratio and the dry film thickness. However, in some cases, the exposure may exceed 500 mJ / cm2. 2 (via a 365nm sensor.) This step allows the pixel size to be fine-tuned, enabling high resolution to be achieved.

[0177] (3) Development

[0178] In the development method, after the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed parts to form a pattern. Through this step, contours can be formed to achieve high resolution, and color uniformity can be ensured to improve clarity.

[0179] Some embodiments provide a display device including a photosensitive resin layer.

[0180] The display device may be a micro organic light emitting diode (OLED) display device.

[0181] The micro organic light emitting diode (OLED) display device may include an OLED substrate and a color filter layer, wherein the OLED substrate is deposited on a silicon wafer, and the color filter layer is stacked on the OLED substrate and converts white light generated from the OLED substrate into light of multiple colors, wherein the color filter layer includes a red filter, a green filter, and a blue filter.

[0182] For example, a micro organic light emitting diode (OLED) display device may include: an OLED substrate deposited on a silicon wafer; an inorganic layer stacked on the OLED substrate; an adhesive protective layer stacked on the inorganic layer; and a color filter layer stacked on the adhesive protective layer and converting white light generated from the OLED substrate into light of multiple colors, wherein the color filter layer includes a red filter, a green filter, and a blue filter.

[0183] For example, the photosensitive resin composition according to some embodiments is a green photosensitive resin composition, and the green color filter in the micro OLED display device may be a low-temperature cured layer of the green photosensitive resin composition.

[0184] Conventionally, an OLED substrate in which an OLED is deposited on a glass substrate or a polyimide substrate has been used, but a micro OLED display device according to some embodiments may be more advantageous in realizing a micro display due to an OLED deposited on a silicon wafer. These micro displays have attracted much attention as next-generation displays, and it is expected that the micro displays will be applied to devices such as MR. In fact, Apple, Meta, and LG Display have all entered or announced their entry into the next-generation MR device market.

[0185] For example, the micro OLED display device may further include a micro lens array. The micro lens array may be located on the adhesive protective layer and may surround the color filter layer.

[0186] By depositing WOLED on a highly integrated silicon wafer, a micro OLED display device having the above structure can be driven on a pixel basis, and the transmission wavelength can be easily controlled through a color filter layer patterned with a resolution of less than or equal to about 3 μm, enabling high color reproduction and ensuring high resolution.

[0187] For example, the adhesive protection layer may have a thickness of less than or equal to about 1 μm. In this case, the above effect can be further maximized.

[0188] For example, the color filter layer may have a thickness of about 1.1 μm to about 1.6 μm.

[0189] If the thickness of the color filter layer is controlled as described above, it may be more advantageous to realize a micro OLED display device.

[0190] For example, the inorganic layer may have a thickness of less than or equal to about 2 μm. Even with WOLED, light does not always diffuse in a direction perpendicular to the OLED substrate, so that color mixing of red, green, and blue is inevitable. Therefore, in the past, an inorganic layer was deposited on the OLED substrate to prevent such color mixing. However, since color mixing cannot be completely prevented even by depositing an inorganic layer, in some embodiments, a subtle light leakage phenomenon can be prevented by thinning the inorganic layer, for example, controlling the thickness of the inorganic layer to be less than or equal to about 2 μm.

[0191] Finally, as described above, the photosensitive resin composition according to some embodiments enables the production of a cured layer by only low temperature (100° C.) curing during pre-bake and i-line light curing, and there is bound to be a huge difference in achievable resolution compared to conventional display devices.

[0192] Hereinafter, preferred examples of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

[0193] (Example)

[0194] (Preparation of Photosensitive Resin Composition)

[0195] Examples 1 to 10 and Comparative Examples 1 and 2

[0196] Using the compositions shown in Tables 1 and 2, a polymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Here, a binder resin and a polymerizable monomer were added and stirred at room temperature for 1 hour. After adding other additives and a colorant thereto, the solution was stirred at room temperature for 1 hour, and then the entire solution was stirred for 2 hours. The solution was filtered three times to remove impurities, thereby preparing each photosensitive resin composition.

[0197] (Table 1)

[0198] (Unit: weight %)

[0199]

[0200] (A) Binder resin

[0201] (A-1) Acrylic binder resin including a structural unit represented by Chemical Formula A (Showa Denko) (8000 g / mol)

[0202] [Chemical formula A]

[0203]

[0204] (A-2) Acrylic binder resin including a structural unit represented by Chemical Formula A (Showa Denko) (5000 g / mol)

[0205] (A-3) Acrylic binder resin including a structural unit represented by Chemical Formula B (Showa Denko) (5000 g / mol)

[0206] [Chemical formula B]

[0207]

[0208] (A-4) Acrylic binder resin including a structural unit represented by Chemical Formula A (Showa Denko) (4000 g / mol)

[0209] (A-5) Acrylic binder resin including a structural unit represented by Chemical Formula A (Showa Denko) (9000 g / mol)

[0210] (A-6) Epoxy binder resin (EHPE3150, Daicel Chemical Industry Co., Ltd.)

[0211] (A-7) Silsesquioxane binder resin (EHPE3150, Daicel Chemical Industries, Ltd.)

[0212] (B) Colorants

[0213] Pigment dispersion (Sanyo, BA6136)

[0214] (C) polymerizable monomer

[0215] (C-1) Dipentaerythritol hexa(meth)acrylate (DPHA, Nippon Kayaku Co., Ltd.)

[0216] (C-2) Pentaerythritol triacrylate (PE-3A, Gongyoungsa Co., Ltd.)

[0217] (D) Polymerization initiator

[0218] Oxime initiator (SPI-03, Samyang Corp.)

[0219] (E) Solvent

[0220] Propylene glycol monomethyl ether acetate (PGMEA, Daicel Corporation)

[0221] (F) Other additives

[0222] (F-1) Leveling agent (F-554, DIC Co., Ltd.)

[0223] (F-2) Silane coupling agent (KBM503, ShinEtsu)

[0224] (F-3) Antioxidant (2-methylhydroquinone, JH Chemical (JHChem))

[0225] evaluate

[0226] Each of the photosensitive resin compositions according to Examples 1 to 10 and Comparative Examples 1 and 2 was coated on an 8-inch silicon wafer using a K-spin 8 device (Track) (SEMES) at revolutions per minute (rpm) that could achieve a predetermined thickness (1.5 μm) of each sample. Subsequently, the coated wafer was baked on a hot plate of the Track device at 100° C. for 3 minutes, and then exposed to form a pattern by adjusting the exposure dose (exposure condition = dose: 800 ms / focal length: −0.3) using an i-line stepper manufactured by Nikon Inc. In the exposure process, after measuring the thickness by using KLA_Tencor, the exposed wafer was developed to reveal the pattern. Herein, development was performed by using an EHD-100S developing solution (tetramethylammonium hydroxide (TMAH)). The pattern of the patterned substrate after development was confirmed to be a 96 μm negative pattern by using a critical dimension-scanning electron microscope (CD-SEM) manufactured by Hitachi, Ltd., and the sensitivity and residue were checked, and the large-area coating uniformity was checked using an optical microscope manufactured by Olympus Corp. The coating uniformity was confirmed with the naked eye, where ○ was given if excellent, △ was given if poor, and X was given if too poor to be commercialized.

[0227] Additionally, additional color changes of the patterned substrate were checked by immersing the patterned substrate in TMAH (2.38%) developer BASF Corp. (5 minutes). The color was measured by using a fine pattern colorimeter (LCF).

[0228] The evaluation results are shown in Table 2 and Figures 1 to 6 middle.

[0229] (Table 2)

[0230]

[0231] Evaluation criteria for residue characteristics

[0232] ○: No residue was observed around the pattern under an optical microscope.

[0233] △: Some residues were observed around the pattern under an optical microscope, but not serious.

[0234] X: There are many residues around the pattern seen under an optical microscope.

[0235] Refer to Table 2 and Figures 1 to 6 , the photosensitive resin composition according to some embodiments achieves a fine pattern despite low temperature curing and exhibits excellent residue characteristics, coating uniformity, and color characteristics, and thus proves to be suitable for use in a micro OLED display device.

[0236] Although the present invention has been described in conjunction with what are currently considered to be practical exemplary embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, it should be understood that the foregoing embodiments are exemplary and do not limit the present invention in any way.

Claims

1. A photosensitive resin composition comprising: Binder resin; Colorants; polymerizable monomers; Polymerization initiator; Solvents, wherein the binder resin includes at least one selected from the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2, and at least two selected from the structural units represented by Chemical Formulas 3 to 5, [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] Among them, in Chemical Formula 1 to Chemical Formula 5, R 1 to R 6 and R 8 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 7 and R 9 are each independently a substituted or unsubstituted C6 to C20 aryl group, and L 1 To L 6 Each is independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

2. The photosensitive resin composition according to claim 1, wherein The binder resin includes structural units represented by Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5.

3. The photosensitive resin composition according to claim 2, wherein In Chemical Formula 1 and Chemical Formula 3 to Chemical Formula 5, R 1 , R 4 and R 6 are each independently a substituted or unsubstituted C1 to C20 alkyl group, R 2 , R 5 and R 8 are each independently a hydrogen atom, and L 1 To L 6 Each is independently a substituted or unsubstituted C1 to C20 alkylene group.

4. The photosensitive resin composition according to claim 1, wherein The binder resin has a weight average molecular weight of 5000 g / mol to 8000 g / mol.

5. The photosensitive resin composition according to claim 1, wherein The binder resin has a double bond equivalent of about 150 to about 500 g / mol.

6. The photosensitive resin composition according to claim 1, wherein The solid content constituting the photosensitive resin composition is included in an amount of 12 wt % to 24 wt % based on the total amount of the photosensitive resin composition.

7. The photosensitive resin composition according to claim 1, wherein The polymerizable monomer includes one or more compounds including three or more functional groups.

8. The photosensitive resin composition according to claim 7, wherein The polymerizable monomer is a mixture of two types of compounds, and The two types of compounds are each independently one or more compounds including three or more functional groups.

9. The photosensitive resin composition according to claim 8, wherein The two types of compounds are a first polymerizable monomer including 3 to 5 functional groups and a second polymerizable monomer including 6 or more functional groups, and the first polymerizable monomer is included in an amount smaller than that of the second polymerizable monomer.

10. The photosensitive resin composition according to claim 1, wherein Based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: 5 to 20 wt % of said binder resin; 70 to 90 wt % of said colorant; 1 wt % to 10 wt % of said polymerizable monomer; 0.1 wt % to 5 wt % of the polymerization initiator; and The balance is the solvent.

11. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition further includes an antioxidant.

12. The photosensitive resin composition according to claim 11, wherein The antioxidant may be included in an amount of 0.01 wt % to 1 wt % based on the total amount of the photosensitive resin composition.

13. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition further comprises the following additives: malonic acid, 3-amino-1,2-propylene glycol, a silane coupling agent, a leveling agent, a surfactant or a combination thereof. 14 . A photosensitive resin layer produced using the photosensitive resin composition according to claim 1 .

15. A display device comprising the photosensitive resin layer according to claim 14.

16. The display device according to claim 15, wherein The display device is a micro organic light emitting diode display device, which includes an organic light emitting diode substrate and a color filter layer, wherein the organic light emitting diode substrate is located on a silicon wafer, and the color filter layer is stacked on the organic light emitting diode substrate and converts white light generated by the organic light emitting diode substrate into light of multiple colors. The color filter layer includes a red color filter, a green color filter, and a blue color filter.

17. A method for manufacturing a photosensitive resin layer, comprising: Applying the photosensitive resin composition as claimed in claim 1; Pre-baking at a temperature of 100° C. or lower after the coating; and exposing to i-line after performing the prebake; and Perform development.

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