KR102368697B1 - Photosensitive resin composition, pixel define layer prepared by using the same, and electronic device comprising the pixel define layer - Google Patents

Abstract

The present application is a photopolymerization initiator; photosensitizers; polyfunctional monomers; black dye; vicardo-based binder polymer; and a photosensitive resin composition including a solvent, a pixel partition layer formed using the photosensitive resin composition, and an electronic device including the pixel partition layer.

Description

A photosensitive resin composition, a pixel compartment layer formed using the same, and an electronic device comprising the pixel compartment layer

The present application relates to a photosensitive resin composition, a pixel partition layer formed using the same, and an electronic device including the pixel partition layer.

In forming a pixel define layer (PDL, hereinafter abbreviated as “PDL”) of an organic light emitting diode (OLED, hereinafter abbreviated as “OLED”), a polyimide-based positive A positive photoresist has been mainly used. However, since the positive photoresist does not contain a black pigment, the PDL layer of the OLED is formed of a yellow or brown translucent thin polymer film. There was a problem.

Therefore, in order to improve the problems of OLED devices manufactured by using the polyimide-based positive photosensitive resin composition, a polymer including a cardo moiety having excellent heat resistance is used as a binder polymer, and a photoinitiator and a multi-pipe The development of a negative type black photosensitive resin composition in which a functional monomer, an additive (adhesion increaser), a black pigment, and an additive are dissolved and dispersed in an organic solvent has been in progress.

However, there is a problem in that the black photosensitive resin composition using a cardo-based polymer as a binder polymer has a low UV exposure sensitivity, it is difficult to obtain a PDL fine pattern required for high resolution of an OLED device, and there is a limit in increasing the concentration of the black pigment.

One embodiment of the present invention is to provide a negative photosensitive resin composition having excellent heat resistance, chemical resistance, and blackness as well as excellent precision of a fine pattern to be formed.

Another aspect of the present invention is to provide a pixel partition layer manufactured using the photosensitive resin composition.

Another embodiment of the present invention is to provide an electronic device including the pixel partition layer.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present invention includes a vicardo-based polymer having excellent photosensitivity and good adhesion as a binder polymer to form a pixel partitioning layer pattern of an electronic device such as an OLED, a photopolymerization initiator, a photosensitizer, a polyfunctional monomer, an additive, Provided is a photosensitive resin composition comprising a black pigment and a solvent.

A second aspect of the present invention provides a pixel partition layer capable of forming a black fine pattern using the technique of the first aspect.

A third aspect of the present invention provides an electronic device such as an OLED, a liquid crystal display, and a touch panel device including the pixel partition layer of the second aspect.

The present invention uses a vicardo-based polymer that is completely dissolved in a solvent of propylene glycol monomethylether acetate (PGMEA, abbreviated as “PGMEA” hereinafter) excellent in eco-friendliness to form a true solution as a binder polymer. By providing a negative type black photosensitive resin composition to form a black PDL fine pattern of an electronic device such as an OLED, there is an effect of increasing visibility by lowering the external light reflectance of an electronic device such as an OLED. That is, the present invention can provide a photosensitive resin composition having excellent pixel graying layer patternability and exposure sensitivity, and having little black residue amount.

1 shows the results of GPC molecular weight analysis of the vicardo-based binder polymer used in Examples 1-5.
2 shows the results of GPC molecular weight analysis of the non-cardo-based binder polymer used in Example 3-2.
FIG. 3 is a PDL pattern photograph of an OLED device formed through exposure and development through a photomask after spin coating of the photosensitive resin composition according to Example 1-2 and drying; FIG.
4 is a PDL pattern photograph of an OLED device formed through exposure and development through a photomask after spin coating and drying the photosensitive resin composition according to Example 2-2.
FIG. 5 is a photograph showing a PDL pattern of an OLED device, which is formed through exposure and development through a photomask after spin coating of the photosensitive resin composition according to Example 3-2 and drying.

Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present application pertains can easily carry out. However, the present application may be implemented in several different forms and is not limited to the embodiments described herein. And in order to clearly explain the present application in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Hereinafter, if there is no other definition in the technical terms and scientific terms used in the present invention, those of ordinary skill in the art to which this invention belongs have the meaning commonly understood. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

Throughout this specification, when a part is "connected" with another part, this includes not only the case where it is "directly connected" but also the case where it is "electrically connected" with another element interposed therebetween. do.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used throughout this specification, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and are intended to enhance the understanding of this application. To help, precise or absolute figures are used to prevent unfair use by unconscionable infringers of the stated disclosure.

As used throughout this specification, the term "step for" or "step for" does not mean "step for".

Throughout this specification, the term "combination(s) of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, reference to “A and/or B” means “A or B, or A and B”.

Throughout this specification, "organic light emitting diode" may be abbreviated as "OLED", "pixel compartment layer" may be abbreviated as "PDL", and "black dye" means "black dye or pigment" .

Throughout this specification, the terms first, second, third, etc. are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.

Throughout this specification, "cardo system" refers to a structure including all carbons of a fluorene ring structure.

The terminology used throughout this specification is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention. As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

Although not defined otherwise, all terms including technical terms and scientific terms used throughout this specification have the same meaning as those commonly understood by those of ordinary skill in the art to which the present invention belongs. Commonly used terms defined in the dictionary are additionally interpreted as having a meaning consistent with the related technical literature and the presently disclosed content, and unless defined, are not interpreted in an ideal or very formal meaning.

Unless otherwise defined in the chemical formulas in the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded to the position.

In addition, unless otherwise specified in the present specification, "*" means a moiety connected to the same or different atoms or chemical formulas.

Hereinafter, embodiments of the present application will be described in detail. However, this is provided as an example, and the present application is not limited thereto, and the present application is only defined by the scope of the claims described below.

A first aspect of the present application, a photopolymerization initiator; photosensitizers; polyfunctional monomers; additive; black dye; vicardo-based binder polymer; and a solvent, wherein the non-cardo-based binder polymer comprises: a first step of reacting a non-cardo-based diepoxide compound and a carboxyl group-containing compound; And after the first step, it provides a photosensitive resin composition obtained by a manufacturing method comprising a second step of condensation reaction with a dihydride monomer.

The components required for the negative black photosensitive resin composition used to obtain the black PDL micropattern of the OLED device include a UV photoinitiator, a photosensitizer, a binder polymer, a polyfunctional monomer, a black dye dispersion (Black milbase), an organic solvent, and an additive. can The additive may serve as an adhesion promoter, and may be, for example, an acrylic monomer including an alkoxysilane group or a methacrylic monomer including an alkoxysilane group. A siloxane bond is formed between the photosensitive resin composition and the substrate by the alkoxy silane group, thereby enhancing adhesion between the photosensitive resin composition and the substrate. Specifically, the additive may include MSMA (3-(Trimethoxysilyl)propyl methacrylate), but is not limited thereto.

In the photosensitive resin composition, the binder polymer having a double bond group is exposed to UV light through a photomask by a free radical chain polymerization reaction together with a polyfunctional monomer containing a double bond group when the UV photoinitiator is exposed to UV light to form free radicals. By causing cross-linking at the site, it remains undeveloped by the TMAH base aqueous solution in the next process, making it possible to implement black PDL micro-patterns of OLED devices. On the other hand, in the portion not exposed to UV light, since the binder polymer is in a state in which cross-linking has not occurred, the carboxyl group contained in the binder polymer reacts with the TMAH base of the developer to dissolve in the aqueous solution and wash out, thereby forming a black PDL fine pattern. can be formed

Among the black photosensitive resin compositions, the binder polymer is the most important component in forming the black PDL fine pattern of the OLED device. As a binder polymer for this purpose, according to Korean Patent Laid-Open No. 10-2014-0141339, a cardo-based binder polymer given in Scheme 1 below is known.

The cardo-based binder polymer shown in Scheme 1 below is synthesized by a condensation reaction between a fluorene epoxy acrylate (FEA) monomer containing two alcohol groups (-OH) and BPDA, which is one of the dianhydride monomers. However, since the molecular weight of the repeat unit of the binder polymer containing the FEA monomer having a diol group is high, the weight molar ratio of the acrylate double bond group per repeating unit of the cardo-based polymer containing FEA (mmol/g polymer) is 2.22, and The site that controls (reduces) the polymerization reactivity of the double bond group has a bulky pullorene group, so the UV exposure sensitivity of the black photosensitive resin composition including it is low, and it is difficult to obtain a high-resolution PDL pattern of the OLED device. However, there is a limit to increasing the concentration of the black pigment, so there is a problem in that the optical density (OD) is low.

However, according to one embodiment, the first step of reacting a non-cardo-based diepoxide compound and a carboxyl group-containing compound with a binder polymer; And, after the first step, the above-mentioned problems can be solved by using the non-cardo-based binder polymer obtained by the manufacturing method comprising a second step of condensation reaction with the dihydride monomer.

In one embodiment of the present application, the photosensitive resin composition may be a negative photosensitive resin composition for forming a pixel compartment layer of an organic light emitting diode (OLED), but may not be limited thereto. For example, the photosensitive resin composition may be a black negative photosensitive resin composition used to form a black pixel compartment layer pattern for OLED, but may not be limited thereto.

For example, the polyfunctional monomer included in the photosensitive resin composition refers to a monomer having two or more double bonds in one molecule, and is produced by the action of the photopolymerization initiator and the photosensitizer when exposed to ultraviolet rays. By forming a three-dimensional network structure in the polymer film composed of the binder polymer by polymerization by free radicals that become It may be attached on a plane and serve to form a black pixel partition layer pattern, but may not be limited thereto. For example, the polyfunctional monomer may be a polyfunctional monomer commonly used in the photosensitive resin composition for OLED, and may not be limited to any one type of polyfunctional monomer.

For example, the black dye included in the photosensitive resin composition may perform a function of remarkably reducing the intensity of reflected light by absorbing external light by coloring the fine pattern of the pixel compartment layer for OLED black. , which may not be limited thereto. For example, as the black dye pigment, a black dye pigment commonly used in the photosensitive resin composition for OLED may be used in the form of a dispersion, and may not be limited to any one type of black dye pigment. For example, as the black dye, an organic dye such as lactam black, or a lactam black/carbon black dye mixture having a size of about 50 nm or less is uniformly mixed in an organic solvent. It may be in the form of a dispersed dispersion, but may not be limited thereto. In this case, the photosensitive resin composition may further include a dispersant, and the dispersant may be included in an amount of 1 wt% to 5 wt% based on the total amount of the photosensitive resin composition, but is not necessarily limited thereto.

A black negative photosensitive resin composition using a cardo-based polymer as a binder polymer has been used to implement black PDL micropatterns of OLED devices or black spacers and black matrixes of liquid crystal display devices. Silver has a low UV exposure sensitivity, so there is a problem in that there is a limit to obtaining a high-resolution black fine pattern.

For example, according to Korean Patent Application Laid-Open No. 10-2014-0141339, a black photosensitive resin composition using a cardo-based polymer as a binder polymer contains 1 to 20% by weight of a black pigment and has an OD (optical density) of about 0.5/μm. Because it shows blackness, there is a problem in realizing black PDL fine patterns of OLED devices that require OD of 1/μm or more.

According to the Korean Patent Application Laid-Open No. 10-2014-0141339, a representative cardo-based polymer (CBP) used as a binder polymer of the black photosensitive resin composition is fluorene epoxy acrylate (FEP; 9,9) as shown in Scheme 1 below. Esterification condensation polymerization of two alcohol (-OH) groups of -Bis(4-glycidyloxyphenyl)fluorene) with two anhydride groups of BPDA (4,4'-Biphthalic Anhydride) monomers shown in Table 1 below. synthesized by reaction.

In general, a compound containing carbon of a ring structure (fluorene ring structure) indicated by an asterisk (*) in the fluorene epoxy acrylate structure of Scheme 1 is called a cardo-based compound, and in the present specification, a fluorene ring A compound containing carbon in the structure is defined as a cardo-based compound.

[Scheme 1]

Code names for simplifying structures, names, and names of various compounds used to synthesize the vicardo-based binder polymer are shown in Tables 1 to 4 below.

Monomer type dianhydride code name English name chemical structural formula 6FDA 4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride

MCDA 5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride

BPDA 4,4'-Biphthalic Anhydride (purified by sublimation)

BTDA Benzophenone-3,3

''-tetracarboxylic dianhydride

For example, the dihydride monomer is 6FDA (4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride), MCDA (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride), and BPDA (4,4'-Biphthalic Anhydride (purified by sublimation)) may be at least one selected from the group consisting of.

Monomer type diepoxide code name English name chemical structural formula BEP Bisphenol A diglycidyl ether

CHEP 1,4-Cyclohexanedimethanol diglycidyl ether

JEP 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate

REP Resorcinol diglycidyl ether

SIEP 1,3-Bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane

For example, the bicardo-based diepoxide compound is CHEP (1,4-Cyclohexanedimethanol diglycidyl ether), JEP (3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate), REP (Resorcinol diglycidyl ether), SIEP (1,3 -Bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane), and at least one selected from the group consisting of BEP (bisphenol A diglycidyl ether) can

Monomer type Dior code name English name chemical structural formula SDO Bis[4-(2-hydroxyethoxy)phenyl] Sulfone

XDO 3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane

4DO 1,4-Butanediol

For example, the diol monomer is SDO (Bis[4-(2-hydroxyethoxy)phenyl] Sulfone), XDO (3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8, 10-tetraoxaspiro [5.5] undecane), and 4DO (1,4-Butanediol) may be at least one selected from the group consisting of.

Monomer type monocarboxylic acid code name English name chemical structural formula AcOH Acetic acid

AA Acrylic acid

MAA Methacrylic acid

TBBA 4-tert-Butylbenzoic acid

PBA Biphenyl-4-carboxylic acid

FPAC 4-Fluorophenylacetic acid

6FB 3,5-Bis(trifluoromethyl)benzoic acid

For example, the carboxyl group-containing double bond monomer may be at least one selected from the group consisting of acrylic acid and methacrylic acid.

For example, the double bond-free monocarboxylic acid monomer is AcOH (Acetic acid), TBBA (4-tert-Butylbenzoic acid), PBA (Biphenyl-4-carboxylic acid), FPCA (4-Fluorophenylacetic acid), and 6FB (3,5-Bis(trifluoromethyl)benzoic acid) may be at least one selected from the group consisting of.

[Scheme 2]

BP-1-1

In the vicardo-based binder polymer including the structural unit represented by BP-1-1, n is an integer of 1 to 20.

A representative synthesis example of the vicardo-based binder polymer according to the present invention is shown in Scheme 2 above. Looking at the process of synthesizing the non-cardo-based binder polymer in Scheme 2, commercially available cyclohexyl dimethylol diglycidyl ether (CHEP) was used as the starting material, and the detailed synthesis process is as follows.

In a 100 mL three-necked flask under nitrogen atmosphere, 3.1 g of PGMEA solvent, 5 mmol of CHEP, 11 mmol of AA, 0.025 mmol of BHT as a polymerization inhibitor, and 0.05 mmol of TBPB as catalyst were added and stirred at 110° C. for 3 hours to obtain an epoxyacrylate intermediate, here 5 mmol of 6FDA and additional 2.7 g of PGMEA were added, and condensation polymerization was performed while stirring at 110° C. for 3 hours to obtain a non-cardo-based binder polymer BP-1-1 having an acrylic double bond and a carboxyl (-COOH) group. The reaction is a one-pot reaction method to obtain an epoxyacrylate intermediate first without separation of the intermediate in one reactor, and secondly to obtain a vicardo-based binder polymer containing an acrylic double bond group and -COOH. A process for synthesizing a final compound at low cost using a simple reaction apparatus is provided. In the non-cardo-based binder polymer represented by BP-1-1 shown in Scheme 2, the carboxyl group present in the main chain reacts with the developing solution, TMAH basic aqueous solution, and is ionized, so it is changed to a water-soluble polymer and removed, contributing to the formation of the PDL pattern of the OLED device. . The vicardo-based binder shown in Scheme 2 may have a weight average molecular weight (Mw) in the range of 1,000 to 4,000 g/mol depending on reaction conditions as a result of polymer gel permeation chromatography (GPC) measurement.

[Scheme 3]

In Scheme 2, a black photosensitive resin using cyclohexyl dimethyl diglycidyl ether (CHEP) as a starting material instead of bisglycidyloxyphenyl fluorene (FEP), which is a starting material of a commercial cardo-based binder polymer. A method for synthesizing the non-cardo-based binder polymer of the composition was presented. In Scheme 3, the first-step reaction was shown using JEP, REP, SIEP and BEP as starting materials serving the same function other than CHEP instead of FEP, which is the starting material of a commercial cardo-based binder polymer. The remaining reaction steps of synthesizing non-cardo-based binder polymers (BP-1-2, BP-1-3, BP-1-4, BP-1-5) using JEP, REP, SIEP and BEP as starting materials; and Reaction conditions are similar to those of Scheme 2, and thus are omitted. The results of GPC molecular weight analysis of the vicardo-based binder polymer (BP-1-5) are shown in FIG. 1 .

[Scheme 4]

BP-2-1

In the non-cardo-based binder polymer including the structural unit represented by BP-2-1, n is an integer of 1 to 20.

In Scheme 4, when synthesizing a vicardo-based binder polymer using CHEP as a starting material, acetic acid (AcOH) as another organic acid was added together with acrylic acid (AA) to indicate that the first step reaction for synthesizing the vicardo-based binder polymer was performed. it was In the first stage reaction, three types of mixtures are produced, but they all have two alcohol groups for the next stage of condensation polymerization, so they are polymerized with a dianhydride monomer (for example, 6FDA) to form a non-cardo-based binder polymer BP-2-1. can be synthesized. Detailed reaction conditions are as follows.

In a 100mL 3-neck flask under nitrogen atmosphere, 3.0 g of PGMEA solvent, 5 mmol of CHEP, 5.5 mmol of AA, 5.5 mmol of AcOH, 0.0125 mmol of BHT as a polymerization inhibitor, and 0.05 mmol of TBPB as catalyst were added and stirred at 110°C for 3 hours to obtain an epoxyacrylate intermediate. Obtained, 6FDA and additionally 2.7 g of PGMEA solvent were added thereto, and condensation polymerization was carried out while stirring at 110° C. for 3 hours again. polymer was obtained.

The vicardo-based binder polymer represented by BP-2-1 shown in Scheme 4 may have a weight average molecular weight (Mw) in the range of 2,000 to 4,000 g/mol depending on reaction conditions.

[Scheme 5]

In Scheme 5, CHEP is used as a starting material for synthesizing the non-cardo-based binder polymer as in Scheme 4, but as another organic acid to react with acrylic acid (AA), the first step reactions using various organic acids other than acetic acid (AcOH) are shown. will be.

As other organic acids other than acrylic acid (AA), using the first-step reaction products synthesized using PBA, TBBA, FPAC, and 6FB, respectively, as in Scheme 4, condensation polymerization reaction with 6FDA and other dianhydride monomers was carried out to BP- Bicado-based binder polymers respectively represented by 2-2, BP-2-3, BP-2-4, and BP-2-5 can be synthesized.

[Scheme 6]

BP-3-1

In the non-cardo-based binder polymer including the structural unit represented by BP-3-1, m and n are each independently an integer of 1 to 20.

Scheme 6 shows a one-step reaction of synthesizing acrylic acid (AA) and a vicardo-based binder polymer using disiloxane diepoxide (SIEP) among diepoxides. In the two-step reaction, it was shown that a non-cardo-based binder polymer was synthesized by copolymerization (condensation polymerization) with a dianhydride monomer (6FDA) using SDO in a diol monomer together with the diol intermediate synthesized in the first step reaction. Detailed reaction conditions are as follows.

In a 100 mL three-necked flask under a nitrogen atmosphere, 2.5 g of PGMEA solvent, 3 mmol of SIEP, 6 mmol of AA, 0.03 mmol of BHT as a polymerization inhibitor, and 0.1 mmol of TBPB as catalyst were added and stirred at 110° C. for 3 hours to obtain a diol intermediate, which was copolymerized 2 mmol of monomer SDO, 5 mmol of 6FDA and additionally 4.3 g of PGMEA solvent were added, and condensation polymerization was performed while stirring at 110 ° C. for 3 hours. -1) was obtained.

The non-cardo-based binder polymer (BP-3-1) shown in Scheme 6 may have a weight average molecular weight (Mw) in the range of 2,000 to 8,000 g/mol depending on reaction conditions.

[Scheme 7]

In the vicardo-based binder polymer including the structural units represented by BP-3-2 and BP-3-3, m and n are each independently an integer of 1 to 20.

In Scheme 7, the structure of the vicardo-based binder polymers obtained by using the diol intermediate obtained in the first step reaction of Scheme 6 as it is and using the SDO diol monomer of Scheme 6 and other diol monomers XDO and 4DO, respectively, is shown. The two-step reaction of Scheme 7 was carried out under the same conditions as the two-step reaction of Reaction Scheme 6, and vicardo-based binder polymers having the same structural units as BP-3-2 and BP-3-3, respectively, were obtained. As a result of GPC molecular weight analysis, the vicardo-based polymer (BP-3-2) showed a high weight average molecular weight (Mw) of 8,210 g/mol as shown in FIG. 2 , which is considered to be due to the high molecular weight of each of the structural units.

In one embodiment of the present application, the first step may be a step of reacting a non-cardo-based diepoxide compound and a carboxyl group-containing double bond monomer. This step is a necessary step for preparing a non-cardo-based binder polymer including structural units represented by BP-1-1 to BP-1-5 and BP-3-1 to BP-3-3 among the non-cardo-based binder polymers. can

In one embodiment of the present application, the first step may be a step of reacting a non-cardo-based diepoxide compound, a carboxyl group-containing double bond monomer, and a double bond-free monocarboxylic acid monomer. This step may be a step necessary for preparing the non-cardo-based binder polymer including the structural units represented by BP-2-1 to BP-2-5 among the non-cardo-based binder polymers.

In one embodiment of the present application, the non-cardo-based binder polymer comprises a first step of reacting a non-cardo-based diepoxide compound and a carboxyl group-containing compound; It can be obtained by a manufacturing method comprising a second step of condensation-copolymerizing the compound produced in the first step with a diol monomer and a dianhydride monomer, wherein the compounds represented by BP-3-1 to BP-3-3 A non-cardo-based binder polymer including a structural unit can be obtained.

In one embodiment of the present application, the photosensitive resin composition, about 3 wt% to about 8 wt% of the photopolymerization initiator, about 1 wt% to about 3 wt% of the photosensitizer, about 3 wt% to the polyfunctional monomer about 12% by weight, about 30% to about 60% by weight of the black dye, and about 15% to about 40% by weight of the vicardo-based binder polymer, and the remaining amount of the solvent, for example, 5% to 20% by weight It may be included in weight %, but may not be limited thereto.

For example, the photosensitive resin composition may include about 3 wt% to about 6 wt%, about 3 wt% to about 8 wt%, or about 5 wt% to about 8 wt% of the photopolymerization initiator, This may not be limited. For example, the photosensitive resin composition may include about 1 wt% to about 2 wt%, about 2 wt% to about 3 wt%, about 1 wt% to about 3 wt% of the photosensitizer, This may not be limited. For example, the photosensitive resin composition comprises about 3 wt% to about 6 wt% of the polyfunctional monomer, about 3 wt% to about 7 wt%, about 3 wt% to about 10 wt%, about 3 wt% to about 12 wt%, about 5 wt% to about 7 wt%, about 5 wt% to about 10 wt%, about 5 wt% to about 12 wt%, about 6 wt% to about 10 wt%, or about 6 wt% to about 12% by weight, but may not be limited thereto. For example, the photosensitive resin composition may include about 30 wt% to about 60 wt% of the black dye pigment, about 30 wt% to about 59 wt%, about 30 wt% to about 58 wt%, about 30 wt% to about 57%, about 35% to about 56%, about 35% to about 60%, about 35% to about 60%, about 40% to about 60%, about 40% to about 60% by weight, or about 45% to about 60% by weight may be included, but may not be limited thereto. For example, the photosensitive resin composition may include about 1% to about 3% by weight, about 3% to about 5% by weight, or about 1% to about 5% by weight of the dispersant, but is limited thereto it may not be For example, the photosensitive resin composition may include about 15 wt% to about 40 wt% of the vicardo-based binder polymer, about 15 wt% to about 35 wt%, about 15 wt% to about 30 wt%, about 15 wt% to About 25% by weight, about 17% by weight to about 35% by weight, or about 20% by weight to about 30% by weight may be included, but may not be limited thereto. For example, the solvent is, in the photosensitive resin composition, the photopolymerization initiator, the photosensitizer, the polyfunctional monomer, the black dye, the dispersant, and the vicardo-based binder polymer. However, it may not be limited thereto.

In one embodiment of the present application, the solvent may include a PGMEA (propyleneglycol monomethylether acetate) single solvent, or a PGMEA mixed solvent in which PGMEA and other solvents of about 85% by weight or more are mixed, and the PGMEA mixed solvent The other solvent included in DMAc (N,N-dimetylacetamide), EGME (ethylene glycol monomethyl ether), and PGME (propylene glycol methyl ether) may be at least one selected from the group consisting of, but may not be limited thereto. For example, the solvent may be about 85% by weight of PGMEA and the other solvents mixed, about 90% PGMEA and the other solvents mixed, about 95% PGMEA and the other solvents mixed by weight. It may be a mixture of about 98% by weight of PGMEA and the other solvents, or PGMEA alone, but may not be limited thereto.

For example, the solvent included in the photosensitive resin composition may be selected in consideration of various aspects from the viewpoint of environmental and human harm, and similar to the solvent used in the negative photosensitive resin composition used for purposes other than OLED. PGMEA may be used as the solvent, but may not be limited thereto. For example, all components other than the solvent included in the photosensitive resin composition have excellent compatibility with the solvent, and may be completely dissolved in the solvent to form a true solution, but is not limited thereto. it may not be For example, the black millbase, which may be included as the black dye pigment in the photosensitive resin composition, is also uniformly sized to a size of about 50 nm or less in the solvent by surface treatment or adding a dispersant to the organic dye pigment. It may be used in the form of a dispersed dispersion, but may not be limited thereto.

In one embodiment of the present application, the vicardo-based binder polymer may be completely dissolved in the solvent to form a true solution, but may not be limited thereto. It is suitable for the vicardo-based binder polymer to have complete solubility in the solvent, like other components included in the photosensitive resin composition. For example, when the vicardo-based binder polymer does not have complete solubility in the solvent, it affects the dispersion state of the black dye pigment dispersion to form aggregates or coagulates larger than microns in size. Therefore, by making the edge line of the black pixel compartment layer pattern for OLED formed through the photolithography process in a jagged shape or by increasing the roughness of the upper surface layer, the desired purpose of the black pixel compartment layer pattern for high-definition OLED may make it difficult to form, but may not be limited thereto.

In one embodiment of the present application, the non-cardo-based binder polymer may have a weight average molecular weight of about 1,000 g/mol to about 15,000 g/mol, about 2,000 g/mol to about 10,000 g/mol, but may not be limited thereto. there is.

According to one embodiment, a photopolymerization initiator; photosensitizers; polyfunctional monomers; additive; black dye; vicardo-based binder polymer; and a solvent, wherein the non-cardo-based binder polymer includes at least one of the structural units described in Group 1 below.

[Group 1]

BP-1-1

BP-1-2

BP-1-3

BP-1-4

BP-1-5

BP-2-1

BP-2-2

BP-2-3

BP-2-4

BP-2-5

BP-3-1

BP-3-2

BP-3-3

In group 1,

m and n are each independently an integer from 1 to 20.

The composition of the photosensitive resin composition is as described above.

The present application, using the photosensitive resin composition of the first aspect of the present application, may provide a photolithography (photolithography) process.

The photolithography process may include a coating process of applying the photosensitive resin composition; a soft bake process of heat-treating after the application process; exposure process using ultraviolet rays; a hard bake process of heat-treating after the exposure process; developing process using an alkaline solution; cleaning process; drying process; and a post cure process may be sequentially included, but may not be limited thereto.

For example, the photolithography process may further include a nitrogen gas spraying process after the cleaning process and before the drying process, but may not be limited thereto.

In one embodiment of the present application, the application process may include using a spin coating method, but may not be limited thereto. For example, the application process may be performed once or may be repeatedly performed a plurality of times, but may not be limited thereto. For example, the application process may be performed once using the photosensitive resin composition according to the first aspect of the present application, and may be additionally performed once using a conventional photosensitive resin composition, but may not be limited thereto. . Or, for example, the application process is performed once using the photosensitive resin composition in which only the black dye is removed from the photosensitive resin composition according to the first aspect of the present application, and then the photosensitive resin composition according to the first aspect of the present application It may be one additionally performed using, but may not be limited thereto. For example, when the coating process is repeatedly performed a plurality of times, the soft bake process may also be additionally performed between the coating processes, but may not be limited thereto.

In one embodiment of the present application, the soft bake process may be performed at about 110° C. for about 100 seconds, the hard bake process may be performed at about 100° C. for about 120 seconds, and the post-curing process is about It may be carried out at 230° C. for about 30 minutes, but may not be limited thereto.

For example, the photolithography process may include: the coating process of spin coating (about 5000 rpm) the photosensitive resin composition in a range of about 0.1 μm to about 1.5 μm; the soft bake process of heat-treating for a time of about 50 seconds to about 150 seconds at a temperature range of about 80° C. to about 120° C. after the application process; the exposure process of performing ultraviolet exposure of about 80 mJ to about 150 mJ; the hard bake process of heat-treating for a time of about 50 seconds to about 150 seconds at a temperature range of about 80 °C to about 120 °C after the exposure process; the developing process performed using about 2.0 wt% to about 3.0 wt% of an aqueous tetramethylammonium hydroxide (TMAH) solution as an alkaline solution; the cleaning process performed for about 20 seconds to about 1 minute using pure water; a nitrogen gas spraying process of spraying nitrogen gas for about 5 seconds to about 15 seconds; the drying process being performed for about 20 seconds to about 1 minute in ambient temperature atmosphere; and the post-curing process performed in a temperature range of about 200° C. to about 300° C. for a time of about 20 minutes to about 40 minutes, but may not be limited thereto.

For example, by performing the post-curing process, the heat resistance of the black pixel compartment layer obtained through the photolithography process may be further improved, and the manufacturing yield of the OLED device may be further improved, but may not be limited thereto. . For example, by performing the post-curing process, it is possible to introduce a taper angle to the pattern of the black pixel compartment layer obtained through the photolithography process, thereby preventing leakage current, and ultimately, the lifetime of the OLED device. may be improved, but may not be limited thereto.

In one embodiment of the present application, the developing process may include using a tetramethylammonium hydroxide (TMAH) aqueous solution having an appropriate concentration range, but may not be limited thereto. In one embodiment of the present application, the developing process may include using about 2.0 wt% to about 3.0 wt% of an aqueous TMAH solution, but may not be limited thereto. For example, the developing process may include, without limitation, an alkaline aqueous solution normally used in the developing process in addition to the TMAH aqueous solution, and may not be limited to any one type of developer.

The black PDL fine pattern of the OLED device obtained by using the photolithography process of the black photosensitive resin composition has a thickness of about 1.0 to 1.5 μm after post-heat treatment. After the photolithography process, the 10Х10 ㎛ size wafer surface, where the black PDL thin film layer has been developed, is a pixel part on which the OLED light emitting material is laminated. If undeveloped nanometer-sized spots or impurities exist in this area, the impurities will act as a cause of dark point formation during long-term use of the OLED device manufactured after the organic material deposition of the OLED pixel, thereby preventing deterioration of the OLED device. because it promotes

The key factor affecting the purity of the PDL pattern surface after the photolithography process of the black photosensitive resin composition is the binder polymer. Because it contains (-CF ₃ ) groups, it has excellent compatibility with black dye pigments made using PGMEA solvent, which is an important factor in spot formation, and does not form fine aggregates when mixing the two components. leaving no impurities.

In one embodiment of the present application, the photolithography process may further include, before the application process, a pre-coating process of applying the photosensitive resin composition - removing the black dye pigment from which the black dye is removed from the photosensitive resin composition. , which may not be limited thereto.

For example, in the photolithography process, a black dye removal-photoresist composition (first photosensitive resin composition) from which the black dye is removed from the photosensitive resin composition is spin coated in a range of about 0.1 μm to about 1 μm. the pre-applying process; the soft bake process of heat-treating for a time of about 50 seconds to about 150 seconds at a temperature range of about 80° C. to about 120° C. after the pre-coating process; the application process of spin-coating the photosensitive resin composition (second photosensitive resin composition; photosensitive resin composition according to an embodiment) in a range of about 0.5 μm to about 1.5 μm; the soft bake process of heat-treating for a time of about 50 seconds to about 150 seconds at a temperature range of about 80° C. to about 120° C. after the application process; the exposure process of performing ultraviolet exposure of about 80 mJ to about 150 mJ; the hard bake process of heat-treating for a time of about 50 seconds to about 150 seconds at a temperature range of about 80 °C to about 120 °C after the exposure process; the above developing process performed using about 2.0 wt% to about 3.0 wt% of an aqueous TMAH solution as an alkaline solution; the cleaning process performed for about 20 seconds to about 1 minute using pure water; a nitrogen gas spraying process of spraying nitrogen gas for about 5 seconds to about 15 seconds; the drying process being performed for about 20 seconds to about 1 minute in ambient temperature atmosphere; and the post-curing process performed in a temperature range of about 200° C. to about 300° C. for a time of about 20 minutes to about 40 minutes, but may not be limited thereto.

For example, when the multilayer film structure is formed in a manner including the pre-applying process, the thin film layer not containing the black dye pigment is located under the thin film layer containing the black dye pigment, and when exposed to ultraviolet rays, ultraviolet rays There is an advantage that a black pixel pattern can be obtained in a sophisticated shape by increasing the reach depth, and the residue, which is a fine lump including a black dye, does not remain in the unexposed area, so that the yield of manufacturing an OLED without black spots is increased. There is an advantage, and since the pixel size is increased to a nano size in an unexposed area by light scattering from the upper layer during UV exposure, an OLED pixel structure having a tapered angle that contributes to preventing leakage current when driving the OLED can be formed. However, it may not be limited thereto.

That is, when a PDL pattern for an OLED device is formed by a photolithography process using the method including the pre-coating process, fine agglomerates or impurities that cause dark spots in the OLED device can be thoroughly removed. This process is carried out by dividing the photolithography process for obtaining the PDL pattern into two steps. In the first process, the photosensitive resin composition that does not contain the black dye pigment dispersion dispersed in PGMEA during the preparation of the black photosensitive resin composition of the present invention is applied to the OLED device substrate. On top of that, spin coating and soft baking are performed first. In the secondary process, spin coating, soft baking, UV exposure, and even hard baking are performed using the photosensitive resin composition containing the black dye dispersion, followed by development and drying, and post-heat treatment. In this multilayer OLED device PDL pattern, there is no black pigment dispersion in the lower layer during the development process, so fine lumps or impurities are not left on the substrate by the TMAH 2.3% aqueous developer solution.

A second aspect of the present application provides a single-layer or multi-layer pixel compartment layer formed using the photosensitive resin composition of the first aspect of the present application.

Since the second aspect of the present application relates to a single-layer or multi-layer pixel partition layer formed using the photosensitive resin composition of the first aspect of the present application, that is, formed using the photolithography process, the description of the first aspect of the present application and Overlapping descriptions have been omitted, and various embodiments have been described below in detail, but the present application may not be limited thereto. Also, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted from the second aspect of the present application.

For example, when the photolithography process does not include the pre-coating process described above and includes only the application process once, a single-layer pixel partition layer may be obtained, and the single-layer pixel partition layer has a thickness of about 0.1 μm to about 0.1 μm. It may be about 1.0 μm thick, but may not be limited thereto.

For example, when the photolithography process includes a plurality of application processes by including the pre-coating process described above, a multilayer pixel partition layer may be obtained, wherein the multilayer pixel partition layer is a two-layer multilayer film The structure and thickness may be from about 0.5 μm to about 1.5 μm, but may not be limited thereto.

A third aspect of the present application provides an electronic device including the pixel traverse side of the second aspect of the present application.

The electronic device may include, but is not limited to, an organic light emitting diode, a liquid crystal display, or a touch screen panel. The negative-type black photosensitive resin composition of the present invention is a liquid crystal display device or a black column spacer formed between the TFT and the color filter substrate of the liquid crystal display device and the black matrix pattern formation of the liquid crystal display device. It can also be used to form a black bezel electrode pattern at the edge of a touch screen panel installed on an OLED display.

Hereinafter, preferred examples of the present application, comparative examples, and evaluation examples thereof will be described. However, the following examples are only examples of preferred embodiments of the present application, and the present application may not be limited to the following examples.

Example

1. Preparation and evaluation of photosensitive resin composition

The photosensitive resin compositions according to Example 1-1, Example 2-1, Example 3-1 and Comparative Example 1 were prepared according to the compositions shown in Table 5 below, and exposure sensitivity and double bond group concentration were measured and the results were obtained. It is shown in Table 5 below.

Example 1-1 Example 2-1 Example 3-1 Comparative Example 1 photopolymerization initiator SPI-03 (Samyang Corporation) 6.0 6.0 6.0 6.0 photosensitizer Darocure ITX (Ciba, Switzerland) 2.0 2.0 2.0 2.0 binder polymer CBP (see Scheme 1, 45 wt%, PGMEA) - - - 20 BP-1-1 (see Scheme 2, 40 wt%, PGMEA) 22 - - - BP-2-1 (see Scheme 4, 40 wt%, PGMEA) - 22 - - BP-3-1 (see Scheme 6, 40 wt%, PGMEA) - - 22 - polyfunctional monomer PETA 6.0 6.0 6.0 6.0 additive MSMA 1.0 1.0 1.0 1.0 menstruum PGMEA 7.0 7.0 7.0 9.0 black dye BK-4926 (Mikuni, Japan) 56 56 56 56 Sum weight% 100 100 100 100 exposure sensitivity mJ 100 100 100 120 double bond concentration Mmol/g polymer 2.37 1.18 1.13 2.22

As shown in Table 5, in Comparative Example 1 using a cardo-based binder polymer (CBP) in the black photosensitive resin composition, the presence of bulky fluorene groups present in FEA, the starting material, resulted in a crosslinking reaction of the double bond group The UV exposure sensitivity of Examples 1-1, 2-1 and 3-1 in which a vicardo-based binder polymer was used in the black photosensitive resin composition was required to be as high as 120 mJ due to a large steric hinderance effect. It can be confirmed that it is excellent at 100 mJ.

2. Preparation and evaluation of photosensitive resin composition

Exposure sensitivities were prepared by preparing photosensitive resin compositions according to Examples 1-1 to 1-5, Examples 2-1 to 2-5, and Examples 3-1 to 3-3 according to the compositions shown in Tables 6 to 8 below. And the double bond group concentration was measured, and it was confirmed what composition could further lower the exposure sensitivity. In addition, after performing the photolithography process in each of the above examples, the pixel partition layer pattern formability and the degree of black residue were confirmed and shown in Tables 6 to 8 below.

photosensitive resin composition
ingredient Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 photopolymerization initiator SPI-03 (Samyang Corporation) 6.0 6.0 6.0 6.0 6.0 photosensitizer Darocure-ITX (ciba, Switzerland) 2.0 2.0 2.0 2.0 2.0 Vicardo-based binder polymer BP-1-1
(40 wt% PGMEA solution) 22 - - - - BP-1-2
(40 wt% PGMEA solution) - 22 - - - BP-1-3 (40 wt% PGMEA solution) - - 22 - - BP-1-4 (40 wt% PGMEA solution) - - - 22 - BP-1-5 (40 wt% PGMEA solution) - - - - 22 multifunctionality
monomer PETA 6.0 6.0 6.0 6.0 6.0 participation system MSMA 1.0 1.0 1.0 1.0 1.0 menstruum PGMEA 7.0 7.0 7.0 7.0 7.0 black dye BK-4926
(MIKUNI, Japan) 56 56 56 56 56 Sum weight % 100 100 100 100 100 pixel block layer pattern Good(1) to Bad(5) 3 4 4 2 2 exposure sensitivity mJ 100 50 60 80 80 double bond concentration mmol/g polymer 2.37 2.38 2.38 2.06 2.15 black residue Good(1) to Bad(5) 3 4 4 2 2

When BP-1-2 and BP-1-3 were used as vicardo polymers, the UV exposure sensitivity was good at 50 and 60 mJ, but the PDL pattern was poor and fine black spots (black residues) were high after development and drying. This is interpreted as over-crosslinking by UV light because the double bond group concentration is too high and the steric hindrance effect is small. FIG. 3 shows a PDL pattern optical microscope (OM) photograph of an OLED device obtained as a result of a photolithography process using a black photosensitive resin composition including a structural unit represented by the vicardo-based polymer BP-1-2.

When a non-cardo-based binder polymer containing each of the structural units represented by BP-1-4 and BP-1-5 is used, the double bond group concentration is low and there is a relatively steric hindrance effect, so the UV sensitivity is suitable, and the PDL pattern and black residue The evaluation was also found to be excellent.

In Table 7 below, CHEP is used as a diepoxide starting material, and a diol intermediate produced after performing a one-step reaction with acrylic acid (AA) and acetic acid (AcOH) at 50:50 mol% compared to CHEP is subjected to condensation polymerization with 6FDA dianhydride A non-cardo-based binder polymer (BP-2) using a non-cardo-based binder polymer (BP-2-1) obtained through polyesterification and various monocarboxylic acids having a molecular weight and molecular size larger than that of acetic acid instead of acetic acid (AcOH) in the above reaction -2, BP-2-3, BP-2-4, BP-2-5) were obtained and the photolithography process characteristics of black photosensitive resin compositions using them were investigated.

photosensitive resin composition
ingredient Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 photopolymerization initiator SPI-03 (Samyang Corporation) 6.0 6.0 6.0 6.0 6.0 photosensitizer Darocure-ITX (ciba, Switzerland) 2.0 2.0 2.0 2.0 2.0 Vicardo-based binder polymer BP-2-1
(40 wt% PGMEA solution) 22 - - - - BP-2-2
(40 wt% PGMEA solution) - 22 - - - BP-2-3 (40 wt% PGMEA solution) - - 22 - - BP-2-4 (40 wt% PGMEA solution) - - - 22 - BP-2-5 (40 wt% PGMEA solution) - - - - 22 multifunctionality
monomer PETA 6.0 6.0 6.0 6.0 6.0 additive MSMA 1.0 1.0 1.0 1.0 1.0 menstruum PGMEA 7.0 7.0 7.0 7.0 7.0 black dye BK-4926
(MIKUNI, Japan) 56 56 56 56 56 Sum weight % 100 100 100 100 100 pixel block layer pattern Good(1) to Bad(5) 4 3 3 3 One exposure sensitivity mJ 100 50 60 80 80 double bond concentration mmol/g polymer 1.18 1.03 1.05 1.08 0.97 black residue Good(1) to Bad(5) 4 3 3 3 One

Referring to Table 7, when the structural unit-containing binder polymer represented by BP-2-1 was used, the PDL pattern, exposure sensitivity and black color were slightly higher than when the structural unit-containing binder polymer represented by BP-1-1 of Table 6 was used. Residue evaluation was improved, which seems to be the effect of reducing the amount of double bond causing crosslinking because the amount of acrylic acid (AA) is reduced using acetic acid (AcOH). Meanwhile, in the case of the black photosensitive resin composition using non-cardo-based binder polymers obtained by using monocarboxylic acids having a molecular size larger than that of acetic acid (AcOH), the PDL pattern formation was slightly improved as shown in FIG. 4 . In the case of the black photosensitive resin composition using the binder polymer containing the structural unit represented by BP-2-5, the evaluation of the photolithography process such as the PDL pattern was improved. It is considered that overcure between double bond groups in the binder polymer is reduced due to a steric hinderance effect when monocarboxylic acids having a large molecular size are used.

Looking at the evaluation of the photolithography process characteristics for obtaining the PDL micropattern of the OLED device in Tables 6 and 7 above, in the case of the black photosensitive resin composition using the vicardo-based binder polymer, the molar concentration of the double bond group per repeating unit of the main chain of the binder polymer ( mmol/g binder polymer) has a significant effect on PDL micro-pattern formation. That is, when the molar concentration of the double bond group per repeating unit of the binder polymer main chain is large, the UV exposure sensitivity is excellent, but the crosslinking reaction of the double bond groups increases, thereby reducing the PDL pattern or increasing the black residue. In Table 7 above, in order to reduce the molar concentration of double bond groups per repeating unit of the binder polymer main chain, when the diepoxide starting material is reacted with acrylic acid (AA) and acetic acid (AcOH), which is not a double bond group, or monocarboxylic acids with a large molecular size, PDL It was confirmed that the photolithography process for forming fine patterns was improved.

In Table 8 below, SIEP having a large molecular weight is used as the diepoxide starting material for synthesizing the non-cardo-based binder polymer, and a diol intermediate obtained by reacting SIEP with acrylic acid (AA) is first synthesized, and then a diol without a double bond group (SDO, etc.) It was mixed with 50:50 mol% and then subjected to condensation copolymerization with 6FDA dianhydride to evaluate the vicardo-based binder polymer (BP-3-1). And the photolithography process characteristics were also evaluated for vicardo-based binder polymers (BP-3-2 and BP-3-3) obtained using the same method and using XDO and 4DO as diols without a double bond group.

photosensitive resin composition
ingredient Example 3-1 Example 3-2 Example 3-3 photopolymerization initiator SPI-03 (Samyang Corporation) 6.0 6.0 6.0 photosensitizer Darocure-ITX (ciba, Switzerland) 2.0 2.0 2.0 Vicardo-based binder polymer BP-3-1
(40 wt% PGMEA solution) 22 - - BP-3-2
(40 wt% PGMEA solution) - 22 - BP-3-3 (40 wt% PGMEA solution) - - 22 multifunctionality
monomer PETA 6.0 6.0 6.0 additive MSMA 1.0 1.0 1.0 menstruum PGMEA 7.0 7.0 7.0 black dye BK-4926
(MIKUNI, Japan) 56 56 56 Sum weight % 100 100 100 pixel block layer pattern Good(1) to Bad(5) 3 One 4 exposure sensitivity mJ 100 50 60 double bond concentration mmol/g polymer 1.13 1.10 1.24 black residue Good(1) to Bad(5) 3 One 2

As shown in Table 8, in the case of the structural unit-containing binder polymer represented by BP-3-1, it can be seen that the characteristics of the PDL micropattern of the OLED are slightly improved as the molar concentration of double bond groups per repeating unit is decreased. However, in the case of the black photosensitive resin composition containing the structural unit-containing binder polymer represented by BP-3-3 having a small molecular weight and molecular size of the diol monomer, the steric hindrance effect of the double bond group is remarkably reduced, thereby preventing the deterioration of the PDL micropattern. Able to know. On the other hand, in the case of the structural unit-containing binder polymer represented by BP-3-2, as shown in FIG. 5 , it can be seen that the double bond group molar concentration is reduced and the steric hindrance effect is increased, so that the PDL fine pattern formation process is remarkably improved.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and this is also It goes without saying that it falls within the scope of the invention.

Claims (17)

photoinitiator;
photosensitizers;
polyfunctional monomers;
black dye;
vicardo-based binder polymer;
additive; and
menstruum
including,
The non-cardo-based binder polymer is prepared in a first step of reacting a non-cardo-based diepoxide compound, a carboxyl group-containing double bond monomer, and a double bond-free monocarboxylic acid monomer; and
After the first step, a second step of condensation reaction with a dihydride monomer
Obtained by a manufacturing method comprising a,
A photosensitive resin composition.
According to claim 1,
The photosensitive resin composition is a black negative photosensitive resin composition for forming a pixel partition layer of an organic light emitting diode,
A photosensitive resin composition.
According to claim 1,
The photosensitive resin composition, with respect to the total amount of the photosensitive resin composition,
3 wt% to 8 wt% of the photopolymerization initiator;
1 wt% to 3 wt% of the photosensitizer;
3% to 12% by weight of the polyfunctional monomer;
0.5% to 2% by weight of the additive;
30% to 60% by weight of the black dye,
15% to 40% by weight of the vicardo-based binder polymer, and
5% to 20% by weight of the solvent
containing,
A photosensitive resin composition.
delete delete According to claim 1,
A first step of reacting the non-cardo-based binder polymer with a non-cardo-based diepoxide compound, a carboxyl group-containing double bond monomer, and a double bond-free monocarboxylic acid monomer; and
a second step of condensation-copolymerizing the compound produced in the first step with a diol monomer and a dianhydride monomer;
Obtained by a manufacturing method comprising a,
A photosensitive resin composition.
According to claim 1,
The vicardo-based diepoxide compound is
CHEP (1,4-Cyclohexanedimethanol diglycidyl ether),
JEP (3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate),
Resorcinol diglycidyl ether (REP);
SIEP (1,3-Bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane), and
BEP (Bisphenol A diglycidyl ether)
At least one selected from the group consisting of
A photosensitive resin composition.
According to claim 1,
The dihydride monomer is
6FDA (4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride),
MCDA (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride), and
BPDA (4,4'-Biphthalic Anhydride (purified by sublimation))
At least one selected from the group consisting of
A photosensitive resin composition.
According to claim 1,
The carboxyl group-containing double bond monomer,
At least one selected from the group consisting of acrylic acid and methacrylic acid,
A photosensitive resin composition.
According to claim 1,
The double bond-free monocarboxylic acid monomer,
AcOH (Acetic acid),
TBBA (4-tert-Butylbenzoic acid),
Biphenyl-4-carboxylic acid (PBA),
FPCA (4-Fluorophenylacetic acid), and
6FB (3,5-Bis(trifluoromethyl)benzoic acid)
At least one selected from the group consisting of
A photosensitive resin composition.
7. The method of claim 6,
The diol monomer is
SDO (Bis [4- (2-hydroxyethoxy) phenyl] Sulfone),
XDO (3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane), and
4DO (1,4-Butanediol)
At least one selected from the group consisting of
A photosensitive resin composition.
According to claim 1,
The solvent is
Contains PGMEA (propyleneglycol monomethylether acetate) single solvent, or PGMEA mixed solvent in which PGMEA and other solvents are mixed,
The other solvent included in the PGMEA mixed solvent is,
DMAc (N,N-dimetylacetamide),
EGME (ethylene glycol monomethyl ether), and
PGME (propylene glycol methyl ether)
At least one selected from the group consisting of
A photosensitive resin composition.
According to claim 1,
The additive is an acrylic monomer containing an alkoxysilane group or a methacrylic monomer containing an alkoxysilane group. The photosensitive resin composition.
14. The method of claim 13,
The additive is a photosensitive resin composition comprising MSMA (3-(Trimethoxysilyl)propyl methacrylate).
delete Formed using the photosensitive resin composition of claim 1,
pixel block layer.
An electronic device comprising the pixel compartment layer of claim 16 .

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