KR102360718B1 - Negative-tone black photoresist with polyester-imide binder polymer and electronic devices by using the same - Google Patents

Abstract

The present invention provides a binder polymer for a photosensitive resin composition, a manufacturing method thereof, a photosensitive resin composition comprising the same, a pixel partition layer formed using the same, and an electronic device.
A method for producing a binder polymer for a photosensitive resin composition according to an embodiment of the present invention comprises: a first reaction step comprising imidating at least one of amino acids and amino alcohols, and dianhydride; and a second reaction step in which the product generated in the first reaction step is subjected to a condensation polymerization reaction with at least one of a dianhydride monomer, a diol copolymerized monomer having a double bond, and a diepoxide.

Description

Polyester-imide binder polymer containing black photosensitive resin composition and electronic device using same {NEGATIVE-TONE BLACK PHOTORESIST WITH POLYESTER-IMIDE BINDER POLYMER AND ELECTRONIC DEVICES BY USING THE SAME}

The present invention relates to a binder polymer for a photosensitive resin composition, a manufacturing method thereof, a photosensitive resin composition comprising the same, a pixel partition layer formed using the same, and an electronic device. More specifically, a binder polymer for a photosensitive resin composition used to form a pixel partition layer of an organic light emitting diode and fine patterns of other electronic devices, a manufacturing method thereof, a photosensitive resin composition comprising the same, a pixel partition layer formed using the same, and It relates to electronic devices.

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, a polymer containing a cardo moiety having excellent heat resistance is used as a binder polymer, and a photoinitiator, a polyfunctional monomer, a black pigment, and an additive are dissolved and dispersed in an organic solvent. A black negative photosensitive resin composition Development to improve the problems of OLED devices using

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 (photoresist) having excellent heat resistance, chemical resistance, and blackness as well as excellent precision of a fine pattern to be formed. Another embodiment of the present invention is to provide an OLED, a liquid crystal display device, a touch screen panel, etc. manufactured using the negative photosensitive resin composition.

A method for preparing a binder polymer for a photosensitive resin composition according to an embodiment of the present invention includes: a first reaction step comprising imidating at least one of amino acids and amino alcohols, and dianhydride; and a second reaction step in which the product generated in the first reaction step is subjected to a condensation polymerization reaction with at least one of a dianhydride monomer, a diol copolymerized monomer having a double bond, and a diepoxide.

The first reaction step comprises an imidation reaction of an amino acid and a dianhydride to produce a dicarboxylic acid, and further comprising reacting the dicarboxylic acid product with a monoepoxide having a double bond to produce a diol and the second reaction step may be a condensation polymerization reaction of the diol product with a dianhydride monomer.

In this case, in the step of reacting a dicarboxylic acid product with a monoepoxide having a double bond to generate a diol, the monoepoxide having a double bond may be glycidyl methacrylate (GMA).

In this case, the step of reacting the dicarboxylic acid product with a monoepoxide having a double bond to generate a diol may be a reaction by further including a dicarboxylic acid monomer.

At this time, the dicarboxylic acid monomer is, 2,2-bis (4-carboxyphenyl) hexafluoropropane (2,2-Bis (4-carboxyphenyl) hexafluoropropane 6FDC), 4,4'-dicarboxydiphenyl ether (4, 4'-Dicarboxydiphenyl Ether (ODC), itaconic acid (ITC), methylene disalicylic acid (MLDC) and octafluoroadipic acid (8FDC) contains at least one of may be doing

In this case, the second reaction step may be a condensation polymerization reaction by further including a diol monomer.

In this case, the diol monomer is 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorine, FDO), bis[4 -(2-hydroxyethoxy)phenyl] sulfone (Bis[4-(2-hydroxyethoxy)phenyl] Sulfone, SDO), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2, 4,8,10-tetraoxaspiro [5.5] undecane (3,9-Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, XDO), and It may include one or more of 1,4-butanediol (1,4-Butanediol, 4DO).

Meanwhile, in the first reaction step, an imidization reaction of an amino alcohol and dianhydride is performed to generate a diol, and the second reaction step is condensation polymerization of the diol product with a diol copolymer monomer having a double bond and a dianhydride monomer It may be a reaction.

Meanwhile, the first reaction step is to imidize an amino acid and dianhydride to produce dicarboxylic acid, and the second reaction step is to condensation polymerization the dicarboxylic acid product with diepoxide, and the second reaction step It may further comprise the step of reacting the product produced in the anhydride having a double bond.

In this case, in the step of reacting the product generated in the second reaction step with an anhydride having a double bond, the anhydride may be itacone anhydride (ITA).

Amino acids are trans-4-(aminomethyl)cyclohexanecarboxylic acid (trans-4-(Aminomethyl)cyclohexanecarboxylic Acid, CYAA), 4-aminobenzoic acid (4-Aminobenzoic acid, 4-AB), 3-aminobenzoic acid ( 3-Aminobenzoic acid, 3-AB), 4-(aminomethyl)benzoic acid (AMBA), 4-aminophenylacetic acid (APAA), and β-alanine (β- Alanine, BAA) may be one containing one or more.

Amino alcohol is, ethanolamine (ETM), trans-4-aminocyclohexanol (trans-4-Aminocyclohexanol, CYAO), and 2- (4-aminophenyl) ethanol (2- (4-Aminophenyl) ethanol, APE) may include one or more of.

Dianhydride is 4-4'-(hexafluoroisopropylidene)di-phthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride, 6FDA), 5-(2,5-dioxytetra Hydropril)-3-methyl-3-cyclohexane-1,2-dicarboxyl anhydride (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride, MCDA) , and 4-4'-biphthalic anhydride (4,4'-Biphthalic Anhydride, BPDA).

The diol copolymer monomer having a double bond may include fluorene epoxy acrylate (FEA).

The diepoxide is 9-9-bis(4-glycidyloxyphenyl)fluorene (9,9-Bis(4-glycidyloxyphenyl)fluorine, FEP), 1,4-cyclohexanedimethanol diglycidyl ether (1,4-Cyclohexanedimethanol diglycidyl ether, CHEP), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (JEP), resorcinol diglycidyl ether (REP) ), and 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (1,3-Bis[ 2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, SIEP) may be included.

The binder polymer for the photosensitive resin composition according to an embodiment of the present invention is polyester-imide-based, and includes a repeating unit represented by Chemical Formula 1.

[Formula 1]

In Formula 1,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

The binder polymer for the photosensitive resin composition of another embodiment of the present invention is polyester-imide-based, and includes repeating units represented by Chemical Formulas 2 and 3.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Q is a linking group represented by at least one of the following formulas Q-1 to Q-6,

T includes a linking group represented by the following formula T-1.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Q-1]

[Formula Q-2]

[Formula Q-3]

[Formula Q-4]

[Formula Q-5]

[Formula Q-6]

[Formula T-1]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes a repeating unit represented by Formula 4-1 or Formula 4-2.

[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

Z ₁ is a linking group represented by at least one of the following formulas Z _1-1 to Z _1-3 ,

Z ₂ is a linking group represented by at least one of the following formulas Z ₂ -1 to Z ₂ -2,

R is a linking group represented by one or more of the following formulas R-1 to R-5.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula Z ₁ -1]

[Formula Z ₁ -2]

[Formula Z _1-3 ]

[Formula Z ₂ -1]

[Formula Z ₂ -2]

[Formula R-1]

[Formula R-2]

[Formula R-3]

[Formula R-4]

[Formula R-5]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes repeating units represented by Chemical Formulas 1 and 5.

[Formula 1]

[Formula 5]

In Formula 1 and Formula 5,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

W is a linking group represented by at least one of the following formulas W-1 to W-4.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula W-1]

[Formula W-2]

[Formula W-3]

[Formula W-4]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes repeating units represented by Chemical Formulas 1 and 6.

[Formula 1]

[Formula 6]

In Formula 1 and Formula 6,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

V is a linking group represented by at least one of the following formulas V-1 to V-5.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula V-1]

[Formula V-2]

[Formula V-3]

[Formula V-4]

[Formula V-5]

The photosensitive resin composition according to an embodiment of the present invention comprises: the binder polymer according to any one of claims 16 to 20; photoinitiator; photosensitizers; polyfunctional monomers; black dye; additive; and solvents.

The photosensitive resin composition may be a black negative photosensitive resin composition for forming a pixel compartment layer of an organic light emitting diode.

17 wt% to 40 wt% of binder polymer, 3 wt% to 8 wt% of photopolymerization initiator, 0.5 wt% to 3 wt% of photosensitizer, 3 wt% to 12 wt% of polyfunctional monomer, 37 wt% to 60 wt% black dye % by weight, 0.5% to 2% by weight of additives; And the solvent may be included in the balance.

The solvent includes a PGMEA (propyleneglycol monomethylether acetate) single solvent or a PGMEA mixed solvent in which 85% by weight or more of PGMEA and the balance of other solvents are mixed, and the other solvents are DMAc (N,N-dimetylacetamide), EGME (ethylene It may be at least one selected from the group consisting of glycol monomethyl ether), and propylene glycol methyl ether (PGME).

The pixel partition layer according to an embodiment of the present invention is formed using the above-described photosensitive resin composition.

An electronic device according to an embodiment of the present invention includes the above-described pixel partition layer.

An embodiment of the present invention is a polyester that is completely dissolved in a solvent of propylene glycol monomethylether acetate (PGMEA, hereinafter abbreviated as “PGMEA”) excellent in eco-friendliness to form a true solution- By providing a negative-type black photosensitive resin composition using an imide-based polymer as a binder polymer to form black PDL fine patterns of the OLED device, there is an effect of increasing the visibility by lowering the external light reflectance of the OLED device.

The polyester-imide-based binder polymer according to an embodiment of the present invention has excellent heat resistance and photosensitivity.

1 is a GPC graph showing the molecular weight of the polyester-imide-based binder polymer BP-001.
2 is a GPC graph showing the molecular weight of the polyester-imide-based binder polymer BP-002.
3 is an optical micrograph of a PDL pattern for OLED obtained by using the photosensitive resin composition Comparative Example 1.
4 is an optical micrograph of a PDL pattern for OLED obtained using the photosensitive resin composition Example 2;
5 is a PDL pattern optical micrograph for OLED obtained using the photosensitive resin composition Example 4;

The terms first, second and 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.

The terminology used herein 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. The meaning of "comprising," as used herein, specifies a particular characteristic, region, integer, step, operation, element and/or component, and includes the presence or absence of another characteristic, region, integer, step, operation, element and/or component. It does not exclude additions.

When a part is referred to as being “on” or “on” another part, it may be directly on or on the other part, or the other part may be involved in between. In contrast, when a part is referred to as being "directly above" another part, the other part is not interposed therebetween.

A "substituted" group is one in which one or more hydrogen atoms are replaced by one or more non-hydrogen atoms, provided that valence requirements are met and a chemically stable compound results from the substitution.

"Alkyl" generally means a straight-chain or branched saturated hydrocarbon group having the specified number of carbon atoms (i.e., C 1-6 alkyl refers to an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms, Cl -12 alkyl refers to an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms). Examples of alkyl groups include, without limitation, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, pent-1-yl, pent-2-yl, pent-3 -yl, 3-methylbut-1-yl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2,2-trimethyleth-1-yl, n-hexyl and the like .

"Alkenyl" means a straight-chain or branched hydrocarbon group having one or more unsaturated carbon-carbon bonds, generally having the specified number of carbon atoms. Examples of alkenyl groups include, without limitation, ethenyl, 1-propen-1-yl, 1-propen-2-yl, 2-propen-1-yl, 1-buten-1-yl, 1-butene- 2-yl, 3-buten-1-yl, 3-buten-2-yl, 2-buten-1-yl, 2-buten-2-yl, 2-methyl-1-propen-1-yl, 2 -methyl-2-propen-1-yl, 1,3-butadien-1-yl, 1,3-butadien-2-yl, and the like.

"Alkynyl" means a straight-chain or branched hydrocarbon group having one or more triple carbon-carbon bonds, generally having the specified number of carbon atoms.

Examples of alkynyl groups include, without limitation, ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 1-butyn-1yl, 3-butyn-1-yl, 3-butyne-2- yl, 2-butyn-1-yl, and the like.

"Alkanoyl" and "alkanoylamino" mean, respectively, alkyl-C(O)- and alkyl-C(O)-NH- containing the specified number of carbon atoms, generally including the carbonyl carbon, wherein Alkyl is as defined above. Examples of alkanoyl groups include, without limitation, formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, and the like.

"Alkenoyl" and "alkynoyl" mean alkenyl-C(O)- and alkynyl-C(O)-, respectively, where alkenyl and alkynyl are as defined above. Alkenoyl and alkinoyl generally contain the specified number of carbon atoms excluding the carbonyl carbon. Examples of alkenoyl groups include, without limitation, propenoyl, 2-methylpropenoyl, 2-butenoyl, 3-butenoyl, 2-methyl-2-butenoyl, 2-methyl-3-butenoyl, 3-methyl -3-butenoyl, 2-pentenoyl, 3-pentenoyl, 4-pentenoyl, and the like. Examples of alkinoyl groups include, without limitation, propinoyl, 2-butinoyl, 3-butinoyl, 2-pentinoyl, 3-pentinoyl, 4-pentinoyl, and the like.

"Alkoxy," "alkoxycarbonyl," and "alkoxycarbonylamino" are respectively alkyl-O-, alkenyl-O, and alkynyl-O; alkyl-O-C(O)-, alkynyl-O-C(O)-; and alkyl-O-C(O)-NH-, and alkynyl-O-C(O)-NH-, wherein alkyl, alkenyl, and alkynyl are as defined above. Examples of alkoxy groups include, without limitation, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, and the like. include Examples of alkoxycarbonyl groups include, without limitation, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, s-butoxycarbonyl, t-part toxycarbonyl, n-pentoxycarbonyl, s-pentoxycarbonyl, and the like.

“alkylamino,” “alkylaminocarbonyl,” “dialkylaminocarbonyl,” “alkylsulfonyl,” “alkylsulfinyl,” “sulfonylaminoalkyl,” and “alkylsulfonylaminocarbonyl” are each Alkyl-NH-, Alkyl-NH-C(O)-, Alkyl2-NC(O)-, Alkyl-S(02)-, Alkyl-S(=O)-, HS(02)-NH-alkyl- , and alkyl-S(O)-NH-C(O)-, wherein alkyl is as defined above.

"Aminoalkyl" and "cyanoalkyl" mean NH2-alkyl and N=C-alkyl, respectively, wherein alkyl is as defined above.

“Halo,” “halogen” and “halogeno” can be used interchangeably and refer to fluoro, chloro, bromo and iodo.

“haloalkyl,” “haloalkenyl,” “haloalkynyl,” “haloalkanoyl,” “haloalkenoyl,” “haloalkynoyl,” “haloalkoxy,” and “haloalkoxycarbonyl” are each alkyl, alkenyl, alkynyl, alkanoyl, alkenoyl, alkinoyl, alkoxy, and alkoxycarbonyl groups substituted with one or more halogen atoms, wherein alkyl, alkenyl, alkynyl, alkanoyl, alkenoyl, Alkinoyl, alkoxy, and alkoxycarbonyl are as defined above. Examples of haloalkyl groups include, without limitation, trifluoromethyl, trichloromethyl, pentafluoroethyl, pentachloroethyl, and the like.

"Hydroxyalkyl" and "oxoalkyl" refer to HO-alkyl and O=alkyl, respectively, wherein alkyl is as defined above. Examples of hydroxyalkyl and oxoalkyl groups include, without limitation, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, oxomethyl, oxoethyl, 3-oxopropyl, and the like.

"Cycloalkyl" means saturated monocyclic and bicyclic hydrocarbon rings having the specified number of carbon atoms, generally including the ring (ie, C3-7 cycloalkyl contains 3, 4, 5, 6 or 7 carbon atoms as ring members). refers to a cycloalkyl group having A cycloalkyl group may be attached to a parent group or substituent at any ring atom provided that attachment does not violate valence requirements. Likewise, a cycloalkyl group may contain one or more non-hydrogen substituents provided that the substitution does not violate valence requirements.

Examples of monocyclic cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Bicyclic cycloalkyl groups include, but are not limited to, bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.0] Hexyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.0]heptyl, bicyclo[3.1.1]heptyl, bicyclo[4.1.0]heptyl, bicyclo [2.2.2]octyl, bicyclo[ 3.2.1]octyl, bicyclo[4.1.1]octyl, bicyclo[3.3.0]octyl, bicyclo[4.2.0]octyl, bicyclo[3.3.1]nonyl, bicyclo[4.2.1]nonyl , bicyclo[4.3.0]nonyl, bicyclo[3.3.2]decyl, bicyclo[4.2.2]decyl, bicyclo[4.3.1]decyl, bicyclo[4.4.0]decyl, bicyclo[3.3 .3]undecyl, bicyclo[4.3.2]undecyl, bicyclo[4.3.3]dodecyl, etc., which are attached to the parent group or substituent at any ring atom provided that attachment does not violate valency requirements. can be attached.

"Cycloalkenyl" refers to monocyclic and bicyclic hydrocarbon rings having one or more unsaturated carbon-carbon bonds and having the specified number of carbon atoms, generally including the ring (ie, C3-7 cycloalkenyl is 3, 4 as a ring member). , refers to a cycloalkenyl group having 5, 6 or 7 carbon atoms). A cycloalkenyl may be attached to a parent group or substituent at any ring atom provided that attachment does not violate valence requirements.

Likewise, a cycloalkenyl group may contain one or more non-hydrogen substituents so long as the substitution does not violate valence requirements. Useful substituents include, without limitation, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkoxycarbonyl, alkanoyl and halo as defined above, and hydroxy, mercapto, nitro and contains amino.

"Cycloalkanoyl" and "cycloalkenoyl" refer to cycloalkyl-C(O)- and cycloalkenyl-C(O)-, respectively, wherein cycloalkyl and cycloalkenyl are as defined above. Cycloalkanoyl and cycloalkenoyl generally contain the specified number of carbon atoms excluding the carbonyl carbon. Cycloalkanoyl groups include, but are not limited to, cyclopropanonyl, cyclobutanoyl, cyclopentanoyl, cyclohexanoyl, cycloheptanoyl, 1-cyclobutenoyl, 2-cyclobutenoyl, 1-cyclopentenoyl, 2-cyclo pentenoyl, 3-cyclopentenoyl, 1-cyclohexenoyl, 2-cyclohexenoyl, 3-cyclohexenoyl, and the like.

"Cycloalkoxy" and "cycloalkoxycarbonyl" refer to cycloalkyl-O- and cycloalkenyl-O, respectively, and cycloalkyl-OC(O)- and cycloalkenyl-OC(O)-, respectively, wherein cyclo Alkyl and cycloalkenyl are as defined above. Cycloalkoxy and cycloalkoxycarbonyl generally contain the specified number of carbon atoms excluding the carbonyl carbon.

Examples of cycloalkoxy groups include, without limitation, cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohesoxy, 1-cyclobutenoxy, 2-cyclobutenoxy, 1-cyclopenteneoxy, 2-cyclopenteneoxy, 3 -cyclopentenoxy, 1-cyclohexenoxy, 2-cyclohexenoxy, 3-cyclohexenoxy, and the like. Examples of cycloalkoxycarbonyl groups include, without limitation, cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohesoxycarbonyl, 1-cyclobuteneoxycarbonyl, 2-cyclobuteneoxycarbonyl, 1-cyclopenteneoxycarbonyl, 2-cyclopenteneoxycarbonyl, 3-cyclopenteneoxycarbonyl, 1-cyclohexeneoxycarbonyl, 2-cyclohexeneoxycarbonyl, 3-cyclohexeneoxycarbonyl, etc. do.

"Aryl" and "arylene" refer to monovalent and divalent aromatic groups, including 5- and 6-membered monovalent aromatic groups, each containing 0 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur. Examples of monocyclic aryl groups include, without limitation, phenyl, pyrrolyl, furanyl, thiophenyl, thiazolyl, isothiazolyl, imidazolyl, triazolyl, tetrazolyl, pyrazolyl, oxazolyl, isoxazolyl, pyridinyl , pyrazinyl, pyridazinyl, pyrimidinyl, and the like. Aryl and arylene groups also include bicyclic, tricyclic, and the like, including fused 5- and 6-membered rings as defined above. Examples of polycyclic aryl groups include, without limitation, naphthyl, biphenyl, anthracenyl, pyrenyl, carbazolyl, benzoxazolyl, benzodioxazolyl, benzothiazolyl, benzoimidazolyl, benzothiophenyl, quinolinyl, isoquinolinyl, indolyl, benzofuranyl, purinyl, indolizinyl, and the like. The aryl and arylene groups may be attached to the parent group or substituent at any ring atom provided that attachment does not violate valence requirements.

Likewise, aryl and arylene groups may contain one or more non-hydrogen substituents so long as the substitution does not violate valence requirements. Useful substituents include, without limitation, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkenyl, alkoxy, cycloalkoxy, alkanoyl, cycloalkanoyl, cycloalke as defined above. noyl, alkoxycarbonyl, cycloalkoxycarbonyl, and halo, and hydroxy, mercapto, nitro, amino, and alkylamino.

"Heterocycle" and "heterocyclyl" refer to a saturated, partially unsaturated, or unsaturated monocyclic or bicyclic ring having 5 to 7 or 7 to 11 ring members, respectively. These groups have a ring member consisting of carbon atoms and 1 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur, and may include any bicyclic group in which any monocyclic heterocycle as defined above is fused to a benzene ring. The nitrogen and sulfur heteroatoms may optionally be oxidized. Hetecyclic rings may be attached to the parent group or substituent at any heteroatom or carbon atom, provided that attachment does not violate valence requirements. Likewise, any carbon or nitrogen ring member may contain a non-hydrogen substituent so long as the substitution does not violate valence requirements. Useful substituents include, without limitation, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkenyl, alkoxy, cycloalkoxy, alkanoyl, cycloalkanoyl, cycloalkenoyl as defined above. , alkoxycarbonyl, cycloalkoxycarbonyl and halo, and hydroxy, mercapto, nitro, amino, and alkylamino.

Examples of heterocycles include, without limitation, acridinyl, azosinyl, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzy Soxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carborinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H, 6H-1,5, 2-dithiazinyl, dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl , indolizinyl, indolyl, 3H-indolyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, morpholinyl , naphthalidinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4 -oxadiazolyl, oxazolidinyl, oxazolyl, oxazolidinyl, pyrimidinyl, phenantridinyl, phenanthrolineyl, phenazinyl, phenothiazinyl, phenoxathienyl, phenoxazinyl, phthalazinyl, Piperazinyl, piperidinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole , pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuran Yl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, 6H-1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5 -Thiadiazolyl, 1,3,4-thiadiazolyl, thiantrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, triazinyl, 1,2, 3-triazolyl, 1,2,4-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl, and xanthenyl.

"Heteroaryl" and "heteroarylene" refer to monovalent and divalent heterocycle or heterocycle groups as defined above, each being aromatic. The heteroaryl and heteroarylene groups represent a subset of the aryl and arylene groups, respectively.

"Arylalkyl" and "heteroarylalkyl" mean aryl-alkyl and heteroaryl-alkyl, respectively, wherein aryl, heteroaryl and alkyl are as defined above. Examples of these include, without limitation, benzyl, fluorenylmethyl, imidazol-2-yl-methyl, and the like.

"Arylalkanoyl", "heteroarylalkanoyl", "arylalkenoyl", "heteroarylalkenoyl", "arylalkynoyl", and "heteroarylalkynoyl" are respectively aryl-alkanoyl, heteroaryl - alkanoyl, aryl-alkenoyl, heteroaryl-alkenoyl, aryl-alkynoyl, and heteroaryl-alkynoyl, wherein aryl, heteroaryl, alkanoyl, alkenoyl, and alkinoyl as defined. Examples thereof include, without limitation, benzoyl, benzylcarbonyl, fluorenoyl, fluorenylmethylcarbonyl, imidazol-2-oil, imidazol-2-yl-methylcarbonyl, phenylethenecarbonyl, 1- Phenylethenecarbonyl, 1-phenyl-propenecarbonyl, 2-phenyl-propenecarbonyl, 3-phenyl-propenecarbonyl, imidazol-2-yl-ethenecarbonyl, 1- (imidazole- 2-yl)-ethenecarbonyl, 1-(imidazol-2-yl)-propenecarbonyl, 2-(imidazol-2-yl)-propenecarbonyl, 3-(imidazol-2-yl) )-propenecarbonyl, phenylethynecarbonyl, phenylpropynecarbonyl, (imidazol-2-yl)-ethynecarbonyl, (imidazol-2-yl)-propynecarbonyl and the like.

"Arylalkoxy" and "heteroarylalkoxy" refer to aryl-alkoxy and heteroaryl-alkoxy, respectively, wherein aryl, heteroaryl, and alkoxy are as defined above. Examples thereof include, without limitation, benzyloxy, fluorenylmethyloxy, imidazol-2-yl-methyloxy, and the like.

"Aryloxy" and "heteroaryloxy" refer to aryl-O- and heteroaryl-O-, respectively, wherein aryl and heteroaryl are as defined above. Examples thereof include, without limitation, phenoxy, imidazol-2-yloxy, and the like.

"Aryloxycarbonyl", "heteroaryloxycarbonyl", "arylalkoxycarbonyl", and "heteroarylalkoxycarbonyl" are respectively aryloxy-C(O)-, arylalkoxy-C(O)-, heteroarylalkoxy-C(O)-, wherein aryloxy, heteroaryloxy, arylalkoxy, and heteroarylalkoxy are as defined above. Examples thereof include, without limitation, phenoxycarbonyl, imidazol-2-yloxycarbonyl, benzyloxycarbonyl, fluorenylmethyloxycarbonyl, imidazol-2-yl-methyloxycarbonyl, and the like. .

"Alkylthio", "alkylthioalkyl", and "arylthio" mean -S-alkyl, alkyl substituted with alkylthio, and -S-aryl, respectively, where alkyl and aryl are as defined above.

"Arylsulfonyl" and "arylsulfinyl" mean aryl-S(O ₂ )- and aryl-S(=O)-, respectively, where aryl is as defined above.

The compound of the chemical structure represented by the formula may be substituted or unsubstituted. In the case of a substituted compound, the substitutable moiety may be substituted with the aforementioned substituents.

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

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.

Although not defined otherwise, all terms including technical terms and scientific terms used herein 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.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Throughout the specification of the present invention, "organic light emitting diode" may be abbreviated as "", and "pixel partition layer" may be abbreviated as "".

One embodiment of the present invention is to present binder polymers having a vicardo structure. These binder polymers have excellent solubility in PGMEA solvent, which is the main solvent used for forming fine patterns of the PDL layer of OLED, and can maintain the dispersibility of the black pigment dispersed in the PGMEA solvent in the form of small particles of 100 nanometers or less. A pattern can be obtained, and a negative type black photosensitive resin composition can be prepared under the condition of a high concentration of black pigment.

A method for preparing a binder polymer for a photosensitive resin composition according to an embodiment of the present invention includes: a first reaction step comprising imidating at least one of amino acids and amino alcohols, and dianhydride; and a second reaction step in which the product generated in the first reaction step is subjected to a condensation polymerization reaction with at least one of a dianhydride monomer, a diol copolymerized monomer having a double bond, and a diepoxide.

The first reaction step comprises imidating an amino acid and dianhydride to produce a dicarboxylic acid, and further comprising reacting the dicarboxylic acid product with a monoepoxide having a double bond to produce a diol. , the second reaction step may be a condensation polymerization reaction of the diol product with a dianhydride monomer.

In this case, in the step of reacting the dicarboxylic acid product with a monoepoxide having a double bond to generate a diol, the epoxide may be glycidyl methacrylate (GMA).

In addition, the step of reacting the dicarboxylic acid product with a monoepoxide having a double bond to generate a diol may include further reacting the dicarboxylic acid monomer.

At this time, the dicarboxylic acid monomer is, 2,2-bis (4-carboxyphenyl) hexafluoropropane (2,2-Bis (4-carboxyphenyl) hexafluoropropane 6FDC), 4,4'-dicarboxydiphenyl ether (4, 4'-Dicarboxydiphenyl Ether (ODC), itaconic acid (ITC), methylene disalicylic acid (MLDC) and octafluoroadipic acid (8FDC) contains at least one of may be doing

In addition, the second reaction step may be a condensation polymerization reaction by further including a diol monomer.

In this case, the diol monomer is 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorine, FDO), bis[4 -(2-hydroxyethoxy)phenyl] sulfone (Bis[4-(2-hydroxyethoxy)phenyl] Sulfone, SDO), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2, 4,8,10-tetraoxaspiro [5.5] undecane (3,9-Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, XDO), and It may include one or more of 1,4-butanediol (1,4-Butanediol, 4DO).

The first reaction step is to imidize an amino alcohol and dianhydride to produce a diol, and the second reaction step is a condensation polymerization reaction of the diol product with a diol copolymer monomer having a double bond and a dianhydride monomer it could be

The first reaction step is to imidize an amino acid and dianhydride to produce dicarboxylic acid, and the second reaction step is to condensation polymerization reaction of the dicarboxylic acid product with diepoxide, which is produced in the second reaction step It may further include the step of reacting the product with anhydride.

In this case, in the step of reacting the product generated in the second reaction step with anhydride, the anhydride may be itacone anhydride (ITA).

Amino acids are trans-4-(aminomethyl)cyclohexanecarboxylic acid (trans-4-(Aminomethyl)cyclohexanecarboxylic Acid, CYAA), 4-aminobenzoic acid (4-Aminobenzoic acid, 4-AB), 3-aminobenzoic acid ( 3-Aminobenzoic acid, 3-AB), 4-(aminomethyl)benzoic acid (AMBA), 4-aminophenylacetic acid (APAA), and β-alanine (β- Alanine, BAA) may be included.

Amino alcohol is, ethanolamine (ETM), trans-4-aminocyclohexanol (trans-4-Aminocyclohexanol, CYAO), and 2- (4-aminophenyl) ethanol (2- (4-Aminophenyl) ethanol, APE) may include one or more of.

Dianhydride is 4-4'-(hexafluoroisopropylidene)di-phthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride, 6FDA), 5-(2,5-dioxytetra Hydropril)-3-methyl-3-cyclohexane-1,2-dicarboxyl anhydride (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride, MCDA) , and 4-4'-biphthalic anhydride (4,4'-Biphthalic Anhydride, BPDA).

The diol copolymer monomer having a double bond may include fluorene epoxy acrylate (FEA).

The diepoxide is 9-9-bis(4-glycidyloxyphenyl)fluorene (9,9-Bis(4-glycidyloxyphenyl)fluorine, FEP), 1,4-cyclohexanedimethanol diglycidyl ether (1,4-Cyclohexanedimethanol diglycidyl ether, CHEP), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (JEP), resorcinol diglycidyl ether (REP) ), and 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (1,3-Bis[ 2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, SIEP) may be included.

Code names and chemical structures of the compounds used to synthesize the binder polymers are shown in Tables 1 to 6.

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)

Monomer type diepoxide code name English name chemical structural formula FEP 9,9-Bis(4-glycidyloxyphenyl)fluorene

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

Monomer type dicarboxylic acid code name English name chemical structural formula 6FDC 2,2-Bis(4-carboxyphenyl)hexafluoropropane

ODC 4,4'-Dicarboxydiphenyl Ether

ITC Itaconic acid

MLDC Methylenedisalicylic Acid (mixture of isomers)

8FDC Octafluoroadipic Acid

Monomer type Dior code name English name chemical structural formula FDO 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene

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

Monomer type amino acid code name English name chemical structural formula 4-AB 4-Aminobenzoic acid

3-AB 3-Aminobenzoic acid

AMBA 4-(Aminomethyl)benzoic acid

APAA 4-Aminophenylacetic acid

CYAA trans-4-(Aminomethyl)cyclohexanecarboxylic Acid

BAA β-Alanine

Monomer type amino alcohol code name English name chemical structural formula ETM Ethanolamine

CYAO trans-4-Aminocyclohexanol

APE 2-(4-Aminophenyl)ethanol

The binder polymer for the photosensitive resin composition prepared by the above-described process is as follows.

The binder polymer for the photosensitive resin composition according to an embodiment of the present invention is polyester-imide-based, and includes a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based and includes repeating units represented by the following Chemical Formulas 2 and 3 below.

[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Q is a linking group represented by at least one of the following formulas Q-1 to Q-6,

T includes a linking group represented by the following formula T-1.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Q-1]

[Formula Q-2]

[Formula Q-3]

[Formula Q-4]

[Formula Q-5]

[Formula Q-6]

[Formula T-1]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes a repeating unit represented by the following Chemical Formula 4-1 or Chemical Formula 4-2.

[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

Z ₁ is a linking group represented by at least one of the following formulas Z _1-1 to Z _1-3 ,

Z ₂ is a linking group represented by at least one of the following formulas Z ₂ -1 to Z ₂ -2,

R is a linking group represented by one or more of the following formulas R-1 to R-5.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula Z ₁ -1]

[Formula Z ₁ -2]

[Formula Z _1-3 ]

[Formula Z ₂ -1]

[Formula Z ₂ -2]

[Formula R-1]

[Formula R-2]

[Formula R-3]

[Formula R-4]

[Formula R-5]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes repeating units represented by the following Chemical Formulas 1 and 5.

[Formula 1]

[Formula 5]

In Formula 1 and Formula 5,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

W is a linking group represented by at least one of the following formulas W-1 to W-4.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula W-1]

[Formula W-2]

[Formula W-3]

[Formula W-4]

The binder polymer for the photosensitive resin composition according to another embodiment of the present invention is polyester-imide-based, and includes repeating units represented by Chemical Formulas 1 and 6 below.

[Formula 1]

[Formula 6]

In Formula 1 and Formula 6,

X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,

X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,

Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,

V is a linking group represented by at least one of the following formulas V-1 to V-5.

[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula V-1]

[Formula V-2]

[Formula V-3]

[Formula V-4]

[Formula V-5]

The binder polymer may have a weight average molecular weight of about 1,000 g/mol to about 15,000 g/mol, or about 2,000 g/mol to about 10,000 g/mol, but may not be limited thereto.

The photosensitive resin composition according to an embodiment of the present invention, the above-described binder polymer; photoinitiator; photosensitizers; polyfunctional monomers; black dye; additive; and solvents.

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.

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), a solvent, and the like.

The photosensitive resin composition may further include an additive, which may serve as an adhesion promoter. The additive 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. When an additive is included, it may be included in an amount of 0.5 wt% to 2 wt%.

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

Since the binder polymer has been described above, overlapping descriptions will be omitted.

As the photopolymerization initiator and the photosensitizer, a compound generally used in the photosensitive resin composition may be used. Specifically, SPI-03 of Samyang Corporation as a photopolymerization initiator and Darocure ITX of Ciba Co. as a photosensitizer can be used.

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 in black, but is not limited thereto. can 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 include a dispersing agent. As the dispersant, a compound widely known in the photosensitive resin composition may be used without limitation. 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 limited thereto.

In an embodiment of the present invention, the photosensitive resin composition comprises 17 wt% to 40 wt% of a binder polymer, 3 wt% to 8 wt% of a photopolymerization initiator, 0.5 wt% to 3 wt% of a photosensitizer, 3 wt% of a polyfunctional monomer % to 12% by weight, 37% to 60% by weight of black dye, 0.5% to 2% by weight of additives, and the solvent may be included in the balance, but may not be limited thereto.

In this case, the binder polymer may include 20 wt% to 40 wt%. More specifically, it may include 20 wt% to 30 wt%, or 25 wt% to 40 wt%. More specifically, it may include 17 wt% to 40 wt%, or 17 wt% to 30 wt%. More specifically, it may include 25 wt% to 30 wt%.

In this case, the photopolymerization initiator may include 4 wt% to 8 wt%, or 3 wt% to 7 wt%. More specifically, it may include 3 wt% to 6 wt%. More specifically, it may include 3.5 wt% to 5 wt%.

In this case, the photosensitizer may include 0.5 wt% to 2 wt%. More specifically, 1 wt% to 2 wt% may be included. More specifically, 1 wt% to 1.5 wt% may be included.

In this case, the polyfunctional monomer may include 4 wt% to 10 wt%. More specifically, it may include 4 wt% to 8 wt%. More specifically, it may include 5 wt% to 7 wt%.

In this case, the black dye may include 30% to 60% by weight. More specifically, 35 wt% to 57 wt% may be included. More specifically, 40 wt% to 57 wt%, 45 wt% to 57 wt%, 50 wt% to 57 wt% may be included.

In this case, the additive may include 0.5 wt% to 2 wt%. More specifically, it may include 0.5 wt% to 1.5 wt%. More specifically, it may include 0.7 wt% to 1.2 wt%.

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.

The second aspect of the present application may provide a photolithography process of applying, exposing, and developing the photosensitive resin composition of the first aspect of the present application by forming a single layer or a double layer.

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 10Х㎛ size of the wafer surface, where the black PDL thin film layer is developed, is the pixel part where 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 a (-CF3) group, 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. will not leave behind

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 performed for about 20 seconds to about 1 minute in ambient temperature atmosphere; and the post-curing process performed for a time of about 20 minutes to about 40 minutes at a temperature range of about 200° C. to about 300° C., 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 with 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. In addition, 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 disclosure may provide an electronic device including the pixel traversing side of the second aspect of the present disclosure.

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, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, the present invention may be embodied in various different forms, and is not limited to the embodiments described herein.

Reference Example 1: Synthesis of cardo-based polymer binder

As in the reaction scheme of Reference Example 1 below, two alcohol (-OH) groups of fluorene epoxy acrylate (hereinafter referred to as "FEA") and various compounds used in the present invention shown in Tables 1 to 6 It was synthesized by esterification reaction with two anhydride groups of BPDA, which is one of the

[Reference Example 1: Synthesis of KBR 101]

In the fluorene epoxy acrylate (FEA) structure of Reference Example 1, a compound containing carbon having a ring structure represented by c* is called a cardo-based compound. However, the molecular weight of the FEA monomer, which is a diol structure, is high as 607 g/mol, and the weight ratio of the acrylate double bond group contained in the FEA diol is low as 0.237 wt %. The UV exposure sensitivity of the black photosensitive resin composition including it is low, and the OLED device It was difficult to obtain a high-resolution PDL pattern, and there was a problem in that the optical density (OD) was low because there was a limit to increasing the concentration of the black pigment.

Preparation Example: Synthesis of non-cardo-based binder polymer containing imide group

Due to the high UV exposure sensitivity, it is possible to obtain a fine PDL pattern required for high resolution of the OLED device, and it is possible to increase the concentration of the pigment (black millbase) in the negative-type black photosensitive solution, so that the optical density (OD, optical density) of the black PDL layer of the OLED device can be increased. ), various non-cardo-based binder polymers containing an imide group in the main chain of the polymer were synthesized.

Preparation Example 1: Synthesis of polyester-imide-based binder polymer of formula 1 repeating unit structure

[Formula 1]

An example of synthesizing a polyester-imide-based binder polymer having a structure including a repeating unit represented by Chemical Formula 1 is shown in Preparation Example 1.

[Preparation Example 1: Preparation of BP-001]

[Scheme 1]

In a nitrogen atmosphere, 1.81 g of PGMEA solvent, 1 mmol of 6FDA, and 2 mmol of CYAA were added to a 100 mL three-necked flask under a nitrogen atmosphere, and reacted at room temperature for 1 hour to imidize at 130° C. for 23 hours to obtain diimide-acid. After cooling, 2 mmol of GMA, 0.0025 mmol of BHT as a polymerization inhibitor, 0.01 mmol of TBPB as a catalyst, and 0.66 g of additional PGMEA were added and stirred at 110° C. for 3 hours to obtain a diimide-epoxymethacrylate intermediate. 1 mmol of 6FDA and 1.03 g of additional PGMEA were added thereto, and polyesterification was performed while stirring at 110° C. for 3 hours. The binder of a homopolymer structure having an imide group, a double bond and a carboxyl (-COOH) group as shown in Example 1 Polymer BP-001 was obtained.

The carboxyl group present in the non-cardo-based binder polymer shown in Chemical Formula BP-001 is ionized by reacting with the tetramethyl ammonium hydroxide (TMAH) basic aqueous solution developer because the polyester is not cross-linked in the area not exposed to UV, so it is changed to a water-soluble polymer It was removed during the development process, enabling the formation of PDL patterns of OLEDs. The polyester-imide BP-001 shown in Preparation Example 1 had a molecular weight of Mw=1,000 to 2,000 g/mol, and specifically, it was about 1,234 g/mol from the result of FIG. 1 . It was suitable for PDL pattern formation of OLED.

Binder polymer BP-001 has two acrylate groups and carboxyl groups per repeat unit, so it has similarities to the cardo-based binder polymer of Reference Example 1, but the difference is that it contains an imide group with high heat resistance in one repeat unit. . 6FDA was used as a starting material in Preparation Example 1, but the same effect could be obtained by using other dianhydrides such as MCDA or BPDA instead of 6FDA.

One of the important concepts in synthesizing the binder polymer BP-001 is to start the reaction in a reactor in which the starting materials 6FDA and CYAA are put in PGMEA as a solvent, until the final binder polymer BP-001 is obtained. In the middle of the reaction, the reaction material was collected and reacted again, such as precipitation, separation, and filtration. This reaction process is also called a so-called one-pot reaction, and has the characteristic that the final target product can be synthesized at the lowest process cost.

Preparation Example 2: Polyester of Formula 2 and Formula 3 repeating unit structure- Synthesis of imide-based binder polymer

[Formula 2]

[Formula 3]

An example of synthesizing the non-cardo-based binder polymer having the repeating unit structures of Chemical Formulas 2 and 3 is shown in Preparation Example 2.

[Preparation Example 2: Synthesis of BP-002]

[Scheme 2]

In Preparation Example 2, unlike Preparation Example 1, using an amino alcohol compound to obtain a diimide-diol intermediate and using this as a comonomer and FEA shown in Reference Example 1 to synthesize a polyester-imide binder polymer containing an imide group was presented.

In a 100 mL three-necked flask under a nitrogen atmosphere, 3.00 g of PGMEA solvent, 5 mmol of MCDA, and 10 mmol of ETM were added, reacted at room temperature for 1 hour, imidized at 130 ° C. for 23 hours, and cooled to obtain an intermediate diimide-diol.

In a nitrogen atmosphere, 1.00 g of the intermediate (40 wt%), 2.24 g of PGMEA, 1.5 mmol of FEA, 2.5 mmol of 6FDA, 0.005 mmol of BHT as a polymerization inhibitor, and 0.025 mmol of TBPB as catalyst were added and polyesterification was performed at 110 ° C. for 3 hours while stirring. A binder polymer having a copolymer structure having an imide, a double bond group and a carboxyl (-COOH) group in the main chain shown in Example 2 was obtained. In Preparation Example 2, MCDA was used as a starting material, but the same effect can be obtained by using other dianhydrides such as 6FDA or BPDA instead of MCDA. Polyester BP-002 shown in Preparation Example 2 had a molecular weight of Mw=2,000 to 4,000 g/mol. Specifically, it was 2,340 g/mol from the result of FIG. 2 .

Preparation Example 3: Polyester of Formula 4-1 or Formula 4-2 repeating unit structure- Synthesis of imide-based binder polymer

[Formula 4-1]

[Formula 4-2]

An example of synthesizing a non-cardo-based binder polymer having a repeating unit structure shown in Chemical Formula 4 is shown in Preparation Example 3.

[Preparation Example 3: Synthesis of BP-003]

In Preparation Example 3, the diimide-diacid intermediate shown in Preparation Example 1 was polymerized with fluorene diepoxide (FEP) to synthesize a polyester-imide containing an imide group, which was then reacted with itaconic acid to form two carboxyl groups per repeating unit. A polyester-imide having two acrylate groups was synthesized.

[Scheme 3]

The diimide-diacid intermediate (1 mmol) shown in Preparation Example 3 was synthesized in the same manner as in Preparation Example 1. After cooling the diimide-diacid intermediate, 1 mmol of FEP, 0.0025 mmol of BHT, a polymerization inhibitor, 0.01 mmol of TBPB, and 1.30 g of additional PGMEA were added and stirred at 110° C. for 3 hours to obtain a polyester intermediate. 0.5 mmol of ASA and 0.0025 mmol of BHT, a polymerization inhibitor, were added thereto, and esterification was performed while stirring at 110° C. for 3 hours to obtain BP-003, a binder polymer having a homopolymer structure having an imide group, a double bond and a carboxyl (-COOH) group. The polyester BP-003 shown in Example 3 had a molecular weight in the range of Mw=2,000 to 3,000 g/mol. In the second reaction of Preparation Example 3, FEP was used as diepoxide, and the same effect could be obtained by using other diepoxides such as CHEP, JEP, REP, and SIEP instead of FEP.

[Preparation Example 4] Polyester of formula 1 and formula 5 repeating unit structure- Synthesis of imide-based binder polymer

[Formula 1]

[Formula 5]

An example of synthesizing the non-cardo-based binder polymer having the repeating unit structure shown in Chemical Formulas 1 and 5 is shown in Preparation Example 4.

[Preparation Example 4: Synthesis of BP-004]

In Preparation Example 4, the diimide-diacrylate/diol intermediate shown in Preparation Example 1 was used as a comonomer with XDO diol and dianhydride and polyesterification were performed to synthesize a copolymer-type polyester-imide containing a carboxyl group and an acrylate group at the same time.

[Scheme 4]

The diimide-epoxymethacrylate intermediate (1 mmol) shown in Preparation Example 4 was synthesized in the same manner as in Preparation Example 1. Here, 1 mmol of XDO and 2 mmol of 6FDA, which are copolymerized monomers, were added and reacted at 110° C. for 3 hours to obtain BP-004, a binder polymer having an imide, a double bond and a carboxyl (-COOH) group in the main chain. The binder polymer BP-004 of the copolymer structure shown in Scheme 4 had a molecular weight in the range of Mw=2,000 to 3,000 g/mol. In Example 4, 6FDA was used as a starting material, but the same effect could be obtained by using MCDA or BPDA instead of 6FDA.

[Preparation Example 5] Polyester of formula 1 and formula 6 repeating unit structure-Synthesis of imide-based binder polymer

[Formula 1]

[Formula 6]

An example of synthesizing the non-cardo-based binder polymer having the repeating unit structure shown in Chemical Formulas 1 and 6 is shown in Preparation Example 5.

[Preparation Example 5: Synthesis of BP-005]

In Preparation Example 5, the diimide-diacid intermediate shown in Preparation Example 1 was mixed with the diacid represented by 6FDC, and then reacted with GMA to obtain a diol containing imide and a diol containing ester, and dianhydride copolymerization was performed to synthesize a copolymer-type polyester-imide. .

[Scheme 5]

The diiimide-diacid intermediate (1 mmol) shown in Scheme 5 was synthesized in the same manner as in Preparation Example 1. Here, 1 mmol of 6FDC, 4 mmol of GMA, a polymerization inhibitor, 0.0025 mmol of BHT, 0.01 mmol of TBPB, and additionally 0.64 g of PGMEA were added and reacted at 110° C. for 3 hours to obtain a diimide-epoxymethacrylate mixture. Here, 2 mmol of 6FDA and 1.21 g of additional PGMEA were added, and reacted again at 110° C. for 3 hours to obtain BP-005, a binder polymer having a copolymer structure having an imide, double bond and carboxyl (-COOH) group in the polymer main chain. was found in the range of Mw=2,000 to 3,000 g/mol. 6FDA was used as a starting material in Preparation Example 5, and the same effect could be obtained by using other dianhydrides such as MCDA or BPDA instead of 6FDA.

Experimental Example 1: Preparation of photosensitive resin composition

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. . In the photosensitive resin composition, the binder polymer having a double bond group is a UV photoinitiator and a photosensitizer when exposed to UV light to form free radicals, through a photomask by free radical chain polymerization with a polyfunctional monomer containing a double bond. By causing cross-linking at the site exposed to , it remains undeveloped by the TMAH base aqueous solution in the next process, so black PDL micro-patterns of OLED devices can be realized. On the other hand, in the portion not exposed to UV light, since the binder polymer is in a state in which crosslinking does not occur, 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, resulting in black PDL micro A pattern may be formed.

The most important component in the black photosensitive resin composition is a binder polymer, and all of the polyester-imide binder polymers shown in Preparation Examples 1 to 5 described above have solubility enough to form a true solution in PGMEA, a common solvent of the black photosensitive resin composition. It has excellent heat resistance because the polymer main chain is connected by an imide bond.

In this experimental example, a negative type black photosensitive resin composition was prepared using KBR101 of Kyung-In Corporation, a commercial cardo-based bind polymer used to obtain black PDL fine patterns of OLED devices, and the polyester-imide-based binder polymers of the present invention. The prepared and evaluated characteristics through the photolithography process are shown in Table 7 below.

Photosensitive resin composition component Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 light curing
initiator SPI-03 (Samyang Corporation) 4.0 4.0 4.0 4.0 4.0 4.0 photosensitizer Darocure ITX
(Ciba, Switzerland) 1.0 1.0 1.0 1.0 1.0 1.0 bookbinder
polymer KBR 101 ( CBP )
(45% by weight, PGMEA) 20 BP-001
(30% by weight, PGMEA) 27 BP-002 (40% by weight, PGMEA) 27 BP-003 (30% by weight, PGMEA) 27 BP-004 (30% by weight, PGMEA) 27 BP-005 (30% by weight, PGMEA) 27 multisensory
monomer PM6 6.0 6.0 6.0 6.0 6.0 6.0 additive MSMA One One One One One One menstruum PGMEA 12 5.0 5.0 5.0 5.0 5.0 black dye BK-4926
(Mikuni, Japan) 56 56 56 56 56 56 Sum Weight (g),% 100 100 100 100 100 100 Binder polymer structure homopolymer
or
Copolymer homopolymer homopolymer Copolymer homopolymer Copolymer Copolymer per repeat unit
[Carboxyl (C)/
Acrylate (A)]
structure of functional groups [2C/2A] [2C/2A] [2C/2A] [2C/-] [2C/2A] [2C/2A] [2C/-] [2C/2A] pixel
compartment layer
pattern Good (O), Medium (Δ),
Bad (×) O △ O X O X phenomenon
shape flake, dispersion dispersion dispersion dispersion flake dispersion flake

In the photosensitive resin composition, two basic properties may be required for a binder polymer that is important for generating a PDL fine pattern of an OLED device. First, the binder polymers must have good solubility to form a true solution in the PGMEA solvent commonly used to prepare the photosensitive resin composition. Second, the lactam black-based black organic pigment itself is uniformly dispersed in a PGMEA solvent with a size of 100 nanometers or less with the help of a pigment dispersant. When the solvent shock (solvent shock) impacts the dispersed state of the organic pigment well dispersed in nanometer size, it should not be agglomerated into plate-shaped flakes.

When the size of these fine lumps is increased, the solids of the black photoresist composition develop into irregular lumps of plate acid when developing in the photolithography process, and the sharpness of the pattern is deteriorated. This development characteristic is called “flake-type phenomenon” and the development form is described at the bottom of Table 7 above. If these black plate-like masses are further increased, the edge boundary of the PDL micro-pattern appears as a fine sawtooth shape, and the straightness deteriorates. If the size of the black plate-like masses is greatly increased, it can be seen that the square-shaped PDL patterns gradually shrink or appear as a whole black surface without distinguishing the square pattern. On the other hand, in the developing process, it is observed that the black photosensitive thin film is melted in the form of spreading black inks in water.

In a photolithography experiment for forming a PDL micro-pattern for an OLED device using the negative black photosensitive resin composition shown in Table 7, Examples 1, 3, and 5 had poor PDL micro-pattern formation. As can be seen from the structure of the binder polymer in Table 7, each of the binder polymers synthesized in Examples 1, 3, and 5 contained two carboxyl groups and two acrylic groups per repeating unit, so the acrylate participating in the UV light crosslinking reaction was too high. This can be interpreted as many On the other hand, the polyester-imide binder polymers used in Examples 2 and 4 were subjected to a polyesterification reaction with 6FDA using MSIO and XDO diol comonomers not having an acrylate group in the synthesis process. Binder polymers having less than half of the acrylate groups were synthesized, and thus the density of the photocrosslinking reaction by UV exposure was low, and at the same time, the carboxyl groups were increased more than in Examples 1, 3, and 5, so the dispersion type in the photolithography process (dispersion) phenomenon occurred and could be interpreted as enabling the PDL micro-pattern of OLED. In Comparative Example 1, as shown in Reference Example 1, it has a homopolymer structure and has two carboxyl groups and two acrylate groups per repeating unit, but the molecular weight of the FEA monomer is larger than that of Examples 1, 3, and 5 per repeating unit. It was interpreted that the PDL fine pattern formation of OLED was possible because the weight ratio of the acrylate group was low as 0.237 wt%, which lowered the crosslinking density in the UV light crosslinking reaction and the fluorene group increased the dispersibility of the black pigment.

Meanwhile, in Comparative Example 1 and Examples 1 to 5, the black dye was added in an amount of 56 wt%. When the black photosensitive resin composition using a cardo-based polymer as a binder polymer contains about 1 to 20% by weight of a black pigment, the OD (optical density) shows a blackness of about 0.5/μm, so the OD is required to be 1/μm or more. There may be problems in realizing the black PDL fine pattern of the OLED device. In addition, a black negative photosensitive resin composition using a cardo-based polymer as a binder polymer has been used to form a black matrix pattern of a liquid crystal display device as well as a black PDL fine pattern of an OLED device. There may be problems in that exposure sensitivity is low and there is a limit to obtaining a high-resolution fine pattern.

The present invention is not limited to the embodiments, but can be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains can use other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that this may be practiced. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (26)

a first reaction step comprising imidating at least one of an amino acid and an amino alcohol, and a dianhydride;
a second reaction step of carrying out a condensation polymerization reaction of the product generated in the first reaction step with at least one of a dianhydride monomer, a diol copolymer monomer having a double bond, and a diepoxide;
A method for producing a binder polymer for a photosensitive resin composition comprising a.
According to claim 1,
The first reaction step includes imidating an amino acid and a dianhydride to produce a dicarboxylic acid, and further comprising reacting the dicarboxylic acid product with a monoepoxide having a double bond to produce a diol to do,
In the second reaction step, the diol product is subjected to a condensation polymerization reaction with a dianhydride monomer,
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The first reaction step is to imidize an amino alcohol and a dianhydride to produce a diol,
In the second reaction step, the diol product is subjected to a condensation polymerization reaction with a diol copolymer monomer having a double bond and a dianhydride monomer,
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The first reaction step is to imidize an amino acid and a dianhydride to produce a dicarboxylic acid,
The second reaction step is a condensation polymerization reaction of the dicarboxylic acid product with diepoxide,
Further comprising the step of reacting the product produced in the second reaction step with an anhydride having a double bond,
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The amino acid is, trans-4- (aminomethyl) cyclohexanecarboxylic acid (trans-4- (Aminomethyl) cyclohexanecarboxylic Acid, CYAA), 4-aminobenzoic acid (4-Aminobenzoic acid, 4-AB), 3-aminobenzoic acid (3-Aminobenzoic acid, 3-AB), 4-(Aminomethyl)benzoic acid (AMBA), 4-Aminophenylacetic acid (APAA), and β-alanine (β -Alanine, BAA) comprising one or more of,
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The amino alcohol is ethanolamine (Ethanolamine, ETM), trans-4-aminocyclohexanol (trans-4-Aminocyclohexanol, CYAO), and 2- (4-aminophenyl) ethanol (2- (4-Aminophenyl) ethanol , APE) comprising one or more of,
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The dianhydride is, 4-4'-(hexafluoroisopropylidene)di-phthalic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride, 6FDA), 5-(2,5-dioxy Tetrahydropril)-3-methyl-3-cyclohexane-1,2-dicarboxyl anhydride (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride, MCDA ), and 4-4 '-biphthalic anhydride (4,4'-Biphthalic Anhydride, BPDA),
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The diol copolymer monomer having the double bond, comprising a fluorene epoxy acrylate (FEA),
A method for producing a binder polymer for a photosensitive resin composition.
According to claim 1,
The diepoxide is, 9-9-bis(4-glycidyloxyphenyl)fluorene (9,9-Bis(4-glycidyloxyphenyl)fluorine, FEP), 1,4-cyclohexanedimethanol diglycidyl Ether (1,4-Cyclohexanedimethanol diglycidyl ether, CHEP), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (JEP), resorcinol diglycidyl ether (Resorcinol diglycidyl ether, REP), and 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane (1,3-Bis [2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, SIEP) comprising at least one of,
A method for producing a binder polymer for a photosensitive resin composition.
3. The method of claim 2,
In the step of reacting the dicarboxylic acid product with a monoepoxide having a double bond to produce a diol,
The monoepoxide having the double bond is glycidyl methacrylate (GMA),
A method for producing a binder polymer for a photosensitive resin composition.
3. The method of claim 2,
The step of generating a diol by reacting the dicarboxylic acid product with a monoepoxide having a double bond comprises:
The reaction by further comprising a dicarboxylic acid monomer,
A method for producing a binder polymer for a photosensitive resin composition.
12. The method of claim 11,
The dicarboxylic acid monomer is, 2,2-bis (4-carboxyphenyl) hexafluoropropane (2,2-Bis (4-carboxyphenyl) hexafluoropropane 6FDC), 4,4'-dicarboxydiphenyl ether (4,4 '-Dicarboxydiphenyl Ether, ODC), itaconic acid (ITC), methylene disalicylic acid (MLDC) and octafluoro adipic acid (Octafluoroadipic Acid, 8FDC) containing at least one of that is,
A method for producing a binder polymer for a photosensitive resin composition.
3. The method of claim 2,
The second reaction step is
Condensation polymerization reaction by further comprising a diol monomer,
A method for producing a binder polymer for a photosensitive resin composition.
14. The method of claim 13,
The diol monomer is 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorine, FDO), bis[4- (2-hydroxyethoxy)phenyl] sulfone (Bis[4-(2-hydroxyethoxy)phenyl] Sulfone, SDO), 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4 ,8,10-tetraoxaspiro[5.5]undecane (3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, XDO), and 1 , which comprises at least one of 4-butanediol (1,4-Butanediol, 4DO),
A method for producing a binder polymer for a photosensitive resin composition.
5. The method of claim 4,
In the step of reacting the product produced in the second reaction step with an anhydride having a double bond,
The anhydride is itacon anhydride (ITA),
A method for producing a binder polymer for a photosensitive resin composition.
polyester-imide-based,
A binder polymer for a photosensitive resin composition comprising a repeating unit represented by the following formula (1).
[Formula 1]

(In Formula 1,
X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,
X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,
Y is a linking group represented by at least one of the following formulas Y-1 to Y-6.)
[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

polyester-imide-based,
A binder polymer for a photosensitive resin composition comprising a repeating unit represented by the following Chemical Formulas 2 and 3.
[Formula 2]

[Formula 3]

(In Formula 2 and Formula 3,
X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,
X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,
Q is a linking group represented by at least one of the following formulas Q-1 to Q-6,
T includes a linking group represented by the following formula T-1.)
[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Q-1]

[Formula Q-2]

[Formula Q-3]

[Formula Q-4]

[Formula Q-5]

[Formula Q-6]

[Formula T-1]

polyester-imide-based,
A binder polymer for a photosensitive resin composition comprising a repeating unit represented by the following Chemical Formula 4-1 or Chemical Formula 4-2.
[Formula 4-1]

[Formula 4-2]

(In Formulas 4-1 and 4-2,
X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,
Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,
Z ₁ is a linking group represented by at least one of the following formulas Z _1-1 to Z _1-3 ,
Z ₂ is a linking group represented by at least one of the following formulas Z ₂ -1 to Z ₂ -2,
R is a linking group represented by at least one of the following formulas R-1 to R-5.)
[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula Z ₁ -1]

[Formula Z ₁ -2]

[Formula Z _1-3 ]

[Formula Z ₂ -1]

[Formula Z ₂ -2]

[Formula R-1]

[Formula R-2]

[Formula R-3]

[Formula R-4]

[Formula R-5]

polyester-imide-based,
A binder polymer for a photosensitive resin composition comprising a repeating unit represented by the following Chemical Formulas 1 and 5.
[Formula 1]

[Formula 5]

(In Formula 1 and Formula 5,
X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,
X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,
Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,
W is a linking group represented by at least one of the following formulas W-1 to W-4.)
[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula W-1]

[Formula W-2]

[Formula W-3]

[Formula W-4]

polyester-imide-based,
A binder polymer for a photosensitive resin composition comprising a repeating unit represented by the following Chemical Formulas 1 and 6.
[Formula 1]

[Formula 6]

(In Formula 1 and Formula 6,
X ₁ is a linking group represented by at least one of the following formulas X _1-1 to X _1-3 ,
X ₂ is a linking group represented by at least one of the following formulas X ₂ -1 to X ₂ -3,
Y is a linking group represented by at least one of the following formulas Y-1 to Y-6,
V is a linking group represented by at least one of the following formulas V-1 to V-5.)
[Formula X ₁ -1]

[Formula X ₁ -2]

[Formula X _1-3 ]

[Formula X ₂ -1]

[Formula X ₂ -2]

[Formula X ₂ -3]

[Formula Y-1]

[Formula Y-2]

[Formula Y-3]

[Formula Y-4]

[Formula Y-5]

[Formula Y-6]

[Formula V-1]

[Formula V-2]

[Formula V-3]

[Formula V-4]

[Formula V-5]

The binder polymer according to any one of claims 16 to 20;
photoinitiator;
photosensitizers;
polyfunctional monomers;
black dye;
additive; and
A photosensitive resin composition comprising a solvent.
22. The method of claim 21,
The photosensitive resin composition is a black negative photosensitive resin composition for forming a pixel partition layer of an organic light emitting diode, the photosensitive resin composition.
22. The method of claim 21,
17% to 40% by weight of the binder polymer,
3 wt% to 8 wt% of the photopolymerization initiator;
0.5 wt% to 3 wt% of the photosensitizer;
3% to 12% by weight of the polyfunctional monomer;
37 wt% to 60 wt% of the black dye;
0.5% to 2% by weight of the additive, and
containing the solvent in the balance,
A photosensitive resin composition.
22. The method of claim 21,
The solvent is
Contains PGMEA (propyleneglycol monomethylether acetate) alone solvent, or PGMEA mixed solvent in which 85% by weight or more of PGMEA and the balance of other solvents are mixed,
The other solvents are
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.
A pixel partition layer formed using the photosensitive resin composition according to claim 21 .
An electronic device comprising the pixel compartment layer of claim 25 .

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