KR102417834B1 - Egative photosensitive resin composition and electronic device having organic insulating film using same - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition having excellent pattern adhesion as well as excellent process characteristics and pattern formation, and an electronic device having an organic insulating film using the same.

Description

EGATIVE PHOTOSENSITIVE RESIN COMPOSITION AND ELECTRONIC DEVICE HAVING ORGANIC INSULATING FILM USING SAME

The present invention relates to a negative photosensitive resin composition and an optical element having an organic insulating film using the same.

There are various materials as a material for an organic insulating film used in a color filter or a pixel portion of an organic EL (electro-luminescence) device, but photosensitive polyimide is well known as a material having photosensitivity and heat resistance.

It is used in the form of a photosensitive polyimide precursor composition and is easy to apply, and after the polyimide precursor composition is applied on a semiconductor device, patterning by ultraviolet rays, development, thermal imidization, etc. are performed to provide a surface protection film and an interlayer insulating film The back can be easily formed.

Since the photosensitive polyimide materials have photosensitivity in the material itself, productivity can be expected to be improved, such as reducing the number of manufacturing steps required when patterning a non-photosensitive material and improving yield. Moreover, it is attracting attention because it becomes a process with low environmental load, such as being able to reduce the usage-amount of solvent.

The photosensitive characteristic can be divided into a negative type and a positive type. In the negative type, the photosensitive material in the portion irradiated with light is insolubilized. By removing the soluble portion (non-photosensitive portion) with the organic solvent of the developer and heat-treating it, a resin film with a pattern is obtained (Patent Documents 1 to see 4). In the positive type, the portion irradiated with light is solubilized in the developer. As in the case of the negative type, a portion soluble in a developer is removed and heat-treated to obtain a resin film with a pattern formed thereon. (See Patent Documents 5 to 8) As a developer used for the negative and positive types, an aqueous alkali solution is generally used.

Patent Document 1: Japanese Patent Publication No.-55-030207

Patent Document 2: Japanese Patent Publication No. 55-041422

Patent Document 3: Japanese Patent Application Laid-Open No. 54-145794

Patent Document 4: Japanese Patent Application Laid-Open No. 59-160140

Patent Document 5: Japanese Patent Application Laid-Open No. 62-145239

Patent Document 6: US Patent No. 4093461

Patent Document 7: US Patent No. 4845183

Patent Literature Japanese Unexamined Patent Publication No. 63-096162

A method of forming the photosensitive organic insulating film by applying a photosensitive resin composition to a substrate by photolithography is known.

Conventionally, application|coating of the photosensitive resin composition is performed using the spin coating method. As the size of the substrate increases, application by the spin coating method becomes difficult, and a coating method by the slit coating method has been proposed.

When the photosensitive composition is applied to the substrate surface by the slit coating method, the viscosity of the photosensitive resin composition is preferably less than 3.5 mPas in order to obtain good film thickness uniformity, although it may depend on the application rate. When the viscosity of the photosensitive resin composition is high, the photosensitive resin composition supplied from the slit nozzle is not smoothly supplied due to the high viscosity, resulting in an uncoated portion on the surface of the substrate.

In addition, when the photosensitive resin composition is applied by the slit coating method, it is necessary to wash the solidified material of the photosensitive resin composition that adheres or remains on the slit nozzle during repeated use before application. When the resolubility of this solidified material in the photosensitive resin composition is low, the solidified material remaining in the nozzle part remains as a protrusion, and when the photosensitive resin composition is applied to the substrate, streaks are generated in the direction of the nozzle. There is a problem in that the solidified material of the photosensitive resin composition falls off and adheres to the substrate, thereby reducing the yield.

In the case of a negative resin composition, it is mainly used in a color filter process, and in the case of a positive resin composition, it is mainly used in a TFT process.

It is common to arrange a grid-like black pattern called a black matrix between the pixels of a color filter for the purpose of improving the contrast. In the conventional black matrix, a method of forming a pattern by depositing and etching chromium (Cr) as a pigment on the entire glass substrate was used. A problem has occurred.

For this reason, research on a black matrix by a pigment dispersion method capable of micro-processing is being actively conducted, and research on preparing a black composition with a color pigment other than carbon black is also in progress. However, since color pigments other than carbon black have weak light-shielding properties, the blending amount must be increased to an extremely large amount. there was a problem with

Currently, in the industry, many studies on photosensitive resin compositions are being conducted in response to requests for continuous performance improvement. For example, a color filter composition to which a newly developed binder is applied to improve sensitivity, a black matrix tank composition with improved sensitivity using a high-sensitivity photopolymerization initiator, a black matrix with improved sensitivity by introducing a photopolymerization repellent and an organic phosphoric acid compound into the composition resin composition and the like.

An object of the present invention is to provide a negative photosensitive resin composition, an organic insulating film, and an electronic device having excellent pattern adhesion and excellent process characteristics and pattern formation.

In one aspect, the present invention provides a negative photosensitive resin composition comprising at least one compound represented by the following formula (1).

In another aspect, the present invention provides a photosensitive resin composition, an organic insulating film, and an electronic device comprising at least one polymer material represented by the following formula (1).

The polyamic acid according to the present invention, a photosensitive resin composition using the polyamic acid, a film, and an electronic device have excellent pattern adhesion, as well as excellent process characteristics and pattern formation.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same components are given the same reference numerals as much as possible even though they are indicated on different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms. When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is formed between each component. It should be understood that elements may also be “connected,” “coupled,” or “connected.” Further, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” another component, but also when another component is in between. It should be understood that cases may be included. Conversely, when it is said that an element is "on top of" another part, it should be understood to mean that there is no other part in the middle.

As used in this specification and the appended claims, unless otherwise indicated, the following terms have the following meanings.

As used herein, the term “halo” or “halogen” refers to fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond of 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups and cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” refers to an alkyl group substituted with halogen unless otherwise specified.

The term "alkenyl group" or "alkynyl group" used in the present invention, unless otherwise specified, has a double or triple bond of 2 to 60 carbon atoms, respectively, and includes a straight or branched chain group, and is limited thereto it is not

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

As used herein, the term “alkoxy group” or “alkyloxy group” refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term “aryloxyl group” or “aryloxy group” refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R' and R" are all hydrogen in the following structures, respectively, unless otherwise specified, " A substituted fluorenyl group" or "substituted fluorenylene group" means that at least one of the substituents R, R', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to It includes the case of forming a compound as a spy together.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto. In the present invention, the aryl group or the arylene group includes a monocyclic type, a ring conjugate, a fused multiple ring system, a spiro compound, and the like.

The term "heterocyclic group" as used in the present invention includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, the number of carbon atoms each containing at least one heteroatom It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Si, unless otherwise specified, and the heterocyclic group is a monocyclic group containing a heteroatom, a ring conjugate, a fused multiple ring system, a spy means a compound or the like.

In addition, the "heterocyclic group" may include a ring containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.

As used herein, the term "ring" includes monocyclic and polycyclic rings, and includes hydrocarbon rings as well as heterocycles containing at least one heteroatom, and includes aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, etc., fused multiple ring systems and spiro compounds, and includes aromatic as well as non-aromatic, hydrocarbon Rings include, of course, heterocycles containing at least one heteroatom.

As used herein, the term "ring assemblies" refers to two or more ring systems (single or fused ring systems) directly connected to each other through a single bond or a double bond, and a direct connection between such rings It means that the number of linkages is one less than the total number of ring systems in the compound. In a ring aggregate, the same or different ring systems may be directly linked to each other through single or double bonds.

As used herein, the term “fused multiple ring system” refers to a fused ring type sharing at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. The fused multiple ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and the spiro linkage means a connection formed by sharing only one atom in two rings. At this time, the atoms shared by the two rings are called 'spiro atoms', and they are respectively 'monospiro-', 'dispiro-', 'trispiro-', depending on the number of spiro atoms in a compound. ' It's called a compound.

Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group, where The arylcarbonyl group is a carbonyl group substituted with an aryl group.

In addition, unless otherwise explicitly stated, in the term "substituted or unsubstituted" as used herein, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ Alkoxy group, C ₁ -C ₂₀ Alkylamine group, C ₁ -C ₂₀ Alkylthiophene group, C ₆ -C ₂₀ Arylthiophene group, C ₂ -C ₂₀ Alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, C ₈ -C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and O, N, S, Si and P containing at least one heteroatom selected from the group consisting of C ₂ -C ₂₀ heterocyclic group means substituted with one or more substituents selected from the group consisting of and is not limited to these substituents.

In addition, unless there is an explicit explanation, the formula used in the present invention applies the same as the definition of the substituent by the exponential definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omitted.

Hereinafter, each component of the photosensitive resin composition according to an embodiment of the present invention will be described in detail.

high molecular compound

The present invention provides a negative photosensitive resin composition comprising at least one compound represented by the following formula (1).

In Formula 1,

로 이루어진 군에서 어느 하나로 선택되고,A ¹ is hydrogen or

selected from the group consisting of

X is a single bond, O, S, CR ^a R ^b _, NR, CH ₂ , C=O, SO ₂ , C(CF ₃ ) ₂ is selected from the group consisting of any one,

R, R ^a , R ^b , R ¹ , R ² , R ³ are each independently the same as or different from hydrogen; heavy hydrogen; halogen; CF ₃ ; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₆₀ Alkyl group; C ₃ ~ C ₆₀ A cycloalkyl group; C ₂ ~ C ₆₀ Alkenyl group; C ₂ ~ C ₆₀ Alkynyl group; C ₁ ~ C ₆₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; an ester group, an ether group; a hydroxyl group; selected from the group consisting of, R ^a and R ^b may combine with each other to form a spiro compound, R ² and R ³ may combine with each other to form a ring,

L is selected from the group consisting of C ₆ ~ C ₆₀ arylene group, C ₁ ~ C ₆₀ alkylene group,

n is selected from any integer from 2 to 100,000,

a and b are each independently the same or different, and are selected from any one of an integer of 1 to 3,

Ar ₁ To Ar ₃ Are each independently the same as or different from each other, C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₁ ~ C ₆₀ Alkylene group; C ₂ ~ C ₆₀ Alkenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; It is selected from the group consisting of the following formula (2-1) or the following formula (2-2);

In the above formulas (2-1) and (2-2),

R ⁴ , R ⁵ , R ⁶ , R′, R′′ are each independently the same as or different from each other, and are hydrogen, deuterium, halogen, CN, CF ₃ , a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₆₀ Alkyl group; C ₃ ~ C ₆₀ A cycloalkyl group; C ₂ ~ C ₆₀ Alkenyl group; C ₂ ~ C ₆₀ Alkynyl group; C ₁ ~ C ₆₀ Alkoxy group; C ₆ ~ C ₆₀ Aryloxy group; an ester group, an ether group; an amide group, an imide group; It is selected from the group consisting of, R' and R'' can combine with each other to form a spiro compound,

X ₁ is a single bond, O, S, CO, CR'R ”, SO ₂ is selected from the group consisting of,

a' and b' are each independently the same as or different from each other, and are selected from any one of an integer of 1 to 4,

c' is selected as any one of an integer from 1 to 6.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylene group, arylene group, alkylene group, fluorenylene group, alkenyl group Rene group, ester group, ether group, amide group, and imide group are each deuterium, halogen, silane group, siloxane group, boron group, cyano group, C ₁ -C ₂₀ alkylthio group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ Alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, fluorene Diyl, C ₂ -C ₂₀ Heterocyclic group, C ₃ -C ₂₀ Cycloalkyl group, C ₇ -C ₂₀ Arylalkyl group, C ₈ -C ₂₀ Arylalkenyl group, carbonyl group, ether group, C ₂ -C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of an alkoxylcarbonyl group, C ₆ -C ₃₀ aryloxy group.

Here, in the case of the aryl group, it may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, 2 to 60 carbon atoms, preferably having 2 carbon atoms. ~30, more preferably may be a heterocyclic ring having 2 to 20 carbon atoms, in the case of the alkyl group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon number It may be an alkyl group of 1-10.

In the case of the above-described aryl group or arylene group, specifically, the aryl group or the arylene group is independently of each other a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, a terphenylene group, a naphthyl group It may be a ren group or a phenanthrylene group.

Formula 1 may be represented by any one of Formulas 3 to 8.

In Formulas 3 to 8,

R ² , R ³ , R ^a , R ^b , R , A ¹ , Ar ₁ , Ar ₂ , Ar ₃ , a, b, n are R ² , R ³ , R ^a , R ^b as defined in claim 1 above. , R, A ¹ , Ar ₁ , Ar ₂ , Ar ₃ , a, b, n.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited thereto.

Hereinafter, Synthesis Examples and Preparation Examples of one or more compounds represented by Formula 1 included in the negative photosensitive resin composition according to the present invention will be described in detail with reference to Examples, but the present invention is limited to the following Examples it is not

In Synthesis Examples and Examples, the abbreviation of the polyimide raw material is used as follows.

BPDA: 3,3’,4,4’-Biphenyltetracarboxylic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

ODPA: 4,4'-Oxydiphthalic anhydride

HEA: 2-hydroxyethyl acrylate

HEMA: 2-hydoxyethyl methacrylate

GLM: Glycidyl methacrylate

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyloractone

DCC: N,N'-Dicyclohexylcarbodiimide

[ Synthesis example ]

The compound (final products) according to the present invention is synthesized by the reaction of Scheme 1 below, but is not limited thereto.

In Scheme 1, Ar ₁ , Ar ₂ , Ar ₃ , R ₁ , n, L and X are the same as Ar ₁ , Ar ₂ , Ar ₃ , R ₁ , n, L and X defined in Formula 1 above.

Synthesis examples of specific compounds of the present invention are as follows.

1. P1-1 Synthesis example

6FDA 22.21g (0.05mol), HEMA 14.31g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) together with 30g NMP in a 250ml 3-neck flask in a nitrogen atmosphere, and heated to 70℃ The temperature was raised and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0 ° C., and stirring for 2 hours, 4',4'''-(6-([ 1,1'-biphenyl]-4-yl)-1,3,5-triazine-2,4-diyl)bis(([1,1'-biphenyl]-4-amine)) 28.38 g (0.05 mol) was dissolved in 25 g of NMP and slowly added, reacted for 1 hour at 0°C, and reacted at room temperature for 8 hours. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol: water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 61.6 g of powder.

2. of P1-6 Synthesis example

6FDA 22.21g (0.05mol), GLM 15.64g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) together with 30g NMP in a 250ml 3-neck flask in a nitrogen atmosphere, and heated to 70℃ The temperature was raised and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0° C., and stirring for 2 hours, 4,4'-(6-(naphthalen-1-) yl)-1,3,5-triazine-2,4-diyl)bis(naphthalen-1-amine) 24.47 g (0.05 mol) was dissolved in 25 g of NMP, slowly added dropwise, reacted at 0 ° C for 1 hour, and then at room temperature reaction for 8 hours. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol: water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 59.2 g of powder.

3. of P1-29 Synthesis example

4,4'-Isopropylidenediphthalic anhydride 16.81g (0.05mol), HEA 12.77g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) in a 250ml 3-neck flask in a nitrogen atmosphere with 30g NMP Put together, the temperature was raised to 70 ℃ and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0 ° C., and stirring for 2 hours, 3-(4-(4-(4-(4) -aminophenoxy)phenyl)-6-(4-phenoxyphenyl)-1,3,5-triazin-2-yl)phenoxy)aniline 29.48g (0.05mol) was dissolved in 25g of NMP and slowly added dropwise at 0℃ for 1 hour and reacted at room temperature for 8 hours. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol:water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 56.1 g of powder.

4. of P1-38 Synthesis example

4,4'-Isopropylidenediphthalic anhydride 16.81g (0.05mol), HEMA 14.31g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) in a 250ml 3-neck flask in a nitrogen atmosphere with 30g NMP Put together, the temperature was raised to 70 ℃ and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0 ° C., and stirring for 2 hours, 4',4'''-(6-( 2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2,4-diyl)bis(2,2'-bis(trifluoromethyl)- [1,1'-biphenyl]-4-amine) 48.78 g (0.05 mol) was dissolved in 25 g of NMP, slowly added dropwise, reacted for 1 hour at 0° C., and reacted at room temperature for 8 hours. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol: water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 75.9 g of powder.

5. of P1-54 Synthesis example

5,5'-thiobis(isobenzofuran-1,3-dione) 16.31g (0.05mol), HEMA 14.31g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g in a 250ml 3-neck flask in a nitrogen atmosphere (0.002 mol) was added together with 30 g of NMP, and the temperature was raised to 70° C. and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0 ° C., and stirring for 2 hours, 4,4'-(((6-(4) -(phenylthio)phenyl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))bis(sulfanediyl))dianiline 33.19g (0.05mol) dissolved in 25g NMP and slowly added and reacted for 1 hour at 0°C, and reacted for 8 hours at room temperature. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol: water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 60.6 g of powder.

6. P1-80 Synthesis example

ODPA 15.51g (0.05mol), GLM 15.64g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) together with 30g NMP in a 250ml 3-neck flask in a nitrogen atmosphere, and the temperature was raised to 70℃ and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0 ° C., and stirring for 2 hours, 3,3'-(((6-(4) -benzylphenyl)-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))bis(methylene))dianiline 30.48g (0.05mol) was dissolved in 25g of NMP and slowly added to 0℃ 1 hour additional reaction at room temperature and 8 hours at room temperature. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol:water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 58.5 g of powder.

7. P1-90 Synthesis example

BPDA 14.71g (0.05mol), HEMA 14.31g (0.11mol), pyridine 17.40g (0.22mol), hydroquinone 0.2g (0.002mol) together with 30g NMP in a 250ml 3-neck flask in a nitrogen atmosphere, and the temperature was raised to 70℃ and stirred for 10 hours. After cooling the completely dissolved solution at room temperature, adding 25 g of NMP, cooling with ice water, adding 20.633 g (0.1 mol) of DCC at 0° C., and stirring for 2 hours, 3',3'''-(6-([ 1,1'-biphenyl]-3-yl)-1,3,5-triazine-2,4-diyl)bis(([1,1'-biphenyl]-4-amine)) 28.38 g (0.05 mol) was dissolved in 25 g of NMP and slowly added, reacted for 1 hour at 0°C, and reacted at room temperature for 8 hours. After stirring, the obtained solution was slowly added dropwise to a mixture of ethanol: water = 1:1 to solidify, and then dried in a vacuum drying oven at 50° C. for one day to obtain 54.5 g of powder.

[ comparative example ]

The compound of Comparative Example is synthesized by the following reaction scheme.

One. comparative example One

Put ODA 10g (0.05mol) in a 250ml three-necked flask in a nitrogen atmosphere and NMP 20g to completely dissolve it at room temperature. After cooling the dissolved solution with ice water, 10.61 g (0.05 mol) of bis(4-aminophenyl)methanone was slowly added at 0° C., and 28 g of additional NMP was added thereto, followed by stirring for 3 hours. After adding 34.4 g of NMP to the mixed solution, and after additional stirring at room temperature for 10 hours, 103 g of a varnish having a final viscosity of 100 to 10,000 cps (measured at 25° C.) was obtained.

2. comparative example 2

Put 9.21 g (0.05 mol) of benzidine in a 250 ml 3-neck flask in a nitrogen atmosphere and 25 g of NMP to completely dissolve it at room temperature. After cooling the dissolved solution with ice water, 14.7 g (0.05 mol) of BPDA was slowly added at 0° C., then 30.79 g of NMP was added and stirred for 3 hours. After adding 39 g of NMP to the mixed solution, and after stirring at room temperature for 10 hours, 119.5 g of a varnish having a final viscosity of 100 to 10,000 cps (measured at 25° C.) was obtained.

photosensitive resin composition

On the other hand, according to another embodiment of the invention, a polymer resin including at least one polymer material (or polymer compound) represented by the above formula (1); acrylic binder (or acrylic resin); photocrosslinking agent; organic solvents; sensitizer; and a photosensitive resin preparation comprising a photopolymerization initiator. In this case, the photosensitive resin composition may be a photosensitive resin composition used as a negative photosensitive resin composition.

The negative photosensitive resin composition of the present invention may include 0.1 to 50 mol% of the repeating unit of Formula 1, and may have a weight average molecular weight of 5,000 to 200,000.

When the repeating unit and the weight average molecular weight of the negative photosensitive resin are within the above ranges, a pattern can be formed without a residue when the light blocking layer is manufactured, there is no loss of film thickness during development, and a good pattern can be obtained. The negative photosensitive resin may be included in an amount of 1 to 30 wt%, more preferably 3 to 20 wt%, based on the total amount of the photosensitive resin composition. When the resin is included within the above range, excellent sensitivity, developability, and adhesion or adhesion may be obtained.

The composition of the acrylic binder, the photocrosslinking agent, the sensitizer and the photopolymerization initiator included in the above-described photosensitive resin composition may be as follows, but the present invention is not limited thereto.

(A) Acrylbinder

When the composition is used for alkali development, other polymers having a carboxyl group structure may be mixed and used to improve pattern processing performance in an alkaline developer and to compensate for insufficient developability, but is not limited to acrylate resins. The carboxyl group concentration of the acrylate resin is preferably 30 to 130 mol% with respect to the structural unit. If it is less than this, it has little solubility as an alkali developer, and if it is greater than this, the film thickness during development increases, so caution is required.

A-1: Non-reactive acrylate resin (Acid value: 110, Mw: 11000)

(B) Photocrosslinking agent

A photocrosslinking agent is a compound that forms a bond with a compounding composition such as a resin or other crosslinking agent molecules by the action of heat or acid. Specific examples include a polyfunctional methacrylate compound, an epoxy compound, a hydroxymethyl group-substituted phenol compound, and a compound having an alkoxyalkylated amino group. Among these, the compound which has a methacrylate compound is preferable. Moreover, these crosslinking agents can be used individually by 1 type or in combination of 2 or more type. The content ratio of the photocrosslinking agent is appropriately used so that the film formed of the photosensitive resin composition is sufficiently cured.

M-1: Dipentaerythritol Hexaacrylate

(C) photoinitiators, sensitizers

In order to obtain high sensitivity and high resolution in the pattern after development, it is preferable to contain a photoinitiator and a sensitizer (or a photosensitizer), and the method is not limited, such as using two or more of them.

I-1: 1-[4-(phenylthio)phenyl]-2-( O -benzoyloxime)-1,2-octanedione

E-1: benzanthrone

(D) other additives

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after heat treatment and the support, an appropriate adhesion aid may be added and used. As an adhesion aid, organosilicon compounds such as aminopropylethoxysilane, glycidoxypropyltrimethoxysilane, and oxypropyltrimethoxysilane are mainly used. In addition, aluminum chelate compounds or titanium chelate compounds can be used. The amount varies from 0.01 to 20 wt. % is preferably added. Additionally, the composition may contain a surfactant for the purpose of improving various properties such as applicability, defoaming property, and leveling property. As the type of surfactant, fluorine-based or silicone-based surfactants may be used, and two or more types of surfactants may be mixed and used.

(E) solvent

The photosensitive resin composition of this invention can be made to contain the organic solvent as needed in order to adjust a viscosity and storage stability. The type of solvent that can be contained is not particularly limited, but N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, etc. Some magnetic solvents are used.

In addition, by containing an organic solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate instead of or together with the solvent, coating properties can be improved. can

These solvents can be used individually by 1 type or in combination of 2 or more type. Moreover, a solvent is used normally so that a content rate may become 1-80 mass %.

S-1: PGMEA (propylene glycol monomethyl ether acetate)

S-2: NMP (N-methyl-2-pyrrolidone)

Meanwhile, the photosensitive resin composition may further include a thermal crosslinking agent, a curing accelerator, a phosphorus-based flame retardant, an antifoaming agent, a leveling agent, an anti-gelling agent, or a mixture thereof. Such additives may be used without particular limitation as long as they are known to be usable in the photosensitive resin composition, and may be used in an appropriate amount in consideration of the physical properties of the photosensitive resin composition to be prepared or a film obtained therefrom.

Production evaluation of photosensitive resin composition

Examples 1-5: A photosensitive resin composition was prepared by mixing the polyimide precursor prepared in Synthesis Examples 1-5 with an acrylic resin, a crosslinking agent, a photoinitiator, a sensitizer, and a solvent according to the ratios shown in Table 1 below. Adhesives and surfactants, which are other additives, were mixed in an amount of 0.001 to 1% based on mass%.

Comparative Examples 1-2: A photosensitive resin composition was prepared by mixing the polyimide precursor synthesized in Synthesis Examples 6 to 7 according to the ratio in Table 1, and the ratio of other additives was mixed in the same manner as in Examples.

The input amount in Table 1 is based on mass%, and after evaluating the physical properties of the photosensitive resin composition in the following manner, the results are shown in Table 2 below.

1. Resolution evaluation

The photosensitive resin composition prepared in Examples and Comparative Examples was spin-coated on a 100*100 mm glass plate, and heated at 100° C. for 60 seconds on a hot plate to form a photosensitive resin layer with a thickness of 10 μm. The glass substrate coated with the photosensitive resin layer was vacuum-adhered to the photomask, and then exposed to 30 mJ/cm ² to 150 mJ/cm ² using an i-line exposure machine. After the exposure was completed, it was developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23° C. for 60 seconds, and washed with DI-water for 30 seconds to obtain a pattern in which the exposed part remained clearly. Thereafter, a final heat treatment was performed at 230° C. for 60 minutes using a baking oven to complete the patterning process. For the pattern on which the heat treatment was completed, the resolution of each Example and Comparative Example was measured through SEM analysis.

2. remaining film rate evaluation

The method of coating the photosensitive resin composition on a glass substrate, exposure and heat treatment is the same as the above resolution evaluation, and the thickness of the pattern that has not undergone the final heat treatment process and the thickness of the pattern that has undergone the final heat treatment process is analyzed and compared to evaluate the remaining film rate. .

Remaining film rate = thickness of pattern before final heat treatment / thickness of pattern after final heat treatment X 100

Each evaluation result is shown in Table 2 below.

Example 1 in the resolution evaluation is 30mJ/cm ² All of the patterns were dropped from the , and a pattern with a size larger than 10 μm was formed at 50 and 80 mJ/cm ² . Patterns of sizes larger than 100 and 120 mJ/cm ² including 5 μm were formed, and patterns with sizes smaller than 150 mJ/cm ² and 5 μm were connected to each other and entangled. It was confirmed that the pattern of

Example 2 is 30mJ/cm ² The patterns all dropped at 50, 80, and 100 mJ/cm ² A pattern larger than that including a 5 μm pattern was formed. 120, 150 mJ/cm ² In the patterns of sizes smaller than 10 μm, it was confirmed that the patterns were connected to each other and entangled, and it was confirmed that a larger size pattern was formed.

Example 3 is 30-80mJ/cm ² A pattern larger than that including a 5 μm pattern was formed. ¹²⁰ , 150mJ/cm2 for patterns of ^100mJ /cm2 to 10㎛ and smaller In the patterns with a size smaller than 15 μm, it was confirmed that the patterns were connected to each other and entangled, and it was confirmed that a larger size pattern was formed.

Example 4 is 50-100 mJ/cm ² A pattern larger than that including a 5 μm pattern was formed. 120, 150 mJ/cm ² It was confirmed that the patterns of sizes smaller than 10 μm were connected to each other and entangled, and it was confirmed that a larger size pattern was formed.

Example 5 is 30, 50, 80, 100mJ / cm ² A pattern larger than that including a 5 μm pattern was formed. 120, 150 mJ/cm ² In the patterns of sizes smaller than 10 μm, it was confirmed that the patterns were connected to each other and entangled, and it was confirmed that a larger size pattern was formed.

Comparative Example 1 is 120mJ/cm ² In the above, a pattern having a size larger than that including a 20 μm pattern was formed, and the pattern fell at a light quantity of less than that.

Comparative Example 2 is 150mJ/cm ² In the above, a pattern having a size larger than that including a 20 μm pattern was formed, and the pattern fell at a light quantity of less than that.

In the evaluation of the remaining film rate, Examples 1 and 2 confirmed a remaining film rate of 82 to 85%, and Examples 3, 4 and 5 had a remaining film rate of 90 to 93%. This is because in the case of Examples 1 and 2, the distance between molecules became closer than in Examples 3, 4 and 5 due to the low steric hindrance effect between molecules during the final heat treatment.

Comparative Examples 1 and 2 did not contain a functional group, so it was confirmed that the thickness of the film was reduced after the final heat treatment due to the low steric hindrance effect between molecules.

The present invention is a negative photosensitive resin composition capable of high-resolution patterning at low light intensity, and has high sensitivity and excellent cured film properties.

Organic Insulation Film and Electronic Devices

Meanwhile, according to another embodiment of the present invention, there is provided an organic insulating film including a cured product of the above-described photosensitive resin composition. Specifically, the organic insulating film means an organic insulating film obtained by drying the above-described photosensitive resin composition or an organic insulating film obtained by photocuring or thermosetting the photosensitive resin composition.

The above-described organic insulating film can be prepared by coating the photosensitive resin composition on a support by a known method and drying. It is preferable that the said support body can peel the photosensitive resin composition layer, and the thing with the good transmittance|permeability of light. Moreover, it is preferable that the smoothness of the surface is favorable.

As specific examples of the support, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly(meth)acrylic acid alkyl ester, poly(meth)acrylic acid ester copolymer, polyvinyl chloride, poly Various plastic films such as vinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene can be heard In addition, a composite material composed of two or more thereof can be used, and a polyethylene terephthalate film having excellent light transmittance is particularly preferable. The thickness of the support may be 5 to 150 μm, and more specifically, 10 to 50 μm.

The coating method of the photosensitive resin composition is not particularly limited, and for example, a spray method, a roll coating method, a rotation coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method or a knife A method such as a coating method can be used. The drying of the photosensitive resin composition may be performed at 60 to 100° C. for 30 seconds to 15 minutes, although it varies depending on the type and content ratio of each component or organic solvent.

The thickness of the organic insulating film after drying and curing is 5 to 95 μm, more specifically, 10 to 50 μm.

In this case, the organic insulating film is a base film of a substrate for a display device, an insulating layer of a substrate for a display device, an interlayer insulating film for a display panel, a pixel defining film or bank layer for a display panel, a solder resistor for a display panel, a black matrix for a display panel, a display panel It can be used as one of a color filter substrate for a circuit board, a protective film for a circuit board, a base film for a circuit board, an insulating layer for a circuit board, an interlayer insulating film for a semiconductor, or a solder resist.

Meanwhile, according to another embodiment of the present invention, there is provided an electronic device including a display device including the above-described organic insulating film and a control unit for driving the display device. The above-described display device may be a liquid crystal display device or a display device including an organic electric device, but the present invention is not limited thereto. In addition, although the above-described organic insulating layer is used as a black matrix for a display panel by way of example, the present invention is not limited thereto.

After pre-lamination of the organic insulating film at a temperature of 20 to 50°C by a method such as flat pressing or roll pressing on the forming surface of the display panel, vacuum lamination at 60 to 90°C to achieve photosensitivity A film can be formed.

In addition, the organic insulating layer is exposed to light using a photomask to form a fine structure or a fine width line to form a pattern. The exposure amount may be appropriately adjusted according to the type of light source used for UV exposure and the thickness of the film film, for example, 100 to 1200 m/cm 2 and more specifically, 100 to 500 m/cm 2 , but not limited thereto .

Active rays that can be used include electron beams, ultraviolet rays, X-rays, and the like, and preferably ultraviolet rays. In addition, as a usable light source, a high-pressure mercury lamp, a low-pressure mercury lamp, or a halogen lamp may be used as the light source.

A spray method is generally used for development after exposure, and the photosensitive resin composition is developed using an aqueous alkali solution such as an aqueous sodium carbonate solution, and then washed with water. After that, if the polyamic acid is changed to polyimide according to the pattern obtained by development through the heat treatment process, the heat treatment temperature may be 100 to 250° C. required for imidization. At this time, it is effective to continuously increase the heating temperature over 2 to 4 steps with an appropriate temperature profile, but in some cases, curing may be performed at a constant temperature. Through the above-described steps, a black matrix for a display panel and the like can be obtained.

In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a single color or white lighting device.

The organic electric device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent in processability, and can be manufactured using the existing color filter technology of LCD. Various structures for a white organic light emitting diode mainly used as a backlight device have been proposed and patented. Typically, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are mutually planar, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is a color conversion material (CCM) method using electroluminescence by the blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using the light therefrom, and the present invention could also be applied to such WOLEDs.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, and various computers.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (11)

A negative photosensitive resin composition comprising at least one polymer or oligomer represented by the following formula (1).

In Formula 1,
A ¹ is hydrogen or

selected from the group consisting of
X is a single bond, O, S, CR ^a R ^b _, NR, CH ₂ , C=O, SO ₂ , C(CF ₃ ) ₂ is selected from the group consisting of any one,
R, R ^a , R ^b , R ¹ , R ² , R ³ are each independently the same as or different from hydrogen; heavy hydrogen; halogen; CF ₃ ; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₆₀ Alkyl group; C ₃ ~ C ₆₀ A cycloalkyl group; C ₂ ~ C ₆₀ Alkenyl group; C ₂ ~ C ₆₀ Alkynyl group; C ₁ ~ C ₆₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; an ester group, an ether group; a hydroxyl group; selected from the group consisting of, R ^a and R ^b may combine with each other to form a spiro compound, R ² and R ³ may combine with each other to form a ring,
L is selected from the group consisting of C ₆ ~ C ₆₀ arylene group, C ₁ ~ C ₆₀ alkylene group,
n is selected from any integer from 2 to 100,000,
a and b are each independently the same or different, and are selected from any one of an integer of 1 to 3,
Ar ₁ To Ar ₃ Are each independently the same as or different from each other, C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₁ ~ C ₆₀ Alkylene group; C ₂ ~ C ₆₀ Alkenylene group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; It is selected from the group consisting of the following formula (2-1) or the following formula (2-2);

In the above formulas (2-1) and (2-2),
R ⁴ , R ⁵ , R ⁶ , R′, R′′ are each independently the same as or different from each other, and are hydrogen, deuterium, halogen, CN, CF ₃ , a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₆₀ Alkyl group; C ₃ ~ C ₆₀ A cycloalkyl group; C ₂ ~ C ₆₀ Alkenyl group; C ₂ ~ C ₆₀ Alkynyl group; C ₁ ~ C ₆₀ Alkoxy group; C ₆ ~ C ₆₀ Aryloxy group; an ester group, an ether group; an amide group, an imide group; It is selected from the group consisting of, R' and R'' can combine with each other to form a spiro compound,
X ₁ is a single bond, O, S, CO, CR'R ”, SO ₂ is selected from the group consisting of,
a' and b' are each independently the same as or different from each other, and are selected from any one of an integer of 1 to 4,
c' is selected as any one of an integer from 1 to 6.
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, alkylene group, arylene group, alkylene group, fluorenylene group, alkenyl group Rene group, ester group, ether group, amide group, and imide group are each deuterium, halogen, silane group, siloxane group, boron group, cyano group, C ₁ -C ₂₀ alkylthio group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ Alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryl group substituted with deuterium, fluorene Diyl, C ₂ -C ₂₀ Heterocyclic group, C ₃ -C ₂₀ Cycloalkyl group, C ₇ -C ₂₀ Arylalkyl group, C ₈ -C ₂₀ Arylalkenyl group, carbonyl group, ether group, C ₂ -C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of an alkoxylcarbonyl group, C ₆ -C ₃₀ aryloxy group. According to claim 1,
A negative photosensitive resin composition, characterized in that Formula 1 is represented by the following Formulas 3 to 8.

In Formulas 3 to 8,
R ² , R ³ , R ^a , R ^b , R, A ¹ , Ar ₁ , Ar ₂ , Ar ₃ , a, b, n are R ² , R ³ , R ^a , R ^b as defined in claim 1 above. , R, A ¹ , Ar ₁ , Ar ₂ , Ar ₃ , a, b, n. According to claim 1,
Chemical Formula 1 is a negative photosensitive resin composition represented by any one of the following Chemical Formulas.

According to claim 1,
A negative photosensitive resin composition comprising 0.1 to 50 mol% of the repeating unit of Formula 1 above. According to claim 1,
A negative photosensitive resin composition having a weight average molecular weight of 5,000 to 200,000. According to claim 1,
A polymer resin including a negative photosensitive resin composition represented by Formula 1;
acrylic resin;
photocrosslinking agent;
organic solvents;
sensitizer; and
A negative photosensitive resin composition comprising a photoinitiator. An organic insulating film comprising the photosensitive resin composition of claim 1. 8. The method of claim 7,
Base film for display device substrate, insulating layer for display device substrate, interlayer insulating film for display panel, pixel defining film or bank layer for display panel, solder resistor for display panel, black matrix for display panel, color filter substrate for display panel , an organic insulating film used as one of a protective film for a circuit board, a base film for a circuit board, an insulating layer for a circuit board, an interlayer insulating film for a semiconductor, or a solder resist. A display device comprising the organic insulating film of claim 8; and
An electronic device comprising a; a control unit for driving the display device. 10. The method of claim 9,
The display device is an electronic device including a liquid crystal display device or an organic electric device. 11. The method of claim 10,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and one of monochromatic or white lighting devices.