KR20180061572A - Negative photosensitive resin composition, film and electronic device - Google Patents

Abstract

The present invention provides: a negative photosensitive resin composition, which not only has excellent pattern adhesion but also is excellent process characteristics and pattern formation; a film; and an electronic device.

Description

[0001] NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION, FILM AND ELECTRONIC DEVICE [0002]

The present invention relates to negative photosensitive resin compositions, films and electronic devices.

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

The polyimide precursor composition is applied on a semiconductor device and then subjected to patterning by ultraviolet rays, development, thermal imidization, and the like to form a surface protective film, an interlayer insulating film And the like can be easily formed.

The photosensitive polyimide materials can be expected to be improved in productivity, such as being capable of reducing the number of manufacturing steps required when patterning a non-photosensitive material due to photosensitivity of the material itself, and improving the yield. In addition, the use of the solvent can be reduced, and the process with low environmental burden becomes a focus.

The photosensitive characteristics can be divided into a negative type and a positive type. In the negative type, the photosensitive material of the portion irradiated with light is insoluble. A soluble portion (non-photosensitive portion) is raised by the organic solvent of the developing solution, and a heat treatment is performed to obtain a patterned resin film. 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 the developer is removed, and a heat treatment is performed to obtain a resin film having a pattern formed thereon. In general, an alkali aqueous solution is often used as the developer for the positive and negative types.

A photosensitive organic insulating film is known that a photosensitive resin composition is applied to a substrate and formed by photolithography.

Conventionally, the application of the photosensitive resin composition is carried out by using a spin coating method. As the substrate becomes larger, coating 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 surface of the substrate by the slit coating method, the viscosity of the photosensitive resin composition is preferably less than 3.5 mPas in order to obtain a uniform film thickness uniformity although it may vary depending on the application speed. 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 high viscosity, and a portion not coated on the surface of the substrate is generated.

Also, when the photosensitive resin composition is applied by a slit coating method, there is a need for a step of cleaning the solidified material of the photosensitive resin composition adhering to or remaining in the slit nozzle during repeated use before application. When the solubility of the solidified material in the photosensitive resin composition is low, the solidified material remaining in the nozzle portion remains as protrusions, and when the photosensitive resin composition is applied to the substrate, There is a problem that the solidified material of the photosensitive resin composition falls away and adheres to the substrate, thereby lowering the yield.

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

Between the pixels of the color filter, a lattice-shaped black pattern called a black matrix is generally disposed for the purpose of improving the contrast. In the conventional black matrix, chromium (Cr) is used as a pigment to deposit and etch the entire glass substrate to form a pattern. However, high costs are required for the co-deposition, and problems such as high reflectivity of chromium, environmental pollution A problem has occurred.

For this reason, studies of black matrix by pigment dispersion method capable of micromachining have been actively carried out, and studies for producing a black composition using colored pigments other than carbon black are also under way. However, color pigments other than carbon black have a low light shielding property, and therefore the amount thereof should be increased to an extremely large amount, and as a result, the viscosity of the composition is increased and handling becomes difficult, or the strength of the formed film or the adhesion to the substrate becomes remarkable There was a problem of deterioration.

At present, there is a lot of research on the photosensitive resin composition in accordance with the demand for continuous performance improvement. For example, a color filter composition using a newly developed binder for improving sensitivity, a black matrix resin composition having improved sensitivity using a high-sensitivity photopolymerization initiator, a new photopolymerizer, and a black matrix having improved sensitivity by introducing organic phosphoric acid compounds into the composition And resin compositions.

An object of the present invention is to provide a negative photosensitive resin composition, a film, and an electronic device which are excellent in pattern adhesion, and are excellent in 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, film, and electronic device comprising at least one polymeric material represented by the following formula (1).

The photosensitive resin composition, film, and electronic device using the polyamic acid, the polyamic acid, and the polyamic acid according to the present invention have not only excellent pattern adhesion but also excellent process characteristics and pattern formation.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected." In addition, when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, And the like. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

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

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

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

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R 'and R & 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' Together with a spy compound.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, the aryl group or the arylene group includes a single ring type, a ring bonding compound, a plurality of bonded ring systems, a spiro compound, and the like.

The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group ", but also nonaromatic rings, Means a ring of 2 to 60 rings, but is not limited thereto. The term "heteroatom ", as used herein, unless otherwise indicated, refers to N, O, S, P, or Si, wherein the heterocyclic group includes a single ring, ring junction, And the like.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, and the like, as well as various fused ring systems and spiro compounds, including aromatic as well as non- The ring includes, of course, a heterocycle containing at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (a single ring or a fused ring system) are directly connected to each other through a single bond or a double bond, Means that the number of linkages is one less than the total number of rings in the compound. The ring assemblies may be directly connected to each other through a single bond or a double bond.

As used herein, the term " conjugated ring system "refers to a fused ring form sharing at least two atoms, in which the ring system of two or more hydrocarbons is conjugated and contains at least one heteroatom And at least one hetero ring system bonded thereto. Such conjugated ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and a spiro connection means a connection in which two rings share only one atom. At this time, atoms shared in two rings are called 'spyro atoms', and they are referred to as 'monospyros,' 'di spyroses,' and 'tri-spyros', depending on the number of spyro atoms contained in a compound. 'Compounds.

Also, if the prefixes are named consecutively, it means that the substituents are listed in the order listed first. Means, for example, an alkoxy group substituted with an aryl group in the case of an arylalkoxy group, a carbonyl group substituted with an alkoxy group in the case of an alkoxycarbonyl group, and an alkenyl group substituted with an arylcarbonyl group in the case of an arylcarbonylalkenyl group, The arylcarbonyl group is a carbonyl group substituted with an aryl group.

In addition, a no explicit description, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro _{group, C 1 -C 20, C 1} -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkyl amine group, C ₁ -C ₂₀ alkyl thiophene group, C ₆ -C ₂₀ aryl thiophene group, C ₂ -C ₂₀ alkenyl, C ₂ -C of ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron And a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, with the proviso that at least one substituent And is not limited to these substituents.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

Polymer compound

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

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

R ^a , R ^b , R, R ¹ , R ² , R ³ and Ar ¹ are each independently hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; An alkyl group having ₁ to ₆₀ carbon atoms; A C ₃ to C ₆₀ cycloalkyl group; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₆₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; Ester group, ether group; A hydroxyl group; CF ₃ ; R ^a and R ^b may combine with each other to form a spiro compound,

L each independently represents a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And O, N, S, a heterocyclic C ₂ ~ containing at least one hetero atom of Si and P C ₆₀ group; A C ₁ to C ₆₀ alkylene group,

n is an integer of 2 to 1000,

a and b are independently an integer of 1 to 3, and when a and b are each 2 or more, each of R ² and R ³ may combine to form a ring,

Ar ¹ is a C ₆ to C ₆₀ arylene group; A fluorenylene group; An alkylene group of C ₁ to C ₆₀ ; An alkenylene group having ₂ to ₆₀ carbon atoms; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; Is selected from the group consisting of formulas (2-1) and (2-2)

here,

X1 is selected from a single bond, O, S, the group consisting of CO, CR'R ", SO _2, each independently,

R ⁴ , R ⁵ , R ⁶ , R ', and R "are independently and independently hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; An alkyl group having ₁ to ₆₀ carbon atoms; A C ₃ to C ₆₀ cycloalkyl group; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₆₀ alkoxyl group; An aryloxy group of C ₆ to C ₆₀ ; Ester group, ether group; Amide group, imide group; , ≪ / RTI >

a 'to b' are integers of 1 to 4,

and c 'is an integer of 1 to 6.

The aryl group may be substituted with at least one substituent selected from the group consisting of an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, an alkylene group, an arylene group, the alkenyl group, an ester group, an ether group, amide group, imide groups are each deuterium, a halogen, a silane group, a siloxane group, a boron group, a cyano group, an alkylthio import of _{C 1 -C 20, C 1 -C} 20 alkoxyl an aryl group of group, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ substituted with a C ₆ aryl group, a heavy hydrogen of -C ₂₀ of a, C ₂ -C ₂₀ cycloalkyl group, C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, carbonyl group, ether group, C ₂ -C ₂₀ heterocyclic group, C ₃ -C ₂₀ cycloalkyl group, An alkoxycarbonyl group of C ₂₀ , and an aryloxy group of C ₆ -C ₃₀ .

The aryl group 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 the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene group, Or a phenanthrylene group.

The formula (1) may be represented by any one of the following formulas (3) to (8).

R ¹ , R ² , R ³ , Ar ¹ , A _1, a, b and n are the same as defined in the formula (1).

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

Hereinafter, the synthesis examples and the production examples of the at least one compound represented by the formula (1) contained in the negative-type photosensitive resin composition according to the present invention will be concretely described by way of examples, but the present invention is limited to the following examples It is not.

[ Synthesis Example 1 ]

Synthesis Examples In the Examples, the abbreviations of the polyimide raw materials are used as follows.

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

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

ODPA: 4,4'-Oxydiphthalic anhydride

NDA: naphthalene-1,4-diamine

TFDB: 2,2'-bis (trifluoromethyl) - [1,1'-biphenyl] -4,4'-diamine

ODA: 4,4'-oxydianiline

TDA: 4,4'-thiodianiline

MDA: 4,4'-methylenedianiline

HEA: 2-hydroxyethyl acrylate

HEMA: 2-hydoxyethyl methacrylate

GLM: Glycidyl methacrylate

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyloractone

DCC: N, N'-Dicyclohexylcarbodiimide

Examples of the synthesis of specific compounds are as follows. Wherein Ar ¹ , R ₁ , n and X are the same as defined in the above formula (1).

1. P1-1 Synthetic example

In a nitrogen-atmosphere atmosphere, 22.21 g (0.05 mol) of 6FDA, 14.31 g (0.11 mol) of HEMA, 17.40 g (0.22 mol) of pyridine and 0.2 g (0.002 mol) of hydroquinone were added to 30 g of NMP in a 250 ml three- Lt; / RTI > The solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base and stirred for 2 hours, 9.21 g (0.05 mol) of benzidine was dissolved in 25 g of NMP, The resulting solution was stirred at room temperature for 1 hour and then cooled to room temperature. The solution was slowly added to a mixed solution of ethanol and water at a ratio of 1: 1 to solidify the solution. The resulting solution was dried in a vacuum drying oven at 50 ° C for one day. M-ester resin.

2. P1-6 Synthetic example

In a nitrogen-atmosphere atmosphere, 22.21 g (0.05 mol) of 6FDA, 15.64 g (0.11 mol) of GLM, 17.40 g (0.22 mol) of pyridine and 0.2 g (0.002 mol) of hydroquinone were added to 30 g of NMP in a 250 ml three- Lt; / RTI > The solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base, the solution was stirred for 2 hours and then 9.21 g (0.05 mol) of NDA was dissolved in 25 g of NMP. The resulting solution was stirred at room temperature for 1 hour and then cooled to room temperature. The solution was slowly added to a mixed solution of ethanol and water at a ratio of 1: 1 to solidify the solution. The resulting solution was dried in a vacuum drying oven at 50 ° C for one day. M-ester resin.

3. P1-29 Synthetic example

In a 250 ml three-necked flask, 16.81 g (0.05 mol) of 4,4'-Isopropylidenediphthalic anhydride, 12.77 g (0.11 mol) of HEA, 17.40 g (0.22 mol) of pyridine and 0.2 g The mixture was heated to 70 ° C and stirred for 10 hours. The solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base, the solution was stirred for 2 hours. Then, 10.01 g (0.05 mol) of ODA was dissolved in 25 g of NMP, The resulting solution was stirred at room temperature for 1 hour and then cooled to room temperature. The resulting solution was slowly added to a mixture of ethanol and water at a ratio of 1: 1 to solidify it. The resulting solution was dried in a vacuum drying oven at 50 캜 for one day. M-ester resin.

4. P1-38 Synthetic example

In a nitrogen-atmosphere 250 ml three-necked flask, 16.81 g (0.05 mol) of 4,4'-Isopropylidenediphthalic anhydride, 14.31 g (0.11 mol) of HEMA, 17.40 g (0.22 mol) of pyridine and 0.2 g The mixture was heated to 70 ° C and stirred for 10 hours. The solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base, the solution was stirred for 2 hours and then 16.01 g (0.05 mol) of TFDB was dissolved in 25 g of NMP. The resulting solution was stirred at room temperature for 1 hour and then cooled to room temperature. The solution was slowly added to a mixed solution of ethanol and water at a ratio of 1: 1 to solidify the solution. The resulting solution was dried in a vacuum drying oven at 50 ° C for one day. M-ester resin.

5. P1-54 Synthetic example

In a 250 ml three-necked flask, 16.31 g (0.05 mol) of 5,5'-thiobis (isobenzofuran-1,3-dione), 14.31 g (0.11 mol) of HEMA, 17.40 g (0.22 mol) of pyridine, 0.2 g (0.002 mol) were heated to 30 g of NMP at 70 DEG C and stirred for 10 hours. The solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base, the solution was stirred for 2 hours and then 10.81 g (0.05 mol) of TDA was dissolved in 25 g of NMP. The resulting solution was stirred at room temperature for 1 hour under ice-base, cooled to room temperature, slowly added to a mixed solution of ethanol and water = 1: 1, solidified, and dried in a vacuum drying oven at 50 ° C for a day to obtain 40 g of poly M-ester resin.

6. P1-80 Synthetic example

In a nitrogen-atmosphere atmosphere, 15.51 g (0.05 mol) of ODPA, 15.64 g (0.11 mol) of GLM, 17.40 g (0.22 mol) of pyridine and 0.2 g (0.002 mol) of hydroquinone were heated in 30 g of NMP to 70 ° C. in a 250 ml three- Lt; / RTI > After completely adding 25 g of NMP, 20.633 g (0.1 mol) of DCC was added under ice-base. After stirring for 2 hours, 9.91 g (0.05 mol) of MDA was dissolved in 25 g of NMP, The resulting solution was stirred at room temperature for 1 hour under ice-base, cooled to room temperature, slowly added to a mixed solution of ethanol and water = 1: 1, solidified, and dried in a vacuum drying oven at 50 ° C for a day to obtain 40 g of poly M-ester resin.

7. P1-90 Synthetic example

In a nitrogen-atmosphere atmosphere, 14.71 g (0.05 mol) of BPDA, 14.31 g (0.11 mol) of HEMA, 17.40 g (0.22 mol) of pyridine and 0.2 g (0.002 mol) of hydroquinone were added to 30 g of NMP in a 250 ml three- Lt; / RTI > After completely dissolved, the solution was cooled to room temperature, and 25 g of NMP was added. After 20.633 g (0.1 mol) of DCC was added under ice-base, the mixture was stirred for 2 hours and then 1,1'-biphenyl] -3,3'-diamine (0.05 mol) was dissolved in 25 g of NMP and slowly added. The mixture was stirred under ice-base for 1 hour and at room temperature for 8 hours. The resulting solution was cooled to room temperature, slowly added to a mixture of ethanol and water (1: 1) And dried in a vacuum oven at 50 캜 for one day to obtain 38 g of polyamic ester resin.

[ Comparative Example ]

The compounds of the comparative examples are synthesized by the following reaction formula.

One. Comparative Example 1

In a nitrogen atmosphere, 10 g (0.05 mol) of ODA is added to a 250 ml three-necked flask, and 40 g of NMP is completely dissolved at room temperature. Add slowly 10.61 g (0.05 mol) of bis (4-aminophenyl) methanone under ice-base, add 40 g of additional NMP and stir for 3 hours. 95 g of NMP was further added to the mixed solution, and further stirred at room temperature for 10 hours to obtain 195 g of a varnish having a final viscosity of 100 to 5000 cps (measured at 25 캜).

2. Comparative Example 2

In a nitrogen atmosphere, 9.21 g (0.05 mol) of benzidine and 30 g of NMP are added to a 250 ml three-necked flask and completely dissolved at room temperature. After the addition of NMP 35 to the mixed solution, the resulting solution was further stirred for 10 hours at room temperature, and the final viscosity was 100 to 5000 cps (25 ° C Quot;) was obtained.

Photosensitive resin

According to another embodiment of the present invention, a polymer resin containing at least one polymeric substance represented by the above-mentioned general formula (1) or the like; An acrylic resin or an acrylic binder containing at least one of acrylic acid, methacrylic acid and derivatives thereof as a main component; Photo-crosslinking agent; Organic solvent; And a photopolymerization initiator can be provided. The photosensitive resin composition may include, but is not limited to, sensitizers. The photosensitive resin composition may be a photosensitive resin composition used as a negative photosensitive resin composition.

Wherein the polyamic acid comprises 0.1 to 50 mol%, and the weight average molecular weight may be 5,000 to 200,000, but is not limited thereto.

The photo-crosslinking agent may include, but is not limited to, one of a polyfunctional methacrylate compound, an epoxy compound, a hydroxymethyl-substituted phenol compound, and a compound having an alkoxyalkylated amino group.

The photopolymerization initiator may include, but is not limited to, one or more compounds selected from the group consisting of an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, and an oxime-based compound.

(A) an acrylic resin or an acrylic binder

When the photosensitive resin composition is used for alkali development, other polymers having a carboxyl group structure may be mixed and used in order to improve pattern processing performance in an alkaline developer and to compensate for insufficient developability, which is not limited to an acrylate resin. The carboxyl group concentration of the acrylate resin is preferably from 30 to 130 mol% based on the structural unit, and if it is smaller, the solubility as an alkali developer is almost zero, and if it is larger than this, the film thickness at the time of development becomes large.

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

(B) Photocrosslinking agent

The photo-crosslinking agent is a compound which forms a bond with a compounding composition such as a resin or another crosslinking agent molecule by the action of heat or acid.

Specific examples thereof include a polyfunctional methacrylate compound, an epoxy compound, a hydroxymethyl-substituted phenol compound, and a compound having an alkoxyalkylated amino group. Of these, compounds having a methacrylate compound are preferred. These crosslinking agents may be used alone or in combination of two or more. The content of the cross-linking agent is suitably used so that the film formed by the photosensitive resin composition can be sufficiently cured.

M-1: Dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate)

(C) photoinitiator, photosensitizer

In order to obtain a high sensitivity and a high resolution in a pattern after development, it is preferable to contain a photoinitiator and / or a photosensitizer represented by the following chemical formula, and the method such as using two or more thereof is not limited.

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

E-1: benzanthrone (benzanthrone)

(D) Other additives

In order to improve the adhesion between the coating film of the photosensitive resin composition of the present invention or the polyimide coating film after the heat treatment and the support, a suitable adhesive aid may be added and used.

As the adhesion aid, an organic silicon compound such as aminopropyl ethoxysilane, glycidoxypropyltrimethoxysilane, or oxypropyltrimethoxysilane is mainly used, and other aluminum chelate compounds or titanium chelate compounds can be used. The amount varies from 0.01 to 20 wt. %. In addition, the composition may contain a surfactant for the purpose of improving various properties such as coatability, defoaming property and leveling property. As the surfactant, fluorine or silicon surfactants may be used, or two or more surfactants may be used in combination.

(E) Solvent

The photosensitive resin composition of the present invention may contain an organic solvent if necessary in order to control viscosity and storage stability.

When the solvent is an organic solvent, the polyamic acid, the photo-crosslinking agent, the photopolymerization initiator or the optional additional additives may be easily dissolved, and a solvent which can be easily dried during the coating process is preferable.

The type of the solvent that can be contained is not particularly limited, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone,? -Butyrolactone, dimethylsulfoxide, Some magnetic solvents are used.

In addition, an organic solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, or propylene glycol monobutyl ether acetate may be contained in place of or in addition to the solvent to improve the coating property .

These solvents may be used alone or in combination of two or more. The solvent is usually used so that the content thereof is 1 to 80% by 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 heat crosslinking agent, a curing accelerator, a photo-crosslinking sensitizer, a curing accelerator, a phosphorus flame retardant, a defoaming agent, a leveling agent, an antigelling agent or a mixture thereof. Such an additive may be used without limitation as long as it can be used in a photosensitive resin composition. The additive may be used in an appropriate amount in consideration of the physical properties of the photosensitive resin composition or the film obtained therefrom.

Evaluation of production of photosensitive resin composition

Examples 1 to 5: The photosensitive resin composition was prepared by mixing the polyimide precursor prepared in Synthesis Examples 1 to 5 with an acrylic resin, a crosslinking agent, a photoinitiator, a sensitizer, and a solvent in the proportions shown in Table 1. The amount of the adhesive and the surfactant, which are other additives, was mixed in the range of 0.001 to 1% by mass%.

Comparative Examples 1 and 2: The photosensitive resin composition was prepared according to the ratios of the polyimide precursors synthesized in Synthesis Examples 6 to 7 according to the ratios shown in Table 1, and the ratios of the other additives were the same as in Examples.

The charge amounts in Table 1 are based on mass%, and the physical properties of the photosensitive resin composition were evaluated by the following methods, and the results are shown in Table 2 below.

1. Evaluation of Resolution

The photosensitive resin compositions prepared in the above Examples and Comparative Examples were spin-coated on a 100 * 100 mm glass plate and heated on a hot plate at 100 DEG C for 60 seconds to form a photosensitive resin layer having a thickness of 10 mu m. After the vacuum in close contact with the glass substrate is a photosensitive resin layer coated on a photo mask, i-line by using the exposure device ^{30mJ / cm 2 ~ 150mJ / cm} 2 were respectively exposed. After completing the exposure, the resist film was developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds and washed with DI-water for 30 seconds to obtain a pattern in which the exposed portion remained clearly. Thereafter, the patterning process was completed by a final heat treatment at 230 DEG C for 60 minutes using a baking oven. The pattern of heat treatment was analyzed by SEM analysis and the resolving power of each example and comparative example was measured.

2. Residual film ratio  evaluation

The method of coating a photosensitive resin composition on a glass substrate and exposing and heat-treating the same was the same as the resolution evaluation described above, and the remaining film ratio was evaluated by SEM analysis and comparison of the thickness of the pattern that was not subjected to the final heat treatment and the final heat treatment.

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

The results of each evaluation are shown in Table 2 below.

In the evaluation of resolution, Example 1 was evaluated at 30 mJ / cm < ² > Lt; / RTI >< ^{RTI ID = 0.0} > A pattern with an oversize size including a 10 탆 pattern was formed. 80, 100, 120 mJ / cm < ² > , And the pattern of smaller size including 150 mJ / cm ² to 5 탆 was connected to each other, and it was confirmed that the pattern was clumped together, and that a larger size pattern was formed Respectively.

Example 2 30mJ / cm ² The patterns were all dropped at 50, 80, 100 mJ / cm < ² > A pattern with an oversized size including a 5 탆 pattern was formed. 120, 150 mJ / cm ² The pattern was observed to be connected to each other in a pattern having a size smaller than 10 .mu.m, and it was confirmed that a larger size pattern was formed.

Example 3 has a density of 30 to 80 mJ / cm < ² > A pattern with an oversized size including a 5 탆 pattern was formed. In the pattern of the lower, including 10㎛ at ^{100mJ / cm 2 120, 150mJ /} cm 2 The pattern was observed to be connected to each other in the pattern of less than 15 탆 including the size of 15 탆, and it was confirmed that a larger size pattern was formed.

Example 4 was used in the range of 50 to 100 mJ / cm < ² > A pattern with an oversized size including a 5 탆 pattern was formed. 120, 150 mJ / cm ² The patterns were connected to each other in a pattern having a size smaller than 10 탆 and confirmed to be clumped, and it was confirmed that a larger size pattern was formed.

Example 5 has a transmittance of 30 mJ / cm < ² > The patterns were all dropped at 50, 80, 100 mJ / cm < ² > A pattern with an oversized size including a 5 탆 pattern was formed. 120, 150 mJ / cm ² The pattern was observed to be connected to each other in a pattern having a size smaller than 10 .mu.m, and it was confirmed that a larger size pattern was formed.

In Comparative Example 1, 120 mJ / cm < ² > In the above, a pattern having an oversized size including a 20-μm pattern was formed, and a pattern was dropped at a light amount smaller than that.

In Comparative Example 2, 150 mJ / cm < ² > In the above, a pattern having an oversized size including a 20-μm pattern was formed, and a pattern was dropped at a light amount smaller than that.

In the residual film ratio evaluation, Examples 1, 2, 4, and 5 were confirmed to have a residual film ratio of 83 to 85%, and the residual film ratio of Example 3 was found to be 91%. This is because the functional group of Example 3 is acrylate and the methacrylate series is more rigidly crosslinked at exposure than Examples 1, 2, 4, and 5.

In Comparative Examples 1 and 2, since the functional groups were not included, it was confirmed that the thickness of the film after the final heat treatment was reduced due to the low steric hindrance effect between the molecules.

The present invention is a negative photosensitive resin composition capable of high-resolution patterning at a low light quantity, has excellent pattern adhesion, enables fine patterning, and has excellent cured film characteristics.

Film and electronic devices

According to another embodiment of the present invention, there is provided a film comprising a cured product of the above-mentioned photosensitive resin composition. Specifically, the film refers to a film obtained by drying the photosensitive resin composition described above, or a photosensitive resin composition that is photo-cured or thermally cured.

The above-mentioned film can be produced by applying a photosensitive resin composition on a support by a known method and drying it. It is preferable that the support can peel off the photosensitive resin composition layer and has good light transmittance. It is also preferable that the surface smoothness is good.

Specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, alkyl (meth) acrylates, poly (meth) acrylate copolymers, polyvinyl chloride, poly Various plastic films such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene and polytrifluoroethylene, . A composite material composed of two or more of these materials may also be used, and a polyethylene terephthalate film having excellent light transmittance is particularly preferable. The thickness of the support may be 5 to 150 탆, and more specifically 10 to 50 탆.

The method of applying the photosensitive resin composition is not particularly limited and may be selected from the group consisting of a spray method, a roll coating method, a rotary coating method, a slit coating method, an extrusion coating method, a curtain coating method, a die coating method, Method can be used. The drying of the photosensitive resin composition may be carried out at 60 to 100 占 폚 for 30 seconds to 15 minutes although it depends on the kind of each constituent component, the kind of organic solvent, and the content ratio.

The dry film after drying and curing has a film thickness of 5 to 95 탆, more specifically 10 to 50 탆.

In this case, the film may be 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 color filter substrate, a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, or a solder resist.

According to another embodiment of the present invention, there is provided an electronic device including a display device including an organic electronic device including the above-mentioned film and a control unit for driving the display device. It is exemplified that the above-described film is used as a pixel defining film or bank for a display panel defining each pixel of an organic electronic device, but the present invention is not limited thereto.

The film used as the pixel defining film for a display panel is meant to include a film or a workpiece of the film, for example, a work piece or a photoreaction material laminated on a certain substrate.

 The film is pre-laminated on the formation surface of the display panel at a temperature of 20 to 50 ° C by a method such as a planar pressing or a roll pressing method and then vacuum laminated at 60 to 90 ° C to form a photosensitive film Can be formed.

In addition, the film can be patterned by exposure using a photomask to form a fine structure or a fine-width line. The exposure amount can be appropriately adjusted according to the type of the light source used in the UV exposure and the thickness of the film film, and can be, for example, from 100 to 1200 m / cm2, and more specifically, from 100 to 500 m / .

Examples of the active light rays usable include electron beams, ultraviolet rays, and X-rays. Preferably, ultraviolet rays can be used. As the usable light source, a high-pressure mercury lamp, a low-pressure mercury lamp, a halogen lamp, or the like can be used as a light source.

In the post-exposure development, a spray method is generally used. The photosensitive resin composition is developed using an aqueous alkali solution such as an aqueous solution of sodium carbonate and then washed with water. Thereafter, when the polyamic acid is changed to polyimide according to the pattern obtained by the development through the heat treatment process, the heat treatment temperature may be 100 to 250 ° C, which is necessary for imidization. At this time, it is effective to continuously raise the heating temperature in two to four steps with an appropriate temperature profile, but it may be cured at a constant temperature in some cases. The pixel defining film for a display panel and the like can be obtained through the above-described steps.

The organic electroluminescent device according to the present invention may be one of an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or 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 controller, a navigation device, a game machine, various TVs, and various computers.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for the purpose of limiting the present invention and are not to be construed as limiting the spirit and scope of the present invention. The scope of protection of the present invention should be construed according to the claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (10)

1. A negative-working photosensitive resin composition comprising at least one compound represented by the following formula (1).

Wherein X is independently selected from the group consisting of a single bond, O, S, CR ^a R ^b _, NR, CH ₂ , C = O, SO ₂ , C (CF ₃ ) ₂ ,
R ^a , R ^b , R, R ¹ , R ² , R ³ and Ar ¹ are each independently hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; An alkyl group having ₁ to ₆₀ carbon atoms; A C ₃ to C ₆₀ cycloalkyl group; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₆₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; Ester group, ether group; A hydroxyl group; CF ₃ ; R ^a and R ^b may combine with each other to form a spiro compound,
L each independently represents a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And O, N, S, a heterocyclic C ₂ ~ containing at least one hetero atom of Si and P C ₆₀ group; A C ₁ to C ₆₀ alkylene group,
n is an integer of 2 to 1000,
a and b are independently an integer of 1 to 3, and when a and b are each 2 or more, each of R ² and R ³ may combine to form a ring,
Ar ¹ is a C ₆ to C ₆₀ arylene group; A fluorenylene group; An alkylene group of C ₁ to C ₆₀ ; An alkenylene group having ₂ to ₆₀ carbon atoms; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; Is selected from the group consisting of formulas (2-1) and (2-2)

here,
X1 is selected from a single bond, O, S, the group consisting of CO, CR'R ", SO _2, each independently,
R ⁴ , R ⁵ , R ⁶ , R ', and R "are independently and independently hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; An alkyl group having ₁ to ₆₀ carbon atoms; A C ₃ to C ₆₀ cycloalkyl group; An alkenyl group having ₂ to ₆₀ carbon atoms; An alkynyl group of C ₂ to C ₆₀ ; A C ₁ to C ₆₀ alkoxyl group; An aryloxy group of C ₆ to C ₆₀ ; Ester group, ether group; Amide group, imide group; , ≪ / RTI >
a 'to b' are integers of 1 to 4,
c 'is an integer of 1 to 6,
A heterocyclic group, a fused ring group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an aryloxy group, an alkylene group, an arylene group, an alkylene group, a fluorenylene group, an alkenyl group alkoxyl group group, an ester group, an ether group, amide group, imide groups are each deuterium, a halogen, a silane group, a siloxane group, a boron group, a cyano group, an alkylthio import of _{C 1 -C 20, C 1 -C} 20, an aryl group of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₆ -C ₂₀ substituted with a C ₆ aryl group, a heavy hydrogen of -C ₂₀ of the, fluorene A C ₂ -C ₂₀ heterocyclic group, a C ₃ -C ₂₀ cycloalkyl group, a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C ₂₀ arylalkenyl group, a carbonyl group, an ether group, a C ₂ -C ₂₀ An alkoxycarbonyl group having 1 to ₆ carbon atoms, and an aryloxy group having _{6 to 30} carbon atoms. The method according to claim 1,
Wherein the formula (1) is represented by any one of the following formulas (3) to (8).

R ¹ , R ² , R ³ , Ar ¹ , A _1, a, b and n are the same as defined in the above 1. The method according to claim 1,
Wherein the formula (1) is represented by any one of the following formulas.

The method according to claim 1,
And a weight average molecular weight of 5,000 to 200,000. A polymeric resin comprising the polymeric material of any one of claims 1 to 4;
An acrylic resin containing at least one of acrylic acid, methacrylic acid and derivatives thereof as a main component;
Photo-crosslinking agent;
Organic solvent; And
A photosensitive resin composition comprising a photopolymerization initiator. 6. The method of claim 5,
A photosensitive resin composition used as a negative photosensitive resin composition. A film comprising a cured product of the photosensitive resin composition of claim 6 8. The method of claim 7,
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 protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, or a solder resist. A display device comprising an organic electronic device comprising the film of claim 8; And
And a control unit for driving the display device. 10. The method of claim 9,
Wherein the organic electronic device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a device for monochromatic or white illumination.