CN111448517A - Adhesive resin and photosensitive resin composition or coating solution containing the same - Google Patents

Adhesive resin and photosensitive resin composition or coating solution containing the same Download PDF

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CN111448517A
CN111448517A CN201880079581.9A CN201880079581A CN111448517A CN 111448517 A CN111448517 A CN 111448517A CN 201880079581 A CN201880079581 A CN 201880079581A CN 111448517 A CN111448517 A CN 111448517A
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chemical formula
carbon atoms
independently
weight
substrate
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CN111448517B (en
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柳美善
金根洙
郑统一
林哲圭
林烘圭
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TAKOMA TECHNOLOGY CO LTD
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TAKOMA TECHNOLOGY CO LTD
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyesters Or Polycarbonates (AREA)
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Abstract

The present invention relates to a photoresist composition as an organic material for display devices such as a thin film transistor liquid crystal display device (TFT-L CD), an organic light emitting diode (O L ED), and a Touch Screen Panel (TSP), and a binder resin suitable for a coating material, and the like, and is characterized by having high functionality and high performance characteristics such as heat resistance, chemical resistance, transmittance, high refractive index, mechanical properties, flexibility, developability, and pattern flatness.

Description

Adhesive resin and photosensitive resin composition or coating solution containing the same
Technical Field
The present invention relates to a binder resin having high functionality and high performance characteristics such as heat resistance, chemical resistance, transmittance, high refractive index, mechanical properties, flexibility, developability, pattern flatness, and the like, and a photosensitive resin composition or a coating solution comprising the same.
Background
Photosensitive resin compositions for display devices, which are suitable for thin film transistor liquid crystal display devices (TFT-L CD), organic light emitting diodes (O L ED), Touch Screen Panels (TSP), and the like, are classified into positive photosensitive materials and negative photosensitive materials according to the manner of forming a pattern by causing a curing reaction and a photolytic reaction by Ultraviolet (UV) and ultraviolet irradiation.
In particular, recently, high transmittance and high refractive index have been increasingly important for increasing the light efficiency of a display device. In order to ensure the characteristics of high heat resistance, chemical resistance, high transmittance, and high refractive index of the photosensitive resin composition, the structure and characteristics of the binder in the composition constituting the photosensitive material are very important. For this reason, studies have been actively conducted to impart photosensitivity to a phenol resin system including an acrylic resin-based photosensitive resin used as a representative binder resin of a photosensitive resin composition, and a binder resin such as polyimide. However, the photosensitive resin compositions using acrylic photosensitive resins, phenolic resins, and the like, which have been conventionally used, have a problem in that they have poor heat resistance in a high-temperature heat treatment process at 300 ℃ or higher, and thus impurities due to outgassing are generated to cause serious contamination of the display device, and the transmittance is reduced due to the high-temperature heat treatment to reduce the light efficiency characteristics of the display.
For example, U.S. Pat. No. 4139391 discloses a photosensitive resin composition prepared by using a copolymer of an acrylic compound and an acrylate compound as a binder resin, and by using the acrylate compound as a polyfunctional monomer. However, since the difference in solubility between the exposed portion and the unexposed portion is not large, the developing property is poor, and the binder resin to be left in the developing process is partially dissolved in the developing solution, so that it is difficult to obtain a fine pattern of 10 μm or less.
Further, jp 52-13315 a and jp 62-135824 a disclose photosensitive resist compositions containing a polyamic acid as a polyimide precursor and a naphthoquinone diazide (naphthoquinone) compound as a dissolution inhibitor to improve thermal stability, but have a problem that the difference in the dissolution rate between an exposed portion and a non-exposed portion is not so large as to form a high-resolution pattern.
Further, the photosensitive resin composition has good adhesion to the lower layer and the upper layer, and should have a wide process margin that enables formation of a fine pattern with high resolution under various process conditions tailored to the purpose of use, and high sensitivity characteristics are required as a photosensitive material, and therefore, studies for improving such characteristics are actively being conducted.
Documents of the prior art
Patent document
(patent document 1) Japanese patent laid-open No. S52-13315
(patent document 2) Japanese patent laid-open No. S62-135824
(patent document 3) U.S. granted patent No. 4139391
Disclosure of Invention
The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a photosensitive resin composition, a coating solution, or the like using a binder resin having high functionality and high performance characteristics such as heat resistance, chemical resistance, permeability, high refractive index, mechanical properties, flexibility, developability, pattern flatness, and the like.
In order to achieve the above object, the present invention provides an adhesive resin characterized by being a polymer comprising a monomer represented by the following chemical formula I or both a monomer represented by the following chemical formula I and a monomer represented by the following chemical formula II.
Chemical formula I
Figure BDA0002530990240000031
In the formula I, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of which is (meth) acryloyloxy, the above RaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, the above Z is O, S, N, Si or Se, the above R isb、RcAnd RdIndependently an alkyl group which may or may not contain a hetero element having 1 to 10 carbon atoms or an aryl group which may or may not contain a hetero element having 6 to 20 carbon atoms, g is 0 and h is 0 when the above Z is O, S or Se, g is 1 and h is 0 when the above Z is N, g is 1 and h is 1 when the above Z is Si, and R is 1 when the above Z is Si4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic (cycloaliphatic) hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, wherein A is independently a substituent represented by the formulae I-1 to I-4, and D is O, S, CH2And Se, wherein n is an integer of 1 to 6, and p is independently an integer of 1 to 30.
Chemical formula II
Figure BDA0002530990240000041
In the above chemical formula II, R5And R'5Are each independently (meth) acryloyloxy or are each independently RaZRb(Rc)g(Rd)hR is as defined aboveaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, the above Z is O, S, N, Si or Se, and R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, g is 0, h is 0 when the above-mentioned Z is O, S or Se, g is 1, h is 0 when the above-mentioned Z is N, g is 1, h is 1 when the above-mentioned Z is Si, and R 'is 1 when the above-mentioned Z is Si'4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic (cycloaliphatic) hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, A 'independently is a substituent represented by the formulae I-1 to I-4, and D' is O, S, CH2And Se, wherein m is independently an integer of 1 to 6, and q is independently an integer of 1 to 30.
Chemical formula I-1
Figure BDA0002530990240000042
Chemical formula I-2
Figure BDA0002530990240000051
Chemical formula I-3
Figure BDA0002530990240000052
Chemical formula I-4
Figure BDA0002530990240000053
In the formulae I-1 to I-4, R2And R'2Respectively represent hydrogen, hydroxyl (-OH), thiol (-SH), amino (-NH2), and nitro (-NO)2) Or halogeno, X represents O, S, Se, NR6Or SiR7(R8) R is as defined above6、R7Or R8Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 or 6 to 15 carbon atoms.
As an example, the present invention is characterized in that the binder resin is used as a binder in a photosensitive material for a display device.
As an example, the present invention is characterized in that the binder resin is a resin terminated with an organic acid, an organic acid anhydride or an amic acid.
As an example, the present invention is characterized in that the weight average molecular weight of the binder resin is 1000 to 100000 g/mol.
As an example, the present invention is characterized in that the dispersion degree of the binder resin is 1.0 to 5.0.
The present invention also provides a negative-type photosensitive resin composition comprising the binder resin, a photoinitiator, an organic solvent, and a surfactant.
As an example, the present invention is characterized in that, in the negative type photosensitive resin composition, 100 parts by weight of the binder resin, 1 to 20 parts by weight of the photoinitiator, 0.01 to 5 parts by weight of the surfactant, and 0 to 10 parts by weight of the binding aid are contained in the organic solvent in an amount of 5 to 80% by weight.
The present invention also provides a positive photosensitive resin composition comprising the binder resin, a photoactive compound, an organic solvent, and a surfactant.
As an example, the present invention is characterized in that, in the above positive photosensitive resin composition, 100 parts by weight of a binder resin, 0.1 to 30 parts by weight of a photoactive compound, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of a bonding assistant are contained in an organic solvent in an amount of 5 to 80% by weight.
Also, the present invention provides a substrate including a resin cured pattern formed of the above photosensitive resin composition.
Also, the present invention provides a method for preparing an adhesive resin, comprising the step of polymerizing a monomer represented by chemical formula 13 or a monomer represented by chemical formula 13 and a monomer represented by chemical formula 14 with a carboxylic dianhydride represented by chemical formula 9.
Chemical formula 13
Figure BDA0002530990240000061
In chemical formula 13, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of which is (meth) acryloyloxy, the above RaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, the above Z is O, S, N, Si or Se, the above R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, g is 0, h is 0 when the above Z is O, S or Se, g is 1, h is 0 when the above Z is N, g is 1, h is 0 when the above Z is Si, g is 1, h is 1 when the above Z is Si, the above a is independently a substituent represented by the following chemical formulae I-1 to I-4, the above D is O, S, CH2And Se, wherein n is an integer of 1 to 6.
Chemical formula 14
Figure BDA0002530990240000071
In chemical formula 14, R5And R'5Are each independently (meth) acryloyloxy or are each independently RaZRb(Rc)g(Rd)hWherein A' is a substituent represented by the formulae I-1 to I-4, D is O, S, CH2And Se, wherein m is an integer of 1 to 6.
In the formulae I-1 toIn I-4, R2And R'2Respectively represent hydrogen, hydroxyl (-OH), thiol (-SH), and amino (-NH)2) Nitro (-NO)2) Or halogeno, X represents O, S, Se, NR6Or SiR7(R8) R is as defined above6、R7Or R8Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
Chemical formula 9
Figure BDA0002530990240000072
In the above chemical formula 9, R4A tetravalent alicyclic (cycloaliphatic) hydrocarbon group of 4 to 20 carbon atoms with or without a hetero element or a tetravalent aromatic hydrocarbon group of 6 to 20 carbon atoms with or without a hetero element.
In the present invention, the photosensitive resin composition including the binder resin having optical characteristics of high refractive index and excellent heat resistance and transmittance characteristics exhibits very excellent heat resistance, transmittance and refractive index characteristics, and the binder resin of the present invention has excellent heat resistance, thus minimizing Taper angle (Taper angle) and Outgassing (Outgassing), and has excellent adhesion to a substrate and chemical resistance to strong acids or strong bases, thus exhibiting very excellent characteristics as a high-functional and high-performance coating material as well as applications of the photosensitive material for thin film transistor liquid crystal display devices (TFT-L CD), organic light emitting diodes (O L ED) and Touch Screen Panel (TSP) display devices.
In addition, the binder resin of the present invention has excellent developability with respect to an inorganic alkaline aqueous solution and an organic alkaline aqueous solution, and thus can ensure excellent developability with respect to positive-type and negative-type photosensitive material compositions, and also exhibits excellent resolution characteristics with respect to photosensitive material patterns, and not only can easily adjust the taper angle (taper) of the patterns, but also has a large effect of preventing undercut (undercut) formation when the patterns are embodied, and thus can ensure excellent pattern stability.
Detailed Description
The present invention will be described in detail below.
The present invention relates to a binder resin and a photosensitive resin composition comprising the same.
The photosensitive resin composition may contain a photoinitiator, a photoactive compound, a compatibilizing agent, and the like, in addition to the binder, and may further contain additives such as a heat stabilizer, a thermal crosslinking agent, a photocuring accelerator, a surfactant, and the like.
First, the above-mentioned binder resin will be described in detail.
1. Adhesive resin
The present invention provides an adhesive resin characterized by being a polymer containing a monomer represented by the following chemical formula I or both of the monomer represented by the following chemical formula I and a monomer represented by the following chemical formula II.
Chemical formula I
Figure BDA0002530990240000091
In the above formula I, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of them is (meth) acryloyloxy, Ra is a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, Z is O, S, N, Si or Se, R isb、RcAnd RdIndependently an alkyl group which may or may not contain a hetero element having 1 to 10 carbon atoms or an aryl group which may or may not contain a hetero element having 6 to 20 carbon atoms, g is 0 and h is 0 when the above Z is O, S or Se, g is 1 and h is 0 when the above Z is N, g is 1 and h is 1 when the above Z is Si, and R is 1 when the above Z is Si4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic (cycloaliphatic) hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, wherein A is independently represented by the formulae I-1 to I-4D is O, S, CH2And Se, wherein n is an integer of 1 to 6, and p is independently an integer of 1 to 30.
Chemical formula II
Figure BDA0002530990240000101
In the above chemical formula II, R5And R'5Are each independently (meth) acryloyloxy or are each independently RaZRb(Rc)g(Rd)h，
The above chemical formula II is a compound containing R5And R'5Monomers which are (meth) acryloyloxy with R5And R'5Is RaZRb(Rc)g(Rd)hAs all polymers of monomers, the above RaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, the above Z is O, S, N, Si or Se, the above R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, g is 0, h is 0 when the above-mentioned Z is O, S or Se, g is 1, h is 0 when the above-mentioned Z is N, g is 1, h is 1 when the above-mentioned Z is Si, and R 'is 1 when the above-mentioned Z is Si'4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic (cycloaliphatic) hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, wherein A 'is independently a substituent represented by the formulae I-1 to I-4, and D' is S, CH2And Se, wherein m is independently an integer of 1 to 6, and q is independently an integer of 1 to 30.
Chemical formula I-1
Figure BDA0002530990240000102
Chemical formula I-2
Figure BDA0002530990240000111
Chemical formula I-3
Figure BDA0002530990240000112
Chemical formula I-4
Figure BDA0002530990240000113
In the above-mentioned chemical formulae I-1 to I-4, R2And R'2Respectively represent hydrogen, hydroxyl (-OH), thiol (-SH), and amino (-NH)2) Nitro (-NO)2) Or halogeno, X represents O, S, Se, NR6Or SiR7(R8) R is as defined above6、R7Or R8Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 or 6 to 15 carbon atoms.
For example, p and q may be integers of 3 to 20, 4 to 10, or 4 to 7, and within this range, excellent effects such as heat resistance, chemical resistance, transmittance, high refractive index, and optical characteristics are obtained.
In the present invention, may refer to a polymer comprising a monomer represented by chemical formula I or a polymer comprising both a monomer represented by chemical formula I and a monomer represented by chemical formula II, or may refer to a polymer formed from a monomer represented by chemical formula I or a polymer formed from a monomer represented by chemical formula I and a monomer represented by chemical formula II except for a terminal group derived from a polymerization inhibitor.
As another example, the adhesive resin of the present invention may be synthesized by reacting a monomer including a hydroxyl group having a structure of chemical formula 5 to 8 with a carboxylic dianhydride or including the monomer after synthesizing the monomer from the compound represented by chemical formula 1 to 4.
Or, as an example, may refer to a polymer comprising the monomer represented by chemical formula I or the monomer represented by chemical formula I and the monomer represented by chemical formula II in the main chain, or may refer to a polymer formed from the monomer represented by chemical formula I or the monomer represented by chemical formula I and the monomer represented by chemical formula II, excluding a terminal group derived from a terminator that terminates the polymerization reaction.
As an example, the adhesive resin of the present invention may be prepared by reacting a carboxylic dianhydride with a monomer including a hydroxyl group having a structure of chemical formula 13 or 14 after synthesizing the monomer from the compounds represented by chemical formulas 1 to 4.
Chemical formula 1
Figure BDA0002530990240000121
Chemical formula 2
Figure BDA0002530990240000122
Chemical formula 3
Figure BDA0002530990240000131
Chemical formula 4
Figure BDA0002530990240000132
In the structures of the compounds of the above chemical formulas 1 to 4,
R1、R'1respectively represent a compound containing a hydroxyl group (-OH), a thiol group (-SH), and an amino group (-NH)2) Nitro (-NO)2) An aliphatic or alicyclic alkyl group having 1 to 20 carbon atoms containing a hetero element such as cyano (-CN) or an aryl group having 6 to 20 or 6 to 15 carbon atoms containing a hetero element, R2、R'2Respectively represent hydrogen or hydroxyl (-OH), thiol (-SH), amino (-NH)2) Nitro (-NO)2) Or a halo group. Here, X represents O, S, N, Si or Se.
In the present invention, "each" includes the case where two components are the same and the case where they are different "independently".
As an example, in the structures of the compounds of chemical formulas 1 to 4, R1、R'1May be a hetero element-containing one having 1 to 10, 3 to 3 carbon atoms8 or 3 to 5 aliphatic or cycloaliphatic alkyl groups or aryl groups containing a heteroatom and having 6 to 15, 6 to 10 or 7 to 10 carbon atoms.
Chemical formula 13
Figure BDA0002530990240000141
In the above chemical formula 13, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of which is (meth) acryloyloxy, the above RaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, the above Z is O, S, N, Si or Se, the above R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, g is 0, h is 0 when the above Z is O, S or Se, g is 1, h is 0 when the above Z is N, g is 1, h is 0 when the above Z is Si, g is 1, h is 1 when the above Z is Si, the above a is independently a substituent represented by chemical formulae I-1 to I-4, the above D is O, S, CH2, Se, and the above N is an integer of 1 to 6.
Chemical formula 14
Figure BDA0002530990240000142
In the above chemical formula 14, R5And R'5Are each independently (meth) acryloyloxy or are each independently RaZRb(Rc)g(Rd)hWherein A' is a substituent represented by the formulae I-1 to I-4, D is O, S, CH2And Se, wherein m is an integer of 1 to 6.
Chemical formula 5
Figure BDA0002530990240000143
Chemical formula 6
Figure BDA0002530990240000151
Chemical formula 7
Figure BDA0002530990240000152
Chemical formula 8
Figure BDA0002530990240000153
In the monomer structures of the above chemical formulas 5 to 8,
R2、R'2respectively represent hydrogen or hydroxyl (-OH), thiol (-SH), amino (-NH)2) Nitro (-NO)2) Or a halo group. Here, X represents O, S, N, Si or Se. And, R3、R'3Respectively, an alkyl group containing or not containing a hetero element having 1 to 20 carbon atoms, an aryl group containing or not containing a hetero element having 6 to 20 carbon atoms or an RC (═ O) R' substituent, and n is an integer of 1 to 6.
For example, R isb、RcAnd RdMay be an alkyl group having 1 to 5 or 1 to 3 carbon atoms or an aryl group having 6 to 10 or 6 to 8 carbon atoms, respectively.
For example, R may be a bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
For example, R' may be an alkyl group or an alkenyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
For example, n and m may be 1 to 3 or 1 to 2, respectively.
In the present invention, the hetero element means a monovalent or divalent or more group of an element other than carbon and hydrogen, and is, for example, one or more selected from the group consisting of oxygen, nitrogen, sulfur, halogen, selenium (Se), silicon, and the like, and the R is, for example, the above-mentionedaZRb(Rc)g(Rd)hCan be RaSRbIn this case, the composition has excellent heat resistance, transmittance, and high refractive index, and also has excellent developability with an aqueous KOH solution and an aqueous TMAH solution, and has an effect of preventing undercut formation.
As another example, the present invention may be characterized as a binder resin that is a polymer containing a monomer represented by the following chemical formula Ia or a polymer represented by the following chemical formula Ia.
Chemical formula Ia
Figure BDA0002530990240000161
In the above formula Ia, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of which is (meth) acryloyloxy, the above RaIs a bond (bonding), an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, the above Z is O, S, N, Si or Se, the above R isb、RcAnd RdIndependently an alkyl group which may or may not contain a hetero element having 1 to 10 carbon atoms or an aryl group which may or may not contain a hetero element having 6 to 20 carbon atoms, g is 0 and h is 0 when the above Z is O, S or Se, g is 1 and h is 0 when the above Z is N, g is 1 and h is 1 when the above Z is Si, and R is 1 when the above Z is Si4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic (cycloaliphatic) hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, wherein A is independently a substituent represented by the formulae I-1 to I-4, and D is O, S, CH2And Se, wherein n is an integer of 1 to 6, and p is independently an integer of 1 to 30.
In the above chemical formula Ia, n may be 1 to 3 or 1 to 2, as an example, and in this case, the heat resistance, the transmittance, and the high refractive index are excellent.
For example, in the binder resin represented by the above chemical formula Ia, p is an integer of 1 to 30 or an integer of 1 to 10, and within this range, the binder resin has excellent properties of heat resistance, transmittance, and high refractive index.
As an example, the method for preparing the adhesive resin of the present invention may include a step of polymerizing the monomer represented by chemical formula 13 or the monomer represented by chemical formula 13 and the monomer represented by chemical formula 14 with the carboxylic dianhydride represented by chemical formula 9.
As an example, the monomer represented by chemical formula 13 and the monomer represented by chemical formula 14 may be represented by 1: 99 to 99: 1 molar ratio.
As another example, the method for preparing the adhesive resin of the present invention may include a step of polymerizing one or more of the monomers represented by chemical formulas 5 to 8 with the carboxylic dianhydride represented by chemical formula 9.
As another example, the method for preparing the adhesive resin of the present invention may include reacting R in the monomer represented by chemical formulas 5 to 83And R'3Is more than one monomer of acryloxy and R3And R'3Is RaSRbA step of polymerizing one or more monomers with the carboxylic acid dihydrate represented by chemical formula 9.
Chemical formula 9
Figure BDA0002530990240000181
In the above chemical formula 9, R4Is a tetravalent alicyclic (cycloaliphatic) hydrocarbon group having 4 to 20 carbon atoms and containing or not containing a hetero element or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms and containing or not containing a hetero element.
As another example, in chemical formula 9, R4Is a tetravalent alicyclic (cycloaliphatic) hydrocarbon group having 4 to 10 or 4 to 6 carbon atoms and optionally containing a hetero element, a tetravalent aromatic hydrocarbon group having 6 to 15 or 6 to 12 carbon atoms and optionally containing a hetero element, within which heat resistance and high permeability are exhibitedAnd excellent high-refractive-index characteristics.
Specific examples of the carboxylic acid dianhydride include pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 2',3,3' -benzophenonetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, Bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorenic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,2,4, 5-benzene tetracarboxylic dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,6,7, 12-tetrachloroperylene tetracarboxylic dianhydride, 1,2, 4-perylene tetracarboxylic dianhydride, 1, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,6,7, 12-tetrachloro-perylene tetracarboxylic dianhydride, 1,2,4, 5-benzene tetracarboxylic dianhydride, 1, 3, 4-benzene dianhydride, Octahydrobiphenylene-4 a,8b 4b,8 a-tetracarboxylic dianhydride, 2-bromo-1, 4,5, 8-naphthalenetetracarboxylic dianhydride, 4' -isopropylidene-di-phthalic acid-dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 3, 7-diphenyl-tetrahydro-pyrazolo [1,2-a ] pyrazole-1, 2,5, 6-tetracarboxylic acid-1, 2,5, 6-dianhydride, 7, 8-diphenyl-bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid-2, 3,5, 6-dianhydride, 2, 6-dibromonaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,3',4' -benzophenone dianhydride, 2,3, 6-tetracarboxylic acid dianhydride, 2, 6-dibromonaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,3',4' -benzophenone dianhydride, 3,3',4,4' -diphenyl ether-tetracarboxylic dianhydride, 4-dibromo-2, 3,5, 6-benzenetetracarboxylic dianhydride, 1' -binaphthyl-4, 4',5,5' -tetracarboxylic dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid-2, 3,5, 6-f-dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 3-methyl-benzene-1, 2,4, 5-tetracarboxylic acid-1, 2,4, 5-dianhydride, 2- (4- (2, 3-dicarboxyphenoxy) phenyl) -2- (4- (3, 4-dicarboxyphenoxy) phenyl) propane dianhydride, 2- (4, 3-dicarboxyphenoxy) phenyl) propane dianhydride, Aromatic ring tetracarboxylic acid dianhydride such as 2,3,6, 7-naphthalene tetracarboxylic acid 2,3:6, 7-dianhydride, alicyclic tetracarboxylic acid dianhydride such as 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3, 4-cyclohexane tetracarboxylic acid 1,2:3, 4-dianhydride, or 3,3',4,4' -diphenylsulfone tetracarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, 1,2,3, 4-butane tetracarboxylic acid dianhydride, 1,4,7, 8-tetrachlorobicyclo [ 2.2.2.2 ] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, diamine tetraacetic acid dianhydride, or, Tricyclo (4.2.2.02,5) dec-7-ene-3, 4,9, 10-tetracarboxylic dianhydride, (+ -) -1, 8-dimethyl-bicyclo [2.2.2] oct-7-ene-2 exo, 3 exo, 5 exo, 6 exo-tetracarboxylic dianhydride-2, 3,5, 6-dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, vinyltetracarboxylic dianhydride, and the like.
For example, the polymerization reaction may be carried out at a temperature of 100 to 130 ℃ or 110 to 120 ℃ for 2 hours to 24 hours or 4 hours to 12 hours.
For example, the carboxylic dianhydride may be added in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight, based on 100 parts by weight of the total amount of monomers.
For example, the method for preparing the adhesive resin of the present invention may include a step of adding an end-capping reagent (end-capping reagent) to the adhesive resin after the polymerization reaction is started to perform the reaction.
As an example, the above-mentioned end-capping reaction may be carried out at a temperature of 100 to 130 ℃ or 110 to 120 ℃ for 30 minutes to 4 hours or 1 hour to 3 hours.
For example, the end-capping agent may be added in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.
As an example, the weight average molecular weight of the binder resin may be 1000 to 100000g/mol, preferably 2000 to 50000g/mol, more preferably 2000 to 12000g/mol, and most preferably 3000 to 5000g/mol, within which range it has excellent heat resistance, and is suitable for development by the developing speed of the photosensitive material and the developing solution, so that the pattern formation is good and the residual film ratio is high.
The weight average molecular weight of the present invention can be measured by a Gel Permeation Chromatography (GPC) method.
For example, the dispersion degree (PDI) of the binder resin is in the range of 1.0 to 5.0, preferably 1.5 to 4.0, and within this range, the binder resin has the effects of excellent heat resistance, good pattern formation and high residual film ratio because the development speed of the photosensitive material and the development by the developer are appropriate.
The degree of dispersion of the present invention can be measured by a Gel Permeation Chromatography (GPC) measurement method.
As an example, the above binder resin has a refractive index of 1.50 to 1.70 or 1.60 to 1.69, preferably 1.61 to 1.68 or 1.63 to 1.67, within which range there is an excellent effect of the refractive index of the prepared film and the transmittance after curing.
For example, the binder resin has a transmittance of 90% or more, 95% or more, or 96% or more, preferably 96% to 99%, within which the refractive index of the prepared film and the transmittance after curing are excellent.
The method for measuring the refractive index and the transmittance of the binder resin is not particularly limited as long as it is a conventional method for measuring the refractive index and the transmittance of the binder resin, which is considered to be the technical field of the present invention.
For example, the binder resin has an acid value of 30 to 180mgKOH/g, and within this range, has excellent heat resistance, and is suitable for development by a developing solution and a developing speed of a photosensitive material, and thus has an effect of good pattern formation and a high residual film ratio.
The acid value in the present invention is not particularly limited as long as it is a value obtained by an acid value measurement method commonly used in the art, and as a specific example, 0.5g of the binder polymer is sampled and dissolved in 100m L mixed solvent (25 wt% of H)2O, 75 weight percent Acetone (Acetone)), can be determined by titration with 0.1N-KOH ethanol.
The binder resin of the present invention can be used as a photosensitive resin composition for a black matrix containing a binder resin, a pigment and a photopolymerization initiator, or can be applied to a touch panel containing a black matrix or a columnar spacer for supporting between two Thin Film Transistors (TFTs) having the black matrix material and a C/F substrate with a liquid crystal layer interposed therebetween, as an example.
As another example, the binder resin of the present invention may be used for a color filter, and when the color filter prepared from the binder resin of the present invention is applied to an image display device, light passing through a light source emits self-luminescence and an optical path is increased by scattering particles, so that more excellent light efficiency can be achieved.
Also, as a substance for forming a Pixel Defined (PD L) layer for distinguishing and insulating the boundaries between respective pixels in an organic light emitting diode (O L ED) display device from each other, the binder resin of the present invention can be used, and in this case, effects of not only improving the insulating property but also improving the heat resistance, very low moisture absorption rate, and further improved sensitivity can be obtained.
2. Negative photosensitive resin composition
The negative-type photosensitive resin composition of the present invention is characterized by containing the binder resin of the present invention, a photoinitiator, an organic solvent, and an additive.
As another example, the negative-type photosensitive resin composition of the present invention is characterized in that the binder resin of the present invention contains a photoinitiator, a crosslinkable compound having an ethylenically unsaturated bond, an additive, and an organic solvent.
As another example, the negative-type photosensitive resin composition of the present invention may include (a) the binder resin of the present invention, (B) a crosslinkable compound having an ethylenically unsaturated bond, (C) one or more photoinitiators, (D) a solvent, and (E) an additive.
In the negative photosensitive resin composition of the present invention, the photoinitiator is a component that generates an active material that can initiate polymerization of the binder resin described above by visible light, ultraviolet light, far ultraviolet light, charged particle beams, X-rays, and the like.
Examples of the photoinitiator include oxime ester compounds, bisimidazoles, benzoin compounds, acetophenone compounds, benzophenone compounds, α -dione compounds, polyquinone compounds, phosphine compounds, triazine compounds, and the like.
The oxime ester compound has the following advantages: the resin has excellent exposure sensitivity, excellent pattern stability after a developing process, stable developing pattern formation with a small exposure amount, excellent adhesion to a substrate, light shielding property, and insulation property, and excellent flatness without residue.
For example, the oxime ester compound may be 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (0-acetyloxime), 1, 3-octanedione-1 [ (4-phenylthio) phenyl ] 2-benzoyl-oxime, or the like.
Examples of the acetophenone compounds include α -hydroxyketone compounds, α -aminoketone compounds and compounds other than these.
Specific examples of the α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexylphenyl ketone, and specific examples of the α -aminoketone compound include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and specific examples of compounds other than these include 2, 2-dimethoxyacetophenone, 2-diethoxyacetophenone, and 2, 2-dimethoxy-2-phenylacetophenone.
Specific examples of the bisimidazoles include 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -bisimidazole, 2' -bis (2-bromophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -bisimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -bisimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -bisimidazole, 2' -bis (2,4, 6-trichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-bromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-tribromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, and the like.
Among the above biimidazole compounds, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2,4, 6-trichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole and the like are preferable, and particularly, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole is preferable.
As an example, the photoinitiator may be contained in an amount of 1 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the binder resin.
The crosslinkable compound having the ethylenically unsaturated bond is usually a crosslinkable monomer having two or more ethylenically double bonds, and may be selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butanediol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentaacrylate, and mixtures thereof, Polyfunctional (meth) acrylic monomers and oligomers such as dipentaerythritol pentamethyl methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, Cardo-epoxy diacrylate and poly (poly-) compounds thereof (polyethylene glycol diacrylate); a polyester (meth) acrylate obtained by reacting a polyester prepolymer obtained by condensing a polyol with a monobasic acid or a polybasic acid with (meth) acrylic acid, a urethane (meth) acrylate obtained by reacting a polyol group with a compound having two isocyanate groups and then with (meth) acrylic acid; at least one epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a phenol or cresol novolac-type epoxy resin, a resol-type epoxy resin, a triphenolmethane-type epoxy resin, a polyglycidyl ester of a polycarboxylic acid, a polyglycidyl ester of a polyhydric alcohol, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, or a dihydroxybenzene epoxy resin with (meth) acrylic acid. In addition, when the exposure sensitivity and the like are taken into consideration, it may be more advantageous to use a polyfunctional (meth) acrylic monomer.
The crosslinkable compound having the ethylenically unsaturated bond is preferably contained in an amount of 10 to 200 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin, and within this range, by virtue of a sufficient degree of curing with the photosensitive resin, there is an effect that a pattern is sufficiently realized and hardness and resolution of the formed pattern are excellent.
The organic solvent used for preparing the negative-type photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve the above-mentioned polymer in an organic solvent such as acetate, ether, glycol, ketone, alcohol, and carbonate used in a general photopolymerizable composition. For example, the solvent is at least one selected from the group consisting of ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, and the like.
As an example, the content of the solvent may include 20 to 95 parts by weight, preferably 30 to 90 parts by weight, and more preferably 50 to 80 parts by weight, relative to 100 parts by weight of the total content of the photosensitive resin composition, within which a thin film may be easily formed using an existing coating method and a thin film having a desired thickness may be easily obtained after coating.
Additives may be used in the present invention as needed. Examples of such additives include a heat stabilizer, a heat crosslinking agent, a light curing accelerator, a surfactant, a matrix quencher (base quencher), an antioxidant, an adhesion promoter, a light stabilizer, and an antifoaming agent, and they may be used alone or in combination as necessary.
Among the additives typically contained in the above additives, the adhesion promoter is a component having an action of improving adhesion to a substrate, and is preferably a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, a mercapto group, and specifically one or more selected from trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
As an example, the content of the bonding aid is preferably 0 to 10 parts by weight, 0.01 to 10 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 part by weight based on 100 parts by weight of the binder resin, within which range there is an excellent effect of bonding force with the substrate.
The surfactant is a component having an effect of improving coatability and coatability to a substrate, uniformity and stain release property, and one or more selected from the group consisting of a fluorine-based surfactant, a silicon-based surfactant and a nonionic surfactant may be used in combination, preferably a silicon-based surfactant, and as an example, a polyether-modified polysiloxane (polyether-modified polydimethylsiloxane) is given, and as a more specific example, a polyether-modified polydimethylsiloxane (polyether-modified polydimethylsiloxane) is given.
As an example, the content of the surfactant is preferably 0.01 to 5 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 part by weight, based on 100 parts by weight of the binder resin.
The bonding assistant is not particularly limited when it is a bonding assistant generally used in photosensitive resin compositions, but is preferably at least one selected from the group consisting of isocyanate compounds, epoxy compounds, acrylate compounds, vinyl compounds and mercapto compounds, more preferably an epoxy compound, and includes, as an example, an organic silane compound having an epoxy group, and more specifically, a methoxysilane compound having an epoxy group.
For example, the stabilizer may be a heat stabilizer, a light stabilizer, or a mixture thereof.
The heat stabilizer is not particularly limited when it is a heat stabilizer that can be generally used in a photosensitive resin composition, but it is, for example, a heat stabilizer that can suppress a decrease in permeability and improve the permeability of a residual organic film in a subsequent heat treatment process of a formed organic film, and preferably may be one or more selected from the group consisting of a phenol (phenolic) type heat stabilizer, a phosphite (phosphite) type heat stabilizer, and a lactone (lactone) type heat stabilizer, and more preferably may be a heat stabilizer represented by the following chemical formulae 10 to 12.
Chemical formula 10
Figure BDA0002530990240000261
Chemical formula 11
Figure BDA0002530990240000262
Chemical formula 12
Figure BDA0002530990240000263
The light stabilizer is not particularly limited when it is a light stabilizer that can be generally used in a photosensitive resin composition, but may be one that maximizes the light resistance of an organic insulating film composition, and preferably may be one or more selected from the group consisting of benzotriazole-based light stabilizers, triazine-based light stabilizers, benzophenone-based light stabilizers, hindered amino ether-based light stabilizers, and hindered amine-based light stabilizers.
The photosensitive adhesive composition may be suitably used in the preparation of semiconductor devices, devices for liquid crystal display devices (L CD), devices for organic light emitting diodes (O L ED), devices for solar cells, devices for flexible display devices, devices for touch screen preparation or devices for nanoimprint lithography.
The negative (negative) type photosensitive resin composition of the present invention can be used for the preparation of a color conversion medium layer, and can be suitably used for the preparation of a color conversion plate including an insulating substrate, a color conversion medium layer, and a light shielding member positioned between the color conversion medium layers.
As an example, in the photosensitive resin composition of the present invention, the sensitivity may be 140mJ/cm2100 to 20mJ/cm below2Or 60 to 30mJ/cm2Within this range, the effect of excellent optical characteristics of the photosensitive material is obtained.
For example, in the photosensitive resin composition of the present invention, the residual film ratio after development may be 91% or more, 95% or more, or 96 to 98%, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
For example, in the photosensitive resin composition of the present invention, the residual film ratio after curing may be 89% or more, 93% or more, or 94 to 97%, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
For example, in the photosensitive resin composition of the present invention, the taper angle may be 45 degrees or more, 50 degrees or more, or 55 to 75 degrees, within which range, there is an effect of excellent heat resistance.
For example, in the photosensitive resin composition of the present invention, the refractive index (reactive index) may be 1.51 or more, 1.60 or more, or 1.62 to 1.66, within which range there is an effect that the optical characteristics of the photosensitive material are excellent.
For example, in the photosensitive resin composition of the present invention, the transmittance after curing may be 94% or more, 95% or more, or 96 to 99%, within which the photosensitive material has an excellent effect on optical characteristics.
3. Positive photosensitive resin composition
The present invention provides a positive photosensitive resin composition comprising the above binder resin. The photosensitive resin composition of the present invention is characterized in that the binder resin contains a photoactive compound, an additive and an organic solvent.
In the present invention, the photoactive compound (PAG) generally used in a photoresist is not particularly limited, but may be a photoacid generator, for example.
As another example, the positive photosensitive resin composition of the present invention may include (a) the binder resin of the present invention, (F) a photoactive compound, (G) a matrix quencher, (D) a solvent, and (E) an additive.
The above-mentioned photoacid generator is a compound that generates an acid when irradiated with actinic light or radiation. The photoacid generator described above has an appropriate absorbance at a wavelength of 250nm to 450nm, and any substance may be used as long as it does not adversely affect film formation.
For example, the photoacid generator may be one or more selected from the group consisting of diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidazolium sulfonates, oxime sulfonates, diazodisulfones, disulfones, ortho-nitrobenzyl sulfonates, and triazine compounds.
For example, the content of the photoacid generator as the photoactive compound is 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the binder resin, and within this range, the amount of acid generated is sufficient, pattern formation is good, solubility to a solvent in the composition is not lowered, compatibility is good, and thus there is no concern that solid particles are precipitated.
The substrate quencher is not particularly limited, but may be one or more selected from the group consisting of primary amines, secondary amines, tertiary amines, and amide compounds, for example.
In order to prepare the positive photosensitive resin composition according to the present invention, an organic solvent and an additive may be included in the same kind and content as those of the organic solvent and the additive used for preparing the negative photosensitive resin composition.
As an example, in the photosensitive resin composition of the present invention, the sensitivity may be 200mJ/cm2100 to 20mJ/cm below270 to 30mJ/cm2Within this range, the effect of excellent optical characteristics of the photosensitive material is obtained.
For example, in the photosensitive resin composition of the present invention, the residual film ratio after development may be 90% or more, 91% or more, or 92 to 97%, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
For example, in the photosensitive resin composition of the present invention, the residual film ratio after curing may be 85% or more, 87% or more, or 88 to 92%, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
For example, in the photosensitive resin composition of the present invention, the taper angle may be 41 degrees or more, 45 degrees or more, or 49 to 65 degrees, within which range, there is an effect of excellent heat resistance.
As an example, in the photosensitive resin composition of the present invention, the refractive index may be 1.51 or more, 1.60 to 1.70, 1.63 to 1.68, or 1.64 to 1.66, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
For example, in the photosensitive resin composition of the present invention, the transmittance after curing may be 94% or more, 95% or more, 96% or more, or 96 to 98%, within which range there is an excellent effect of the optical characteristics of the photosensitive material.
The method of coating the photosensitive resin composition including the adhesive resin of the present invention on a display device such as a thin film transistor liquid crystal display device (TFT-L CD), an organic light emitting diode (O L ED), a touch screen panel, and the like, is not particularly limited, and a method known in the art to which the present invention pertains may be used, for example, a coating method such as Spin coating (Spin coating), dip coating (dip coating), roll coating (roll coating), screen coating (screen coating), spray coating (spray coating), flow coating (flow coating), screen printing (screen printing), inkjet (ink jet), drop coating (drop coating), and the like may be used.
The photosensitive resin composition of the present invention can use an alkaline aqueous solution as a developer, which is more environmentally friendly and economical than organic solvents. Examples of the above-mentioned alkaline developing solution include an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, an aqueous solution of an amine such as ammonia, ethylamine, diethylamine or triethylamine, KOH, NaOH or NaHCO3And the like, among which, in view of achieving the inherent object, an aqueous KOH solution and an aqueous tetramethylammonium hydroxide (TMAH) solution are preferable.
The photosensitive adhesive resin composition may be suitably used in the preparation of semiconductor devices, devices for liquid crystal display devices (L CD), devices for organic light emitting diodes (O L ED), devices for solar cells, devices for flexible display devices, devices for touch screen preparation, or devices for nanoimprint lithography.
The present invention is further illustrated in detail by the following specific synthetic examples and examples. The following examples are intended to illustrate the present invention, and the scope of the present invention is not limited to these examples.
Synthesis example 1
Synthesis of monomer I
Step 1: 2,2' - (((((9H-fluorene-9, 9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (ethylene oxide) (2,2' - (((9H-fluor)ene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis Synthesis of (methylene)) bis (oxirane) ((Oxirane))
Step A, after a reflux condenser (refloxcondensor) and a thermometer were installed in a three-necked flask (3-Neok flash), 42.5g of 9,9-bisphenol fluorene (9, 9-bisphenoylfluorene) was added, and 2- (chloromethyl) oxirane (2- (chloromethyl) oxirane) was quantitatively measured at 220m L, and then injected, after 100mg of Tetrabutylammonium bromide (Tetrabutylammonium bromide) was added, stirring was started while the temperature was raised to 90 ℃ and then distillation was carried out under reduced pressure.
Cooling, injecting dichloromethane (dichromethane), slowly adding NaOH, confirming the product by high performance liquid chromatography (HP L C), dripping HCl aqueous solution, stopping the reaction, extracting, separating the layers, and collecting the organic layer with MgSO4Dried, and then concentrated by distillation under reduced pressure using a rotary evaporator. After dichloromethane (dichloromethane) and methanol (methanol) were added to the concentrated product, the solid formed was filtered and dried in vacuo to obtain 52.7g (yield 94%) of a white solid, the structure of which was confirmed by the following 1H NMR results.
1H NMR in CDCl3：7.75(2H)，7.36-7.25(6H)，7.09(4H)，6.74(4H)，4.13(2H)，3.89(2H)，3.30(2H)，2.87(2H)，2.71(2H)。
In addition, the monomers having the structures of chemical formulas 2 to 4 may be conventionally prepared according to the method suggested in the synthesis method of step 1.
Step 2: synthesis of 3,3'- (((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol) (3,3' - (((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol))
After a reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of the product epoxide (epoxide) prepared in step 1, 52.4g of thiophenol (thiophenol), and 61.7g of ethanol were added, stirred, 32.8g of triethylamine (triethylamine) was slowly dropped into the reaction solution, and after the product was confirmed by a high performance liquid chromatography (HP L C), the reaction was terminated, ethanol was removed by distillation under reduced pressure, the organic matter was dissolved in dichloromethane (dichromethane), washed with water, and after the organic solvent was distilled under reduced pressure, ether was dropped to obtain 94.5g (64% yield) of a pale yellow oil, the structure of which was confirmed by 1H NMR.
1H NMR in CDCl3：7.82(2H)，7.38-6.72(20H)，6.51(4H)，4.00(2H)，3.97(2H)，3.89(2H)，3.20(2H)，3.01(2H)，2.64(2H)。
In addition, the monomers having the structures of chemical formulas 6 to 8 may be conventionally prepared according to the method suggested in the synthesis method of step 2.
Synthesis example 2
Synthesis of monomer II
Step 1: the synthesis was carried out by the same synthesis method as in step 1 of synthesis example 1.
Step 2: synthesis of ((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (2-hydroxypropane-3,1-diyl) diacrylate ((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (2-hydroxyphenyl-3, 1-diyl) diacrylate)
After a reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 60.0g (0.13mol) of the product (epoxide) of step 1, 20.5g (0.29mol) of acrylic acid (acrylic acid), and 0.4g (1mmol) of Tetrabutylammonium bromide (Tetrabutylammonium bromide) were added under room temperature conditions in 60.0g of Propylene Glycol Methyl Ether Acetate (PGMEA) solvent, and further stirred under reaction temperature conditions of 100 ℃ to 120 ℃ for 4 hours.
The structure thereof was confirmed by the following 1H NMR results.
1H NMR in CDCl3：7.82(2H)，7.38-6.72(10H)，6.51(4H)，6.50(2H)，6.29(2H)，6.09(2H)，4.05(2H)，3.94(2H)，3.85(2H)，3.17(2H)，2.99(2H)，2.60(2H)。
In addition, the monomers having the structures of chemical formulas 6 to 8 may be conventionally prepared according to the method proposed in the synthesis method of step 2 of synthesis example 2.
Synthesis example 3
Synthesis of monomer III
Step 1: the synthesis was carried out by the same synthesis method as in step 1 of synthesis example 1.
Step 2: synthesis of 1,1- (4- (9- (4- (oxiran-2-ylmethoxy) phenyl) -9H-fluoren-9-yl) phenoxy) -3- (phenylsulfanyl) propan-2-ol (1.1- (4- (9- (4- (oxoman-2-ylmethoxy) phenyl) -9H-fluoro-9-yl) phenoxy) -3- (phenylthio) propan-2-ol)
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 20g (0.043mol) of epoxide (epoxide), 5.2g (0.047mol) of thiophenol (thiophenol), and 125g of ethanol, which were the product of step 1, were added, and stirred, after triethylamine (triethamine) (3.3g, 0.037mol) was added dropwise to the reaction solution, after confirming the product by a high performance liquid chromatography (HP L C) method, the reaction was terminated, after the reaction was completed, ethanol was removed by distillation under reduced pressure, after the organic dichloromethane (dichlomelane), washed with water, and then the organic solvent was removed by distillation under reduced pressure, 15g (51% yield) of pale yellow (pallelow) was obtained, and the structure thereof was confirmed by 1H NMR results as follows.
1H NMR in CDCl3：7.81(2H)，7.39-6.76(15H)，6.50(4H)，4.10(1H)，4.01(1H)，3.97(1H)，3.89(1H)，3.20(2H)，2.89(1H)，2.64(2H)。
In addition, the monomers having the structures of chemical formulas 2 to 4 may be conventionally prepared according to the method proposed in the synthesis method of step 2 of synthesis example 3.
And step 3: synthesis of propyl 2,2-hydroxy-3- (4- (9- (4- (2-hydroxy-3- (phenylthio) propoxy) phenyl) -9H-fluoren-9-yl) phenoxy) acrylate (2,2-hydroxy-3- (4- (9- (4- (2-hydroxy-3- (phenylthio) propoxy) phenyl) -9H-fluoro-9-yl) phenyl) propyl acrylate)
After a reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 5g (0.009mol) of the compound prepared in Synthesis example 2, 1.3g (0.012mol) of thiophenol (thiophenol), and 30g of ethanol were placed under Propylene Glycol Methyl Ether Acetate (PGMEA) solvent, stirred, 32.8g of triethylamine (triethylamine) was slowly dropped into the reaction solution, and after confirming the product by high performance liquid chromatography (HP L C), the reaction was terminated, after the reaction was completed, ethanol was removed by distillation under reduced pressure, the organic matter was dissolved in dichloromethane (dichloromethane), washed with water, and then the organic solvent was distilled under reduced pressure to obtain 5.1g (yield 70%) of which the structure was confirmed by 1H NMR results as follows.
1H NMR in CDCl3：7.82(2H)，7.38-6.72(15H)，6.51(4H)，6.42(1H)，6.17(1H)，6.02(1H)，4.14(2H)，4.02(2H)，3.95(1H)，3.89(1H)，3.60(2H)，3.47(2H)。
In addition, the monomers having the structures of chemical formulas 6 to 8 may be conventionally prepared according to the method proposed in the synthesis method of step 3 of synthesis example 3.
Preparation of the adhesive
Preparation example 1: preparation of BTCP/PMDA Binder
Figure BDA0002530990240000341
After a reflux condenser (reflux condenser) and a thermometer were installed (setting) in a three-necked flask (3-hackflash), I, BTCP 200g of monomer dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was added and the temperature was raised to 115 ℃. After 21.1g of the monomer PMDA was added dropwise at a temperature of 115 ℃ and stirred for 6 hours. Then, 7.35g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 1 can prepare a BTCP/PMDA binder having a molecular weight with a weight average molecular weight of 2000g/mol to 20000g/mol according to the amount of PMDA used.
In addition, an adhesive may be prepared using a monomer having a structure of chemical formula 6 to chemical formula 8 and a carboxylic dianhydride according to the synthetic method of preparation example 1.
Preparation example 2: preparation of BTCP/BPDA Binder
Figure BDA0002530990240000351
After a reflux condenser (reflux condenser) and a thermometer were installed (setting) in a three-necked flask (3-hackflash), I, BTCP 200g of monomer dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was added and the temperature was raised to 115 ℃. After BPDA31.1g was added dropwise at 115 ℃ the mixture was stirred for 6 hours. 7.35g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 2 can prepare a BTCP/BPDA binder having a molecular weight with a weight average molecular weight of 2000g/mol to 20000g/mol according to the amount of BPDA used.
In addition, an adhesive may be prepared using a monomer having a structure of chemical formula 6 to chemical formula 8 and a carboxylic dianhydride according to the synthetic method of preparation example 2.
Preparation example 3: preparation of BTCP/BTDA Binder
Figure BDA0002530990240000352
After a reflux condenser (reflux condenser) and a thermometer were installed (setting) in a three-necked flask (3-hackflash), I, BTCP 200g of monomer dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was added and the temperature was raised to 115 ℃. After BTDA28.4g was added dropwise at 115 ℃ the mixture was stirred for 6 hours. Then, 7.35g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 3 can prepare a BTCP/BTDA binder having a molecular weight with a weight average molecular weight of 2000g/mol to 20000g/mol according to the amount of BTDA used.
In addition, an adhesive may be prepared using a monomer having a structure of chemical formula 6 to chemical formula 8 and a carboxylic dianhydride according to the synthetic method of preparation example 3.
Preparation example 4: preparation of monomer I/monomer II/CBDA Binders
Figure BDA0002530990240000361
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer I and 100g of monomer II dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 20.0g of CBDA was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 7.1g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 4 can be carried out at a molar ratio of 99: 1 to 1: 99 applies to monomers I and II and can make use of the monomer CBDA to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared by using the monomer I and the monomer II and the carboxylic dianhydride according to the synthesis method of preparation example 4.
Preparation example 5: preparation of monomer I/monomer II/CHDA Binder
Figure BDA0002530990240000371
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer I and 100g of monomer II dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. 22.4g of CHDA was added dropwise thereto at 110 ℃ and the mixture was stirred for 4 hours. Then, 7.1g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation 5 can be carried out at 99: 1 to 1: 99 applies to monomers I and II and can make use of monomer CHDA to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared by using the monomer I and the monomer II and the carboxylic dianhydride according to the synthesis method of preparation example 5.
Preparation example 6: preparation of monomer I/monomer II/PMDA Binder
Figure BDA0002530990240000391
After a reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer I and 100g of monomer II dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 21.8g of PMDA was added dropwise at 110 ℃ and stirred for 4 hours. Then, 7.1g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 3500g/mol was obtained.
The polymerization reaction shown in preparation example 6 can be carried out at 99: 1 to 1: 99 applies to monomers I and II and can make use of the monomer PMDA to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared by using the monomer I and the monomer II and the carboxylic dianhydride according to the synthesis method of preparation example 6.
Preparation example 7: preparation of monomer I/monomer II/BPDA Binder
Figure BDA0002530990240000401
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer I and 100g of monomer II dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After BPDA29.4g was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 7.1g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 3500g/mol was obtained.
The polymerization reaction shown in preparation example 7 can be carried out at 99: 1 to 1: 99 ratio of monomers I and II and the use of monomer BPDA to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared according to the synthesis method of preparation example 7 using monomer I and monomer II and a carboxylic dianhydride.
Preparation example 8: preparation of monomer I/monomer II/BTDA Binder
Figure BDA0002530990240000411
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer I and 100g of monomer II dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After BTDA32.2g was added dropwise at 110 ℃, the mixture was stirred for 4 hours. Then, 7.1g of Tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation 8 can be carried out at 99: 1 to 1: 99 applies to monomers I and II and can make use of monomer BTDA to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared by using the monomer I and the monomer II and the carboxylic dianhydride according to the synthesis method of preparation example 8.
Preparation example 9: preparation of monomer III/CBDA Binders
Figure BDA0002530990240000421
After a setting reflux condenser (reflux condenser) and thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer III dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 10.2g of CBDA was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 3.0g of tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 9 can be carried out at 99: 1 to 1: 99 ratio of monomer III and monomer CBDA and using monomer CBDA to prepare an adhesive having a molecular weight of 2000g/mol to 20000g/mol weight average molecular weight.
Further, an adhesive can be prepared according to the synthetic method of preparation example 9 using monomer III and a carboxylic dianhydride.
Preparation example 10: preparation of monomer III/CHDA Binders
Figure BDA0002530990240000431
After a setting reflux condenser (reflux condenser) and thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer III dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 12.0g of CHDA was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 3.0g of tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 10 can be carried out at a ratio of 99: 1 to 1: 99 applies to monomer III and monomer CHDA, and monomer CHDA can be utilized to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared according to the synthetic method of preparation example 10 using monomer III and a carboxylic dianhydride.
Preparation example 11: preparation of monomer III/PMDA Binder
Figure BDA0002530990240000432
After a setting reflux condenser (reflux condenser) and thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer III dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 11.5g of PMDA was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 3.0g of tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 3500g/mol was obtained.
The polymerization reaction shown in preparation example 11 can be carried out at a ratio of 99: 1 to 1: 99 is suitable for the monomer III and the monomer PMDA, and the monomer PMDA can be used to prepare adhesives having a molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared according to the synthetic method of preparation example 11 using monomer III and a carboxylic dianhydride.
Preparation example 12: preparation of monomer III/BPDA Binder
Figure BDA0002530990240000441
After a setting reflux condenser (reflux condenser) and thermometer were installed in a three-necked flask (3-hackflash), 100g of monomer III dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent were added and the temperature was raised to 110 ℃. After 15.4g of BPDA was added dropwise at 110 ℃ the mixture was stirred for 4 hours. Then, 7.35g of tetrahydrophthalic anhydride (THPA) was added thereto, and the reaction was terminated after further stirring for 2 hours. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 12 can be carried out at a ratio of 99: 1 to 1: the ratio of 99 applies to monomer III and monomer BPDA can be used to prepare adhesives having a molecular weight of 2000g/mol to 20000g/mol weight average molecular weight.
Further, an adhesive can be prepared according to the synthetic method of preparation example 12 using monomer III and a carboxylic dianhydride.
Preparation example 13: preparation of monomer III/BTDA Binder
Figure BDA0002530990240000451
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 100g of the compound of Synthesis example 3 dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was added and the temperature was raised to 110 ℃. 16.9g of BTDA was added dropwise at 110 ℃ and the mixture was stirred for 4 hours. After 3.0g of Tetrahydrophthalic anhydride (THPA) was added and further stirred for 2 hours, the reaction was terminated. After cooling, a binder solution with a weight average molecular weight of 4000g/mol was obtained.
The polymerization reaction shown in preparation example 13 can be carried out at 99: 1 to 1: the ratio of 99 applies to monomer III and monomer BTDA can be used to prepare adhesives having a molecular weight with a weight average molecular weight of 2000g/mol to 20000 g/mol.
Further, an adhesive can be prepared according to the synthetic method of preparation example 13 using monomer III and a carboxylic dianhydride.
Preparation of photosensitive resin composition
Reference example 1
35g of the adhesive resin prepared by the above adhesive preparation example 1 and
Figure BDA0002530990240000452
3g of the solution was dissolved in Propylene Glycol Methyl Ether Acetate (PGMEA) which is an organic solvent so that the solid content thereof became 35 wt%, and 0.03g of a silicon-based surfactant (BYK333, Germany Bikk (BYK)) and 0.02g of an epoxy-based adhesion aid (KBM403, Shinetsu) were added to 60g of the above solution and mixed to prepare a positive type organic insulating film composition.
Reference example 2
A positive type organic insulating film composition was prepared in the same manner as in the above-mentioned reference example 1, except that 35g of the binder resin prepared by the above-mentioned binder preparation example 2 was used.
Reference example 3
A positive type organic insulating film composition was prepared in the same manner as in the above-mentioned reference example 1, except that 35g of the binder resin prepared by the above-mentioned binder preparation example 3 was used.
Example 1
A positive type organic insulating film composition was prepared in the same manner as in the above-mentioned reference example 1, except that 35g of the binder resin prepared by the above-mentioned binder preparation example 4 was used.
Example 2
A positive type organic insulating film composition was prepared in the same manner as in the above-mentioned reference example 1, except that 35g of the binder resin prepared by the above-mentioned binder preparation example 5 was used.
Example 3
35g of the adhesive resin prepared in preparation example 6 of the adhesive and 1.0g of an oxime ester photoinitiator were mixed
Figure BDA0002530990240000461
The negative photosensitive resin composition was prepared by dissolving Propylene Glycol Methyl Ether Acetate (PGMEA) in an organic solvent so that the concentration thereof was 35 parts by weight with respect to Propylene Glycol Methyl Ether Acetate (PGMEA) in the organic solvent, and adding 0.03g of a surfactant (BYK333) and 0.02g of an adhesion promoter (KBM403) to the above solution, followed by mixing.
Example 4
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 7 was used.
Example 5
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 8 was used.
Example 6
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 9 was used.
Example 7
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 10 was used.
Example 8
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 11 was used.
Example 9
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin prepared by the above binder preparation example 12 was used.
Example 10
A negative-type photosensitive resin composition was prepared in the same manner as in example 3 above, except that 35g of the binder resin was prepared by the above binder preparation example 13.
Comparative example 1
In the above reference example 1, a positive type organic insulating film composition was prepared in the same manner as in the above example 1 except that 30g of an acrylic polymer having a weight average molecular weight of 15000g/mol polymerized with 30 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid and 10 parts by weight of a styrene monomer in a solid content of 40 weight percent in Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was used instead of the BTCP/BPDA binder.
Comparative example 2
In the above reference example 1, 30g of an acrylic polymer having a weight average molecular weight of 15000g/mol and a photoinitiator were polymerized in a solid content of 40 weight percent in the presence of 30 parts by weight of benzyl methacrylate, 10 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid and 10 parts by weight of a styrene monomer in Propylene Glycol Methyl Ether Acetate (PGMEA) solvent
Figure BDA0002530990240000481
1.0g of a negative type photosensitive resin composition was prepared by dissolving Propylene Glycol Methyl Ether Acetate (PGMEA) in an organic solvent so that the concentration thereof was 35% by weight based on the weight of the Propylene Glycol Methyl Ether Acetate (PGMEA) in the organic solvent, and adding 0.03g of a surfactant (BYK333) and 0.02g of a bonding assistant (KBM403) to the above solution, followed by mixing.
Comparative example 3
After a setting reflux condenser (reflux condenser) and a thermometer were installed in a three-necked flask (3-hackflash), 149g of 2,2' - ((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene) oxide synthesized as an example of chemical formula 1 in the above-mentioned step 1, 46g of acrylic acid, 1.5g of TBAB, and 200g of Propylene Glycol Methyl Ether Acetate (PGMEA) were added to make the concentration 50 weight percent, and then heated to 115 ℃ to synthesize a monomer.
After confirming that the content of the above ethylene oxide compound was 0.5%, 56g of BPDA was added dropwise thereto and stirred for 6 hours. Then, 14g of Tetrahydrophthalic anhydride (THPA) was added thereto, and after further stirring for 2 hours, the reaction was terminated to obtain an adhesive solution having a weight average molecular weight of 4000 g/mol.
To the above adhesive 35g was added
Figure BDA0002530990240000482
3g of a positive type organic insulating film composition was prepared by dissolving Propylene Glycol Methyl Ether Acetate (PGMEA) in an organic solvent so that the solid content became 35 weight percent, and adding 0.03g of a silicon-based surfactant (BYK333, BYK, Germany) and 0.02g of an epoxy-based adhesion aid (KBM403, Shinetsu, Japan) to 60g of the above adhesive solution and mixing them.
Comparative example 4
35g of the adhesive of comparative example 3 and a photoinitiator
Figure BDA0002530990240000491
1.0g of Propylene Glycol Methyl Ether Acetate (PGMEA) dissolved in an organic solvent so that the solid content became 35% by weight, 0.03g of a surfactant (BYK333) and 0.02g of an adhesion aid (KBM403) were added to the above solution, and mixed to prepare a negative-type photosensitive resin composition.
Evaluation of physical Properties
Each of the photosensitive resin compositions obtained by the above-described reference examples 1 to 3,1 to 10 and 1 to 4 was coated at 800 to 900rpm for 15 seconds in a spin coater, and then dried at 90 ℃ for 100 seconds in a hot plate. After exposure using a predetermined mask and an ultra-high pressure mercury lamp as a light source, the substrate was subjected to spin development in an aqueous alkaline developer at 25 ℃ for 60 seconds and then washed with water. After water washing and drying, the resultant was Post-baked (Post baker) in an oven at 230 ℃ for 40 minutes to obtain a pattern, and physical properties were evaluated according to the following items.
(1) Evaluation of sensitivity
Each of the above-mentioned photosensitive resin compositions was applied to a Glass substrate (Samsung Corning Precision Glass, Eagle2000) by a spin coater, dried at 90 ℃ for 1 minute by a hot plate, and then measured by a stylus type film thickness measuring instrument (K L A-Tencor, Ltd., a-step 500) after drying to obtain a photosensitive film, and then exposed to an ultra-high pressure mercury lamp and spray-developed by a water-soluble alkaline developer to obtain a resist pattern, showing that an appropriate exposure amount (mJ/cm) capable of forming a mask pattern of a size of, for example, 20 μm or the like was obtained2). That is, a resist with a small exposure amount can be patterned with a small amount of light energy, and thus exhibits high sensitivity.
(2) Residual film rate
In the above sensitivity evaluation process, the pattern thickness after development was measured to measure the residual film rate after development, and then post-baked in an oven at 230 ℃ for 40 minutes to measure the residual film rate after curing.
(3) Permeability of liquid
The above composition was spin-coated on a glass substrate to have the same thickness of 3 μm, and then subjected to spin coating at 400mJ/cm2The front surface of the film was exposed to light and post-baked at 240 ℃ for 40 minutes, and the average transmittance between 400nm and 800nm was measured by an ultraviolet spectrophotometer (UV spectrometer) in each step.
(4) Cone angle (taper angle)
In the above evaluation, after development, a pattern substrate having the same sensitivity as a 20 μm mask pattern formation size was subjected to post-baking at 240 ℃ for 40 minutes, and then the taper angle of the pattern was measured using a Scanning Electron Microscope (SEM).
(5) Adhesion property
According to the test method of JIS D0202, after exposure and development, the coating film heated at 240 ℃ for 40 minutes was crossed in a lattice shape, and then, a peeling test was carried out by a cellophane tape to observe and evaluate the state of peeling in the lattice shape, and when no peeling was observed, ○ was set, and when peeling was confirmed, X was set.
(6) Refractive index
The above composition was spin-coated on a glass substrate to have the same thickness of 3 μm, and then the refractive index was measured by a prism coupler.
The results of sensitivity, residual film ratio and adhesion evaluation on the physical properties of the photosensitive resin compositions obtained in examples 1 to 13 and comparative examples 1 to 4 are shown in table 1.
TABLE 1
Figure BDA0002530990240000501
Figure BDA0002530990240000511
Further, the results of measuring the taper angle for confirming the heat resistance to be confirmed in the present invention and the results of measuring the refractive index and the transmittance after curing of the thin film prepared from the composition disclosed in each example are shown in the following table 2.
TABLE 2
Figure BDA0002530990240000512
Figure BDA0002530990240000521
In the photosensitive materials suitable for the thin film transistor liquid crystal display (TFT-L CD) process, the organic light emitting diode (O L ED) process, and the Touch Screen Panel (TSP) process, the characteristics of the organic film photosensitive material are particularly important for the characteristics of the display device.
As shown in the above table 1, it can be confirmed that the organic film compositions according to examples 1 to 10 exhibit excellent high sensitivity characteristics compared to the organic film compositions of comparative examples 1 to 4. The adhesive structure of the present invention is excellent in interaction with a photoactive material (PAC) or a photoinitiator affecting sensitivity characteristics, and thus such characteristics maximize a difference in dissolution rate between an exposed region and a non-exposed region, and thus it is known that sensitivity characteristics are excellent.
Further, it was confirmed that the interaction characteristics between the binder and the photoactive material according to the present invention are very excellent in the residual film ratio after development and the adhesion characteristics, as compared to the photosensitive resin composition of the comparative example using the acrylic binder.
Also, since the adhesive prepared by the present invention is excellent in heat resistance, the taper angle (taper) and Outgassing (evacuation) characteristics can be controlled. In particular, since the TFT process is applied to a high-temperature heat treatment process at 300 ℃ or higher, the heat resistance of the binder is very important in securing the heat resistance of the organic film photosensitive material. The organic film photosensitive material to which the conventional acrylic binder having low heat resistance is applied is decomposed in the high-temperature heat treatment process, and thus impurities or foreign substances are found in the process, which causes the degradation of the characteristics of the display device. Also, it is difficult to adjust the shape of the pattern or the taper angle, and thus it is difficult to realize the high resolution characteristics of the photosensitive material. The adhesive structure of the present invention can secure heat resistance characteristics of 300 ℃ or more, and thus can solve the problem of characteristic degradation due to impurities according to a high-temperature heat treatment process, and can realize a pattern having high resolution characteristics.
As shown in table 2, the adhesive structure of the present invention was confirmed to exhibit high refractive index and transmittance characteristics. Since the adhesive structure of the present invention includes a specific monomer structure and a specific element, it can exhibit high refractive index characteristics compared to adhesives of a general acrylic structure. The high refractive index characteristic of such a photosensitive material can minimize a decrease in optical characteristics of a display device due to light, and thus can improve light transmittance characteristics or definition characteristics of the display device. In particular, a film prepared by using the photosensitive resin composition of the binder of the present invention also shows very excellent transmittance characteristics of 97% or more after being thermally cured at a temperature of 200 ℃ or more. The transmittance characteristics of such a photosensitive material can realize clear characteristics of a display device and can realize a wide aperture ratio of a TFT layer, and thus a display device excellent in contrast can be realized and power consumption for driving can be reduced.
For reference, as shown in the above tables 1 and 2, the organic film compositions according to the present invention (examples 1 to 10) were excellent in optical characteristics and the like, and in particular, it was confirmed that the transmittance was improved, compared to the reference examples 1 to 3 using different monomers.
In conclusion, it was confirmed that by using the binder resin according to the present invention, a photosensitive resin composition having very excellent characteristics such as sensitivity, heat resistance, transmittance, and refractive index can be prepared.

Claims (14)

1. An adhesive resin which is a polymer comprising a monomer represented by the following chemical formula I or a monomer represented by the following chemical formula I and a monomer represented by the following chemical formula II,
chemical formula I
Figure FDA0002530990230000011
In the chemical formula I, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of is (meth) acryloyloxy, said RaIs a bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, Z is O, S, N, Si or Se, R isb、RcAnd RdIndependently an alkyl group with or without a heteroatom having 1 to 10 carbon atoms or an aryl group with or without a heteroatom having 6 to 20 carbon atoms, when said Z is O, S or Se, g is 0, h is 0, when said Z is N, g is 1, h is 0, when said Z is Si, g is 1, h is 1, said R is 14Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, A independently a substituent represented by the formulae I-1 to I-4, D is O, S, CH2Se, n is an integer from 1 to 6, p is independently an integer from 1 to 30,
chemical formula II
Figure FDA0002530990230000021
In the chemical formula II, R5And R'5Independently is (meth) acryloyloxy or independently is RaZRb(Rc)g(Rd)hSaid R isaIs a bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, said Z is O, S, N, Si or Se, said R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, when Z is O, S or Se, g is 0, h is 0, when Z is N, g is 1, h is 0, when Z is Si, g is 1, h is 1, and R 'is'4Independently a tetravalent aromatic hydrocarbon group which may or may not contain a hetero element having 6 to 20 carbon atoms or a tetravalent alicyclic hydrocarbon group which may or may not contain a hetero element having 4 to 20 carbon atoms, A 'independently a substituent represented by the formulae I-1 to I-4, D' is O, S, CH2Se, m is independently an integer from 1 to 6, q is independentlyIs an integer of 1 to 30, and,
chemical formula I-1
Figure FDA0002530990230000022
Chemical formula I-2
Figure FDA0002530990230000031
Chemical formula I-3
Figure FDA0002530990230000032
Chemical formula I-4
Figure FDA0002530990230000033
In the formulae I-1 to I-4, R2And R'2Respectively represent hydrogen, hydroxyl (-OH), thiol (-SH), and amino (-NH)2) Nitro (-NO)2) Or halogeno, X represents O, S, Se, NR6Or SiR7(R8) Said R is6、R7Or R8Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
2. The adhesive resin according to claim 1, wherein the adhesive resin is used as an adhesive in a photosensitive material for a display device.
3. The adhesive resin of claim 1, wherein the adhesive resin is a resin terminated with an organic acid, an organic anhydride, or an amic acid.
4. The adhesive resin according to claim 1, wherein the weight average molecular weight of the adhesive resin is 1000g/mol to 100000 g/mol.
5. The adhesive resin according to claim 1, wherein the dispersity of the adhesive resin is 1.0 to 5.0.
6. A negative-type photosensitive resin composition comprising the binder resin according to any one of claims 1 to 5, a photoinitiator, an organic solvent, and a surfactant.
7. The negative-type photosensitive resin composition of claim 6, wherein, in the negative-type photosensitive resin composition, 100 parts by weight of the binder resin, 1 to 20 parts by weight of the photoinitiator, 0.01 to 5 parts by weight of the surfactant, and 0 to 10 parts by weight of the adhesion promoter are contained in the organic solvent in an amount of 5 to 80 percent by weight.
8. A positive photosensitive resin composition comprising the binder resin according to any one of claims 1 to 5, a photoactive compound, an organic solvent, and a surfactant.
9. The positive photosensitive resin composition according to claim 8, wherein in the positive photosensitive resin composition, 100 parts by weight of the binder resin, 0.1 to 30 parts by weight of the photoactive compound, 0.01 to 5 parts by weight of the surfactant, and 0 to 10 parts by weight of the bonding assistant are contained in the organic solvent at 5 to 80% by weight.
10. A substrate comprising a resin cured pattern formed from the photosensitive resin composition according to claim 6.
11. The substrate of claim 10, wherein the substrate is a color filter, an organic light emitting diode substrate, a liquid crystal display device substrate, a semiconductor substrate, a solar cell substrate, a flexible display substrate, a touch screen substrate, or a nanoimprint lithography substrate.
12. A substrate comprising a resin cured pattern formed from the photosensitive resin composition according to claim 8.
13. The substrate of claim 12, wherein the substrate is a color filter, an organic light emitting diode substrate, a liquid crystal display device substrate, a semiconductor substrate, a solar cell substrate, a flexible display substrate, a touch screen substrate, or a nanoimprint lithography substrate.
14. A method for preparing an adhesive resin, comprising the step of polymerizing a monomer represented by chemical formula 13 or a monomer represented by chemical formula 13 and a monomer represented by chemical formula 14 with a carboxylic dianhydride represented by chemical formula 9,
chemical formula 13
Figure FDA0002530990230000051
In chemical formula 13, R3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R'3Independently is (meth) acryloyloxy or RaZRb(Rc)g(Rd)h，R3And R'3At least one of is (meth) acryloyloxy, said RaIs a bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms, said Z is O, S, N, Si or Se, said R isb、RcAnd RdIndependently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, when the Z is O, S or Se, g ═ 0, h ═ 0, when the Z is N, g ═ 1, h ═ 0, when the Z is Si, g ═ 1, h ═ 1, when the Z is Si, the a is independently a substituent represented by formulae I-1 to I-4, the D is O, S, CH2Se, wherein n is an integer of 1 to 6,
chemical formula 14
Figure FDA0002530990230000061
At the placeIn the following chemical formula 14, R5And R'5Independently is (meth) acryloyloxy or independently is RaZRb(Rc)g(Rd)hWherein A' is independently a substituent represented by the formulae I-1 to I-4, and D is O, S, CH2Se, m is an integer of 1 to 6,
chemical formula I-1
Figure FDA0002530990230000062
Chemical formula I-2
Figure FDA0002530990230000063
Chemical formula I-3
Figure FDA0002530990230000071
Chemical formula I-4
Figure FDA0002530990230000072
In the formulae I-1 to I-4, R2And R'2Respectively represent hydrogen, hydroxyl (-OH), thiol (-SH), and amino (-NH)2) Nitro (-NO)2) Or halogeno, X represents O, S, Se, NR6Or SiR7(R8) Said R is6、R7Or R8Represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms,
chemical formula 9
Figure FDA0002530990230000081
In the chemical formula 9, the first and second,
R4is a tetravalent alicyclic hydrocarbon group of 4 to 20 carbon atoms with or without a hetero element or is a tetravalent alicyclic hydrocarbon group of 6 to 20 carbon atoms with or without a hetero elementOr a tetravalent aromatic hydrocarbon group containing no hetero element.
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