CN109153658A - Oxime ester derivative compound, Photoepolymerizationinitiater initiater and photosensitive composite comprising it - Google Patents

Oxime ester derivative compound, Photoepolymerizationinitiater initiater and photosensitive composite comprising it Download PDF

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Publication number
CN109153658A
CN109153658A CN201780030503.5A CN201780030503A CN109153658A CN 109153658 A CN109153658 A CN 109153658A CN 201780030503 A CN201780030503 A CN 201780030503A CN 109153658 A CN109153658 A CN 109153658A
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China
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hydroxyl
photosensitive composite
alkyl
oxime ester
butyl
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CN201780030503.5A
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CN109153658B (en
Inventor
李元重
吴泉林
李得洛
李栽训
赵镛
赵镛一
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Samyang Corp
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Samyang Corp
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Priority claimed from PCT/KR2017/005250 external-priority patent/WO2017200354A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Abstract

The invention discloses a kind of oxime ester derivative compound and a kind of Photoepolymerizationinitiater initiaters and photosensitive composite comprising the oxime ester derivative compound.

Description

Oxime ester derivative compound, Photoepolymerizationinitiater initiater and photosensitive composite comprising it
Technical field
The present invention relates to oxime ester derivative compound and include its Photoepolymerizationinitiater initiater and photosensitive composite.More Body, the present invention relates to a kind of oxime esters with excellent susceptibility, heat resistance, light resistance, chemical resistance and curing performance to spread out Raw compounds, and Photoepolymerizationinitiater initiater and photosensitive composite comprising it.
Background technique
Representative instance as Photoepolymerizationinitiater initiater used in photosensitive composite, it is known that there are many type, For example, acetophenone derivs, diphenylmethyl ketone derivatives, pyrrolotriazine derivatives, united imidazole derivative, acylphosphine oxide derivative With oxime ester derivative compound, wherein the advantages of oxime ester derivative compound is that they absorb ultraviolet lights but almost colourless and have height Free radical luminous efficiency, with the good compatibility and outstanding stability of photosensitive composite material.However, early stage opens The oxime ester derivative compound of hair has low light-initiated efficiency, especially because low sensitivity during pattern exposure and need Increase exposure dose, yield is caused to reduce.
Therefore, exploitation have high lightsensitivity Photoepolymerizationinitiater initiater will lead to can be achieved on a small quantity enough susceptibilitys, The effect for saving cost is generated, and since high sensitive reduces exposure dose, increase yield.
However, when forming pattern using conventional Photoepolymerizationinitiater initiater, due in the exposure process that pattern is formed Low sensitivity needs to increase the amount of Photoepolymerizationinitiater initiater or increases exposure dose, and its generated disadvantage is exposed By-product caused by after mask is contaminated in journey, and Photoepolymerizationinitiater initiater decomposes during crosslinking at high temperature reduces production Rate, and increase since the exposure-processed time increases with exposure dose, there are problems that yield reduction, therefore, is endeavouring In solving the problems, such as this.
Pertinent literature
Patent document
(patent document 1) WO02/100903 (on December 19th, 2002)
(patent document 2) Japanese patent application publication No.: 2005-025169 (on January 27th, 2005)
(patent document 3) WO07/071497 (on June 28th, 2007)
(patent document 4) Korean Patent Publication No. 2013-0124215 (on November 13rd, 2013)
(patent document 5) Korean Patent Publication No.: 2013-0115272 (on October 21st, 2013).
Summary of the invention
Technical problem
The present invention relates to provide a kind of oxime ester with excellent susceptibility, heat resistance, chemical resistance and curing performance to spread out Raw compounds, and Photoepolymerizationinitiater initiater and photosensitive composite comprising it.
The present invention further provides a kind of mechanographs of cured product comprising the photosensitive composite.
The display equipment comprising the mechanograph that the present invention further provides a kind of.
Technical solution
In order to achieve the above objectives, according to an aspect of the present invention, the oxime ester derivative compounds of following implementation are provided Object.
First embodiment is related to oxime ester derivative compound shown in formula 1:
<formula 1>
Wherein, R1And R2Respectively stand alone as hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6- C20) aryl (C1-C20) alkyl, hydroxyl (C1-C20) alkyl, hydroxyl (C1-C20) alkoxy (C1-C20) alkyl or (C3- C20) naphthenic base；And
R3For (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl or (C3-C20) cycloalkanes Base.
Second embodiment is related to the oxime ester derivative compound in first embodiment, wherein R1And R2Respectively stand alone as Hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, N-octyl, positive decyl, isodecyl, dodecyl, cyclopenta, cyclohexyl, phenyl, benzyl, naphthalene, xenyl, terphenyl, Anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxyl Ylmethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl are just Hexyl, hydroxyl isohesyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl, hydroxymethoxy butyl, Hydroxyethoxymethyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl or Hydroxyl-oxethyl hexyl；And R3For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, different Amyl, n-hexyl, isohesyl, cyclopenta, cyclohexyl or phenyl.
Third embodiment is related to the oxime ester derivative compound in first or second embodiment, wherein the oxime ester is derivative Compound is selected from the compound of the following Expression 2-1 to 2-19:
<formula 2-1 to 2-19>
According to the one side of the disclosure, the Photoepolymerizationinitiater initiater of following implementation is provided.
4th embodiment is related to a kind of Photoepolymerizationinitiater initiater, includes first to one of third embodiment embodiment party The oxime ester derivative compound of formula.
According to an aspect of the present invention, the photosensitive composite of following implementation is provided.
5th embodiment is related to a kind of photosensitive composite, includes:
(a) alkali soluble resins；
(b) with the polymerizable compound of ethylenic unsaturated bond；And
(c) Photoepolymerizationinitiater initiater includes first to one of third embodiment embodiment oxime ester derivative compounds Object.
Sixth embodiment is related to the photosensitive composite in the 5th embodiment, wherein is based on the photosensitive composition The total amount of object is 100wt%, and the amount of the oxime ester derivative compound is 0.01~10wt%.
7th embodiment is related to the photosensitive composite in the 5th or sixth embodiment, wherein the photopolymerization is drawn Hair agent is further included selected from by thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine system chemical combination At least one in group composed by object, O- acyl group oxime ester (O-acyl oxime ester) based compound and mercaptan based compound Kind.
8th embodiment is related to the photosensitive composite of one of the 5th to the 7th embodiment embodiment, In, the photosensitive composite further includes colorant.
According to an aspect of the present invention, the mechanograph of following implementation is provided and the display comprising the mechanograph is set It is standby.
9th embodiment is related to a kind of mechanograph, the sense comprising one of the 5th to the 8th embodiment embodiment The cured product of photosensitiveness composition.
Tenth embodiment is related to the mechanograph in the 9th embodiment, wherein the mechanograph is array planarization film (array planarization film), insulating film, chromatic filter, column spacer, black column spacer or black Matrix.
11st embodiment be related to include membrane product in the 9th or the tenth embodiment display equipment.
Beneficial effect
The advantages of oxime ester derivative compound of embodiment according to the present invention is, when the oxime ester derivative compound by with With excellent susceptibility when making the Photoepolymerizationinitiater initiater of photosensitive composite, and there is following performance outstanding, for example, residual Film thickness, pattern stability, heat resistance, chemical resistance and the ductility stayed；And in Thin Film Transistor-LCD (TFT- LCD) with during rear baking (post-baking) process, the oxime ester derivative compound makes to be caused by photopolymerization the exposure in manufacture The capacity that agent generates minimizes, to reduce pollution and minimize the defect generated from this.
Specific embodiment
Here, the present invention will be further described.Before describing, it should be understood that in this specification and appended right Term and text used in claim should not be construed as limited to general and dictionary meaning, but based on it is of the invention The corresponding meaning and concept of technical aspect, and term is defined suitably to obtain the original of best interpretations based on permission inventor Then explain these terms and text.
Therefore, embodiment as described herein and example shown in the drawings are only most preferred embodiment, are not represented All technical aspects of the disclosure, it is, therefore, appreciated that can be come when submitting application with various other equivalent and modification Replace these embodiments and examples.
Oxime ester derivative compound according to the one side of the disclosure is indicated by the following Expression 1:
<formula 1>
In formula 1, R1And R2Respectively stand alone as hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) aryl (C1-C20) alkyl, hydroxyl (C1-C20) alkyl, hydroxyl (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) naphthenic base；And
R3For (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl or (C3-C20) cycloalkanes Base.
" alkyl " used herein, " alkoxy " and other substituent groups comprising " alkyl " part include straight chain or branch Chain type, and " naphthenic base " includes monocyclic hydrocarbon and polycyclic hydrocarbon.
In addition, term " aryl " used herein refers to the freedom induced by aromatic hydrocarbon by removing a hydrogen Base, and comprising monocycle or fused ring system, or even comprising passing through singly linked multiple aryl.
In addition, term " hydroxy alkyl " used herein refers to the OH- alkane of hydroxyl and alkyl defined above bond Base, term as used herein " hydroxy alkoxy alkyl " refer to the hydroxy alkyl-O- alkyl of alkoxy and hydroxy alkyl bond, And alkenyl refers to the structure containing ketone of the alkyl or aryl comprising being bonded with it.
In addition, term as used herein " (C1-C20) alkyl " refers to the alkyl with 1 to 20 carbon atom, and described Alkyl can be preferably (C1-C12) alkyl.
" (C6-C20) aryl " refers to the aryl with 6 to 20 carbon atoms, and the aryl can preferably (C6-C18) Aryl." (C1-C20) alkoxy " refers to the alkoxy with 1 to 20 carbon atom, and the alkoxy can preferably (C1- C10) alkoxy, and more preferably (C1-C4) alkoxy.
" (C6-C20) aryl (C1-C20) alkyl " refers to the tool that a hydrogen is replaced by the aryl with 6 to 20 carbon atoms There is the alkyl of 1 to 20 carbon atom, and can be preferably (C6-C18) aryl (C1-C10) alkyl, and more preferably (C6-C18) Aryl (C1-C6) alkyl.
" hydroxyl (C1-C20) alkyl " refers to the alkyl with 1 to 20 carbon atom that a hydrogen is optionally substituted by a hydroxyl group, and can To be preferably hydroxyl (C1-C10) alkyl, and more preferably hydroxyl (C1-C6) alkyl.
" hydroxyl (C1-C20) alkoxy (C1-C20) alkyl " refers to a hydrogen by the alkoxy with 1 to 20 carbon atom Replace, and the alkyl with 1 to 20 carbon atom that another hydrogen is optionally substituted by a hydroxyl group, and can be preferably hydroxyl (C1-C10) alkane Oxygroup (C1-C10) alkyl, and more preferably hydroxyl (C1-C4) alkoxy (C1-C6) alkyl.
" (C3-C20) naphthenic base " refers to the naphthenic base with 3 to 20 carbon atoms, and can be preferably (C3-C10) ring Alkyl.
According to embodiment of the present disclosure, R1And R2Hydrogen, methyl, ethyl, n-propyl, isopropyl, just can respectively be stood alone as Butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, positive decyl, isodecyl, n-dodecane Base, cyclopenta, cyclohexyl, phenyl, benzyl, naphthalene, xenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, Positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyl Base normal-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl n-hexyl, hydroxyl isohesyl, hydroxymethoxy first Base, hydroxymethoxy ethyl, hydroxymethoxy propyl, hydroxymethoxy butyl, hydroxyethoxymethyl, hydroxyl-oxethyl second Base, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl or hydroxyl-oxethyl hexyl.
In addition, R3It can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isoamyl Base, n-hexyl, isohesyl, cyclopenta, cyclohexyl or phenyl.
More specifically, R1And R2Methyl, ethyl, n-propyl, isopropyl, normal-butyl, n-pentyl, just can respectively be stood alone as Octyl, positive decyl, isodecyl, dodecyl, cyclohexyl, phenyl or benzyl；And R3It can be methyl, ethyl, n-propyl Or phenyl.
According to embodiment of the present disclosure, chemical combination of the oxime ester derivative compound including but not limited to the following Expression 2-1 to 2-19 Object:
<formula 2-1 to 2-19>
It can be prepared by such as following formulas 1 according to the oxime ester derivative compound of the formula 1 of the disclosure:
<reaction equation 1>
In reaction equation 1, R1To R3It is identical as defined in formula 1, and X is halogen.
In addition, Photoepolymerizationinitiater initiater according to the one side of the disclosure includes oxime ester shown in the formula 1 of at least one type Derivative compound.
In addition, photosensitive composite according to the one side of the disclosure, includes:
(a) alkali soluble resins；
(b) with the polymerizable compound of ethylenic unsaturated bond；And
(c) Photoepolymerizationinitiater initiater, the oxime ester derivative compound comprising formula 1.
Here, the oxime ester derivative compound can be used as Photoepolymerizationinitiater initiater.
Photosensitive composite according to the one side of the disclosure is excellent in terms of pattern properties modulability, and has such as resistance to Hot and chemical resistance protrusion film characteristics.Detailed description presented below.
(a) alkali soluble resins
The alkali soluble resins includes acrylic acid series polymeric compounds or has the propylene of acrylic acid series unsaturated bond on side chain Sour based polymer.
The acrylic acid series polymeric compounds refer to the polymer (comprising homopolymer and copolymer) of acrylic monomer, acrylic acid Be monomer example include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Pentylmethacrylate, hexyl methacrylate, cyclohexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, Nonyl methacrylate, decyl-octyl methacrylate, lauryl ester, lauryl ester, metering system Sour tetradecane ester, methacrylic acid hexadecane ester, isobornyl methacrylate, methacrylic acid Buddha's warrior attendant alkyl ester, metering system Sour two ring pentyl esters, methacrylic acid dicyclopentenyl ester, benzyl methacrylate, methacrylic acid 2- methoxy ethyl ester, methyl Acrylic acid 2- ethoxy ethyl ester, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid mono alkyl ester, clothing Health acid monoalkyl ester, fumaric acid monoalkyl ester, Glycidyl Acrylate, glycidyl methacrylate, methacrylic acid 3, 4- epoxy butyl ester, methacrylic acid 2,3- epoxy cyclohexyl, methacrylic acid 3,4- epoxycyclohexanecarboxylate, 3- methyl oxa- ring Butane -3- methylmethacylate, 3- Ethyloxetane -3- methylmethacylate, styrene, Alpha-Methyl benzene second Alkene, acetoxy-styrene, N- methylmaleimido, n-ethylmaleimide, N- propylmaleimide, N- butyl horse Come acid imide, N- N-cyclohexylmaleimide, Methacrylamide and N- methyl methacrylamide, they can independent or group It closes and uses.
In addition, having the acrylic acid series polymeric compounds of acrylic acid series unsaturated bond in side chain is by epoxy resin and comprising carboxylic acid The addition reaction of acrylic acid series copolymer be formed by copolymer, and including passing through epoxy resin and acrylic acid carboxylic-containing acid The adhesive resin that the addition reaction of based copolymer obtains at 40~180 DEG C, the epoxy resin are such as acrylic acid epoxy Propyl ester, glycidyl methacrylate, methacrylic acid 3,4- epoxy butyl ester, methacrylic acid 2,3- epoxy cyclohexyl and methyl Acrylic acid 3,4- epoxycyclohexanecarboxylate, the packet acrylic acid series copolymer carboxylic-containing acid is by the inclusion of carboxylic acid (for example, propylene Acid, methacrylic acid, itaconic acid, maleic acid and maleic acid mono alkyl ester) acrylic monomer and at least two alkyl methyls The copolymerization of acrylate monomer and obtain, at least two alkylmethacrylate system's monomer be such as metering system Sour methyl esters, hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid Buddha's warrior attendant alkyl ester, Two ring pentyl ester of methacrylic acid, methacrylic acid dicyclopentenyl ester, benzyl methacrylate, methacrylic acid 2- methoxy ethyl Ester, methacrylic acid 2- ethoxy ethyl ester, styrene, α-methylstyrene, acetoxy-styrene, N- methyl maleimide Amine, n-ethylmaleimide, N- propylmaleimide, N- butyl maleimide, N- N-cyclohexylmaleimide, methyl Acrylamide and N- methyl methacrylamide.
Another example in side chain with the acrylic acid series polymeric compounds of acrylic acid series unsaturated bond is by carboxylic acid and packet The addition reaction of acrylic acid series copolymer containing epoxy group is formed by copolymer, and includes by the inclusion of carboxylic acid (for example, third Olefin(e) acid, methacrylic acid, itaconic acid, maleic acid and maleic acid mono alkyl ester) acrylic monomer with comprising epoxy group third The adhesive resin that the addition reaction of olefin(e) acid based copolymer obtains at 40~180 DEG C, the acrylic acid series comprising epoxy group Copolymer be by the inclusion of the acrylic monomer of epoxy group and the copolymerization of two or more methacrylate monomers and It obtains, the acrylic monomer comprising epoxy group is such as Glycidyl Acrylate, glycidyl methacrylate, first Base acrylic acid 3,4- epoxy butyl ester, methacrylic acid 2,3- epoxy cyclohexyl and methacrylic acid 3,4- epoxycyclohexanecarboxylate, Described two or more alkyl methacrylate systems monomer is such as methyl methacrylate, hexyl methacrylate, methyl Cyclohexyl acrylate, isobornyl methacrylate, methacrylic acid Buddha's warrior attendant alkyl ester, two ring pentyl ester of methacrylic acid, methyl-prop Olefin(e) acid dicyclopentenyl ester, benzyl methacrylate, methacrylic acid 2- methoxy ethyl ester, methacrylic acid 2- ethyoxyl second Ester, styrene, α-methylstyrene, acetoxy-styrene, N- methylmaleimido, n-ethylmaleimide, N- third Base maleimide, N- butyl maleimide, N- N-cyclohexylmaleimide, Methacrylamide and N- methyl propylene Amide.
According to embodiment of the present disclosure, in order to adjust the film of pattern properties and imparting such as heat resistance and chemical resistance Performance, the total amount based on the photosensitive composite are 100wt%, and the amount of the alkali soluble resins can be 3~50wt%, especially It is 5~45wt%, more specifically 8~40wt%.
Alkali soluble resins can have weight average molecular weight 2, and 000~300,000, in particular 4,000~100,000, And dispersion degree is 1~10.0.
(b) with the polymerizable compound of ethylenic unsaturated bond
The polymerizable compound with ethylenic unsaturated bond is crosslinked when forming pattern by light reaction, and is had Help pattern to be formed, and when accompany each other at high temperature heat when, it is described with ethylenic unsaturated bond polymerizable compound crosslinking with Assign chemical resistance and heat resistance.
Total amount based on the photosensitive composite is 100wt%, the polymerism chemical combination with ethylenic unsaturated bond The amount of object can be 0.001~40wt%, in particular 0.1~30wt%, more particularly 1~20wt%.
When the polymerizable compound with ethylenic unsaturated bond has excessive, its shortcoming is that the degree mistake of crosslinking Amount increases, and the ductility reduction of pattern.
The polymerizable compound with ethylenic unsaturated bond specifically includes the Arrcostab of methacrylic acid, for example, first Base methyl acrylate, ethyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid ten Dialkyl, glycidyl methacrylate, the polyethylene glycol monomethacrylate with 2~14 ethylene oxide groups, second Diol dimethacrylate, has 2~14 at the polyethylene glycol dimethacrylate with 2~14 ethylene oxide groups Dimethacrylate, trimethylolpropane dimethacrylate, the bisphenol-A two of a propylene oxide group shrink sweet Oily ether acrylic acid adduct, the ditridecyl phthalate of beta-hydroxy ethylmethyl acrylate, beta-hydroxy ethyl methacrylate The toluene di-isocyanate(TDI) addition product of ester, by polyalcohol and α, compound obtained from the esterification of beta-unsaturated carboxylic acid is (for example, three Methylolpropane trimethacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, two seasons penta Tetrol pentamethacrylate, dipentaerythritol hexamethacrylate and dipentaerythritol trimethyl acrylic ester) and it is poly- Glycidyl compound acrylic acid adduct (for example, the addition product of trihydroxymethylpropanyltri diglycidyl ether acrylic acid, they It can be used alone or in combination.
(c) Photoepolymerizationinitiater initiater
In the photosensitive composite of the disclosure, as Photoepolymerizationinitiater initiater, the oxime ester derivative compounds of formula 1 can be used Object.Be 100wt% based on the photosensitive composite total amount, the amount of Photoepolymerizationinitiater initiater be 0.01~10wt% be more effectively, Preferably 0.1~5wt%, to enhance the transparency while minimize exposure dose.
(d) auxiliary binder
In addition, if needing, the photosensitive composite of the disclosure can further include the silicon with epoxy group or amido Oxyalkyl compound is as auxiliary binder.
Silicone-based compound with epoxy group or amido can improve viscous between ITO electrode and photosensitive composite Property, and heat resistance is improved after hardening.Silicone-based compound with epoxy group or amido includes (3- glycidoxy third Base) trimethoxy silane, (3- glycidoxypropyl group) triethoxysilane, (3- glycidoxypropyl group) methyl dimethoxy oxygroup Silane, (3- glycidoxypropyl group) methyldiethoxysilane, (3- glycidoxypropyl group) dimethyl methoxy silane, (3- glycidoxypropyl group) dimethylethoxysilane, 3,4- epoxy group butyl trimethoxy silane, 3,4- epoxy group butyl Triethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- expoxycyclohexyl) ethyl three Ethoxysilane and aminocarbonyl propyl trimethoxy silane, they can be used alone or in combination.
It is 100wt% based on the photosensitive composite total amount, the silicone-based compound with epoxy group or amido Amount can be 0.0001~3wt%.When content is less than the range, additional effect is not found, and when content is more than When the range, the deterioration in characteristics of unexposed area, dross (scum) and residue can be stayed on lower substrate, ITO or glass substrate.
(e) other additives
If it is desirable, photosensitive composite of the invention can further include the additive with compatibility, for example, light Quick dose, thermal polymerization inhibitor, defoaming agent and levelling agent.
It is 100wt% based on the photosensitive composite total amount, the amount of other additives can be 0.1~10wt%, and work as When content is less than the range, additional effect is not found, and when content is more than the range, it is possible to create excessive floating Slag.
(f) solvent
The photosensitive composite of the disclosure is used to be coated by addition solvent, on substrate, irradiates purple using mask Outside line and pattern is formed using the method that alkaline developing solution develops.
Accordingly, the content of adjustable solvent is so that the contents of the other compositions of the content and photosensitive composite of solvent Summation is 100wt%, so, the content of solvent can change according to the content of the other compositions of photosensitive composite.For example, It is preferred that adjust the content of solvent, so that be 100wt% based on the photosensitive composite total amount, the amount of the solvent of addition is 10~ 95wt% and make 1~50 centipoise of range of viscosities (cps).
In view of the compatibility with alkali soluble resins, photoinitiator and other compounds, the solvent includes acetic acid second Ester, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxypropionate, ethyl ethoxy-c Acid esters (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PGMEP), propylene glycol first Ether, propylene glycol propyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetic acid ester, diethylene glycol second Yl acetate, acetone, methyl iso-butyl ketone (MIBK), cyclohexanone, dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), N- Methyl -2- pyrrolones (NMP), gamma-butyrolacton, diethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran (THF), Methanol, ethyl alcohol, propyl alcohol, isopropanol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol ether, dipropyl two Alcohol methyl ether, toluene, dimethylbenzene, hexane, heptane and octane, they can be used alone or in combination.
(g) other Photoepolymerizationinitiater initiaters
For Photoepolymerizationinitiater initiater, photosensitive composite of the invention can be used alone oxime ester derivative compound, can also By oxime ester derivative compound and selected from by thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine system Close at least one of group compound combination composed by object, O- acyl group oxime ester based compound and mercaptan (thiol) based compound It uses.
Total amount based on the photosensitive composite is 100wt%, the Photoepolymerizationinitiater initiater of addition can for 0.01~ 5wt%.
Thioxanthones based compound includes, for example, thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthones, 2- isopropylthioxanthones Ketone, 4-isopropylthioxanthone, bis- clopenthixal ketone of 2,4-, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone and 2,4- bis- are different Propyl thioxanthones.
Acetophenone based compound includes, for example, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinyl propyl- 1- ketone, 2- Benzyl -2- dimethyl amido -1- (4- morpholino phenyl) butyl- 1- ketone and 2- (4- methylbenzyl) -2- (dimethyl amido) -1- (4- morpholino phenyl) butyl- 1- ketone.
Bisglyoxaline based compound include bis- (2- chlorphenyl) -4,4', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of such as 2,2'-, Bis- (2,4 dichloro benzene base) -4,4', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of 2,2'- and bis- (the 2,4,6- trichloro-benzenes of 2,2'- Base) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxaline.
Triazine based compound includes, for example, 2,4,6- tri- (trichloromethyl)-s- triazines, bis- (three chloromethanes of 2- methyl -4,6- Base)-s- triazine, 2- [2- (5- methylfuran -2- base) vinyl] bis- (trichloromethyl)-s- triazines of -4,6-, 2- [2- (furans - 2- yl) vinyl] bis- (the trichloromethyl)-s- triazines of -4,6-, 2- [2- (4- diethyl amido -2- aminomethyl phenyl) vinyl] -4, Bis- (the trichloromethyl)-s- triazines of 6-, 2- [2- (3,4- Dimethoxyphenyl) vinyl] bis- (trichloromethyl)-s- triazines of -4,6-, Bis- (the trichloromethyl)-s- triazines of 2- (4- methoxyphenyl) -4,6-, bis- (three chloromethanes of 2- (4- ethoxystyrene base) -4,6- Base)-s- triazine and bis- (the trichloromethyl)-s- triazines of 2- (4-n- butoxy phenyl) -4,6-.
O- acyl group oxime ester based compound includes, for example, 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (o- benzene first Acyl group oxime), ethyl ketone -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- (o-acetyl base oxime), ethyl ketone - 1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base methoxybenzoyl base) -9H- carbazole -3- base] -1- (o-acetyl base oxime) And ethyl ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) methoxybenzoyl base } - 9H- carbazole -3- base] -1- (o-acetyl base oxime).
Mercaptan based compound includes pentaerythrite four (3-thiopropionate).
(h) colorant
The photosensitive composite of embodiment according to the present invention may further include colorant, be used to form colored filter The anti-erosion application of light device or black matrix".
The colorant includes various pigment, for example, red, green, the additive colo(u)r system of blue and brown, that is, blue-green, The pigment of carmetta, yellow and black, more specifically, obtainable pigment include C.I. pigment Yellow 12,13,14,17,20,24, 55,83,86,93,109,110,117,125,137,139,147,148,153,154,166,168；C.I. pigment orange 36,43, 51,55,59,61；C.I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220,223, 224,226,227,228,240；C.I. pigment violet 19,23,29,30,37,40,50；C.I pigment blue 15,15:1,15:4,15: 6,22,60,64；C.I. pigment Green 7,36；C.I. pigment brown 23,25,26；C.I. pigment black 7；And titanium is black.
It is 100wt% based on the photosensitive composite total amount, the amount of the colorant can be 5~50wt%.When content is small When the range, shading performance decline, and when content is more than the range, it may occur however that failure exposure or solidification.
According to an aspect of the present invention, the mechanograph of the cured product comprising the photosensitive composite is provided.
The mechanograph includes but is not limited to array planarization film (array planarization film), insulating film (insulating film), chromatic filter (color filter), column spacer (column spacer), black column Spacer (black column spacer) or black matrix" (black matrix).
In addition, according to an aspect of the present invention, the various forms of displays including the mechanograph are provided, for example, Liquid crystal display and OLED.
The photosensitive composite of embodiment according to the present invention can by rotation coating machine, roll-coater, rod coater, Slit coater, curtain application device and various known printings and deposition method are applied to soda-lime glass, quartz glass, half Conductor substrate, metal, paper and plastics supporting substrate.Furthermore, it is possible to form film on supporting substrate, then transfer to Another supporting substrate, to its applying method, there is no limit.
Hereinafter, in order to fully understand the purpose of the present invention, embodiment and comparative example the present invention is described in detail will be passed through Representative compound, and embodiment according to the present invention can modify in many different forms, and the scope of the present invention is not answered It is construed as limited to embodiment mentioned below.Embodiments of the present invention are provided to those skilled in the art with more completely The description present invention.
Embodiment
<preparation of oxime ester derivative compound>
Embodiment 1
The synthesis of step 1:10- butyl -10H- phenothiazine
10H- phenothiazine (30g) is dissolved in dimethyl sulfoxide (90ml) in reactor, and tetrabutyl bromine is added Change ammonium (2g) and 50% sodium hydroxide solution (120ml).After stirring 30 minutes, 1- bromobutane (32.6ml) is added dropwise and in room Temperature lower stirring 24 hours.To after the reaction was completed, extracted 3 times with ethyl acetate and water, with the dry organic layer of anhydrous magnesium sulfate and The lower concentration of decompression.Use hexane to be purified as developing solvent (developing solvent) by column chromatography, produces Raw target compound (27.0g, 70.5%).
1H NMR(δppm；CDCl3):0.93(3H,t),1.40-1.50(4H,m),1.74-1.82(2H,q),6.71- 7.05(2H,m),7.11-7.14(2H,m)
MS(m/e):255
The synthesis of step 2:1,1'- (10- butyl -10H- phenothiazine -3,7- diyl) two butyl- 1- ketone
The product of step 1 (27g) is dissolved in methylene chloride (135ml) in reactor, under 0 DEG C or lower temperature Aluminium chloride (42.0g) and butyl chloride (33.6g) is added, and is stirred at room temperature 8 hours.After completion of the reaction, by reaction solution It is added in ice water, stirs and stand to remove water layer, be washed with water organic layer 2 times.Simultaneously with the dry organic layer of anhydrous magnesium sulfate It is concentrated under reduced pressure.With ethyl acetate: hexane (1:10) is purified as developing solvent by column chromatography, generates target Product (17.0g, 41%).
1H NMR(δppm；CDCl3):0.96(3H,t),1.23(6H,t),1.35-1.70(6H,m),1.82-2.01 (2H,m),2.45-2.76(4H,m),4.10-4.14(2H,m),7.46-7.50(2H,m),8.29-8.33(2H,m),8.75 (2H,s)
MS(m/e):395
The synthesis of step 3:1,1'- (10- butyl -10H- phenothiazine -3,7- diyl) bis- (2- (hydroxyl imide base) butyl- 1- ketone)
The product of step 2 (17.0g) is added to after tetrahydrofuran (85ml) in reactor, is slowly added dropwise strong salt Sour (10.8mL) and isobutyl nitrite (13.3g).Then it is stirred at room temperature 30 minutes 1 hour, is extracted with ethyl acetate and water It takes 3 times, dries organic layer with anhydrous magnesium sulfate, and crystallized with ethyl acetate, generate target compound (10.7g, 55.0%).
1H NMR(δppm；CDCl3):1.08(3H,t),1.24-1.28(6H,m),1.51-1.70(2H,m),1.82- 2.01(2H,m),2.70-2.76(4H,q),4.10-4.14(2H,m),7.48-7.51(2H,m),8.30-8.34(2H,m), 8.76(2H,s)
MS(m/e):453
Step 4:1,1'- (10- butyl -10H- phenothiazine -3,7- diyl) is bis- (2- (acetoxyl group imido grpup) butyl- 1- ketone) Synthesis
Ethyl acetate (107ml) is added in the product of step 3 (10.7g) in reactor, is sequentially added dropwise at room temperature Enter Trimethylamine (7.3g) and chloroacetic chloride (5.65g).After being stirred at room temperature 1 hour, distilled water is added.It has been washed with distilled water , be then concentrated under reduced pressure machine layer for 2 times, and dry with anhydrous magnesium sulfate, products therefrom ethyl acetate and hexane (1:1) it is molten Agent crystallization, generates target compound (8.7g, 67.4%).
1H NMR(δppm；CDCl3):1.09(3H,t),1.18-1.26(6H,m),1.59-1.67(2H,m),1.85- 2.01(2H,m),2.31(6H,s),2.80-2.87(4H,m),4.29-4.34(2H,m),7.54(2H,d),8.48(2H,d), 8.81(2H,s)
MS(m/e):537
Decomposition point: 200.8 DEG C
Embodiment 2 to 19
Under the same conditions as example 1, oxime ester derivative compound is synthesized according to the composition in following table 1 and 2.
[table 1]
[table 2]
<preparation of alkali soluble resins>
Synthesis example 1
The azobis isobutyronitrile (AIBN) of the propylene glycol monomethyl ether (PGMEA) of 200mL and 1.5g are added extremely In the aggregation container of 500mL, methacrylate, glycidyl third are added with the molar ratio of 20:20:40:20 respectively Ester, methyl methacrylate and dicyclopentanyl acrylate and 40wt% acrylic monomers solids, then in nitrogen atmosphere and 70 It stirs 5 hours and is polymerize at DEG C, to prepare acrylic acid series polymeric compounds (a-1).The weight average molecular weight of resulting polymers is 25,000, and dispersion degree is 1.9.
Synthesis example 2
The AIBN of the propylene glycol monomethyl ether of 200mL and 1.0g is added into the aggregation container of 500mL, respectively Methacrylate, styrene, methyl methacrylate and cyclohexyl methacrylate is added with the molar ratio of 40:20:20:20 With 4wt% acrylic monomers solids, then stirs 5 hours and polymerize with synthetic copolymer at nitrogen atmosphere and 70 DEG C. By the N of 0.3g, N- dimethylaniline and with the methacrylic acid ring relative to 100 moles of total monomer solids for 20 molar ratios Oxygen propyl ester is put into reactor, and is stirred 10 hours at 100 DEG C, to prepare have acrylic acid series unsaturated bond in side chain third Olefin(e) acid based polymer (a-2).The weight average molecular weight of resulting polymers is 20,000, and dispersion degree is 2.0.
Synthesis example 3
The AIBN of the propylene glycol monomethyl ether of 200mL and 1.0g is added into the aggregation container of 500mL, respectively Glycidyl methacrylate, styrene, methyl methacrylate and methacrylic acid is added with the molar ratio of 40:20:20:20 The acrylic monomers solids of cyclohexyl and 40wt% then stirs 5 hours at nitrogen atmosphere and 70 DEG C and is polymerize, to close At polymer.By the N of 0.3g, N- dimethylaniline and with the propylene relative to 100 moles of total monomer solids for 20 molar ratios Acid is put into reactor, and is stirred 10 hours at 100 DEG C, to prepare the acrylic acid for having acrylic acid series unsaturated bond in side chain Based polymer (a-3).The weight average molecular weight of resulting polymers is 18,000, and dispersion degree is 1.8.
Embodiment 20~35: the preparation of photosensitive composite
In embodiment 20~35, by institute alkali soluble resins a-1 to a-3；Polymerism chemical combination with ethylenic unsaturated bond Object；Photoepolymerizationinitiater initiater of the invention；And FC-430 (3M levelling agent) is sequentially put according to ingredient listed by the following table 3 and content Enter in the reaction mixing channel with UV masking and blender, is then stirred at room temperature, the solvent PGMEA of surplus is added, makes group The total weight percent for closing object is 100wt%, to prepare photosensitive composite.
Embodiment 36~37: the preparation of coloring photosensitive combination
Coloring photosensitive combination is prepared by method identical with embodiment 17, in addition to having in embodiment 36 There is the carbon black dispersion that 50wt% is added in the PGMEA of 25wt% solids, and in embodiment 37, solid with 25wt% Paratonere 177 (P.R.177) dispersion of 50wt% is added in the PGMEA of body object, as described in the following table 3.
Embodiment 38
Photosensitive composite is prepared by method identical with embodiment 17, in addition to by the chemical combination of embodiment 1 and following formula 3 The mixture of object is as Photoepolymerizationinitiater initiater, as described in the following table 3.
<formula 3>
<ingredient>
(a) alkali soluble resins
(b) with the polymerizable compound of ethylenic unsaturated bond
B-1: dipentaerythritol hexaacrylate
B-2: Dipentaerythritol Pentaacrylate
B-3: pentaerythritol triacrylate
B-4: pentaerythritol acrylate trimethyl
B-5: trimethylolpropane trimethacrylate
B-6: glycol diacrylate
B-7: bisphenol-A diepoxide propionic ester addition product
B-8: trimethylolpropane tris glycidyl ethers acrylate addition product
(c) Photoepolymerizationinitiater initiater
(e) levelling agent: FC-430 (3M levelling agent)
(h) colorant
H-1: carbon black (solids of 25wt%)
H-2: pigment red 177 (P.R.177) (solids of 25wt%)
[table 3]
Comparative example 1
Photopolymerizable composition is prepared by method identical with embodiment 17, other than Photoepolymerizationinitiater initiater, under use The compound of formula 4 replaces the compound of embodiment 1.
<formula 4>
Comparative example 2
Photopolymerization constituent is prepared by method identical with embodiment 17, other than Photoepolymerizationinitiater initiater, uses formula 5 Compound replace embodiment 1.
<formula 5>
<evaluation>
The evaluation of photosensitive composite prepared by embodiment 20~38 and comparative example 1~2 is carried out on the glass substrate, Measure performance such as susceptibility, residual film thickness, pattern stability, chemical resistance and the ductility of photosensitive composite, evaluation As the result is shown in the following table 4.
1) susceptibility
On the glass substrate by photoresist spin coating, prebake 1 minute and at 100 DEG C is then carried out using stepping mask Exposure, and develop in 0.04% potassium hydroxide aqueous solution.Thickness based on stepping mask pattern maintains original depth 80% exposure dose evaluates susceptibility.
2) residual film thickness
After photosensitive composite is coated on substrate using spin coater, prebake conditions (pre-baking) 1 is carried out at 100 DEG C Minute, it then exposes under 365nm light, then toast (post-baking) 20 minutes after carrying out at 230 DEG C, is toasted after measurement The thickness ratio (%) of the etchant resist of front and back.
3) pattern stability
By the silicon wafer with photoresist pattern along the direction cutting perpendicular to sectional hole patterns, and shown using electron microscope Observation result in the cross-sectional direction of pattern is shown.The side wall of pattern is upright with 55 degree or bigger of angle relative to substrate, And it is defined as " excellent " without film reduction, observes that the reduction of film is defined as " film reduction ".
4) chemical resistance
After photosensitive composite is coated on substrate using spin coater, it will be handled by prebake conditions and rear baking processing is formed Etchant resist be immersed at 40 DEG C in stripping solution 10 minutes, and observe the transmissivity of etchant resist and thickness whether have it is any Variation.2% or the variation of transmissivity below and thickness be defined as " excellent ", 2% or more transmissivity and the variation of thickness It is defined as " bad ".
5) ductility
Photosensitive composite is spin-coated on substrate, then prebake conditions 1 minute at 100 DEG C, under the susceptibility of photoresist It is exposed, and develops under potassium hydroxide aqueous solution, to form the pattern of 20 μm of 20 μ m.By the pattern of formation by 20 packing of baking is crosslinked after at 230 DEG C, and using nano-indenter test instrument measurement pattern to judge ductility.It is negative in 5g power Carry the lower measurement for carrying out nano-indenter test instrument, total amount of variability be 500nm or more than be defined as " excellent " and total amount of variability It is defined as " bad " for 500nm or less.
[table 4]
By table 4 it can be found that the oxime ester derivative compound of the disclosure has significant excellent susceptibility, and have outstanding Performance, such as degree, pattern stability, chemical resistance and ductility after residual film, or even when used as photosensitive composite Photoepolymerizationinitiater initiater when be a small amount of.

Claims (12)

1. oxime ester derivative compound shown in a kind of formula 1:
<formula 1>
Wherein, R1And R2Respectively stand alone as hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C1-C20) alkoxy, (C6-C20) Aryl (C1-C20) alkyl, hydroxyl (C1-C20) alkyl, hydroxyl (C1-C20) alkoxy (C1-C20) alkyl or (C3-C20) ring Alkyl；And
R3For (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl or (C3-C20) naphthenic base.
2. oxime ester derivative compound as described in claim 1, wherein R1And R2Respectively stand alone as hydrogen, methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, positive decyl, isodecyl Base, dodecyl, cyclopenta, cyclohexyl, phenyl, benzyl, naphthalene, xenyl, terphenyl, anthryl, indenyl, phenanthryl, first Oxygroup, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxyl Base n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl n-hexyl, hydroxyl isohesyl, hydroxyl Ylmethoxymethyl, hydroxymethoxy ethyl, hydroxymethoxy propyl, hydroxymethoxy butyl, hydroxyethoxymethyl, hydroxyl Ethoxyethyl group, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl or hydroxyl-oxethyl hexyl；And
R3For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, dissident Base, cyclopenta, cyclohexyl or phenyl.
3. oxime ester derivative compound as described in claim 1, wherein the oxime ester derivative compound is selected from by the following Expression 2-1 To 2-19 compound represented:
<formula 2-1 to 2-19>
4. a kind of Photoepolymerizationinitiater initiater includes oxime ester derivative compound of any of claims 1-3.
5. a kind of photosensitive composite, includes:
(a) alkali soluble resins；
(b) with the polymerizable compound of ethylenic unsaturated bond；And
(c) Photoepolymerizationinitiater initiater includes oxime ester derivative compound of any of claims 1-3.
6. photosensitive composite as claimed in claim 5, wherein the total amount based on the photosensitive composite is 100wt%, The amount of the oxime ester derivative compound is 0.01~10wt%.
7. photosensitive composite as claimed in claim 5, wherein the Photoepolymerizationinitiater initiater is further included selected from by thioxanthene Ketone based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, o- acyl group oxime ester based compound and sulphur At least one of group composed by alcohol based compound.
8. photosensitive composite as claimed in claim 5, wherein the photosensitive composite further includes colorant.
9. photosensitive composite as claimed in claim 7, wherein the photosensitive composite further includes colorant.
10. a kind of mechanograph, the cured product comprising the photosensitive composite described in claim 5.
11. mechanograph as claimed in claim 10, wherein the mechanograph is array planarization film, insulating film, colorized optical filtering Device, column spacer, black column spacer or black matrix".
12. a kind of display equipment includes mechanograph described in any one of claim 10.
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