CN105753694A - Polycarboxyl functionalization acrylate for color resistor and preparation method thereof - Google Patents
Polycarboxyl functionalization acrylate for color resistor and preparation method thereof Download PDFInfo
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- CN105753694A CN105753694A CN201610197561.4A CN201610197561A CN105753694A CN 105753694 A CN105753694 A CN 105753694A CN 201610197561 A CN201610197561 A CN 201610197561A CN 105753694 A CN105753694 A CN 105753694A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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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
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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
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Abstract
The invention discloses polycarboxyl functionalization acrylate for a color resistor.The polycarboxyl functionalization acrylate is of the structure shown in the formula (I), wherein R1 contains at least one group shown in the description and at least one -COOH group.After the polycarboxyl functionalization acrylate is applied to the color resistor, the product hardness is high, the adhesive force is strong, and the excellent heat resistance, aging resistance and chemical corrosion resistance are achieved.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of how carboxy-functionalized acrylate for chromatic photoresist
And preparation method thereof.
Background technology
Colored filter is the Primary Component that liquid crystal display realizes colour display.As technology-intensive industries, this neck
Territory barrier to market entry is higher, only has a handful of big factory of Japan and Korea S. and China Taiwan to have volume production energy the most in the world
Power, and in terms of high-order product, it is limited by manufacturer of Japan completely.
Photoresist is the core preparing colored filter, and its key technology rests in several Japan-funded enterprises handss completely
In, this is relatively big to the restriction of China TFT-LCD vertical industry chain, becomes a bottle of development China liquid crystal display related industry
Neck.Therefore, there is in the urgent need to research and development the photoresist of independent intellectual property right, thus grasp the core skill of colored filter
Art, fills up the blank in domestic colored filter field, breaks the situation of external monopolization, reduces the manufacturing cost of TFT-LCD, make state
Interior TFT-LCD overall technology level more steps to a new level, and drives the necks such as chemical color, machining, semiconductor technology simultaneously
Territory is developed further.
The main component of photoresist includes light-cured resin, light trigger, pigment, organic solvent etc..Wherein, photocuring tree
Fat determines the key property of photocuring product, including hardness, pliability, adhesive force, optical property, ageing-resistant etc..It can be said that
Light-cured resin is the key of photoresist research and development.Currently, light-cured resin mainly includes polyimide resin, polyvinyl alcohol tree
Fat, epoxy resin and acrylate etc., acrylate application is at most.
Summary of the invention
It is an object of the invention to provide a kind of how carboxy-functionalized acrylate for chromatic photoresist.It is applied to colour
After photoresistance, product hardness is high, and adhesive force is strong, and has thermostability, resistance to ag(e)ing and the resistance to chemical corrosion of excellence.
In order to achieve the above object, the present invention adopts the following technical scheme that.
A kind of how carboxy-functionalized acrylate for chromatic photoresist, has a structure as shown in following formula (I):
Wherein, R1Containing at least oneGroup and at least one-COOH base
Group.
As optimal technical scheme, in above-mentioned formula (I) structure, R1It is selected from Constituted
Group, and R therein2It is located close to the side that formula (I) terminal carboxylic acid group is-COOH；
R2It is each independently selected from
R3It is each independently selected from-CH2-,-CH=CH-,-CH2CH2-、-
CH2CH2CH2-、
In the present invention, term " independently of one another " represents that this group in structural formula can be identical, it is also possible to different.
Correspondingly, the invention still further relates to the preparation method of how carboxy-functionalized acrylate shown in above-mentioned formula (I), comprise as
Lower step:
(1) under nitrogen protection, Bis(pentaerythritol) and the dibasic acid anhydride with unsaturated double-bond are mixed in containing polymerization inhibitor
In the organic solvent of MEHQ, there is esterification at a reflux temperature, obtain intermediate 1；
Reaction equation is as follows:
Wherein, with the linking group of unsaturated double-bond during R1 ' represents anhydride；
(2) hydrogen peroxide and formic acid are joined in reaction system, react 3-8 hour at 20-30 DEG C, make R1-C=in '
C-epoxy turns toObtain intermediate 2；
(3) intermediate 2 is mixed with (methyl) acrylic acid monohydroxy ester, at polymerization inhibitor MEHQ and catalyst hydrogen
Under sodium oxide existence condition, 50-60 DEG C is reacted 2-3 hour, to epoxide group reaction completely, obtains intermediate 3；
(4) under nitrogen protection, intermediate 3 and anhydride are mixed in the organic solvent containing polymerization inhibitor MEHQ
In, there is esterification at a reflux temperature, obtain formula (I) compound.
In above-mentioned steps (1), by esterification, Bis(pentaerythritol) structure chains double bond containing hydroxy-acid group.
The organic solvent kind used is not particularly limited, as long as can dissolving reaction raw materials and having no adverse effects reaction i.e.
Can, such as dichloromethane, dichloroethanes, toluene, dimethylbenzene, acetonitrile etc..In esterification, described with the two of unsaturated double-bond
Unit's anhydride preferably is selected from maleic anhydride, 2,3-dimethyl maleate acid anhydride, carbic anhydride, tetrahydrophthalic acid
Acid anhydride, methyl tetrahydrophthalic anhydride.That is, R1' it preferably is selected from following structure:
-CH=CH-,
In step (3), the hydroxyl effect in the epoxide group open loop of intermediate 2, with (methyl) acrylic acid monohydroxy ester, enter
Row additive reaction, thus chain (methyl) acrylate group accordingly closing on the side that terminal carboxylic acid group is-COOH
(opposite side generation hydroxyl).Described (methyl) acrylic acid monohydroxy ester is preferably R2One or more in H.Now, intermediate 2
'sWith R2H reacts, and generates-C (OH)-C (R2)-, and R2Be located close to intermediate 3 terminal carboxylic acid group i.e.-
The side of COOH.
In the esterification of step (4), pass through-C (OH)-C (R2)-in hydroxyl, intermediate 3 and anhydride effect, occur
Esterification.The organic solvent used in reaction is not particularly limited, as long as reaction raw materials can be dissolved and to reaction nothing
Harmful effect, such as dichloromethane, dichloroethanes, toluene, dimethylbenzene, acetonitrile etc..Described anhydride is preferablyIn one or more.
In the preparation method of the present invention, reaction raw materials is all known compound of the prior art, commercially available or
It is prepared from by known synthetic method.Further, the reaction related in each step is all based on the common reactant in organic field
Mechanism.On the basis of being realised that synthesis thinking disclosed by the invention, concrete reaction condition is to those skilled in the art
Easily determine.
Preferably but not compulsorily, in step (1), with unsaturated double-bond dibasic acid anhydride and Bis(pentaerythritol) mole
Ratio is 6:1.In step (2), hydrogen peroxide is 6:1-10:1 with the mol ratio of formic acid, hydrogen peroxide and original Bis(pentaerythritol)
Mol ratio is 6:1.In step (3), (methyl) acrylic acid monohydroxy ester is 6:1 with the mol ratio of original Bis(pentaerythritol).Step
(4), in, anhydride is 6:1 with the mol ratio of original Bis(pentaerythritol).
The present invention, with Bis(pentaerythritol) as initial feed, with double bond containing dibasic acid anhydride generation esterification, then incites somebody to action double
Key epoxidation, then with the monohydroxy ester addition of (methyl) acrylic acid, last and anhydride carries out secondary esterification, thus is finally produced
Product.This products application is when chromatic photoresist, and the multiple carboxyls in molecular structure can form hydrogen bond with substrate surface, strengthens attachment
Power, promotes photoresistance hardness, can make it have thermostability, resistance to ag(e)ing and the resistance to chemical corrosion of excellence simultaneously.Further, this
Bright synthetic route is simple, and side reaction is less, pollution-free, without purifying in course of reaction, i.e. can obtain the product with superperformance
Product.
Detailed description of the invention
Below with reference to specific embodiment, the present invention is described in further detail, but should not be construed as the present invention
The restriction of protection domain.
Embodiment 1
1.0 moles of Bis(pentaerythritol)s, 6.0 moles of maleics are added in 1L is with the flask of condenser and mechanical agitator
Dicarboxylic anhydride, 1g MEHQ and 300g acetonitrile, be heated to backflow under nitrogen protection, obtain faint yellow clarification after about 30 minutes
Liquid.Continue reaction 6 hours, be then cooled to room temperature.
Filter, filtrate is transferred in the 2L flask with magnetic stirring apparatus, add 1 mole of formic acid and 820 gram 25%
The hydrogen peroxide of concentration, room temperature (about 25 DEG C) stirs, and after reacting 6 hours, decompression distillation obtains light yellow viscous liquid.
Light yellow viscous liquid is moved in the flask being furnished with condenser and mechanical agitator, add 6 mol propylene acid hydroxyls
Ethyl ester, 5 grams of sodium hydroxide and 2 grams of MEHQ, 50 DEG C are reacted 3 hours, are then cooled to room temperature, it is thus achieved that light yellow liquid
Body.
The weak yellow liquid obtained and 2 grams of MEHQ, 6 moles of malonic anhydrides are joined with condenser and machine
In the flask of tool agitator, and add 400g acetonitrile, after being stirred at room temperature 30 minutes under nitrogen protection, be to slowly warm up to backflow, protect
Hold thermotonus 6 hours, be then cooled to room temperature.
In a large amount of water being poured slowly in high-speed blender by reaction solution, fully washing is placed on separatory funnel, concussion
Rear standing 30 minutes, takes off a layer solution, is dried 12 hours subsequently, obtains slightly yellow solid in vacuum drying oven.
Product structure passes through1H NMR and mass spectrum are confirmed:
1H NMR(400MHz,CDCl3,ppm):5.775-6.560(18H；CH2=CH-CO-), 4.945-5.450
(12H,-OC-CH(OR)-),4.335(24H；-O-CH2CH2-O-),3.196(12H；-OC-CH2-CO-)；3.297(4H；-O-
CH2-C(CH2-R)3),4.005(12H；O-CH2-C(CH2-R)3)。
Q-Tof-MS(m/z):calcd for C82H94O67,2150.3680.Found:2151.7582[M+H]+
Take synthesized resin 100 mass parts, solvent propylene glycol methyl ether acetate 100 mass parts, light trigger 2-hydroxyl-
2-methyl isophthalic acid-phenyl-1-acetone (1173) about 3 mass parts, organic pigment paratonere 7 about 1 mass parts, wetting agent T-1004 about 1
Mass parts, mixing is put in container, carries out pre-dispersed on SFJ-400 type multiple purpose aeroplane, pre-dispersed mixed under the conditions of rotating speed 1000rpm
Close 30min.Taking 3ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is 1000rpm, and the time is 10s.Glass by film forming
Glass sheet puts into 60 DEG C of baking oven front bakings 5min, is then exposed with light source Fusion-LH6, light exposure 2000mJ/cm2, then exist
The KOH solution of 1% concentration is developed, 90 DEG C of after bake 1h subsequently, obtain light resistance coating 1.
Embodiment 2
1g MEHQ, 1.0 moles of double Ji Wusi are added in 1L is with the flask of condenser and mechanical agitator
Alcohol, 6.0 mole 2,3-dimethyl maleate acid anhydride and 300g acetonitrile, under nitrogen protection, heating blends to backflow, about
After 30 minutes, it is thus achieved that faint yellow supernatant liquid.Keep reaction temperature 6 hours, be then cooled to room temperature.
Filter, clear filtrate is transferred in the 2L flask with magnetic stirring apparatus, adds 0.6 mole of formic acid and 820
The hydrogen peroxide of gram 25% concentration, is stirred at room temperature, and after reacting 6 hours, decompression distillation obtains light yellow viscous liquid.
The weak yellow liquid obtained is moved in the flask being furnished with condenser and mechanical agitator, add 6 moles of Ji Wusi
Alcohol trimethyl acrylic ester, 5 grams of sodium hydroxide and 2 grams of MEHQ, reaction temperature 50 DEG C, 3 hours response time, with
After be cooled to room temperature obtain weak yellow liquid.
The liquid obtained and 2 grams of MEHQ, 6 moles of tetrabydrophthalic anhydrides are joined with condenser and
In the flask of mechanical agitator, and add 400g acetonitrile, after being stirred at room temperature 30 minutes under nitrogen protection, be to slowly warm up to backflow
Temperature, keeps temperature 6 hours, is then cooled to room temperature.
In a large amount of water being poured slowly in high-speed blender by reaction solution, fully washing is placed on separatory funnel, concussion
Rear standing 30 minutes, takes off a layer solution, is dried 12 hours subsequently, obtains faint yellow solid in vacuum drying oven.
Product structure passes through1H NMR and mass spectrum are confirmed:
1H NMR(400MHz,CDCl3,δ):5.575-6.560(48H；CH2=C (CH3)-CO-,-CH=CH-), 3.295
(16H；O-CH2-C(CH2-R)3),4.015(48H；-O-CH2-C(CH2-R)3),1.940(48H,-CH3),2.150-2.360
(24H,-CH2-CH=CH-).
Q-Tof-MS(m/z):calcd for C196H250O91,4059.2610.Found:4060.2332[M+H]+
Take synthesized resin 100 mass parts, solvent propylene glycol methyl ether acetate 100 mass parts, light trigger 2-phenyl
Benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone (369) about 3 mass parts, organic pigment pigment yellow 185 about 1 part, moistening
Agent T-1004 about 1 mass parts.The mixing of each raw material is put in container, SFJ-400 type multiple purpose aeroplane is carried out pre-dispersed, rotating speed
Pre-dispersed mixing 30min under the conditions of 1000rpm.Taking 3ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is 1000rpm, time
Between be 10s.The sheet glass of film forming is put into 60 DEG C of baking oven front bakings 5min, is then exposed with light source Fusion-LH6, expose
Light quantity 2000mJ/cm2, develop in the KOH solution of 1% concentration, 90 DEG C of after bake 1h subsequently, obtain light resistance coating 2.
Embodiment 3
1g MEHQ, 1.0 moles of double Ji Wusi are added in 1L is with the flask of condenser and mechanical agitator
Alcohol, 6.0 moles of tetrabydrophthalic anhydrides and 300g acetonitrile, under nitrogen protection, heating blends to backflow, about 30 minutes
After, it is thus achieved that faint yellow supernatant liquid.Keep reaction temperature 6 hours, be then cooled to room temperature.
Filter, clear filtrate is transferred in the 2L flask with magnetic stirring apparatus, adds 0.8 mole of formic acid and 820
The hydrogen peroxide of gram 25% concentration, is stirred at room temperature, and after reacting 6 hours, decompression distillation obtains light yellow viscous liquid.
The weak yellow liquid obtained is moved in the flask being furnished with condenser and mechanical agitator, add 6 moles of double seasons penta
Tetrol five acrylate, 5 grams of sodium hydroxide and 2 grams of MEHQ, reaction temperature 50 DEG C, 3 hours response time, subsequently
It is cooled to room temperature, it is thus achieved that weak yellow liquid.
The liquid obtained and 2 grams of MEHQ, 6 moles of 3-nitrophthalic acid acid anhydrides are joined with condenser
With in the flask of mechanical agitator, and add 400g acetonitrile, after being stirred at room temperature 30 minutes under nitrogen protection, be to slowly warm up to back
Stream temperature, keeps temperature 6 hours, is then cooled to room temperature.
In a large amount of water being poured slowly in high-speed blender by reaction solution, fully washing is placed on separatory funnel, concussion
Rear standing 30 minutes, takes off a layer solution, is dried 12 hours subsequently, obtains faint yellow solid in vacuum drying oven.
Product structure passes through1H NMR and mass spectrum are confirmed:
1H NMR(400MHz,CDCl3, δ): 8.440-9.260 (18H, Ar-H), 5.575-6.560 (90H；CH2=C
(CH3)-CO-),3.295(28H；O-CH2-C(CH2-R)3),4.015(84H；-O-CH2-C(CH2-R)3),1.750-2.360
(24H,-CHCH2CH-),2.360-2.660(12H,-OC-CHCH-CO-)。
Q-Tof-MS(m/z):calcd for C256H280N6O133,5565.1010.Found:5566.1432[M+H]+
Take synthesized resin 100 mass parts, solvent propylene glycol methyl ether acetate 100 mass parts, light trigger 2-phenyl
Benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone (369) about 3 mass parts, organic pigment paratonere 183 about 1 part, moistening
Agent T-1004 about 1 mass parts.The mixing of each raw material is put in container, SFJ-400 type multiple purpose aeroplane is carried out pre-dispersed, rotating speed
Pre-dispersed mixing 30min under the conditions of 1000rpm.Taking 3ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is 1000rpm, time
Between be 10s.The sheet glass of film forming is put into 60 DEG C of baking oven front bakings 5min, is then exposed with light source Fusion-LH6, expose
Light quantity 2000mJ/cm2, develop in the KOH solution of 1% concentration, 90 DEG C of after bake 1h subsequently, obtain light resistance coating 3.
Embodiment 4
1g MEHQ, 1.0 moles of double Ji Wusi are added in 1L is with the flask of condenser and mechanical agitator
Alcohol, 6.0 moles tetrabydrophthalic anhydrides and 300g acetonitrile, under nitrogen protection, heating blends to backflow, about 30
After minute, it is thus achieved that faint yellow supernatant liquid.Keep reaction temperature 6 hours, be then cooled to room temperature.
Filter, clear filtrate is transferred in the 2L flask with magnetic stirring apparatus, add 1 mole of formic acid and 820 grams
The hydrogen peroxide of 25% concentration, is stirred at room temperature, and after reacting 6 hours, decompression distillation obtains light yellow viscous liquid.
The liquid obtained is moved in the flask being furnished with condenser and mechanical agitator, add 6 mole hydroxyls
Propyl ester, 5 grams of sodium hydroxide and 2 grams of MEHQ, reaction temperature 50 DEG C, in 3 hours response time, it is then cooled to room
Temperature, it is thus achieved that weak yellow liquid.
The liquid obtained and 2 grams of MEHQ, 6 moles of 2,3-dimethyl maleate acid anhydrides are joined with cold
In the flask of condenser and mechanical agitator, and add 400g acetonitrile, after being stirred at room temperature 30 minutes under nitrogen protection, slowly heat up
To reflux temperature, keep temperature 6 hours, be then cooled to room temperature.
In a large amount of water being poured slowly in high-speed blender by reaction solution, fully washing is placed on separatory funnel, concussion
Rear standing 30 minutes, takes off a layer solution, is dried 12 hours subsequently, obtains faint yellow solid in vacuum drying oven.
Product structure passes through1H NMR and mass spectrum are confirmed:
1H NMR(400MHz,CDCl3,δ):5.575-6.560(12H；CH2=C (CH3)-CO-), 3.650,4.335
(12H；-O-CH2CH(CH3)-O-),3.295(4H；O-CH2-C(CH2-R)3),4.015(12H；-O-CH2-C(CH2-R)3),
1.180-1.920(88H,-CH2CH2CH2-,-CH3)。
Q-Tof-MS(m/z):calcd for C142H190O67,2967.5293.Found:2968.6742[M+H]+
Take synthesized resin 100 mass parts, solvent propylene glycol methyl ether acetate 100 mass parts, light trigger 1-hydroxyl
Cyclohexyl phenyl ketone (184) about 3 mass parts, organic pigment paratonere 7 about 1 part, wetting agent T-1004 about 1 mass parts.Will be each
Raw material mixing is put in container, carries out pre-dispersed on SFJ-400 type multiple purpose aeroplane, pre-dispersed mixed under the conditions of rotating speed 1000rpm
Close 30min.Taking 3ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is 1000rpm, and the time is 10s.Glass by film forming
Glass sheet puts into 60 DEG C of baking oven front bakings 5min, is then exposed with light source Fusion-LH6, light exposure 2000mJ/cm2, 1%
The KOH solution of concentration is developed, 90 DEG C of after bake 1h subsequently, obtain light resistance coating 4.
Embodiment 5
1g MEHQ, 1.0 moles of double Ji Wusi are added in 1L is with the flask of condenser and mechanical agitator
Alcohol, 6.0 moles of carbic anhydrides and 300g acetonitrile, under nitrogen protection, heating blends to backflow, about 30 minutes
After, it is thus achieved that faint yellow supernatant liquid.Keep reaction temperature 6 hours, be then cooled to room temperature.
Filter, clear filtrate is transferred in the 2L flask with magnetic stirring apparatus, add 1 mole of formic acid and 820 grams
The hydrogen peroxide of 25% concentration, is stirred at room temperature, and after reacting 6 hours, decompression distillation obtains light yellow viscous liquid.
The liquid obtained is moved in the flask being furnished with condenser and mechanical agitator, add 6 mole of trimethylol propane
Diacrylate, 5 grams of sodium hydroxide and 2 grams of MEHQ, reaction temperature 50 DEG C, in 3 hours response time, cool down subsequently
To room temperature, it is thus achieved that weak yellow liquid.
The liquid obtained and 2 grams of MEHQ, 6 moles of phthalic anhydrides are joined with condenser and machinery
In the flask of agitator, and add 400g acetonitrile, after being stirred at room temperature 30 minutes under nitrogen protection, be to slowly warm up to backflow temperature
Degree, keeps temperature 6 hours, is then cooled to room temperature.
In a large amount of water being poured slowly in high-speed blender by reaction solution, fully washing is placed on separatory funnel, concussion
Rear standing 30 minutes, takes off a layer solution, is dried 12 hours subsequently, obtains faint yellow solid in vacuum drying oven.
Product structure passes through1H NMR and mass spectrum are confirmed:
1H NMR(400MHz,CDCl3,δ):7.230-8,550(12H,Ar-H),5.575-6.560(9H；CH2=CH-
CO-),3.295(14H；O-CH2-C(CH2-R)3),4.015(16H；-O-CH2-C(CH2-R)3),0.955-1.940(15H,-C
(R)3CH2-CH3),4.950-5.320(12H,-OC-CHRCHR-CO-)。
Q-Tof-MS(m/z):calcd for C184H202O79,3675.7244.Found:3676.7742[M+H]+
Take synthesized resin 100 mass parts, solvent propylene glycol methyl ether acetate 100 mass parts, light trigger 2-phenyl
Benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone (369) about 3 mass parts, organic pigment pigment yellow 2 about 1 part, wetting agent
T-1004 about 1 mass parts.The mixing of each raw material is put in container, SFJ-400 type multiple purpose aeroplane is carried out pre-dispersed, rotating speed
Pre-dispersed mixing 20～30min under the conditions of 1000rpm.Taking 3ml mixture film forming on sol evenning machine, sol evenning machine rotating speed is
1000rpm, the time is 10s.The sheet glass of film forming is put into baking oven front baking 5min of 60 DEG C, then uses light source Fusion-LH6
It is exposed, light exposure 2000mJ/cm2, develop in the KOH solution of 1% concentration, 90 DEG C of after bake 1h subsequently, obtain photoresistance and be coated with
Layer 5.
Performance characterization
To above-described embodiment 1-5 prepare light resistance coating 1-5 carry out performance characterization, including adhesive force, case hardness, resistance to always
The property changed, thermostability and endurance.Concrete detection method and step are as follows:
(1) adhesive force measures: the detection method with reference to standard GB/T/T1720-1979 carries out test grading, is divided into 1-7
Level, 1 grade preferably, and paint film is intact.
(2) case hardness measures: the detection method with reference to standard GB/T/T 6739-1996 carries out test grading, grading
Number is the highest, represents that performance is the best.
(3) ageing-resistant performance measures and evaluation methodology: chromatic photoresist coating is positioned over ATLAS-UV 2000 ageing device even
Continuous irradiation 200 hours, then tests light resistance coating by light resistance coating with desk-top aberration spectrophotometer Datacolor 600 and irradiates
Aberration (Δ E) front and back, Δ E value is the least, represents that light resistance coating resistance to ag(e)ing is the best.
(4) Heat-tolerance Determination and evaluation methodology: by the thermal decomposition of TGA-Q500 test light resistance coating of chromatic photoresist coating
Temperature (Td), TdIt is worth the biggest, represents that photoresistance coating heat resistance is the best.
(5) chemical resistance measures: chromatic photoresist coating is put in the vacuum drying oven of 60 DEG C and toasts 8 hours, takes out
Light resistance coating is fully immersed in analytically pure acetone soln 30 minutes, is then placed on air dry oven 40 DEG C and is dried 1
Hour, observe light resistance coating with or without wrinkling, foaming, variable color and eclipsed phenomenon.
Characterization result is as shown in the table.
As can be seen from the above table, the white light resistance coating attachment that the how carboxy-functionalized acrylate of the present invention prepares is utilized
Power is the highest, all reaches 1 grade, and paint film is intact, and has the highest hardness, and Δ E is little for aberration.The thermal decomposition temperature of each coating
Degree (Td) all more than 400 DEG C, fine heat-resisting performance.Soaking 30 minutes in analytically pure acetone soln and dried, photoresistance is coated with
Layer, without wrinkling, foaming, variable color and eclipsed phenomenon, shows good chemical resistance.
To sum up, the how carboxy-functionalized acrylate of the present invention can be used for preparing chromatic photoresist, and prepared product hardness is high,
Adhesive force is strong, and has thermostability, resistance to ag(e)ing and the resistance to chemical corrosion of excellence, has a extensive future.
Claims (7)
1., for the how carboxy-functionalized acrylate of chromatic photoresist, there is structure as shown in following formula (I):
Wherein, R1Containing at least one2, base and at least one-COOH group.
How carboxy-functionalized acrylate the most according to claim 1, it is characterised in that:
R1It is selected from The group constituted, and R therein2It is located close to formula (I) terminal carboxylic
Group is the side of-COOH；
R2It is each independently selected from
R3It is each independently selected from-CH2-,-CH=CH-,-CH2CH2-、-CH2CH2CH2-、
3. the preparation method of the how carboxy-functionalized acrylate described in claim 1 or 2, comprises the steps of:
(1) under nitrogen protection, Bis(pentaerythritol) and the dibasic acid anhydride with unsaturated double-bond are mixed in containing polymerization inhibitor hydroxyl
In the organic solvent of base methyl phenyl ethers anisole, there is esterification at a reflux temperature, obtain intermediate 1；
Reaction equation is as follows:
Wherein, R1' represent the linking group with unsaturated double-bond in anhydride；
(2) hydrogen peroxide and formic acid are joined in reaction system, react 3-8 hour at 20-30 DEG C, make R1-C=C-epoxy in '
Turn toObtain intermediate 2；
(3) intermediate 2 is mixed with (methyl) acrylic acid monohydroxy ester, in polymerization inhibitor MEHQ and catalyst hydroxide
Under sodium existence condition, 50-60 DEG C is reacted 2-3 hour, to epoxide group reaction completely, obtains intermediate 3；
(4) under nitrogen protection, intermediate 3 and anhydride are mixed in the organic solvent containing polymerization inhibitor MEHQ,
There is esterification under reflux temperature, obtain formula (I) compound.
Preparation method the most according to claim 3, it is characterised in that: in step (1), described with the two of unsaturated double-bond
Unit's anhydride is selected from maleic anhydride, 2,3-dimethyl maleate acid anhydride, carbic anhydride, tetrahydrophthalic acid
Acid anhydride, methyl tetrahydrophthalic anhydride.
Preparation method the most according to claim 3, it is characterised in that: in step (3), described (methyl) acrylic acid monohydroxy
Ester is R2One or more in H.
Preparation method the most according to claim 3, it is characterised in that: in step (4), described anhydride isIn one or more.
7. the application in chromatic photoresist of the how carboxy-functionalized acrylate described in claim 1 or 2.
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| CN106444287B (en) * | 2016-09-28 | 2019-07-16 | 江苏博砚电子科技有限公司 | A kind of chromatic photoresist acrylate and preparation method thereof |
| CN110350111A (en) * | 2019-07-12 | 2019-10-18 | 昆山梦显电子科技有限公司 | The preparation method and display module of high-resolution Micro-OLED |
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