CN105753694B - A kind of how carboxy-functionalized acrylate and preparation method thereof for chromatic photoresist - Google Patents
A kind of how carboxy-functionalized acrylate and preparation method thereof for chromatic photoresist Download PDFInfo
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- CN105753694B CN105753694B CN201610197561.4A CN201610197561A CN105753694B CN 105753694 B CN105753694 B CN 105753694B CN 201610197561 A CN201610197561 A CN 201610197561A CN 105753694 B CN105753694 B CN 105753694B
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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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- 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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- 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 present invention discloses a kind of how carboxy-functionalized acrylate for chromatic photoresist, has structure, wherein R shown in formula (I)1Containing at least oneGroup and at least one COOH group.After the how carboxy-functionalized acrylate is applied to chromatic photoresist, product hardness is high, strong adhesive force, and has excellent heat resistance, resistance to ag(e)ing and resistance to chemical corrosion.
Description
Technical field
The invention belongs to organic chemistry fileds, and in particular 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 colored display.As technology-intensive industries, the neck
Domain barrier to market entry is higher, and only the big factory of a handful of of Japan and Korea S. and China Taiwan has volume production energy in the world at present
Power, and it is limited by Japanese manufacturer completely in terms of high-order product.
Photoresist is the core for preparing colored filter, and key technology rests in several Japan-funded enterprises hands completely
In, this is larger to the restriction of China TFT-LCD vertical industry chains, becomes a bottle of development China's liquid crystal display related industry
Neck.Therefore, there is an urgent need to research and develop the photoresist with independent intellectual property right, to 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 levels more step to a new level, while driving the necks such as chemical color, mechanical processing, semiconductor technology
Domain is further developed.
The main component of photoresist includes light-cured resin, photoinitiator, pigment, organic solvent etc..Wherein, photocuring tree
Fat determines the basic performance of photocuring product, including hardness, flexibility, adhesive force, optical property, ageing-resistant etc..It can be said that
Light-cured resin is the key that photoresist research and development.Currently, light-cured resin includes mainly polyimide resin, polyvinyl alcohol tree
Fat, epoxy resin and acrylate etc., acrylate application are most.
Invention content
The purpose of the present invention is to provide a kind of how carboxy-functionalized acrylate for chromatic photoresist.Applied to colour
After photoresist, product hardness is high, strong adhesive force, and has excellent heat resistance, resistance to ag(e)ing and resistance to chemical corrosion.
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 the structure as shown in following formula (I)：
Wherein, R1Containing at least oneGroup and at least one-COOH bases
Group.
As optimal technical scheme, in above-mentioned formula (I) structure, R1It is selected from It is constituted
Group, and R therein2Positioned at the side for close to formula (I) terminal carboxylic acid group being-COOH；
R2It is each independently selected from
R3It is each independently selected from-CH2,-CH=CH-,-CH2CH2-、-
CH2CH2CH2-、
In the present invention, term " each independently " indicates that the group in structural formula may be the same or different.
Correspondingly, the invention further relates to the preparation methods of how carboxy-functionalized acrylate shown in above-mentioned formula (I), including such as
Lower step：
(1) under nitrogen protection, dipentaerythritol and the dibasic acid anhydride with unsaturated double-bond are mixed in containing polymerization inhibitor
In the organic solvent of p-hydroxyanisole, esterification occurs at a reflux temperature, obtains intermediate 1；
Reaction equation is as follows：
Wherein, R1 ' indicates to carry the linking group of unsaturated double-bond in acid anhydrides；
(2) hydrogen peroxide and formic acid are added in reaction system, are reacted 3-8 hours at 20-30 DEG C, makes R1' in-C=
C- epoxies turn toObtain intermediate 2；
(3) intermediate 2 is mixed with (methyl) acrylic acid monohydroxy ester, in polymerization inhibitor p-hydroxyanisole and catalyst hydrogen
Under sodium oxide molybdena existence condition, 50-60 DEG C is reacted 2-3 hours, until the reaction was complete for epoxy group, obtains intermediate 3；
(4) under nitrogen protection, intermediate 3 and acid anhydrides are mixed in the organic solvent of the p-hydroxyanisole containing polymerization inhibitor
In, esterification occurs at a reflux temperature, obtains formula (I) compound.
In above-mentioned steps (1), by esterification, double bond containing carboxylic acid group has been chained in dipentaerythritol structure.
The organic solvent type used is not particularly limited, as long as reaction raw materials can be dissolved and had no adverse effects i.e. to reaction
Can, dichloromethane, dichloroethanes, toluene, dimethylbenzene, acetonitrile etc..In esterification, it is described with unsaturated double-bond two
First acid anhydrides preferably is selected from maleic anhydride, 2,3- dimethyl maleates acid anhydride, carbic anhydride, tetrahydrophthalic acid
Acid anhydride, methyl tetrahydrophthalic anhydride.That is, R1' preferably be selected from lower structure：
- CH=CH-,
In step (3), the hydroxyl effect in the epoxy group open loop of intermediate 2, with (methyl) acrylic acid monohydroxy ester, into
Row addition reaction, to chain corresponding (methyl) acrylate group closing on the terminal carboxylic acid group i.e. side of-COOH
(other side generation hydroxyl).(methyl) the acrylic acid monohydroxy ester is preferably R2It is one or more in H.At this point, intermediate 2
'sWith R2H reacts, generation-C (OH)-C (R2)-, and R2Positioned at 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 acid anhydrides act on, and ester occurs
Change reaction.The organic solvent used in reaction is not particularly limited, as long as reaction raw materials can be dissolved and to reacting without bad
Influence, dichloromethane, dichloroethanes, toluene, dimethylbenzene, acetonitrile etc..The acid anhydrides is preferably
In it is one or more.
The present invention preparation method in, reaction raw materials are known compounds in the prior art, it is commercially available or
It is prepared by known synthetic method.Also, the reaction involved in each step is all based on the common reactant of organic field
Mechanism.On the basis of being realised that synthesis thinking disclosed by the invention, specific reaction condition is to those skilled in the art
It is easy determination.
Preferably but not compulsorily, in step (1), mole of dibasic acid anhydride and dipentaerythritol with unsaturated double-bond
Than being 6:1.In step (2), the molar ratio of hydrogen peroxide and formic acid is 6:1-10:1, hydrogen peroxide and original dipentaerythritol
Molar ratio is 6:1.In step (3), the molar ratio of (methyl) acrylic acid monohydroxy ester and original dipentaerythritol is 6:1.Step
(4) in, the molar ratio of acid anhydrides and original dipentaerythritol is 6:1.
Using dipentaerythritol as initial feed, with double bond containing dibasic acid anhydride esterification occurs for the present invention, then will be double
Key epoxidation, then with the monohydroxy ester addition of (methyl) acrylic acid, finally secondary esterification is carried out with acid anhydrides, to finally be produced
Product.For the products application when chromatic photoresist, multiple carboxyls in molecular structure can form hydrogen bond, enhancing attachment with substrate surface
Power promotes photoresist hardness, while can make it have excellent heat resistance, resistance to ag(e)ing and resistance to chemical corrosion.Also, this hair
Bright synthetic route is simple, and side reaction is less, pollution-free, without purification in reaction process, you can obtain the production with superperformance
Product.
Specific implementation mode
Below with reference to specific embodiment, invention is further described in detail, but should not be construed as to the present invention
The limitation of protection domain.
Embodiment 1
1.0 moles of dipentaerythritols, 6.0 moles of maleics are added in 1L is with the flask of condenser and mechanical agitator
Dicarboxylic anhydride, 1g p-hydroxyanisole and 300g acetonitriles are heated to flowing back under nitrogen protection, faint yellow clarification are obtained after about 30 minutes
Liquid.The reaction was continued 6 hours, is then cooled to room temperature.
Filtrate is transferred in flasks of the 2L with magnetic stirring apparatus, 1 mole of formic acid and 820 gram 25% is added by filtering
The hydrogen peroxide of concentration, (about 25 DEG C) stirrings of room temperature, after reacting 6 hours, vacuum distillation obtains light yellow viscous liquid.
Light yellow viscous liquid is moved into the flask equipped with condenser and mechanical agitator, 6 mol propylene acid hydroxyls are added
Ethyl ester, 5 grams of sodium hydroxides and 2 grams of p-hydroxyanisole, 50 DEG C are reacted 3 hours, and room temperature is then cooled to, and obtain light yellow liquid
Body.
Obtained weak yellow liquid and 2 grams of p-hydroxyanisole, 6 moles of malonic anhydrides are added to condenser and machine
In the flask of tool blender, and 400g acetonitriles are added, after 30 minutes are stirred at room temperature under nitrogen protection, are to slowly warm up to flow back, protects
It holds thermotonus 6 hours, is then cooled to room temperature.
Reaction solution is poured slowly into a large amount of water in high-speed blender, fully washing is placed on separatory funnel, shakes
30 minutes are stood afterwards, removes a layer solution, it is then 12 hours dry in vacuum drying oven, obtain yellowish solid.
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 100 mass parts of resin, 100 mass parts of solvent propylene glycol methyl ether acetate, photoinitiator 2- hydroxyls-
2- methyl-1s-about 3 mass parts of phenyl -1- acetone (1173), about 1 mass parts of organic pigment paratonere 7, wetting agent T-1004 about 1
Mass parts, mixing are put into container, carried out on SFJ-400 type multiple purpose aeroplanes it is pre-dispersed, it is pre-dispersed mixed under the conditions of rotating speed 1000rpm
Close 30min.3ml mixtures are taken to form a film on sol evenning machine, spin coating machine speed 1000rpm, time 10s.The glass that will have been formed a film
Glass piece is put into 60 DEG C of baking oven front baking 5min, is then exposed with light source Fusion-LH6, light exposure 2000mJ/cm2, then exist
Develop in the KOH solution of 1% concentration, dries 1h after subsequent 90 DEG C, obtain photoresist coating 1.
Embodiment 2
1g p-hydroxyanisole, 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 2,3- dimethyl maleates acid anhydrides and 300g acetonitriles, under nitrogen protection, heating mixture is to flowing back, about
After 30 minutes, faint yellow supernatant liquid is obtained.It keeps reaction temperature 6 hours, is then cooled to room temperature.
Clear filtrate is transferred in flasks of the 2L with magnetic stirring apparatus, 0.6 mole of formic acid and 820 is added by filtering
The hydrogen peroxide of gram 25% concentration, is stirred at room temperature, and after reaction 6 hours, vacuum distillation obtains light yellow viscous liquid.
Obtained weak yellow liquid is moved into the flask equipped with condenser and mechanical agitator, 6 moles of Ji Wusi are added
Alcohol trimethyl acrylic ester, 5 grams of sodium hydroxides and 2 grams of p-hydroxyanisole, 50 DEG C of reaction temperature, 3 hours reaction time, with
Postcooling to room temperature obtains weak yellow liquid.
Obtained liquid and 2 grams of p-hydroxyanisole, 6 moles of tetrabydrophthalic anhydrides are added to condenser and
In the flask of mechanical agitator, and 400g acetonitriles are added, after 30 minutes are stirred at room temperature under nitrogen protection, are to slowly warm up to flow back
Temperature, keeps temperature 6 hours, is then cooled to room temperature.
Reaction solution is poured slowly into a large amount of water in high-speed blender, fully washing is placed on separatory funnel, shakes
30 minutes are stood afterwards, removes a layer solution, it is then 12 hours dry in vacuum drying oven, obtain faint yellow solid.
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 100 mass parts of resin, 100 mass parts of solvent propylene glycol methyl ether acetate, photoinitiator 2- phenyl
About 3 mass parts of benzyl -2- dimethyl amines -1- (4- morpholine benzyls phenyl) butanone (369), about 1 part of organic pigment pigment yellow 185, wetting
About 1 mass parts of agent T-1004.Each raw material are mixed and are put into container, pre-dispersed, rotating speed is carried out on SFJ-400 type multiple purpose aeroplanes
Pre-dispersed mixing 30min under the conditions of 1000rpm.3ml mixtures are taken to form a film on sol evenning machine, spin coating machine speed 1000rpm, when
Between be 10s.The sheet glass to have formed a film is put into 60 DEG C of baking oven front baking 5min, is then exposed with light source Fusion-LH6, is exposed
Light quantity 2000mJ/cm2, develop in the KOH solution of 1% concentration, dry 1h after subsequent 90 DEG C, obtain photoresist coating 2.
Embodiment 3
1g p-hydroxyanisole, 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 acetonitriles, under nitrogen protection, heating mixture to reflux, about 30 minutes
Afterwards, faint yellow supernatant liquid is obtained.It keeps reaction temperature 6 hours, is then cooled to room temperature.
Clear filtrate is transferred in flasks of the 2L with magnetic stirring apparatus, 0.8 mole of formic acid and 820 is added by filtering
The hydrogen peroxide of gram 25% concentration, is stirred at room temperature, and after reaction 6 hours, vacuum distillation obtains light yellow viscous liquid.
Obtained weak yellow liquid is moved into the flask equipped with condenser and mechanical agitator, 6 moles of double seasons penta are added
Five acrylate of tetrol, 5 grams of sodium hydroxides and 2 grams of p-hydroxyanisole, 50 DEG C of reaction temperature, 3 hours reaction time, then
It is cooled to room temperature, obtains weak yellow liquid.
Obtained liquid and 2 grams of p-hydroxyanisole, 6 moles of 3- nitrophthalic acid acid anhydrides are added to condenser
In the flask of mechanical agitator, and 400g acetonitriles are added, after 30 minutes are stirred at room temperature under nitrogen protection, are to slowly warm up to back
Temperature is flowed, keeps temperature 6 hours, is then cooled to room temperature.
Reaction solution is poured slowly into a large amount of water in high-speed blender, fully washing is placed on separatory funnel, shakes
30 minutes are stood afterwards, removes a layer solution, it is then 12 hours dry in vacuum drying oven, obtain faint yellow solid.
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 100 mass parts of resin, 100 mass parts of solvent propylene glycol methyl ether acetate, photoinitiator 2- phenyl
About 3 mass parts of benzyl -2- dimethyl amines -1- (4- morpholine benzyls phenyl) butanone (369), about 1 part of organic pigment paratonere 183, wetting
About 1 mass parts of agent T-1004.Each raw material are mixed and are put into container, pre-dispersed, rotating speed is carried out on SFJ-400 type multiple purpose aeroplanes
Pre-dispersed mixing 30min under the conditions of 1000rpm.3ml mixtures are taken to form a film on sol evenning machine, spin coating machine speed 1000rpm, when
Between be 10s.The sheet glass to have formed a film is put into 60 DEG C of baking oven front baking 5min, is then exposed with light source Fusion-LH6, is exposed
Light quantity 2000mJ/cm2, develop in the KOH solution of 1% concentration, dry 1h after subsequent 90 DEG C, obtain photoresist coating 3.
Embodiment 4
1g p-hydroxyanisole, 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 acetonitriles, under nitrogen protection, heating mixture to reflux, about 30
After minute, faint yellow supernatant liquid is obtained.It keeps reaction temperature 6 hours, is then cooled to room temperature.
Clear filtrate is transferred in flasks of the 2L with magnetic stirring apparatus, 1 mole of formic acid and 820 grams is added by filtering
The hydrogen peroxide of 25% concentration, is stirred at room temperature, and after reacting 6 hours, vacuum distillation obtains light yellow viscous liquid.
Obtained liquid is moved into the flask equipped with condenser and mechanical agitator, 6 mole hydroxyls are added
Propyl ester, 5 grams of sodium hydroxides and 2 grams of p-hydroxyanisole, 50 DEG C of reaction temperature in 3 hours reaction time, are then cooled to room
Temperature obtains weak yellow liquid.
Obtained liquid and 2 grams of p-hydroxyanisole, 6 moles of 2,3- dimethyl maleate acid anhydrides are added to cold
In the flask of condenser and mechanical agitator, and 400g acetonitriles are added, after 30 minutes are stirred at room temperature under nitrogen protection, slowly heat up
To reflux temperature, temperature is kept 6 hours, be then cooled to room temperature.
Reaction solution is poured slowly into a large amount of water in high-speed blender, fully washing is placed on separatory funnel, shakes
30 minutes are stood afterwards, removes a layer solution, it is then 12 hours dry in vacuum drying oven, obtain faint yellow solid.
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 100 mass parts of resin, 100 mass parts of solvent propylene glycol methyl ether acetate, photoinitiator 1- hydroxyls
About 1 part of about 3 mass parts of cyclohexyl phenyl ketone (184), organic pigment paratonere 7, about 1 mass parts of wetting agent T-1004.It will be each
Raw material mixing is put into container, carried out on SFJ-400 type multiple purpose aeroplanes it is pre-dispersed, it is pre-dispersed mixed under the conditions of rotating speed 1000rpm
Close 30min.3ml mixtures are taken to form a film on sol evenning machine, spin coating machine speed 1000rpm, time 10s.The glass that will have been formed a film
Glass piece is put into 60 DEG C of baking oven front baking 5min, is then exposed with light source Fusion-LH6, light exposure 2000mJ/cm2, 1%
Develop in the KOH solution of concentration, dries 1h after subsequent 90 DEG C, obtain photoresist coating 4.
Embodiment 5
1g p-hydroxyanisole, 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 acetonitriles, under nitrogen protection, heating mixture to reflux, about 30 minutes
Afterwards, faint yellow supernatant liquid is obtained.It keeps reaction temperature 6 hours, is then cooled to room temperature.
Clear filtrate is transferred in flasks of the 2L with magnetic stirring apparatus, 1 mole of formic acid and 820 grams is added by filtering
The hydrogen peroxide of 25% concentration, is stirred at room temperature, and after reacting 6 hours, vacuum distillation obtains light yellow viscous liquid.
Obtained liquid is moved into the flask equipped with condenser and mechanical agitator, 6 mole of trimethylol propane are added
Diacrylate, 5 grams of sodium hydroxides and 2 grams of p-hydroxyanisole, 50 DEG C of reaction temperature, 3 hours reaction time, with postcooling
To room temperature, weak yellow liquid is obtained.
Obtained liquid and 2 grams of p-hydroxyanisole, 6 moles of phthalic anhydrides are added to condenser and machinery
In the flask of blender, and 400g acetonitriles are added, after 30 minutes are stirred at room temperature under nitrogen protection, are to slowly warm up to reflux temperature
Degree, keeps temperature 6 hours, is then cooled to room temperature.
Reaction solution is poured slowly into a large amount of water in high-speed blender, fully washing is placed on separatory funnel, shakes
30 minutes are stood afterwards, removes a layer solution, it is then 12 hours dry in vacuum drying oven, obtain faint yellow solid.
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 100 mass parts of resin, 100 mass parts of solvent propylene glycol methyl ether acetate, photoinitiator 2- phenyl
About 3 mass parts of benzyl -2- dimethyl amines -1- (4- morpholine benzyls phenyl) butanone (369), about 1 part of organic pigment pigment yellow 2, wetting agent
About 1 mass parts of T-1004.Each raw material are mixed and are put into container, pre-dispersed, rotating speed is carried out on SFJ-400 type multiple purpose aeroplanes
20~30min of pre-dispersed mixing under the conditions of 1000rpm.3ml mixtures are taken to form a film on sol evenning machine, spin coating machine speed is
1000rpm, time 10s.The sheet glass to have formed a film is put into 60 DEG C of baking oven front baking 5min, then uses light source Fusion-LH6
It is exposed, light exposure 2000mJ/cm2, develop in the KOH solution of 1% concentration, dry 1h after subsequent 90 DEG C, obtain photoresist painting
Layer 5.
Performance characterization
Performance characterization carried out to photoresist coating 1-5 made from above-described embodiment 1-5, including adhesive force, case hardness, resistance to old
The property changed, heat resistance and endurance.Specific detection method and steps are as follows：
(1) adhesive force measures：Test grading is carried out with reference to the detection method of standard GB/T/T1720-1979, is divided into 1-7
Grade, 1 grade preferably, and paint film is intact.
(2) case hardness measures：Test grading is carried out with reference to the detection method of standard GB/T/T 6739-1996, is graded
Number is higher, indicates that performance is better.
(3) ageing-resistant performance measurement and evaluation method：Chromatic photoresist coating is positioned over 2000 ageing devices of ATLAS-UV to connect
Continuous irradiation 200 hours, then irradiates the desk-top 600 test light resistance coatings of aberration spectrophotometer Datacolor of photoresist coating
Front and back aberration (Δ E), Δ E values are smaller, indicate that photoresist coating resistance to ag(e)ing is better.
(4) Heat-tolerance Determination and evaluation method：By the thermal decomposition of TGA-Q500 test light resistance coatings of chromatic photoresist coating
Temperature (Td), TdValue is bigger, indicates that photoresist coating heat resistance is better.
(5) chemical resistance measures：Chromatic photoresist coating is put into 60 DEG C of vacuum drying oven and is toasted 8 hours, is taken out
Photoresist coating is fully immersed in analytically pure acetone soln 30 minutes, 40 DEG C of dryings 1 of air dry oven are then placed it in
Hour, whether there is or not corrugation, blistering, discoloration and eclipsed phenomenons for observation photoresist coating.
Characterization result is as shown in the table.
As can be seen from the above table, white light resistance coating made from the how carboxy-functionalized acrylate using the present invention adheres to
Power is very high, reaches 1 grade, and paint film is intact, and has very high hardness, aberration Δ E small.The thermal decomposition temperature of each coating
Spend (Td) more than 400 DEG C, fine heat-resisting performance.After impregnating 30 minutes and drying in analytically pure acetone soln, photoresist applies
Layer shows good chemical resistance without corrugation, blistering, discoloration and eclipsed phenomenon.
To sum up, how carboxy-functionalized acrylate of the invention can be used for preparing chromatic photoresist, and product hardness obtained is high,
Strong adhesive force, and there is excellent heat resistance, resistance to ag(e)ing and resistance to chemical corrosion, it has a extensive future.
Claims (3)
1. a kind of how carboxy-functionalized acrylate for chromatic photoresist has the structure as shown in following formula (I)：
Wherein,
R1It is selected from The group constituted, and R therein2Positioned at close to formula (I)
Terminal carboxylic acid group is the side of-COOH；
R2It is each independently selected from
R3It is each independently selected from-CH2,-CH=CH-,-CH2CH2-、-CH2CH2CH2-、
2. the preparation method of how carboxy-functionalized acrylate described in claim 1, comprises the following steps：
(1) under nitrogen protection, dipentaerythritol and the dibasic acid anhydride with unsaturated double-bond are mixed in containing polymerization inhibitor to hydroxyl
In the organic solvent of base methyl phenyl ethers anisole, esterification occurs at a reflux temperature, obtains intermediate 1；
Reaction equation is as follows：
Wherein, the dibasic acid anhydride with unsaturated double-bond be selected from maleic anhydride, 2,3- dimethyl maleates acid anhydride,
Carbic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, R1' indicate in acid anhydrides with unsaturation
The linking group of double bond；
(2) hydrogen peroxide and formic acid are added in reaction system, are reacted 3-8 hours at 20-30 DEG C, makes R1' in-C=C- epoxies
It turns toObtain intermediate 2；
(3) intermediate 2 is mixed with (methyl) acrylic acid monohydroxy ester, in polymerization inhibitor p-hydroxyanisole and catalyst hydroxide
Under sodium existence condition, 50-60 DEG C is reacted 2-3 hours, until the reaction was complete for epoxy group, obtains intermediate 3；Wherein, the described (first
Base) acrylic acid monohydroxy ester is R2One kind in H；
(4) under nitrogen protection, intermediate 3 and acid anhydrides are mixed in the organic solvent of the p-hydroxyanisole containing polymerization inhibitor,
Esterification occurs under reflux temperature, obtains formula (I) compound；Wherein, the acid anhydrides isIn one kind.
3. application of the how carboxy-functionalized acrylate described in claim 1 in chromatic photoresist.
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| CN102432463A (en) * | 2011-09-06 | 2012-05-02 | 南京工业大学 | Modified epoxy acrylate prepolymer, preparation method and application |
| CN103127955A (en) * | 2013-03-11 | 2013-06-05 | 北京理工大学 | Catalyst for synthesizing dipentaerythritol hexaacrylate, preparation method and application thereof |
| CN104003874A (en) * | 2014-04-25 | 2014-08-27 | 江苏利田科技股份有限公司 | New aliphatic epoxy acrylate with functionality of 4, and preparation method and application thereof |
| JP5729664B2 (en) * | 2011-06-28 | 2015-06-03 | ナガセケムテックス株式会社 | Fluorine-containing (meth) acrylic acid ester compound, composition containing the same, and production method |
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| JP5729664B2 (en) * | 2011-06-28 | 2015-06-03 | ナガセケムテックス株式会社 | Fluorine-containing (meth) acrylic acid ester compound, composition containing the same, and production method |
| CN102432463A (en) * | 2011-09-06 | 2012-05-02 | 南京工业大学 | Modified epoxy acrylate prepolymer, preparation method and application |
| CN103127955A (en) * | 2013-03-11 | 2013-06-05 | 北京理工大学 | Catalyst for synthesizing dipentaerythritol hexaacrylate, preparation method and application thereof |
| CN104003874A (en) * | 2014-04-25 | 2014-08-27 | 江苏利田科技股份有限公司 | New aliphatic epoxy acrylate with functionality of 4, and preparation method and application thereof |
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