CN109456230A - A kind of preparation method of photosensitizer - Google Patents
A kind of preparation method of photosensitizer Download PDFInfo
- Publication number
- CN109456230A CN109456230A CN201811350639.7A CN201811350639A CN109456230A CN 109456230 A CN109456230 A CN 109456230A CN 201811350639 A CN201811350639 A CN 201811350639A CN 109456230 A CN109456230 A CN 109456230A
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- preparation
- filtrate
- added
- dioxane
- condensation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Abstract
The invention belongs to field of new materials, and in particular to a kind of preparation method of photosensitizer, comprising: condensation reaction；Neutralization reaction；Filtering；Crystallization processing is done to filtrate；Precipitate is washed and is filtered；And filter cake is dried in vacuo.Have the advantages that preparation process is simple, save the cost.
Description
Technical field
The present invention relates to field of new materials, and in particular to a kind of preparation method of photosensitizer.
Background technique
Photoresist is the key industrial chemicals for miniaturizeing processing technology in the electronics industry, quick using the chemistry of photoresist
Perception can carry out photochemical reaction, and photoresist is coated in semiconductor, conductor or insulator-base on piece, is stayed after overexposure
Under part play a protective role to substrate, be then etched using etchant, so that it may by the Tiny figure of needs from covering
Film version is transferred on substrate to be processed, and is diffused, ion implanting, the techniques such as metallization.And PAC photosensitizer belong to it is photosensitive
The product of chemical field is one of the critical materials of photodegradation class photoresist.Just at present, there are no a kind of good methods to go
Realize the large-scale production and industrial applications of PAC photosensitizer.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of photosensitizer.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods of photosensitizer, comprising: condensation reaction；
Neutralization reaction；Filtering；Crystallization processing is done to filtrate；Precipitate is washed and is filtered；And filter cake is dried in vacuo.
Further, dioxane, triethylamine, tetracarboxylic benzophenone and 215 naphthalene sulfonyl chlorides nitrogen is blended in sufficiently to set
It in the synthesis reactor changed and heats, the condensation reaction occurs.
Further, the dioxane, triethylamine are suitable for being pre-mixed in blending tank, and persistently add in condensation reaction
Enter.
Further, the neutralization reaction includes: and hydrochloric acid is added into synthesis reactor to adjust PH for acidity, so that in condensation reaction
Unreacted triethylamine generates triethylamine salt.
Further, the method for the filtering includes: to be filtered the product of neutralization reaction；It is abundant that nitrogen is added in filtrate
In displaced crystallization kettle；And recycling filter residue.
Further, the method for the recycling filter residue includes: that filter residue is dissolved in water；Dioxane is distilled off；And add
Enter lye, adjusting PH is alkalinity, is warming up to 100 DEG C, distills out triethylamine, and through condensing recovery.
Further, the crystallization kettle is normal temperature and pressure, and pure water is added and stirs, makes filtrate crystallization.
Further, the method to precipitate washing filtering includes: the addition pure water agitator treating in precipitate；It crosses
Filter；Filtrate is collected in filtrate collecting tank；And filter cake enters baking oven.
Further, the vacuum drying temperature is 40-50 DEG C, vacuum degree 50Pa.
The invention has the advantages that preparation method of the invention passes through condensation reaction, the neutralization reaction successively carried out；So
Filtering, crystallization processing, washing filtering and vacuum drying afterwards, obtain photosensitizer, have that preparation process is simple, save the cost, is easy to
Therefore the advantages of realization, can carry out large-scale industrial production.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the process flow diagram of preparation method of the invention.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.
As shown in Figure 1, present embodiments providing a kind of preparation method of photosensitizer, comprising: condensation reaction；Neutralization reaction；
Filtering；Crystallization processing is done to filtrate；Precipitate is washed and is filtered；And filter cake is dried in vacuo, the PAC photosensitizer is obtained,
That is 2,3,4,4- tetracarboxylic benzophenone-1,2- diazido naphthoquinones -5- sulphonic acid ester.Now have to each process of preparation method
Body description.
(1) condensation reaction.
Dioxane is pumped into the blending tank that nitrogen is sufficiently displaced from, is then pumped into triethylamine, forms mixed liquor, the mixing
A small amount of organic exhaust gas can be generated in the process.Then dioxane is pumped into the synthesis reactor that nitrogen is sufficiently displaced from, opens stirring, so
Tetracarboxylic benzophenone (being also 2,3,4,4- tetracarboxylic benzophenone or HBP) is added afterwards and 215 naphthalene sulfonyl chlorides (are also 2- weight
Nitrogen -1,2- dihydro -1- oxo -5- naphthalene sulfonyl chloride or NAC)；It opens hot water and is warming up to 50 DEG C, under normal pressure, blending tank is slowly added dropwise
In mixed liquor 3h, and maintain normal pressure occur condensation reaction 0.5h.The exhaust gas generated in condensation reaction is by the top of synthesis reactor
After condenser condensation, condensate liquid returns to synthesis reactor.Meanwhile the HCl continuation that condensation reaction generates is reacted with triethylamine, generates three second
Amine hydrochlorate promotes condensation reaction to carry out.Therefore the triethylamine being continuously added into can improve the reaction efficiency of condensation reaction.
(2) neutralization reaction.
31% hydrochloric acid is added into the synthesis reactor after condensation reaction, adjusting PH is 2, so that unreacted in condensation reaction
Triethylamine all generates triethylamine salt, so as to subsequent filter separation.
(3) it filters.
With washing filtering two-in-one kettle by the product (including the mixed liquors such as triethylamine salt, excessive hydrochloric acid) of neutralization reaction into
Row filtering, separates filtrate and filter residue.Wherein, two-in-one kettle is total closed type filtering, non-exhaust emission when filtering, not only environmental protection,
Safety can also avoid exhaust gas from injuring human body.
Recycling filter residue comprises the following processes:
First filter residue is rinsed with a small amount of dioxane, further to wash out the product of neutralization reaction；It is again that filter residue is (main
If triethylamine salt) be directly dissolved in water in two-in-one kettle after, be pumped into recyclable device；Then it is distilled；Due to dioxy six
The azeotropic temperature of ring and water be 87.8 DEG C, can first distill out dioxane and enter dioxane recovery tower group in, then plus
Enter 30% lye, adjusting PH is 9, is warming up to 100 DEG C, redistillation goes out triethylamine under normal pressure, and through condenser condensing recovery；After
It is continuous to distill out waste water, into waste water treatment system.
(4) crystallization
The filtrate filtered in (3) is pumped into the crystallization kettle that nitrogen is sufficiently displaced from, opens stirring, be added under normal temperature and pressure pure water into
Row crystallization, the material in crystallization bottom portion is precipitate.
(5) washing filtering
The material (precipitate) in crystallization bottom portion is pumped into the two-in-one kettle that nitrogen is sufficiently displaced from, opens stirring, be then added
Pure water agitator treating；Then it filters；Repeated washing filter 23-4 times, is collected in filtrate collecting tank for filtrate, to pass through dioxane
Recovery tower group rectification and purification, is then reused, and can not only reduce cost of material, can also reduce pollutant and waste
Discharge amount.
Wherein, include: by the method for dioxane recovery tower group rectification and purification
The dioxane recovery tower group (abbreviation DO tower) includes the recovery tower of 5 normal pressures；
Firstly, filtrate or the dioxane distilled out (dioxane content is 3-8% or so) enter mono- tower of DO (independent gap behaviour
Make), controlled at 90-110 DEG C, top gaseous phase is collected in the medial launder of mono- tower of DO after condenser condenses, and (dioxane contains
Amount is 20% or so), control certain reflux ratio；Materials at bottom of tower (substantially water), can be used as wastewater treatment.
Secondly, the medial launder material of mono- tower of DO is pumped into bis- tower of DO by dehvery pump.Bis- tower of DO (for independent gap operating)
Temperature control at 90-100 DEG C, top gaseous phase is collected in medial launder (the dioxane concentration of bis- tower of DO after condenser condenses
It can achieve 80% or so)；Materials at bottom of tower (dioxane content is 2% or so), can return to mono- tower of DO and recycle again.
Then, the medial launder material of bis- tower of DO is pumped into tri- tower of DO by dehvery pump.Tri- tower of DO (tri- tower of DO, four towers, five towers
Be continuous rectifying tower) temperature control at 60-120 DEG C, top gaseous phase is collected in the centre of tri- tower of DO after condenser condenses
Slot (light fraction is low component in dioxane and raw material, water), can be used as wastewater treatment；(dioxane contains materials at bottom of tower
Amount is 95% or so).
Subsequently, the materials at bottom of tower of tri- tower of DO is pumped into tetra- tower of DO by dehvery pump.The temperature of tetra- tower of DO is controlled in 70-
120 DEG C, top gaseous phase is collected in the medial launder (dioxane content is 20% or so) of tetra- tower of DO after condenser condenses, and is sent into
Bis- tower of DO is recycled；Materials at bottom of tower (dioxane content is 98% or so).
Finally, the materials at bottom of tower of tetra- tower of DO is pumped into five tower of DO by dehvery pump.The temperature of five tower of DO is controlled in 105-150
DEG C, top gaseous phase is collected in the medial launder (dioxane content is 99% or so) of five tower of DO after condenser condenses, can be direct
For condensation reaction；Materials at bottom of tower (dioxane content is 80% or so), is sent into tri- tower of DO and is recycled.
(6) it is dried in vacuo.
Filter cake in (5) is dried using vacuum oven, temperature is controlled at 40-50 DEG C, vacuum degree 50Pa, does
Dry 22h to get arrive the PAC photosensitizer.
In conclusion the preparation method of the application passes through condensation reaction, the neutralization reaction successively carried out；Then it filters, is right
Filtrate does crystallization processing, filtering is washed to precipitate and is dried in vacuo to filter cake, obtains photosensitizer, simple with preparation process,
The advantages of save the cost, is also suitable for industrialized production；By the way that triethylamine is persistently added dropwise in the condensation reaction, condensation reaction can be improved
Reaction efficiency, improve production efficiency；It recycles and reuses with dioxane by being filtered, washed, saved raw material, reduce
Cost, while also improving the purity of PAC photosensitizer.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (9)
1. a kind of preparation method of photosensitizer characterized by comprising
Condensation reaction；
Neutralization reaction；
Filtering；
Crystallization processing is done to filtrate；
Precipitate is washed and is filtered；And
Filter cake is dried in vacuo.
2. preparation method according to claim 1, which is characterized in that
Dioxane, triethylamine, tetracarboxylic benzophenone and 215 naphthalene sulfonyl chlorides are blended in synthesis reactor and are heated, institute occurs
State condensation reaction.
3. preparation method according to claim 2, which is characterized in that
The dioxane, triethylamine are suitable for being pre-mixed in blending tank, and are continuously added into condensation reaction.
4. preparation method according to claim 1, which is characterized in that
The neutralization reaction includes: that hydrochloric acid is added into synthesis reactor to adjust PH for acidity, so that unreacted three in condensation reaction
Ethamine generates triethylamine salt.
5. preparation method according to claim 1, which is characterized in that
The method of the filtering includes:
The product of neutralization reaction is filtered；
Filtrate is added in crystallization kettle；And
Recycle filter residue.
6. preparation method according to claim 5, which is characterized in that
It is described recycling filter residue method include:
Filter residue is dissolved in water；
Dioxane is distilled off；And
Lye is added, adjusting PH is alkalinity, is warming up to 100 DEG C, distills out triethylamine, and through condensing recovery.
7. preparation method according to claim 6, which is characterized in that
The crystallization kettle is normal temperature and pressure, and pure water is added and stirs, makes filtrate crystallization.
8. preparation method according to claim 1, which is characterized in that
It is described to precipitate washing filtering method include:
Pure water agitator treating is added in precipitate；
Filtering；
Filtrate is collected in filtrate collecting tank；And
Filter cake enters baking oven.
9. preparation method according to claim 1, which is characterized in that
The vacuum drying temperature is 40-50 DEG C, vacuum degree 50Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811350639.7A CN109456230A (en) | 2018-11-14 | 2018-11-14 | A kind of preparation method of photosensitizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811350639.7A CN109456230A (en) | 2018-11-14 | 2018-11-14 | A kind of preparation method of photosensitizer |
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| CN109456230A true CN109456230A (en) | 2019-03-12 |
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| CN201811350639.7A Pending CN109456230A (en) | 2018-11-14 | 2018-11-14 | A kind of preparation method of photosensitizer |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290658A (en) * | 1991-04-26 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Positive type photoresist composition comprising polyaromatic hydroxy quinone diazide esters as the photosensitive ingredient |
| JPH06256565A (en) * | 1993-03-03 | 1994-09-13 | Sumitomo Chem Co Ltd | Preparation of radiation-sensitive resin composition |
| JPH06258824A (en) * | 1993-03-02 | 1994-09-16 | Sumitomo Chem Co Ltd | Positive type resist composition |
| JPH08179499A (en) * | 1994-12-21 | 1996-07-12 | Japan Synthetic Rubber Co Ltd | Positive type resist solution |
| JPH09221601A (en) * | 1996-02-19 | 1997-08-26 | Toray Ind Inc | Production of radiation sensitive resist composition |
| JPH09230592A (en) * | 1996-02-23 | 1997-09-05 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH09281704A (en) * | 1996-04-16 | 1997-10-31 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH11218908A (en) * | 1998-02-04 | 1999-08-10 | Nippon Zeon Co Ltd | Positive resist composition for manufacture of photomask |
| CN1208684C (en) * | 2000-05-08 | 2005-06-29 | 东洋合成工业株式会社 | Process for producing 1,2-naphthaquinone dinitride photosensitisers |
| CN106977421A (en) * | 2017-02-16 | 2017-07-25 | 蚁术新材料科技（上海）有限公司 | A kind of method for preparing diazo naphthoquinone type sensitising agent |
-
2018
- 2018-11-14 CN CN201811350639.7A patent/CN109456230A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290658A (en) * | 1991-04-26 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Positive type photoresist composition comprising polyaromatic hydroxy quinone diazide esters as the photosensitive ingredient |
| JPH06258824A (en) * | 1993-03-02 | 1994-09-16 | Sumitomo Chem Co Ltd | Positive type resist composition |
| JPH06256565A (en) * | 1993-03-03 | 1994-09-13 | Sumitomo Chem Co Ltd | Preparation of radiation-sensitive resin composition |
| JPH08179499A (en) * | 1994-12-21 | 1996-07-12 | Japan Synthetic Rubber Co Ltd | Positive type resist solution |
| JPH09221601A (en) * | 1996-02-19 | 1997-08-26 | Toray Ind Inc | Production of radiation sensitive resist composition |
| JPH09230592A (en) * | 1996-02-23 | 1997-09-05 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH09281704A (en) * | 1996-04-16 | 1997-10-31 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH11218908A (en) * | 1998-02-04 | 1999-08-10 | Nippon Zeon Co Ltd | Positive resist composition for manufacture of photomask |
| CN1208684C (en) * | 2000-05-08 | 2005-06-29 | 东洋合成工业株式会社 | Process for producing 1,2-naphthaquinone dinitride photosensitisers |
| CN106977421A (en) * | 2017-02-16 | 2017-07-25 | 蚁术新材料科技（上海）有限公司 | A kind of method for preparing diazo naphthoquinone type sensitising agent |
Non-Patent Citations (2)
| Title |
|---|
| 浦家诚等: "邻叠氮萘醌磺酸酯型光敏剂的合成及其性能的测试", 《影像材料》 * |
| 黄毓礼等: "不同结构的邻叠氮萘醌型光敏剂感光性能的研究", 《影像技术》 * |
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Application publication date: 20190312 |
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