CN104371102B - Negative photo-sensitive polyimide and method for preparing same - Google Patents
Negative photo-sensitive polyimide and method for preparing same Download PDFInfo
- Publication number
- CN104371102B CN104371102B CN201410756196.7A CN201410756196A CN104371102B CN 104371102 B CN104371102 B CN 104371102B CN 201410756196 A CN201410756196 A CN 201410756196A CN 104371102 B CN104371102 B CN 104371102B
- Authority
- CN
- China
- Prior art keywords
- photo
- polyamic acid
- sensitive
- negative photosensitive
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a high-polymer material and a method for preparing the same, and particularly relates to a negative photo-sensitive polyimide and a method for preparing the same. The method includes polymerizing diamine and dianhydride tetracarboxylic acid with carbonyl; blocking aminobenzoic acid to obtain polyamic acid solution; performing acylating chlorination on carbonyl in large molecules of polyamic acid to obtain products; enabling the products and phenols or alcohol with photo-sensitive groups to react with one another; obtaining the negative photo-sensitive polyimide with a high photo-sensitive property after chemical imidization is carried out. The ends of molecules and side chains of the polyamic acid solution contain carboxyl groups. The negative photo-sensitive polyimide and the method have the advantages that the negative photo-sensitive polyimide has the high photo-sensitive property, is excellent in heat resistance and has a broad application prospect in the fields of aviation and aerospace, micro-electronics and the like.
Description
Technical field
The present invention designs a kind of macromolecular material and preparation method thereof, is specially negative photosensitive polyimide and preparation side thereofMethod.
Background technology
Along with the fast development of macromolecular material, polyimides (PI) material exists as the very excellent material of combination propertyPolymeric material field is especially dazzling. Because polyimide resin has outstanding resistance to elevated temperatures, dielectric properties and goodRadiation resistance, therefore, it obtains in microelectronics industry as functional material applying more and more widely, but due to conventionallyPolyimides do not there is photosensitive property, when it is used as membranaceous figure in microelectronic component, must use it simultaneouslyHis photosensitive material, thus make whole photoetching process extremely complicated, and efficiency is very low. For this reason, light-sensitive polyimide (PSPI) materialMaterial is subject to people's great attention. It is domestic that once someone had synthesized a kind of hyperbranched from sensitizing polyimide light-sensitive material, stillLuminous sensitivity is lower. Therefore, the research and development of better photosensitivity polyimides has very profound significance.
Summary of the invention
For above-mentioned technical problem, the present invention introduces photosensitive group from the side chain of polyamic acid, obtains through chemical imidizationArrive a kind of negative photosensitive polyimide. Concrete technical scheme is:
A kind of negative photosensitive polyimide, chemical constitution is
Wherein, Ar1For containing the acid anhydrides of carbonyl;
Ar2For not containing the acid anhydrides of carbonyl;
Ar3With Ar1Or Ar2Identical;
R is the chalcone photosensitive group that contains carbonyl.
Described Ar1Be 3,3,4,4-benzophenone tetracarboxylic dianhydride, structural formula is
Described Ar2For
One or several in above acid anhydrides.
Described R is
The preparation method of negative photosensitive polyimide comprises the following steps:
Each material is according to mole part proportioning;
(1) diamines of 1 part is dissolved in the organic solvent of 5-20 part, after mechanical agitation is dissolved, adds the tetrabasic carboxylic acid of 1.5 partsDianhydride fully reacts under normal temperature and pressure nitrogen atmosphere, then adds 1 part of p-aminobenzoic acid, fully after reaction, is heldThe polyamic acid solution of carboxyl;
(2) taking 2 parts of concentration is 0.0138g/cm3Thionyl chloride solution, in 0 DEG C of ice bath, join step (1) instituteObtain in solution, after sufficient reacting, add material and 0.05 part of catalyst three second of 1.5 parts of chalcone photosensitive groups that contain carbonylAmine, reaction obtains the polyamic acid solution of light sensitivity;
(3), under 50 DEG C of conditions, 1 part of triethylamine and 1 part of acetic anhydride are joined to the polyamic acid solution of step (2) gainedIn, fully after reaction, obtain photo-sensistive polyimide solution;
(4) product that step (3) obtained is repeated multiple times in methyl alcohol or water to be precipitated, filter, washs, and finally existsIn the vacuum drying oven of 60 DEG C, be dried and obtain target product.
Organic solvent be DMF, DMA, methyl-sulfoxide, dichloroethanes, N-methyl-One in pyrrolidones.
The described reacted product of tetracarboxylic dianhydride of step (1) is
Ar refers to Ar1Or Ar2Or Ar3。
A kind of negative photosensitive polyimide provided by the invention, adopting is principal monomer with the tetracarboxylic dianhydride of carbonyl,With after diamine reactant, obtain polyamic acid solution, further on side chain introduce contain carbonyl photosensitive group, therefore increase greatlyAdd dissolubility, and effectively improved current used self-sensitizing type PSPI and have the poor weakness of speed, this negativityLight-sensitive polyimide is a kind of PSPI material of half imidization, and can be by the molecular weight of mole recently controlling of feed changeSize, there is highly sensitive light-sensitive polyimide material so this and will be widely used in optoelectronics industry, microelectronicsIndustry, the fields such as Aero-Space.
Detailed description of the invention
Specific implementation process of the present invention is described in conjunction with the embodiments.
Embodiment 1
By 3 of 0.0025mol, 3,3 ', 4 of 5-diaminobenzoic acid DABA and 0.00375mol, 4 '-benzophenone tetracid twoAcid anhydride BPDA is dissolved in 0.2mol dimethylacetamide solution, mechanical agitation, and react 8h under nitrogen atmosphere, and then add0.0025mol p-aminobenzoic acid continues to react with this understanding 16h and obtains polyamic acid solution. By solution in 0 DEG C of ice bathAdd 0.005mol thionyl chloride, reaction adds 0.005mol 4-hydroxy chalcone and 0.005mol triethylamine after 3h, 2h itAfter solution is warmed up to 50 DEG C of left and right, and 0.0025mol triethylamine and 0.0025mol acetic anhydride are joined in reaction system,Product repeated multiple times precipitation the in methyl alcohol or water obtaining after reaction 6h, filters, and washing, finally in vacuum drying ovenAt 60 DEG C, be dried and obtain the negative photosensitive polyimide that contains chalcone photosensitive group.
Embodiment 2
By 3 of 0.0025mol, 3,3 of 5-diaminobenzoic acid and 0.00175mol ', 4,4 '-biphenyl tetracarboxylic dianhydride and3,3 ', 4,4 of 0.002mol ,-benzophenone tetracarboxylic dianhydride BTDA is dissolved in 0.2mol dimethylacetamide solution, mechanical agitation,And react 8h under nitrogen atmosphere, and then add 0.0025mol p-aminobenzoic acid to continue to react with this understanding 16h and obtainPolyamic acid solution. Solution is added to 0.005mol thionyl chloride in 0 DEG C of ice bath, after reaction 3h, add 0.005mol 4-Hydroxy chalcone and 0.005mol triethylamine, be warmed up to 50 DEG C of left and right by solution after 2h, and by 0.0025mol triethylamine and0.0025mol acetic anhydride joins in reaction system, the product that reaction obtains after 6h in methyl alcohol or water repeated multiple times enterRow precipitation, filters, and washing is finally dried at 60 DEG C and obtains the negativity light that contains chalcone photosensitive group in vacuum drying ovenQuick polyimides.
Claims (4)
1. a negative photosensitive polyimide, is characterized in that: chemical constitution is
Wherein, Ar1Structural formula is:
Ar2Structural formula is the one in following structural formula:
Ar3With Ar1Or Ar2Identical;
R is the one in following structural formula:
2. a kind of negative photosensitive polyimide according to claim 1, is characterized in that: the system of negative photosensitive polyimidePreparation Method comprises the following steps:
Each material is according to mole part proportioning;
(1) diamines of 1 part is dissolved in the organic solvent of 5-20 part, after mechanical agitation is dissolved, adds the tetrabasic carboxylic acid two of 1.5 partsAcid anhydride fully reacts under normal temperature and pressure nitrogen atmosphere, then adds 1 part of p-aminobenzoic acid, fully after reaction, obtains holding carboxylicThe polyamic acid solution of base;
(2) taking 2 parts of concentration is 0.0138g/cm3Thionyl chloride solution, in 0 DEG C of ice bath, join step (1) gained solutionIn, after sufficient reacting, add material and 0.05 part of catalyst of triethylamine of 1.5 parts of chalcone photosensitive groups that contain carbonyl, reactionObtain the polyamic acid solution of light sensitivity;
(3) under 50 DEG C of conditions, 1 part of triethylamine and 1 part of acetic anhydride are joined in the polyamic acid solution of step (2) gained,Fully after reaction, obtain photo-sensistive polyimide solution;
(4) product that step (3) obtained is repeated multiple times in methyl alcohol or water to be precipitated, filter, washs, finally at 60 DEG CVacuum drying oven in be dried and obtain target product.
3. a kind of negative photosensitive polyimide according to claim 2, is characterized in that: organic molten described in step 1Agent is one in DMF, DMA, methyl-sulfoxide, dichloroethanes, N-methyl-pyrrolidonesKind.
4. a kind of negative photosensitive polyimide according to claim 2, is characterized in that: the tetrabasic carboxylic acid that step (1) is describedThe reacted product of dianhydride is
Ar refers to Ar1Or Ar2Or Ar3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410756196.7A CN104371102B (en) | 2014-12-11 | 2014-12-11 | Negative photo-sensitive polyimide and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410756196.7A CN104371102B (en) | 2014-12-11 | 2014-12-11 | Negative photo-sensitive polyimide and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104371102A CN104371102A (en) | 2015-02-25 |
| CN104371102B true CN104371102B (en) | 2017-01-18 |
Family
ID=52550313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410756196.7A Active CN104371102B (en) | 2014-12-11 | 2014-12-11 | Negative photo-sensitive polyimide and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104371102B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109814336B (en) * | 2019-01-21 | 2022-05-17 | 深圳市道尔顿电子材料有限公司 | Alkali-soluble negative photosensitive polyimide resin composition |
| CN110804181B (en) * | 2019-11-06 | 2021-04-20 | 中山大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
| CN111041589B (en) * | 2019-12-03 | 2021-06-29 | 东华大学 | Preparation method of polyimide aerogel fiber |
| CN113388107A (en) * | 2021-06-09 | 2021-09-14 | 广东工业大学 | Photosensitive polyimide resin, polyimide photocuring coating and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195001C (en) * | 2002-10-31 | 2005-03-30 | 上海交通大学 | Negative superbranched polyimide photosensitive material and its preparation method |
| KR100548625B1 (en) * | 2003-03-24 | 2006-01-31 | 주식회사 엘지화학 | High heat resistant transparent polyimide precursor and photosensitive resin composition using same |
| WO2005116770A1 (en) * | 2004-05-31 | 2005-12-08 | Toyo Boseki Kabushiki Kaisha | Photosensitive polyimide precursor composition |
| CN1320032C (en) * | 2005-11-17 | 2007-06-06 | 上海交通大学 | Negative polyimide photosensitive material and preparation process thereof |
| JP4386454B2 (en) * | 2006-08-22 | 2009-12-16 | 信越化学工業株式会社 | Photosensitive polyimide resin soluble in alkaline aqueous solution, composition containing the resin, and film obtained from the composition |
| CN101555318B (en) * | 2009-05-22 | 2011-08-10 | 北京化工大学 | Water-soluble negative light-sensitive polyamic acid salt as well as a preparation method and a developing method thereof |
-
2014
- 2014-12-11 CN CN201410756196.7A patent/CN104371102B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104371102A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104371102B (en) | Negative photo-sensitive polyimide and method for preparing same | |
| CN109734908B (en) | Polyamide acid and preparation method thereof, polyimide and preparation method of polyimide film | |
| CN105566630B (en) | A kind of Kapton and preparation method thereof | |
| CN102604091A (en) | Polyimide containing benzimidazole unit and preparation method thereof | |
| CN106810692B (en) | Preparation method of polyamic acid solution and polyimide film | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| CN112321827A (en) | Application of compound as polyimide curing accelerator, polyimide precursor and preparation method and application thereof | |
| JP2006249166A (en) | Manufacturing process of aromatic polyimide | |
| WO2024060583A1 (en) | Polyester imide copolymer, preparation method therefor, and use thereof | |
| CN113583443A (en) | Transparent polyimide applied to flexible photoelectric field and preparation method thereof | |
| CN114591503A (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
| CN108586740B (en) | Polyimide containing fluorene or fluorenone structure and preparation method and application thereof | |
| CN101775138B (en) | Novel polytriazoles imide resin and preparation method thereof | |
| CN111234225B (en) | Thermoplastic polyimide resin with low thermal expansion coefficient and preparation method thereof | |
| CN115716914B (en) | Imidization method of polyamide acid and polyimide | |
| CN110713598A (en) | Preparation method of soluble low-temperature imidized polyimide | |
| TW201815891A (en) | Method for preparing adamantane-containing polyimide having properties such as low dielectric constant, high glass transition temperature (Tg) and good processability | |
| CN115286793A (en) | Polyimide resin composition and preparation method and application thereof | |
| CN114797506B (en) | Preparation method and application of ionized polyimide gas separation membrane | |
| CN115715939A (en) | Polyimide mixed matrix membrane and preparation method and application thereof | |
| CN114685786B (en) | Polyimide film and preparation method and application thereof | |
| JP2903704B2 (en) | Manufacturing method of aromatic polyimide film | |
| JPH04198229A (en) | Production of aromatic polyimide film | |
| CN111234218B (en) | Preparation method of soluble polyimide containing amino phenylsulfonyl hexafluoropropane structure | |
| JP2007016182A (en) | Method for producing polyimide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |