CN104371102A - Negative photo-sensitive polyimide and method for preparing same - Google Patents
Negative photo-sensitive polyimide and method for preparing same Download PDFInfo
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- CN104371102A CN104371102A CN201410756196.7A CN201410756196A CN104371102A CN 104371102 A CN104371102 A CN 104371102A CN 201410756196 A CN201410756196 A CN 201410756196A CN 104371102 A CN104371102 A CN 104371102A
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- photosensitive polyimide
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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 method thereof.
Background technology
Along with the fast development of macromolecular material, polyimide (PI) material is especially dazzling at polymeric material field as the material that over-all properties is very excellent.Because polyimide resin has outstanding resistance to elevated temperatures, dielectric properties and excellent radiation resistance, therefore, it obtains applying more and more widely as functional materials in microelectronics industry, but because common polyimide does not have photosensitive property, when making it use as membranaceous figure in microelectronic device, must use other photosensitive materials simultaneously, thus make whole photoetching process extremely complicated, efficiency is very low.For this reason, light-sensitive polyimide (PSPI) material is subject to the great attention of people.Domestic once someone synthesized a kind of hyperbranched from sensitizing polyimide light-sensitive material, but photosensitivity is lower.Therefore, the research and development of better photosensitivity polyimide 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 a kind of negative photosensitive polyimide through chemical imidization.Concrete technical scheme is:
A kind of negative photosensitive polyimide, chemical structure is
Wherein, Ar
1for the acid anhydrides containing carbonyl;
Ar
2for the acid anhydrides not containing carbonyl;
Ar
3with Ar
1or Ar
2identical;
R is the phenyl styryl ketone photosensitive group containing carbonyl.
Described Ar
1be 3,3,4,4-benzophenone tetracarboxylic dianhydride, structural formula is
Described Ar
2for
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 molar weight part proportioning;
(1) diamines of 1 part is dissolved in the organic solvent of 5-20 part, mechanical stirring adds the tetracarboxylic dianhydride of 1.5 parts, fully reacts under normal temperature and pressure nitrogen atmosphere after dissolving, add 1 part of para-amino benzoic acid again, fully after reaction, obtain the polyamic acid solution of end carboxyl;
(2) 0.0138g/cm that 2 parts of concentration are is taken
3sulfur oxychloride solution, joins in step (1) gained solution in 0 DEG C of ice bath, adds phenyl styryl ketone photosensitive group and 2 parts of catalyst of triethylamine that 2 parts contain carbonyl, be obtained by reacting the polyamic acid solution of photosensitivity after sufficient reacting;
(3) under 50 DEG C of conditions, 1 part of triethylamine and 1 part of diacetyl oxide are joined in the polyamic acid solution of step (2) gained, fully obtain photo-sensistive polyimide solution after reaction;
(4) product step (3) obtained is repeated multiple times in methyl alcohol or water to carry out precipitating, filter, wash, and in the vacuum drying oven of 60 DEG C, finally carries out drying obtain target product.
Organic solvent is the one in DMF, N,N-dimethylacetamide, methyl-sulphoxide, ethylene dichloride, N-methyl-pyrrolidon.
Tetracarboxylic dianhydride described in step (1) is
Ar refers to Ar
1or Ar
2or Ar
3.
A kind of negative photosensitive polyimide provided by the invention, the tetracarboxylic dianhydride with carbonyl is adopted to be principal monomer, polyamic acid solution is obtained with after diamine reactant, the photosensitive group containing carbonyl is introduced further on side chain, therefore solvability is considerably increased, and effectively improve the weakness that the self-sensitizing type PSPI used at present exists light sensitivity difference, this negative photosensitive polyimide is a kind of PSPI material of half imidization, and the size of molecular weight can be controlled by the mol ratio of feed change, there is so this highly sensitive light-sensitive polyimide material and will be widely used in optoelectronics industry, microelectronics industry, the fields such as aerospace.
Embodiment
Specific implementation process of the present invention is described in conjunction with the embodiments.
Embodiment 1
By 3 of 0.0025mol, 3 of 5-diaminobenzoic acid DABA and 0.00375mol, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride BPDA is dissolved in 0.2mol dimethylacetamide solution, mechanical stirring, and react 8h under nitrogen atmosphere, and then add 0.0025mol para-amino benzoic acid and continue to react 16h with this understanding and obtain polyamic acid solution.Solution is added 0.005mol sulfur oxychloride in 0 DEG C of ice bath, 0.005mol 4-hydroxy-benzalacetophenone and 0.005mol triethylamine is added after reaction 3h, after 2h by solution warms to about 50 DEG C, and 0.0025mol triethylamine and 0.0025mol diacetyl oxide are joined in reaction system, the product obtained after reaction 6h is repeated multiple times in methyl alcohol or water to be precipitated, filter, washing, finally carries out the negative photosensitive polyimide that drying obtains containing phenyl styryl ketone photosensitive group in vacuum drying oven at 60 DEG C.
Embodiment 2
By 3 of 0.0025mol, 3,3', 4 of 5-diaminobenzoic acid and 0.00175mol, 3 of 4'-biphenyl tetracarboxylic dianhydride and 0.002mol, 3 ', 4,4,-benzophenone tetracarboxylic dianhydride BTDA is dissolved in 0.2mol dimethylacetamide solution, mechanical stirring, and react 8h under nitrogen atmosphere, and then add 0.0025mol para-amino benzoic acid and continue to react 16h with this understanding and obtain polyamic acid solution.Solution is added 0.005mol sulfur oxychloride in 0 DEG C of ice bath, 0.005mol4-hydroxy-benzalacetophenone and 0.005mol triethylamine is added after reaction 3h, after 2h by solution warms to about 50 DEG C, and 0.0025mol triethylamine and 0.0025mol diacetyl oxide are joined in reaction system, the product obtained after reaction 6h is repeated multiple times in methyl alcohol or water to be precipitated, filter, washing, finally carries out the negative photosensitive polyimide that drying obtains containing phenyl styryl ketone photosensitive group in vacuum drying oven at 60 DEG C.
Claims (7)
1. a negative photosensitive polyimide, is characterized in that: chemical structure is
Wherein, Ar
1for the acid anhydrides containing carbonyl;
Ar
2for the acid anhydrides not containing carbonyl;
Ar
3with Ar
1or Ar
2identical;
R is the phenyl styryl ketone photosensitive group containing carbonyl.
2. a kind of negative photosensitive polyimide according to claim 1, is characterized in that: described Ar
1be 3,3,4,4-benzophenone tetracarboxylic dianhydride, structural formula is
3. a kind of negative photosensitive polyimide according to claim 1, is characterized in that: described Ar
2for
One or several in above acid anhydrides.
4. a kind of negative photosensitive polyimide according to claim 1, is characterized in that: described R is
5. a kind of negative photosensitive polyimide according to any one of claim 1 to 4, is characterized in that: the preparation method of negative photosensitive polyimide comprises the following steps:
Each material is according to molar weight part proportioning;
(1) diamines of 1 part is dissolved in the organic solvent of 5-20 part, mechanical stirring adds the tetracarboxylic dianhydride of 1.5 parts, fully reacts under normal temperature and pressure nitrogen atmosphere after dissolving, add 1 part of para-amino benzoic acid again, fully after reaction, obtain the polyamic acid solution of end carboxyl;
(2) 0.0138g/cm that 2 parts of concentration are is taken
3sulfur oxychloride solution, joins in step (1) gained solution in 0 DEG C of ice bath, adds phenyl styryl ketone photosensitive group and 0.05 part of catalyst of triethylamine that 1.5 parts contain carbonyl, be obtained by reacting the polyamic acid solution of photosensitivity after sufficient reacting;
(3) under 50 DEG C of conditions, 1 part of triethylamine and 1 part of diacetyl oxide are joined in the polyamic acid solution of step (2) gained, fully obtain photo-sensistive polyimide solution after reaction;
(4) product step (3) obtained is repeated multiple times in methyl alcohol or water to carry out precipitating, filter, wash, and in the vacuum drying oven of 60 DEG C, finally carries out drying obtain target product.
6. a kind of negative photosensitive polyimide according to claim 5, is characterized in that: the organic solvent described in step 1 is the one in DMF, N,N-dimethylacetamide, methyl-sulphoxide, ethylene dichloride, N-methyl-pyrrolidon.
7. a kind of negative photosensitive polyimide according to claim 5, is characterized in that: the tetracarboxylic dianhydride described in step (1) is
Ar refers to Ar
1or Ar
2or Ar
3.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109814336A (en) * | 2019-01-21 | 2019-05-28 | 深圳市道尔顿电子材料有限公司 | Alkali soluble negative photosensitive polyimide resin combination |
CN110804181A (en) * | 2019-11-06 | 2020-02-18 | 中山大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
CN111041589A (en) * | 2019-12-03 | 2020-04-21 | 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 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1405208A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Negative superbranched polyimide photosensitive material and its preparation method |
WO2005116770A1 (en) * | 2004-05-31 | 2005-12-08 | Toyo Boseki Kabushiki Kaisha | Photosensitive polyimide precursor composition |
CN1793200A (en) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | Negative polyimide photosensitive material and preparation process thereof |
US20080057446A1 (en) * | 2006-08-22 | 2008-03-06 | Shin-Etsu Chemical Co., Ltd. | Polyimide resin soluble in aqueous alkaline solution, composition comprising the resin and cured coating prepared from the composition |
CN101555318A (en) * | 2009-05-22 | 2009-10-14 | 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 |
CN100590528C (en) * | 2003-03-24 | 2010-02-17 | Lg化学株式会社 | Transparent, highly heat-resistant polyimide precursor and photosensitive polyimide composition thereof |
-
2014
- 2014-12-11 CN CN201410756196.7A patent/CN104371102B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1405208A (en) * | 2002-10-31 | 2003-03-26 | 上海交通大学 | Negative superbranched polyimide photosensitive material and its preparation method |
CN100590528C (en) * | 2003-03-24 | 2010-02-17 | Lg化学株式会社 | Transparent, highly heat-resistant polyimide precursor and photosensitive polyimide composition thereof |
WO2005116770A1 (en) * | 2004-05-31 | 2005-12-08 | Toyo Boseki Kabushiki Kaisha | Photosensitive polyimide precursor composition |
CN1793200A (en) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | Negative polyimide photosensitive material and preparation process thereof |
US20080057446A1 (en) * | 2006-08-22 | 2008-03-06 | Shin-Etsu Chemical Co., Ltd. | Polyimide resin soluble in aqueous alkaline solution, composition comprising the resin and cured coating prepared from the composition |
CN101555318A (en) * | 2009-05-22 | 2009-10-14 | 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 |
Non-Patent Citations (4)
Title |
---|
K.FENG ET AL: ""Synthesis and Properties of Novel Photosensitive Polyimides Containing Chalcone Moiety in the Main Chain"", 《JOURNAL OF POLYMER SCIENCE PART A:POLYMER CHEMISTRY》 * |
WEIWEI TIE ET AL: ""Synthesis and characterization of novel photosensitive polysulfones with photocrosslinkable side pendants"", 《EUROPEAN POLYMER JOURNAL》 * |
吕兴军 等: ""负性光敏聚酰亚胺的研究进展"", 《化工技术与开发》 * |
李加深 等: ""自增感光敏聚酰亚胺的热失重及光固化研究"", 《河北工业大学学报》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109814336A (en) * | 2019-01-21 | 2019-05-28 | 深圳市道尔顿电子材料有限公司 | Alkali soluble negative photosensitive polyimide resin combination |
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 |
CN110804181A (en) * | 2019-11-06 | 2020-02-18 | 中山大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
CN110804181B (en) * | 2019-11-06 | 2021-04-20 | 中山大学 | Transparent photosensitive polyimide resin, polyimide film and preparation method thereof |
CN111041589A (en) * | 2019-12-03 | 2020-04-21 | 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 |
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