CN103554494A - Preparation method of ionic type negative photosensitive polyimide material - Google Patents
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- CN103554494A CN103554494A CN201310503208.0A CN201310503208A CN103554494A CN 103554494 A CN103554494 A CN 103554494A CN 201310503208 A CN201310503208 A CN 201310503208A CN 103554494 A CN103554494 A CN 103554494A
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Abstract
The invention relates to a preparation method of an ionic type negative photosensitive polyimide material. The preparation method comprises the following steps: a) dissolving aromatic diamine into a proper amount of organic solvent; after the aromatic diamine is completely dissolved, adding aromatic tetradianhydride in a solid suspension polymerization mode; and mechanically stirring, and reacting at room temperature to obtain a polyamide acid solution, wherein the substance amount ratio of the aromatic diamine to the aromatic tetradianhydride is 1:1.04-1:1.06; and b) in a light-shielded condition, adding photosensitive tertiary-amine small molecules into the obtained polyamide acid solution. mechanically stirring and reacting at room temperature to obtain an ionic type negative photosensitive polyamide glue solution, wherein the substance amount ratio of the photosensitive tertiary-amine small molecules to the aromatic diamine in the step a) is 2.1:1, and in the reaction process of the step a) and step b), a proper amount of organic solvent is added to ensure that the solid content of the system is 10-20%. The reaction steps of the preparation method are simple, the yield is high and close to 100%, the production process is highly controllable, and the preparation method is suitable for industrialization.
Description
Technical field
The present invention relates to polyimide material, specifically, relate to a kind of preparation method of ionic negative photosensitive polyimide material.
Background technology
Polyimide (polyimide, PI) refers to a base polymer that contains imide ring on main chain, generally by aromatic diamines and fatty dianhydride or aromatic dianhydride polycondensation, is formed.Due to its half trapezoidal and trapezoidal backbone structure, the resonant interaction of aromatic ring, make it there is outstanding thermostability, chemical stability, electrical insulating property and high physical strength, become the high performance material with widespread use.In addition, it also has the adhesivity good with substrate, and the features such as matching good with semiconductor technology, is therefore widely used in the last few years microelectronic, as insulation layer, passivation layer or the stress-buffer layer of microelectronic device.
Light-sensitive polyimide (photosensitive polyimide, PSPI) generally refer to UV-light, X ray, electron beam israds sensitivity, can expose by mask plate, cause the difference of exposure region and non-exposed area solubleness to realize patterning, thereby simplify the function polyimide of complicated complete processing.With the comparison of non-photosensitivity polyimide, the photoetching of light-sensitive polyimide drawing technological process is simpler, is conducive to improve yield rate, reduces production costs.
Preparation method's great majority of existing light-sensitive polyimide adopt the synthetic method of covalent linkage, and its step is quite loaded down with trivial details, and molecular weight is wayward.Some synthesis technique engineering can be introduced chlorion, and to semiconductor technology, application arrives and bothers.Therefore need that a kind of reactions steps is simple, productive rate is high badly, be suitable for the preparation method of industrialization.
Summary of the invention
The object of the invention is, for deficiency of the prior art, provides a kind of preparation method of ionic negative photosensitive polyimide material.
For achieving the above object, the technical scheme that the present invention takes is:
A preparation method for ionic negative photosensitive polyimide material, comprises the following steps:
A) adopt just reinforced method, first add aromatic diamines, add again fragrant four dicarboxylic anhydrides: aromatic diamines is dissolved in appropriate organic solvent, after it dissolves completely, in solid-state suspension polymerization mode, add fragrant four dicarboxylic anhydrides, mechanical stirring, room temperature reaction obtains polyamic acid solution, and wherein said aromatic diamines and fragrant four dicarboxylic anhydride amount of substance ratios are 1:1.04-1:1.06;
B) under lucifuge condition, in step a) gained polyamic acid solution, add photosensitive tertiary amine small molecules, mechanical stirring, room temperature reaction obtains ionic negative photosensitive polyimide glue, and in wherein said photosensitive tertiary amine small molecules and step a), the amount of substance ratio of aromatic diamines is 2.1: 1;
Above-mentioned steps is a) and in the reaction process of step b), the organic solvent that adds appropriate amount with guarantee system solid content between 10%-20%.
Described aromatic diamines is selected from 4,4 '-diaminodiphenyl oxide.
Described fragrance four dicarboxylic anhydrides are selected from 3, and 3 ', 4, the two Tetra hydro Phthalic anhydrides of 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride or 4,4'-oxygen.
Described photosensitive tertiary amine small molecules is selected from methacrylic acid 2-(dimethylamino) ethyl ester or vinylformic acid 2-(dimethylamino) ethyl ester.
Described organic solvent is selected from N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), DMF (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
The reaction times of step a) is 6 ~ 8 hours.
The reaction times of step b) is 3 ~ 5 hours.
Described system solid content is 15%.
Ionic light-sensitive polyimide prepared by the present invention has following chemical structure:
Wherein:
The invention has the advantages that:
1, the present invention be take aromatic tetrahydric dianhydride and aromatic diamines and is carried out polymerization as raw material, obtain the presoma of polyimide---polyamic acid, then add the photosensitive tertiary amines material of small molecules, make photosensitive tertiary amine and polyamic acid main chain form ionic keyed jointing, finally obtain having the functional type polyimide material of negative light-sensitive performance, the method reactions steps is succinct, productive rate is quite high, approach 100%, production process height is controlled, is suitable for industrialization;
2, the present invention is controlled at solid content between 10% to 20% in reaction process, significantly be conducive to the spin coating of glue and be uniformly distributed, solid content is too high or too lowly all can and be uniformly distributed unfavorablely to the spin coating of glue, and being uniformly distributed of glue is the then basis of exposure imaging of front baking;
3, the reinforced method of just feeding in raw material that adopts of the present invention, first adds aromatic diamines and adds fragrant four dicarboxylic anhydrides again, has effectively suppressed the hydrolysis of fragrant four dicarboxylic anhydrides in solvent, is conducive to generate the product that the polymerization degree is higher, makes system viscosity higher;
4, the present invention adopts solid-state suspension polymerization mode to add fragrant four dicarboxylic anhydrides in reaction, reduced the association between fragrant four dicarboxylic anhydrides and solvent, thereby limiting viscosity is higher, be beneficial to and generate the higher product of the polymerization degree, be also convenient to unified operation and scale operation.
Accompanying drawing explanation
Fig. 1 is the synthetic schematic diagram of embodiment 1 ionic negative photosensitive polyimide.
Fig. 2 is the infrared spectra of embodiment 1 polyamic acid PAA and light-sensitive polyamic acid PSPAA.
Fig. 3 is the hot weightless picture of embodiment 1 polyimide.
Fig. 4 is the hot weightless picture of embodiment 1 light-sensitive polyimide.
Fig. 5 is the exposure photograph of embodiment 1 ionic light-sensitive polyimide.
Embodiment
Below in conjunction with accompanying drawing, embodiment provided by the invention is elaborated.
embodiment 1 preparation method of the present invention (one)
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent 1-Methyl-2-Pyrrolidone (NMP), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.087g(0.0105mol accurately weighing) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) joins in there-necked flask in batches, mechanical stirring is reacted 8h, obtains presoma-polyamic acid (polyamide acid, PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of NMP in good time, and keeping solid content is 15%.
Weigh 3.297g(0.021mol) methacrylic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic negative photosensitive polyimide (PSPI) glue in nmp solution, yield is 99.6%.
Above-mentioned synthesis step as shown in Figure 1.
Upper lower curve in Fig. 2 is representing respectively the infrared spectra of PAA and light-sensitive polyamic acid (photosensitive polyamide acid, PSPAA).From spectrogram, can see 1604cm
-1near amido linkage N-H flexural vibration peak, 1406cm
-1near amido linkage C-N stretching vibration peak, the formation of proved-CONH-amido linkage of the existence of above-mentioned vibration absorption peak.Meanwhile, at 1375cm
-1and 723cm
-1near representing that the position of imide ring structure do not find corresponding vibration absorption peak.Above result shows, the present embodiment has successfully been prepared the presoma PAA of PI.In addition, contrast upper and lower two curves, in the infrared spectrogram of PSPAA, can find 1653cm
-1near the C=C stretching vibration peak of alkene structures, 873cm
-1near alkene C-H out-of-plane deformation vibration peak, and in the infrared spectrogram of PAA, do not find corresponding vibration absorption peak.Therefore can obtain, photosensitive pair of key group successfully introduced in this experiment in PI presoma PAA.
In order to weigh the thermostability that whether affects final PI finished product that adds of photosensitive molecular, we are hot imidization PAA and PSPAA under 250 ℃ of high temperature, has then carried out thermal weight loss (TGA) analysis, and result as shown in Figure 3 and Figure 4.Comparison diagram 3 is known with Fig. 4, the introducing of photosensitive group does not have influence on the thermodynamic stability of final finished PI excellence, the PSPI of 250 ℃ of high temperature imidizations and PI finished product do not have quality change below substantially at 500 ℃, 500 ℃ just start thermolysis later, the rate of weight loss of 700 ℃ is also less than 40%, show that Thermodynamically stable performance is excellent, can meet the requirement in microelectronic application.
Photosensitive property is the core capabilities of ionic negativity PSPI.This experiment has been carried out uv-exposure to the ionic negativity PSPI presoma being spin-coated on clean silicon chip, and time shutter 30s then develops in NMP, in ethanol, shapes, after rear baking at optical microphotograph Microscopic observation exposure effect as shown in Figure 5.As can be seen from Figure, ionic negativity PSPI can form clear exposure photograph.
embodiment 2
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent DMF (DMF), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 2.289g(0.0105mol accurately weighing) pyromellitic dianhydride (PMDA) joins in there-necked flask in batches, and mechanical stirring reaction 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMF in good time, and keeping solid content is 15%.
Weigh 3.297g(0.021mol) methacrylic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic negative photosensitive polyimide (PSPI) glue in DMF solution, yield is 99.5%.
The chemical structural formula of PSPI prepared by this embodiment is:
embodiment 3
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent N,N-dimethylacetamide (DMAc), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.255g(0.0105mol accurately weighing) 4, the two Tetra hydro Phthalic anhydrides (ODPA) of 4'-oxygen join in there-necked flask in batches, and mechanical stirring is reacted 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMAc in good time, and keeping solid content is 10%.
Weigh 3.003g(0.021mol) vinylformic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic light-sensitive polyimide (PSPI) glue in DMAc solution, yield is 99.4%.
The chemical structural formula of PSPI prepared by this embodiment is:
embodiment 4
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent dimethyl sulfoxide (DMSO) (DMSO), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.087g(0.0105mol accurately weighing) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) joins in there-necked flask in batches, and mechanical stirring is reacted 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMSO in good time, and keeping solid content is 20%.
Weigh 3.297g(0.021mol) methacrylic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic negative photosensitive polyimide (PSPI) glue in DMSO solution, yield is 99.2%.
The chemical structural formula of PSPI prepared by this embodiment is:
It should be noted that, the product that the present invention is prepared above-described embodiment 2-4 detects.Through infrared spectra, detect, show all successfully to have prepared the presoma PAA of polyimide, then in polyimide precursor PAA, successfully introduced again photosensitive pair of key group.By thermogravimetic analysis (TGA), result confirms that the introducing of photosensitive group does not have influence on the thermodynamic stability of final finished polyimide excellence, the light-sensitive polyimide of 250 ℃ of high temperature imidizations and polyimide finished product do not have quality change below substantially at 500 ℃, 500 ℃ just start thermolysis later, and the rate of weight loss of 700 ℃ is also less than 40%.By uv-exposure, test and confirm that prepared ionic negative photosensitive polyimide can form clear exposure photograph.
embodiment 5
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent DMF (DMF), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 2.267g(0.0104mol accurately weighing) pyromellitic dianhydride (PMDA) joins in there-necked flask in batches, and mechanical stirring reaction 6h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMF in good time, and keeping solid content is 15%.
Weigh 3.266g(0.0208mol) methacrylic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic negative photosensitive polyimide (PSPI) glue in DMF solution, yield is 98.2%.
The chemical structural formula of PSPI prepared by this embodiment is:
embodiment 6
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent N,N-dimethylacetamide (DMAc), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.286g(0.0106mol accurately weighing) 4, the two Tetra hydro Phthalic anhydrides (ODPA) of 4'-oxygen join in there-necked flask in batches, and mechanical stirring is reacted 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMAc in good time, and keeping solid content is 10%.
Weigh 3.004g(0.0212mol) vinylformic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 3 hours, must be dissolved in ionic light-sensitive polyimide (PSPI) glue in DMAc solution, yield is 97.8%.
The chemical structural formula of PSPI prepared by this embodiment is:
comparative example 1
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent N,N-dimethylacetamide (DMAc), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.255g(0.0105mol accurately weighing) 4, the two Tetra hydro Phthalic anhydrides (ODPA) of 4'-oxygen join in there-necked flask in batches, and mechanical stirring is reacted 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMAc in good time, and keeping solid content is 9%.
Weigh 3.003g(0.021mol) vinylformic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic light-sensitive polyimide (PSPI) glue in DMAc solution, yield is 95.1%.
The chemical structural formula of PSPI prepared by this embodiment is:
The key technical index such as exposure photograph sharpness of testing prepared its spin-coating planeness of ionic negative photosensitive polyimide of confirmation comparative example 1, formation by uv-exposure are significantly lower than the prepared ionic negative photosensitive polyimide of embodiment 3.
comparative example 2
Under room temperature, in the there-necked flask of 250mL, add a certain amount of solvent dimethyl sulfoxide (DMSO) (DMSO), pass into nitrogen half hour, remove oxygen in flask.Adopt positive charging process, accurately weigh 2g(0.01mol) 4,4 '-diaminodiphenyl oxide (ODA) adds there-necked flask, stirs 20 minutes to dissolving completely.Then by the 3.087g(0.0105mol accurately weighing) 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) joins in there-necked flask in batches, and mechanical stirring is reacted 8h, obtains presoma-polyamic acid (PAA) solution of polyimide (PI).Whole preparation process adds a certain amount of DMSO in good time, and keeping solid content is 21%.
Weigh 3.297g(0.021mol) methacrylic acid 2-(dimethylamino) ethyl ester, under lucifuge condition, join in the PAA solution of faint yellow thickness, continue mechanical stirring reaction 5 hours, must be dissolved in ionic negative photosensitive polyimide (PSPI) glue in DMSO solution, yield is 96.3%.
The chemical structural formula of PSPI prepared by this embodiment is:
。
The key technical index such as its sharpness of exposure photograph of testing prepared its spin-coating planeness of ionic negative photosensitive polyimide of confirmation comparative example 2, formation by uv-exposure are significantly lower than the prepared ionic negative photosensitive polyimide of embodiment 4.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the inventive method; can also make some improvement and supplement, these improvement and supplement and also should be considered as protection scope of the present invention.
Claims (8)
1. a preparation method for ionic negative photosensitive polyimide material, is characterized in that, comprises the following steps:
A) aromatic diamines is dissolved in appropriate organic solvent, after it dissolves completely, in solid-state suspension polymerization mode, add fragrant four dicarboxylic anhydrides, mechanical stirring, room temperature reaction obtains polyamic acid solution, and wherein said aromatic diamines and fragrant four dicarboxylic anhydride amount of substance ratios are 1:1.04-1:1.06;
B) under lucifuge condition, in step a) gained polyamic acid solution, add photosensitive tertiary amine small molecules, mechanical stirring, room temperature reaction obtains ionic negative photosensitive polyimide glue, and in wherein said photosensitive tertiary amine small molecules and step a), the amount of substance ratio of aromatic diamines is 2.1: 1;
Above-mentioned steps is a) and in the reaction process of step b), the organic solvent that adds appropriate amount with guarantee system solid content between 10%-20%.
2. preparation method according to claim 1, is characterized in that, described aromatic diamines is selected from 4,4 '-diaminodiphenyl oxide.
3. preparation method according to claim 1, is characterized in that, described fragrance four dicarboxylic anhydrides are selected from 3,3 ', 4, and the two Tetra hydro Phthalic anhydrides of 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride or 4,4'-oxygen.
4. preparation method according to claim 1, is characterized in that, described photosensitive tertiary amine small molecules is selected from methacrylic acid 2-(dimethylamino) ethyl ester or vinylformic acid 2-(dimethylamino) ethyl ester.
5. preparation method according to claim 1, is characterized in that, described organic solvent is selected from N-Methyl pyrrolidone, N,N-dimethylacetamide, DMF or dimethyl sulfoxide (DMSO).
6. preparation method according to claim 1, is characterized in that, the reaction times of step a) is 6 ~ 8 hours.
7. preparation method according to claim 1, is characterized in that, the reaction times of step b) is 3 ~ 5 hours.
8. preparation method according to claim 1, is characterized in that, described system solid content is 15%.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105693625A (en) * | 2016-03-30 | 2016-06-22 | 倚顿新材料(苏州)有限公司 | Method for preparing polyimide polymer with azo-pyrimidine structure unit |
CN111995750A (en) * | 2020-07-14 | 2020-11-27 | 广东工业大学 | Photosensitive polyimide composite material and preparation method thereof |
CN117092884A (en) * | 2023-08-24 | 2023-11-21 | 广东工业大学 | Ion type photosensitive polyimide photoresist composition and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451551A (en) * | 1980-12-17 | 1984-05-29 | Hitachi, Ltd. | Radiation-sensitive poly(amic acid) polymer composition |
-
2013
- 2013-10-24 CN CN201310503208.0A patent/CN103554494A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451551A (en) * | 1980-12-17 | 1984-05-29 | Hitachi, Ltd. | Radiation-sensitive poly(amic acid) polymer composition |
Non-Patent Citations (3)
Title |
---|
TAKAFUMI FUKUSHIMA,ET AL.: "Ionic-bonded negative photosensitive polyimides having pendant aminoalkyl(meth)acrylamide groups", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
匡敏: "光敏聚酰亚胺的合成与表征", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
魏小尉: "水溶性负性光敏聚酰亚胺的制备", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105693625A (en) * | 2016-03-30 | 2016-06-22 | 倚顿新材料(苏州)有限公司 | Method for preparing polyimide polymer with azo-pyrimidine structure unit |
CN105693625B (en) * | 2016-03-30 | 2018-04-24 | 倚顿新材料(苏州)有限公司 | A kind of preparation method of the polyimide polymer with azapyrimidines construction unit |
CN111995750A (en) * | 2020-07-14 | 2020-11-27 | 广东工业大学 | Photosensitive polyimide composite material and preparation method thereof |
CN111995750B (en) * | 2020-07-14 | 2021-07-27 | 广东工业大学 | Photosensitive polyimide composite material and preparation method thereof |
WO2022012074A1 (en) * | 2020-07-14 | 2022-01-20 | 广东工业大学 | Photosensitive polyimide composite material and preparation method therefor |
CN117092884A (en) * | 2023-08-24 | 2023-11-21 | 广东工业大学 | Ion type photosensitive polyimide photoresist composition and preparation method and application thereof |
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