CN1074032C - Polyamide acid paint and its preparation and application - Google Patents
Polyamide acid paint and its preparation and application Download PDFInfo
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- CN1074032C CN1074032C CN98100003A CN98100003A CN1074032C CN 1074032 C CN1074032 C CN 1074032C CN 98100003 A CN98100003 A CN 98100003A CN 98100003 A CN98100003 A CN 98100003A CN 1074032 C CN1074032 C CN 1074032C
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- aromatic diamine
- polyamide acid
- acid paint
- tetracarboxylic dianhydride
- diamine
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Abstract
The present invention discloses polyimide glue for inner coatings, which relates to a polyimide film. The polyimide glue for inner coatings comprises 85 to 95 of organic solvent, 5.0 to 10 of aromatic diamine mixture, 1.0 to 6.0 of aromatic diamine mixture and 0.01 to 2.0 of molecular weight regulator of organosilicon and thickening agent. Being a uniform and transparent liquid and having good storage stability, the polyimide glue for inner coatings can be coated on the surface of single crystal silicon, SiO2, Al or Ni, etc., and after heat curing, can form buffering type inner coating films of microelectronic devices, protection passive films of chips, interconnected layer insulating films of multilayer metal, etc.
Description
The present invention relates to a kind of polyamide acid paint and preparation method thereof.
High purity high-performance polyimide material is a class contains the imide functional group in the chemical molecular chain structure a organic polymer material, have excellent heat-resisting, radiation hardness, anti-α-ray, moisture-resistant tide, resist chemical performance, superior dielectric properties and mechanics mechanical property can be widely used in the manufacturing of microelectronic device and large-scale integrated circuit.
The performance of polyimide material can be regulated from molecular level according to specific application demand, thereby can be satisfied with the application of many various objectives.
Nineteen eighty-two, people such as G.C.Davis (Polyimide siloxane:Properties and characterization forthin film electronic applications In:K.L.Mittal ed.Polyimide:synthesis, characterizationand applications, Vol.2, Plenum press, New York and London, 1982,847-869) reported by 4,4 '-diaminodiphenylmethane and two-(γ aminopropyl)-tetramethyl-silica alkane and 3,3 ', 4, the siliceous polyimide material of 4 '-benzophenone tetracarboxylic dianhydride prepared in reaction in polar solvent and the application in electronic industry thereof.U.S. M﹠amp; T chemical company
2(U.S.Pat.4,139,547) disclose and semiconducting matrix material (as SiO
2, Si etc.) and have a siliceous polyimide forebody coated material of good adhesive property.Because contain the siliceous organic amine of aliphatic chain of higher concentration in this material, its resistance toheat obviously descends, only about 350 ℃ of the heat decomposition temperature of material.1984, and Wang Zongguang etc. (macromolecular material, 1984,4,9-12) reported that heat decomposition temperature reaches 450 ℃ siliceous polyimide material.But there are shortcomings such as room temperature storage poor stability in this class material.1994, (the Jpn Kokai Tokkyo Koho JP 05,222,195 of FDAC chemical company; 06; 37; 459) disclose by 3; 3 ', 4,3 of 4 '-benzophenone tetracarboxylic dianhydride and Fatty Alcohol(C12-C14 and C12-C18) reaction generation; 3 '; 4,4 ' benzophenone, two acid diesters with contain 4, the organic diamine mixture reaction of 4 '-diaminodiphenyl oxide, mphenylenediamine and two-(γ-aminopropyl)-tetramethyl-silica alkane prepares the method for poly amic acid ester and as the application of the interlayer dielectric and the protective membrane of electron device.
It is low that the present invention has overcome in the prior art thermotolerance, the shortcoming of room temperature storage poor stability and a kind of stability, the good polyamide acid paint of thermotolerance are provided.
Another object of the present invention provides above-mentioned interior gummed preparation method and purposes.
Polyamide acid paint of the present invention comprises following compounds and derivative thereof: 1) organic solvent system; 2) aromatic series tetracarboxylic dianhydride; 3) aromatic diamine (1); 4) aromatic diamine (2); 5) the organosilicon molecular weight is transferred
The composition of table 1 polyamide acid paint and compositing range thereof
| Numbering | Component | Content |
| 1 | Organic solvent system | 85-95 |
| 2 | The aromatic series tetracarboxylic dianhydride | 5.0-10 |
| 3 | Aromatic diamine (1) | 0.5-3.0 |
| 4 | Aromatic diamine (2) | 0.5-3.0 |
| 5 | Organosilicon molecular weight regulator and tackifier | 0.01-2.0 |
Above percentage composition sum should equal 100%.
Organic solvent of the present invention means that intensive polar solvent comprises N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide and comprise the mixture system that toluene, phenol, organo-siloxane etc. form by above-mentioned polar solvent and other organic compound.
Aromatic series tetracarboxylic dianhydride of the present invention means the high purity 3,3 ', 4 that adopts special purification process preparation, 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-right-triphen two carbonyl tetracarboxylic dianhydrides, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride etc., its sodium ions content is lower than 1.5ppm, and chloride ion content is lower than 2.5ppm.
Aromatic diamine of the present invention (1) means purified 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminobenzophenone or 4,4 '-diaminodiphenylsulfone(DDS) etc. contain the aromatic series organic diamine that only contains an amino on two or more phenyl ring and each phenyl ring.Aromatic diamine (2) means that purified Ursol D, mphenylenediamine etc. contain the organic diamine that connects two amino on a phenyl ring and this phenyl ring.The sodium ions content of these aminated compoundss is lower than 1.5ppm, and chloride ion content is lower than 2.0ppm.
Organosilicon molecular weight regulator of the present invention and tackifier mean that the silicon-containing organic compound that can regulate the polyamic acid molecular weight and can increase its adhesiveproperties and composition thereof contains at least one amino silicoorganic compound and composition thereof as two-(γ-aminopropyl)-tetramethyl-silica alkane, γ-An Bingjisanyiyangjiguiwan, two-(γ-ammonia butyl)-tetramethyl-silica alkane etc.
Application in semi-conductor of the present invention and the microelectronics industry means in the buffering of microelectronic device and films, the interlayer dielectric layer of protection passive film, alpha particle Protective film and the multiple layer metal interconnection circuit of chip.
Polyamide acid paint of the present invention step in the following order carries out:
Under nitrogen or argon shield, by weight percentage ratio with purified aromatic diamine (I) 0.5-3.0 part and
Under nitrogen or argon shield, percentage ratio is dissolved in purified aromatic diamine (1) 0.5-3.0 part and aromatic diamine (2) 0.5-3.0 part in purified 85-95 part organic solvent system by weight.After treating that solid all dissolves, add 0.01-2.0 part organosilicon molecular weight regulator and tackifier.Under 0-25 ℃, add 5.0-10 part purified aromatic series tetracarboxylic dianhydride in batches.Be reflected under the continuously stirring and continue 6-24 hour, obtain gluing in the transparent even thick liquid.
The fundamental property of table 2 polyamide acid paint
| The name of an article | Polyamide acid paint |
| Outward appearance | Yellow thickness clear solution, |
| Solids content (%) | 5-20 |
| Solvent | The NMP/ hydrocarbon polymer |
| Proportion | 1.04-1.18 |
| The pH value | 4-5 |
| Stability in storage | Room temperature: 5-6 days 0 ℃: the 6-12 month |
| Foreign matter content | Na +:＜5ppm Cl-:＜5ppm Br -:＜4ppm Zn +:＜2ppm |
To adopt appropriate means such as spin-coating method, dip coating or spraying method etc. to be coated in the matrix of cleaning with the polyamide acid paint of the present invention's preparation (as silicon single crystal, SiO
2, Al, Ni etc.) on the surface, adopt following ladder-elevating temperature method to heat up and make polyamide acid paint be solidified into Kapton.The ladder-elevating temperature program is as shown in table 3.
The thermofixation of table 3 polyamic acid changes into the temperature programming table of polyimide
| Temperature (℃) | The constant temperature treatment time (Hrs) |
| 80 | 0.5-4 |
| 120 | 0.5-4 |
| 150 | 0.5-4 |
| 180 | 0.5-4 |
| 220 | 0.5-4 |
| 250 | 0.5-8 |
| 300 | 0.5-8 |
The film even compact, the good toughness that adopt this method to obtain.On the convexo-concave surface, also can obtain continuous, compact protective film.The basic physicals of gained film is as shown in table 4.
The basic physicals of table 3 Kapton
| Tensile strength (MPa) | 80-120 |
| Elongation (%) | 8-40 |
| Second-order transition temperature (℃) | 260-300 |
| Initial weightless temperature (℃) | 460-500 |
| 5% weightless temperature (℃) | 500-540 |
| 10% weightless temperature (℃) | 540-560 |
| Specific inductivity | 3.0-3.4 |
| Tangent of the dielectric loss angle | 0.002-0.01 |
| Dielectric strength (v/ μ m) | 140-200 |
| Volume specific resistance (Ω cm) | 1-5 * 10 15-16 |
| Surface resistivity (Ω) | 1-5 * 10 15-16 |
| Water-intake rate, wt.% | 1.5-2.8 |
| With SiO 2Covering property | Can not peel smoothly, peelable at 120 ℃, the little fashion of 2 normal atmosphere boiling 6-10. |
| Chemical stability | Anti-following organic solvent acetate, acetone, tetracol phenixin, methylphenol, ethyl acetate, ethanol, methyl alcohol, first are stupid, normal hexane, dimethylbenzene etc. |
The present invention discloses a class and has good shelf-stability and easy preceding preparation method and the application in semi-conductor and microelectronics industry of making body-polyamide acid paint of polyimide of covering property, preparation and use technology.
The present invention is open to prepare the method for the polyamide acid paint that molecular weight is controlled, covering property is good and the application in microelectronics industry thereof by aromatic series tetracarboxylic dianhydride and the mixture direct reaction that contains aromatic diamine (1), aromatic diamine (2) and a small amount of organosilicon molecular weight regulator and tackifier.Present method preparation technology is simple, production cost is low; Interior gummed stability in storage is good, is easy to that transportation stores, is difficult for deliquescence, curing process is easy, easy to operate;
Gluing and silicon single crystal, SiO in being somebody's turn to do
2, metallic surface such as aluminium, nickel wetting property good, cover excellent property; it is good to solidify Kapton even compact, mechanics mechanical property, dielectric properties and insulating property that the back forms, is suitable for filming in the buffering as microelectronic device, the interlayer dielectric layer of protection passive film, alpha particle Protective film and the multiple layer metal interconnection circuit of chip etc.
Example 1 is with 13.42g4, and 4 '-diaminodiphenyl oxide and 14.66g mphenylenediamine are dissolved in the N-Methyl pyrrolidone of 900g, adds 5.06g pair-(γ-aminopropyl) tetramethyl-silica alkane.Add 65.42g3,3,4,4 '-benzophenone tetracarboxylic dianhydride then in batches.Under the room temperature, stirring reaction 24 hours gets 1 kilogram of light yellow thick liquid, and limiting viscosity is 1.0-1.2.To adopt proper method to be coated in the semiconductor device die of cleaning and the position of required protection with the polyamic acid glue of method for preparing, baking be 30-60 minute under infrared lamp, adopts the ladder-elevating temperature method to solidify then.Can form densification, covering property excellent protection film at protected position.The device of handling through this process is difficult for bursting apart in follow-up plastic packaging process; Components and parts moisture-resistant tide performance behind the plastic packaging is obviously improved, and has very low leakage current and wears performance with well resisting.
Example 2 is with 40.24g4, and 4 '-diaminodiphenyl oxide and 3.66g mphenylenediamine are dissolved in the N-Methyl pyrrolidone of 900g, adds 5.06g pair-(γ-aminopropyl) tetramethyl-silica alkane.Add 85.26g3 then, 3,4,4 '-right-Tricyclic Dicarbonyl tetracarboxylic dianhydride in batches.Under the room temperature, stirring reaction 24 hours gets light yellow thick liquid, and limiting viscosity is 0.8-1.2.On the monocrystalline silicon surface of cleaning, adopt appropriate means to apply one deck glue, adopt above-mentioned ladder-elevating temperature method to make the polyamic acid thermosetting change into Kapton.With reactive ion etching technology or plasma etching technology drawing, obtain having the polyimide passivation layer of required figure then, this passivation layer has and SiO
2And Si
3N
4Similar deactivation function.
Example 3 is with 40.25g3, and 4 '-diaminodiphenyl oxide and 11.0g mphenylenediamine are dissolved in the N-Methyl pyrrolidone of 900g, adds 25.3g pair-(γ-aminopropyl) tetramethyl-silica alkane.Add 98.13g3,3,4,4 '-benzophenone tetracarboxylic dianhydride then in batches.Under the room temperature, stirring reaction 24 hours gets light yellow thick liquid, and limiting viscosity is 1.2-1.4.On the stromal surface of cleaning, adopt appropriate means to apply the interior gluing of one deck with method for preparing, behind the preliminary drying, resist coating, preliminary drying again.Expose then, after the development, rinsing, adopt alkaline corrosion agent such as tetramethylammonium hydroxide aqueous solution or alcohol/water mixed solution etching polyamic acid layer.Behind the stripping photolithography glue-line, adopt the ladder-elevating temperature method to solidify and obtain having the polyimide film layer of required figure.This above film behind metal line, utilize aforesaid method coating polyimide dielectric layer again.The unicircuit that so can prepare the multiple layer metal interconnect architecture.
Claims (8)
1. polyamide acid paint is characterized in that described polyamide acid paint comprises following component and content (weight percentage):
Component content
Organic solvent 85-95
Aromatic series tetracarboxylic dianhydride 5.0-10
Aromatic diamine (1) 0.5-3.0
Aromatic diamine (2) 0.5-3.0
Organosilicon molecular weight 0.01-2.0
Conditioning agent and adhesion promotor
Above percentage composition sum should equal 100%; Described aromatic diamine (1) is to contain the aromatic series organic diamine that only contains an amino on two or more phenyl ring and each phenyl ring; Aromatic diamine (2) is to contain the organic diamine that connects two amino on a phenyl ring and this phenyl ring; Described organosilicon molecular weight regulator and adhesion promotor are to contain at least one amino silicoorganic compound and composition thereof.
2. a kind of polyamide acid paint according to claim 1, it is characterized in that described organic solvent is: N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, the mixture system that N '-dimethyl formamide or itself and toluene, phenol, methylphenol, ethanol, methyl alcohol are formed.
3. a kind of polyamide acid paint according to claim 1 is characterized in that described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride or 3,3 ', 4,4 '-right-triphen diether tetracarboxylic dianhydride.
4. a kind of polyamide acid paint according to claim 1 is characterized in that described aromatic diamine (1) is 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminobenzophenone or 4,4 '-diaminodiphenylsulfone(DDS).
5. a kind of polyamide acid paint according to claim 1 is characterized in that described aromatic diamine (2) is Ursol D, mphenylenediamine.
6. a kind of polyamide acid paint according to claim 6 is characterized in that described silicoorganic compound are two-(γ-aminopropyl) tetramethyl-silica alkane, γ-An Bingjisanyiyangjiguiwan, two-(γ-ammonia butyl) tetramethyl-silica alkane or its mixture.
7. the preparation method of a kind of polyimide coating glue according to claim 1 is characterized in that following these steps to carrying out:
Under nitrogen or argon shield, percentage ratio is dissolved in purified aromatic diamine (1) 0.5-3.0 part and aromatic diamine (2) 0.5-3.0 part in purified 85-95 part organic solvent system by weight; After treating that solid all dissolves, add 0.01-2.0 part organosilicon molecular weight regulator and adhesion promotor; Under 0-25 ℃, add 5.0-10 part purified aromatic series tetracarboxylic dianhydride in batches; Be reflected under the continuously stirring and continue 6-24 hour, obtain gluing in the transparent even thick liquid.
8. the purposes of a kind of polyimide coating glue according to claim 1 is characterized in that being applied to microelectronic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100003A CN1074032C (en) | 1998-01-04 | 1998-01-04 | Polyamide acid paint and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100003A CN1074032C (en) | 1998-01-04 | 1998-01-04 | Polyamide acid paint and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1222549A CN1222549A (en) | 1999-07-14 |
| CN1074032C true CN1074032C (en) | 2001-10-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98100003A Expired - Lifetime CN1074032C (en) | 1998-01-04 | 1998-01-04 | Polyamide acid paint and its preparation and application |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974155B (en) * | 2010-07-10 | 2013-08-28 | 横店集团东磁股份有限公司 | Method for synthesizing polyimide precursor polymer resin and method for manufacturing single-sided flexible copper-clad plates |
| CN103865471A (en) * | 2012-12-18 | 2014-06-18 | 上海市合成树脂研究所 | Polyimide adhesive and preparation method thereof |
| CN104194618B (en) * | 2014-08-13 | 2017-01-11 | 南京理工大学 | High-adhesion silicon-containing polyimide coating adhesive and preparation method thereof |
| CN104945626B (en) * | 2015-06-24 | 2017-05-17 | 南京理工大学 | Method for preparing polyimide coating adhesive with high adhesive force |
| CN108912968B (en) * | 2018-08-20 | 2021-02-26 | 无锡创彩光学材料有限公司 | Wood-like composite paint and preparation method thereof |
| CN112608675A (en) * | 2020-12-24 | 2021-04-06 | 武汉市美克亚胺科技有限责任公司 | Preparation method and application of polyimide varnish |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127553A (en) * | 1976-04-20 | 1978-11-28 | Hitachi Chemical Company, Ltd. | Electrical insulating resin composition comprising a polyester resin or ester-imide resin |
| US5137751A (en) * | 1990-03-09 | 1992-08-11 | Amoco Corporation | Process for making thick multilayers of polyimide |
| CN1101654A (en) * | 1993-08-19 | 1995-04-19 | 日产化学工业株式会社 | Polyimide varnish |
| CN1154988A (en) * | 1995-10-12 | 1997-07-23 | 有限会社派材料研究所 | Polyimide compositions for electrodeposition and coatings formed of the same |
-
1998
- 1998-01-04 CN CN98100003A patent/CN1074032C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127553A (en) * | 1976-04-20 | 1978-11-28 | Hitachi Chemical Company, Ltd. | Electrical insulating resin composition comprising a polyester resin or ester-imide resin |
| US5137751A (en) * | 1990-03-09 | 1992-08-11 | Amoco Corporation | Process for making thick multilayers of polyimide |
| CN1101654A (en) * | 1993-08-19 | 1995-04-19 | 日产化学工业株式会社 | Polyimide varnish |
| CN1154988A (en) * | 1995-10-12 | 1997-07-23 | 有限会社派材料研究所 | Polyimide compositions for electrodeposition and coatings formed of the same |
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| Publication number | Publication date |
|---|---|
| CN1222549A (en) | 1999-07-14 |
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Granted publication date: 20011031 |