KR0128340B1 - Photopatternable silicon polyamic acid preparation method and the use thereof - Google Patents

Abstract

No content

Description

Silicon polyamic acid capable of photopatterning, a method of manufacturing the same and uses thereof

The present invention relates to silicon polyamic acid that can be photopatterned on a variety of substrates (eg, glass, silicon or aluminum) and methods of making such materials. More specifically, the present invention can be used as an antireflective coating for patterning photoresist, or photopatterned on a transparent substrate (e.g., silicon or glass) and then imidized to provide a color filter. The present invention relates to a silicon polyamic acid capable of photopatterning.

Prior art prior to the present invention covered a variety of substrates to a thickness of about 2.5μ using a polyamic acid solution (eg, Pyralin polyamic acid) using standard spinning techniques. The applied polyamic acid, ie, the copolymer of pyromellitic dianhydride and 4,4'-oxydianiline in N-methylpyrrolidone, had to be frozen at 4 ° C. as far as possible during storage, and this was insoluble in imidization. Switched easily As a result, it was difficult to spin dry the pyralline polyamic acid in a non-adhesive state after applying a positive photoresist to the surface of the substrate and before photopatterning and developing.

Polyamic acid photopatterning is improved by using silicone polyamic acid, which will result from the copolymerization of benzophenone dianhydride with polydiorganosiloxane having terminal amino alkyl groups bonded to silicon by silicon-carbon bonds. Compared to pyralline polyamic acid, the use of such silicone polyamic acid improves adhesion to silicon or glass, but also suffers from early imidization while drying the applied silicone polyamic acid prior to spin coating the photoresist. Turned out to be. In addition, the work-life of the silicone polyamic acid during the development of the coated photoresist as well as the usefulness of the silicone polyamic acid are not satisfactory.

The present invention has been assigned to the same assignee as in the present invention and the siloxanes containing norbornane bis anhydride (DiSiAn) described in Ryang's U.S. Patent No. 4,381,396, incorporated herein by reference Certain silicone polyamic acids produced by mixing with phenone dianhydride (BTADA) and aryldiamine have been found to prevent excessive imidization during the initial drying of the silicone polyamic acid after it has been applied to the substrate. Based on. Non-tacky silicone polyamic acid can be prepared which can be easily patterned during development of a wide patterned photoresist using a temperature of 125 ° C. or less for 60 minutes. Subsequently, when the patterned silicone polyamic acid is used as an antireflective coating, it can be surprisingly easily removed. In addition, the patterned silicone polyamic acid can be fully imidized to make it practically insoluble in conventional organic solvents used in preparing column filters, such as N-methylpyrrolidone.

According to the present invention, less than 2% of the stoichiometric amount is from about 20 to 80 mole% of the norbornane organosiloxane bis, based on the total molar amount of the aryldiamine and the organic dianhydride. Mixtures of anhydrides with about 80 to about 20 mole% of aromatic organic bis anhydride, preferably about 30 to 70 mole% of norbornane organosiloxane bishydride with about 70 to 30 mole% of aromatic organic bis anhydride Spin coating silicon polyamic acid, the product of co-condensation reaction with organic dianhydride, comprising a mixture on the surface of the substrate (1), drying the silicone polyamic acid at a temperature of 100 ° C. or higher (2), positive photosensitive Spin coating the resist on the surface of the silicone polyamic acid to produce a silicone polyamic acid-sensitive resist composite (3), exposing the applied positive photosensitive resist to patterned ultraviolet light. Patterning the silicone polyamic acid on at least a portion of the substrate surface, characterized by patterning the silicone polyamic acid by step (4) and developing the patterned silicon polyamic acid-sensitive resist composite (5). Provide a method.

In another aspect of the invention, the step of spin coating silicon-polyamic acid as defined above on the surface of a transparent substrate (1), drying the silicon polyamic acid at a temperature of 100 ° C. or more (2), positive photoresist corrosion resistance Spin coating the film on the surface of the silicone polyamic acid to produce a silicone polyamic acid-sensitive resist composite (3); exposing the applied positive photosensitive resist to patterned ultraviolet light (4), patterned, obtained Developing the silicone polyamic acid-sensitive resist composite (5), stripping the photosensitive resist from the surface of the silicone polyamic acid (6) and when the obtained patterned silicone polyamic acid is imidized Heating the silicon polyamic acid until step (7), wherein the method of patterning the adhesive silicone-polyimide on the transparent substrate surface to provide.

In a further aspect of the invention, spin coating silicon polyamic acid as defined above, containing an effective amount of organic dye having a maximum absorbance in the range of 200 to 450 nm (1), wherein the silicone polyamic acid has a temperature of at least 100 Drying (2), spin coating the positive photoresist on the surface of the silicone polyamic acid to produce a silicone polyamic acid-sensitive resist composite (3), exposing the applied positive photoresist to the patterned ultraviolet light (4), developing the obtained patterned silicon polyamic acid-photoresist composite (5), and corroding the exposed substrate through the patterned silicon polyamic acid-photoresist composite (6). And (7) stripping the silicon polyamic acid-photoresist composite from the corroded substrate obtained. Silicon - by using the polyamic acid coating provides an optical imaging method of patterning a substrate.

The norbornane anhydride terminal organosiloxane that can be used to practice the invention has been assigned to the same assignee as in the present invention and is incorporated by reference in the amounts of US Pat. Nos. 4,381,396 and 4,404,350. It is described. For example, 5,5 '-(1,1,3,3-tetramethyl-1,1,3,3-disiloxane diyl) -bis-norbornane-2,3-dicarboxylic anhydride can be used. have.

The organic dianhydrides that can be used in combination with the aforementioned norbornane anhydride terminal organosiloxanes are, for example, benzophenone dianhydride, pyromellitic dianhydride, oxybisphthalic anhydride and tetracarboxybiphenyl dianhydride.

Organic diamines that may be used in the practice of the present invention to prepare the silicone polyamic acid described above include, for example, m-phenylenediamine; p-phenylenediamine; 4,4'-diaminodiphenylpropane; 4,4'-diaminodiphenylmethane; Benzidine; 4,4'-diaminodiphenylsulfide; 4,4'-diaminodiphenylsulfone; 4,4'-diaminodiphenyl ether; 1,5-diaminonaphthalene; 3,3'-dimethylbenzidine; 3,3'-dimethoxybenzidine; 2,4-diaminotoluene; 2,6-diaminotoluene; 2,4-diamino-tert-butyl toluene; 1,3-diamino-4-isopropylbenzene; 1,2-bis (3-aminopropoxy) ethane; m-xylenediamine, P-xylenediamine; Bis (4-aminocyclohexyl) methane, decamethylenediamine; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; 2,11-dodecanediamine; 2,2-dimethylpropylenediamine; Octamethylenediamine; 3-methoxyhexamethylenediamine; 2,5-dimethylhexamethylenediamine; 2,5-dimethylheptamethylenediamine; 3-methylheptamethylenediamine; 5-methylnonnamethylenediamine; 1,4-cyclohexanediamine; 1,15-octadecanediamine; Bis (3-aminopropyl) sulfide; N-methyl-bis (3-aminopropyl) amine; Hexamethylenediamine; Heptamethylenediamine; 2,4-diaminotoluene; Nonamethylenediamine; 2,6-diaminotoluene: bis (3-aminopropyl) tetramethyldisiloxane and the like.

Another aspect of the invention relates to a photopatternable silicone polyamic acid containing from 2 to 40 weight percent of a miscible organic dye based on the weight of the silicone polyamic acid, the miscible organic dye being photopatterned. Colored silicone polyimide. For example, in practicing the present invention, silicone polyamic acid, which may be combined with green, red, blue or yellow dyes, may be used to produce color filters useful for liquid crystal displays.

A further aspect of the invention relates to silicone polyamic acid which can contain a sufficient amount of organic dye capable of absorbing within the range of 200 to 450 nm to provide antireflective surface effects during photoimaging. Depending on the absorbance and the thickness of the coating used, the weight percent of the dye may vary. For example, from 2 to 30% by weight of light absorbing dyes such as coumarin may be used based on the weight of the silicone-polyamic acid.

Some organic dyes that can be used to practice the present invention by mixing with silicone polyamic acid to produce dyed silicone-polyimide are, for example, commercially available green dyes (eg Acid green 41, Acid green 25). And Naphthol Green B], red dyes such as Chromotrope 2B and Direct red 81 and blue dyes such as Acid blue 80, Sacigo sky blue blue and Anirlne blue].

The various acid dyes described above may be varied for use in polyamic acid in accordance with the practice of the present invention. The sodium cation, which is characteristic of the acid dye, can be replaced with various onium cations, typically quaternary ammonium or phosphonium cations such as benzyltrimethylammonium, tetrabutylammonium, tetraethylammonium and tetrabutylphosphonium. Modified dyes can be prepared by extracting an aqueous slurry of conventional acid dyes using methylene chloride. Stripping the solvent allows a modified dye to be obtained in high yield. Modified dyes have been found to be soluble in N-methyl pyrrolidone, polyamic acid films and polyimide films. The visible spectrum of the onium salt dye is indistinguishable from the sodium cationic dye.

The silicone polyamic acid used to practice the invention is preferably aryldiamine and norbornane anhydride terminal organosiloxane, referred to herein as DiSiAn, and preferably benzophenone dianhydride or BTDA in the following specification. From a mixture with the mentioned organic aromatic dianhydrides in a two-step process. Co-condensation solutions with 10 to 30 weight percent solids in the bipolar aprotic solvent can be used. N-methylpyrrolidone and N, N-dimethylformamide include among the bipolar aprotic solutions that can be used to prepare the silicone polyamic acid by carrying out the method of the present invention.

Preferably, N-methylpyrrolidone is used as a bipolar aprotic solvent. Preferably, a two-step method can be used that can change the ratio of DiSiAn to BTDA. A preferred method of preparation is to mix the less reactive DiSiAn with aryldiamine at about 90-100 ° C. for 30-60 minutes. Subsequently, incorporation of BTDA can be performed. During the cocondensation, the mixture can be stirred. After dissolving BTDA, the solution can be maintained at 100-110 ° C. for additional time.

If desired, 2-30% by weight of suitable organic dyes miscible with silicone polyamic acid may be added with stirring. The colored polyamic acid is then applied as a thin film of 1 to 20 microns on a suitable transparent substrate (e.g. glass), a silicone substrate or a thermoplastic substrate (e.g. polymethylmethacrylate (trade name: Lexan polycarbonate)). The excess organic solvent can then be removed by heating to a temperature in the range from 100 to 125 ° C. If the dried polyamic acid film is actually non-tacky, a suitable positive photoresist or negative photoresist may be spin coated onto the surface of the substrate. The photoresist may be coated with a thickness of about 0.5 to 2 microns. The resulting composite can then be heated at a temperature of 80 to 100 ° C. to remove excess solvent (eg water or inert organic solvent).

In a preferred method for preparing silicone polyamic acid, excess aryldiamine is avoided in order to minimize the production of gelled particles that can reverse the film properties of the silicone polyamic acid and silicone polyimide obtained.

Killer filterers can be prepared on a transparent substrate following the practice of the method of the present invention using a stepwise manufacturing method for coating colored silicone polyimide. For example, the transparent substrate can be initially patterned with transparent silicone polyamic acid colored in red, according to the method described above. The silicone polyamic acid can then be imidized by heating to a temperature of 200 ° C. for 60 minutes. Red colored silicone polyimide, which can be patterned on a transparent substrate in an array of squares, will transmit 250μ of red light on each surface. In areas without colored silicone polyimide, white light will be transmitted. Subsequently, the substrate can be further treated with colored silicone polyamic acid (eg, silicone polyamic acid colored in blue) and then the method can be repeated. By choosing a better mask and colored silicone polyamic acid, it is possible to produce color filters through which blue, green and red rays can be transmitted completely.

The following examples are given by way of illustration and not by way of limitation. All parts are parts by weight.

Example 1

5,5 '-(1,1,3,3-tetramethyl-1,1,3-disiloxanediyle) bus-norbornane-2,3-dicarboxylic anhydride (DiSiAn) (3.7008 g, 8.00 mmol) ), A mixture of metaphenylenediamine (MPD) (2.1412 g, 19.8 mmol) and N-methylpyrrolidinone (NMP) (23 g) was warmed to 60 ° C. for 30 minutes with stirring to give a complete solution and silicone polyamic acid. To form. Then, while adding to a mixture of benzophenone dianhydride (BTDA) (3.9326 g, 12.20 mmol), the mixture is stirred and fed so that the molar ratio of DiSiAn units to BTDA in the mixture is 40:60. The mixture is then heated to 80 ° C. with stirring and aliquots are recovered at 10 minute intervals. A film of about 5 mils in thickness is drawn on an organic slide and dried at 100 ° C. for 30 minutes. A portion of the film is further baked at 200 ° C. for 30 minutes. The film obtained is then immersed in 0.5% by weight of aqueous tetramethyl ammonium hydroxide or sodium hydroxide solution aqueous caustic to test the solubility of this film, and the film is further baked at 200 ° C. for 30 minutes, Immerse in NMP to test the solubility of the film in NMP. The following results show the aqueous corrosiveness and NMP solubility of the films obtained from aliquots of silicone polyamic acid recovered from the reaction mixture at 10 minute intervals over 0 to 120 minutes.

TABLE 1

Samples dried at 1-about 100 ° C. for 30 minutes and immersed for 30 seconds.

2-Sample dried at about 100 ° C. for 30 minutes, then further dried at about 200 ° C. for 30 minutes, immersed in NMP for 1 minute, and then washed with water.

Availability after 3-60 seconds.

Time at 80 ° C. in 4-reaction vessel.

The above results indicate that photo-patterning of the silicone polyamic acid prepared according to the embodiment of the present invention using a standard aqueous corrosive positive resist developer, and the effect of the subsequent treatment of the organic solvent used to remove the developed photoresist Prevented.

The silicone polyamic acid prepared according to the practice of the present invention was further evaluated for its ability to prevent imidization after heating at 120 ° C. for 30 minutes or more as shown in Table 1 to obtain the following results. .

TABLE 2

1-0.27N Immersion 30 sec in aqueous Bu ₄ NOH.

Baking at 2-200 ° C. for 30 minutes, then immersion for 1 minute.

The above results indicate that silicone polyamic acid prepared according to the practice of the present invention may be organically prepared prior to imidization, without significantly affecting its ability to pattern in aqueous caustic during development of photopatterned positive photoresist. It is shown that it can be dried at 100 ° C. for an extended period of time, while preventing the continuous treatment during the removal of the resist residue using a solvent.

Example 2

According to the method of Example 1, a silicone polyamic acid film mixed with 30% by weight of Sudan Black B was prepared. In addition, pyriline polyamides [commercially available polyamic acid manufactured by EI duPont de Nemours Co. of Wilmington, Delaware, USA, Delaware, Delaware, USA] 30 Mix with weight% Sudan Black B. A polyamic acid film is prepared from the mixture, which is dried at 100 ° C. for 30 minutes and then developed as shown in the table below. The silicone copolymers in Table 3 are silicone polyamic acids prepared according to Example 1:

TABLE 3

1-0.27N Dipping in Bu ₄ NOH.

The above results indicate that the commercially available pyraline polyimide after drying at 120 ° C. for 30 minutes is insoluble in the aqueous caustic. After soaking in an aqueous caustic for 120 seconds, the remaining pyraline polyamic acid is all insoluble but also begins to rupture.

Additional silicone polyamic acid is prepared according to the method shown in Example 1 except that in one example bisphenol-A dianhydride is used in place of DiSiAn to produce silicone polyamic acid having approximately the same ratio of BPADA and BTDA units in silicone polyamic acid. do. Silicone polyamic acid without DiSiAn units was found to be insoluble when dried at 100 ° C. for 30 minutes and then immersed in an aqueous caustic.

Example 3

According to the method of Example 1, a mixture of oxydianiline (39.3483 g, 0.19651 mole) DiSiAn (22.7259 g, 0.04913 mole) and NMP (250 ml) is stirred at 80 ° C. for 1.5 h. After 1.5 h, it is then added to a mixture of NMP (160 ml) and benzophenone dianhydride (47.4900 g, 0.14738 moles). The mixture is warmed to 110 ° C. and mixed to 100 ° C. while mixing. The mixture is stirred and kept at 100 ° C. for 2 hours, then cooled to room temperature.

To a portion of the silicone polyamic acid, a bis (tetrabutylammonium) salt of acid green # 41 dye is added in sufficient amount to provide a mixture containing about 20% by weight of the dye, based on the total weight of the dye and silicone polyamic acid. . The dye is prepared by the following method. Acid Green # 41 (dye content: 40%) (8.7 g, 5.31 mmol), tetrabutyl ammonium chloride (2.95 g, 10.6 mmol), water (150 ml) and methylene chloride (150 ml) were mixed at room temperature for 1 hour. Stir. The mixture is stirred at room temperature for 1 hour and finally separated. The solvent is removed from the organic layer under reduced pressure and the solid obtained is dried under vacuum at 80 ° C. to give a dark green dye (5.1 g, 88%) as a bis (tetrabutylammonium) salt.

The solution of silicone polyamic acid and green dye in N-methyl pyrrolidone sufficient to produce a 20% by weight mixture was used with a headway photoresist spinner model EC101 running at 3500 rpm for 20 seconds. By spin coating on the silicon wafer. After baking the coated silicone polyamic acid at 110 ° C. for 30 minutes, the resulting polyamic acid surface was found to be non-tacky. Subsequently, the photoresist (KTI 80) was spin-coated on the treated silicon wafer and dried at 90 ° C. for 30 minutes to provide a 1 µ photoresist layer on a silicon polyamic acid film of about 4,5 µ. The wafer is then patterned using an Oriel exposure station that is exposed for 30 seconds. Subsequently, the photosensitive resist and the polyamic acid are developed by immersing the wafer treated with a Shipley microposit 312 developer diluted 1: 1 with distilled water at 25 ° C. for 1 minute.

The patterned mixture of resist and silicone polyamic acid is washed to remove the developer and then further dried at 140 ° C. for 30 minutes. Subsequently, the photoresist is removed using a butyl acetate solvent, and the wafer is dried.

The silicon wafer without photopatterned polyamic acid treated resist is then heated to 200 ° C. for 60 minutes to completely imidize the silicon polyamic acid.

3-10 μ thick silicon polyamic acid, converted to silicon-polyimide and patterned into blue, green and red squares (250 μ × 250 μ) by repeating the above method using silicone polyamic acid colored with blue and red dyes To manufacture a color filter consisting of.

Although the above examples relate to only a few of the quite a number of variations that can be used in the practice of the method of the invention and to the products obtained therefrom, the methods and products of the invention describe the above examples. It is to be understood that it is more broadly defined.

Claims (16)

Amounts of less than about 2% of the stoichiometric amount to stoichiometric amounts of aryldiamine, and about 20 to 80 mole percent of norbornane organosiloxane bishydride and 80 to 20 based on the total moles of organic dianhydride Spin-coating an organic dianhydride comprising a mixture of mol% aromatic organic bis anhydride and a silicone polyamic acid, which is a product of co-condensation reaction, on the surface of the substrate (1), drying the silicone polyamic acid at a temperature of 100 ° C. or higher Step (2), spin coating the positive photoresist on the surface of the silicon polyamic acid to produce a silicon polyamic acid-sensitive resist composite (3), exposing the applied positive photoresist to the patterned ultraviolet light (4) ) And developing (5) the patterned silicone polyamic acid-sensitive resist composite to pattern the adhesive silicone polyamic acid on at least a portion of the substrate surface. Way. Spin coating silicon polyamic acid, which is a reaction product of substantially equimolar amounts of aryldiamine with an organic dianhydride comprising a mixture of norbornane organosiloxane bis anhydride and an aromatic organic bis anhydride, on a surface of a transparent substrate ( 1) drying the silicone polyamic acid at a temperature of 100 ° C. or higher (2), spin coating the photosensitive resist on the surface of the silicone polyamic acid (3), exposing the applied positive photosensitive resist to patterned ultraviolet light (4) developing the composite of the spin-coated photoresist and the silicone polyamic acid (5), and stripping the remaining photosensitive resist from the surface of the silicone polyamic acid using an organic solvent (6). And heating (7) the silicone polyamic acid until the silicone polyamic acid is completely imidized. A transparent substrate having a tacky silicon-polyimide film photopatterned on at least a portion of the substrate surface, obtained by photopatterning on the transparent substrate surface. The transparent substrate of claim 2, wherein the silicone polyimide is colored with a dye. A color filter comprising a glass substrate colored and having a silicon polyimide photopatterned on at least a portion of the substrate surface. The color filter according to claim 4, which is colored with a blue dye, a green dye, a red dye or a mixed dye thereof. A polyamic acid composition comprising polyamic acid and up to 40% by weight of miscible onium salt organic dye. The polyamic acid composition according to claim 6, wherein the onium salt is bis (tetrabutylammonium salt). A silicone polyamic acid composition comprising silicone polyamic acid and up to 40% by weight of miscible organic dyes stable at temperatures up to 125 ° C. The silicone polyamic acid composition according to claim 8, wherein the organic dye is a blue dye. The silicone polyamic acid composition according to claim 8, wherein the organic dye is a red dye. The silicone polyamic acid composition of claim 8, wherein the organic dye is a yellow dye. The silicone polyamic acid composition of claim 8, having a maximum absorbance of organic dyes at 200-450 nm. Spin coating (1) the silicon polyamic acid as defined in claim 1 on the substrate, containing an effective amount of an organic dye having a maximum absorbance in the range of 200 to 450 nm, and drying the silicone polyamic acid at a temperature of 100 ° C. or more ( 2) spin coating the positive photoresist on the surface of the silicone polyamic acid to produce a silicone polyamic acid-sensitive resist composite (3), exposing the applied positive photoresist to the patterned ultraviolet light (4), Developing the obtained patterned silicon polyamic acid-resist resist composite (5), corroding the exposed substrate through the silicon polyamic acid-resist resist composite (6) and silicon polyamic acid- from the corroded substrate; An optical imaging method for patterning a substrate, comprising the step (7) of stripping the photoresist composite. The method of claim 13, wherein the organic dye is coumarin. A reflective substrate containing silicon polyamic acid as defined in claim 1, containing an effective amount of organic dye having a maximum absorbance in the range of 200 to 450 nm and spin-coated over the surface of the substrate. The method of claim 13, wherein the substrate is aluminum.