TWI294559B - Coating composition of positive photosensitive polyimide - Google Patents

Description

1294559 发明, DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a positive-type light-sensitive polyimide coating composition which can be used to form an insulating layer of a display. [Prior Art] Polyimine (PI) is widely used in the semiconductor and display industries due to its excellent thermal stability and good mechanical, electrical and chemical properties, such as 1C wafer protective film, wafer level packaging ( Chip scale package, CSP) and the insulating layer (insuiat〇r) on the display. The use of PSPI has been a trend due to the use of light-sensitive polyimine (PSPI) to simplify processes, reduce costs and increase product yield. There are many related literatures on positive-type light-sensitive polyimine, but most of them are quinone imine precursors such as poly-p- lysine, such as US 6329110, US 6291619, US 6232032 and US. 5858584 and other patents disclosed. The pattern of the polyphthalate after development is a standard rectangle, but the requirement of the insulating layer in the display is a pattern of tapered_angle at the cross section, and the polyglycolate finally needs to be 35 〇 high temperature. Imidization is in conflict with process requirements below 250 °C. Therefore, pspi made of polyglycolate is not suitable. In addition, it has been disclosed that the imidized PSPI, as disclosed in US Pat. No. 6,627,377, US Pat. No. 5, 441, 845, and U.S. Patent No. 5,573, 886, discloses that the hard-baked temperature can be low, but it is generally soluble in PI, so it is solvent resistant. The sex is generally poor, and it needs to be developed with a high concentration of alkaline developer, so its practicality is lower than 1294559. s a ο Τ 〇 m i k a w a J 〇 u r n a 1 〇 f p h 〇 t ο ρ ο 1 y in e r

Science and Technology, 2002, 15, 205 to 208, US Pat. No. 6,593,043 and US Pat. No. 65,247,64 disclose the introduction of a polyglycolate having a phenol group at the end of the main chain and the addition of a compound having a phenolic hydroxyl gr0Up as a crosslink. The crosslinking agent can make the pattern have a tapered-angle at the cross section, but the main structure of the polyphthalate is still high temperature when it is imidized. Make sure that the imidization is complete. In Examples 6-13 of US Pat. No. 6,524,764, it is indicated that the shrinkage of the polystyrene from the conversion of θ to the styrene, so that the PSPI composed of the polyphthalate has a lower film thickness retention rate ( 66%), the synthesis steps are also more complicated. SUMMARY OF THE INVENTION A main object of the present invention is to provide a novel positive-type photosensitive polyimide coating composition with simple synthesis steps, which can be developed in a short time with an alkaline aqueous solution, and has high sensitivity and good performance. The resolution, the low hard baking temperature, the high film thickness retention, and the pattern after hardening have a tapered-angle at the cross section. The coating composition of the present invention has good storage properties at room temperature. The positive-type photosensitive polyimide coating composition of the present invention comprises an organic solvent and (a) polyimine dissolved in the organic solvent, and has a phenolic hydroxyl group at the end of the main chain or A carboxyl group '(b) has a phenolic hydroxyl group compound, 1294559 and (e) a sensitizer quinonediazide sulfonate, which is relative to each hundred weight The component (b) is used in an amount of 1 to 50 parts by weight, preferably 5 to 25 parts by weight, and the component (c) is used in an amount of 1 to 50 parts by weight, preferably 5 to 25 parts by weight. Preferably, 5 to 25, the polyimine has the following formula (1) or (2):

In the formulae (1) and (2), η is an integer of 10 to 600, and An is a tetravalent organic group.

Ah is a di- to tetravalent organic group, A. As a divalent aryl group, ri is a hydrazine H group or a COOH group.

Preferably, Aq is 1294559

Preferably, wherein Ar2 is

03⁄4 Cl -H6C3^i-〇-^ ch3 LCH3

1^3%- mCH3 or qing where m is an integer from 1-20, and Χι is 8 1294559 _Ο—, an S—, a C(CF3)2 —. A C(CH3)2 — —CH,-, - S〇2-, -NHCO-,

Wherein m is an integer from 1 to 20, and Z is H or methyl. Preferably, the phenolic hydroxyl group compound of the component (b) has the following structure:

Wherein R3 to R9 are an anthracene, an -OH group, a CVCm alkyl group or a C4-C2 anthracene ring group, and z is an integer of 0-5. More preferably, the ingredient (b) is: 1294559

OH , H丨

-OH

BisP-B

Bis-F

or

Preferably, the sensitizer of the component (C) has the following structure: CH3

CH3

10 1294559 wherein D is hydrogen, 〇 0 o V S〇2 S〇2 S〇2 1 and D is not all hydrogen. Preferably, the weight of the ingredients (a), (b) and (c) is from 5 to 50% by weight based on the total weight of the composition. Preferably, the organic solvent is N-methyl-2-pyrrolidone, γ-butyrolactone, or ethyl lactate. [Embodiment] The synthesis step of the polyimine is to dissolve an appropriate amount of the diamine monomer and the dianhydride monomer in a suitable organic solvent such as N-methyl-2-pyrrolidone (N-methyl-2). -pyrrolidone; NMP) and vigorously mix at 0~4 °C

After 4 hours, an endcapped agent such as a primary amine having a sulfhydryl group or a slow group was added and then dropped for 4 hours. Dixybenzene (xy 1 ene) was added and heated to 180 ° C to reflux. After 3 hours, it was cooled to obtain a polyimine (PI) solution having a phenol group or a carboxyl group at the end of the main chain. The photosensitive polyimine (PSPI) solution of the invention is prepared by adding an appropriate amount of PI solution, adding a phenolic hydroxyl group crosslinking agent and a sensitizer, wherein NMP and γ-butyrolactone (γ) can be added. -butyrolactone, GBL), or ethyl lactate and other solvents to dilute the PSPI solution to the desired concentration for use. The lithography process using the PSPI solution of the present invention is as follows: (丨) Apply PSPI 11 1294559 solution to a suitable substrate by spin coating or other means; (Η) pre-bake; (iii) exposure; (iv) development; And (v) hard baking, the resulting pattern is polyimine. In the above step (1), the positive PSPI solution is applied to a suitable substrate, and the substrate is, for example, a tantalum substrate, glass or IT glass. The above coating method is, for example, spin coating, roller coating, screen coating, curtain coating, immersion plating. (dip coating) and spray coating, but are not limited to the above coating method. In a preferred embodiment of the invention, the film formed by coating is prebaked for 2 minutes at 2 ° C to distill off the solvent therein. Then, the coated substrate is exposed to actinic radiation under a mask, such as X-ray, electron beam, ultraviolet, visible, or other sources that can be used as actinic rays. Wait. After exposure, the coated substrate is subsequently developed by an alkaline aqueous developer to wash away the exposed portions of the film to obtain a photoresist pattern. The above alkaline aqueous developer comprises an alkaline aqueous solution such as an inorganic base (potassium hydroxide, sodium hydroxide), a primary amine (ethylamine), a secondary amine (diethylamine), a tertiary amine (triethylamine). Or an aqueous solution of a quaternary ammonium salt (teti:amethylamm〇niumhydr〇xide), wherein an aqueous solution containing tetramethylammonium hydroxide is preferred. Development can be accomplished by soaking, spraying or laminating or using other known development methods. The developed photoresist pattern is subsequently washed with deionized water and at 18 Torr to 4 Torr. The remaining solvent is drained by performing a post-cure under the armpit to obtain a polyimine pattern having a tapered cross section. 12 1294559 The film thickness retention rate is calculated as follows: Film thickness retention ratio (%) = [(film thickness after hard baking) / (film thickness after prebaking)] The present invention can be implemented by the following The examples are further understood to be illustrative only and not to limit the scope of the invention. drug

Ethylene glycol bis (anhydro-trimellitate (TMEG)),

Bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), 13 1294559

(HAB) (BisAPAF) (3,5-DABA)

(ODA) 3,3-dihydroxybenzidine (HAB), hexafluoro-2,2-di(3-amino-4-hydroxyphenyl) (Hexofluoro-2, 2_bis (3_amino) -4-hydroxyphenyl) (BisAPAF)), 3,5-diaminobenzoic acid (3,5_DΑΒΑ), 4,4'-Oxydianiline (ODA) ),

2>2(2-bis(4-aminophenoxyl)phenyl)propane (BAPP)),

2,2-bis(4-(3-aminophenoxyl)phenyl)sulfone 14 1294559 (m-BAPS))

Where D is

So2 2,3,4-trihydroxy-benzophenone-1,2-diabazonaphthoquinone-5_rexate (2,3?4-trihydroxy-benzophenone-152-diazonaphthoquinone-5-sulfonate (PIC -3), available from KOYO chemicals Inc.) Example 1 A 1000 ml three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet was used, and 18.3 g (50 mmol) of Bis-APAF, 12.3 g was added. (30 millimoles) of BAPP, 2.02 grams (10 millimoles) of ODA, 20_5 grams (50 millimoles) of "000 and 15.5 grams (50 millimoles) of 00? eight, and joined 400 NMP solvent. After stirring the above solution for 4 hours, add 2·18 g (20 mmol) of blocking agent 3-aminophenol, and then stir-fry at room temperature. After adding 80 g of diphenylbenzene, the temperature was raised to 180 ° C and stirred for 3 hours. After cooling, the viscous PI solution PI_1 was obtained. By infrared (IR) spectroscopy, the PI synthesized in this example was 1781 cm·1 and 1377 cm·1 醯imine C = 特性 and CN characteristic absorption, 1294559 as shown in Figure 1. Take 50 grams of PI_1 solution, add 1.875 grams of PIC-3, 1.875 grams of DML-PC and mix evenly, get The photosensitive polyimide coating composition PSPI-1 was then coated onto the ITO glass by spin coating using a hot plate (Hot-Plate) at 110 ° C for 2 minutes. After the soft bake process (prebake), a film having a film thickness of about 1 · 1 μm is obtained. The coated ΙΤ0 glass is then subjected to an unfiltered mercury arc lamp (the wavelength measured is between 250 to 400 nm), an energy of about 100 mj/cm 2 was applied and exposed, and developed with 2.38% by weight of a tetramethylammonium hydroxide (TMAH) aqueous solution developer, and the development time was 35 seconds. A heat-resistant pi pattern is then obtained in a hot air circulating oven at 230 ° C for 30 minutes by post-cure. As shown in Figures 2a and 2b, the pattern has a line width of 10 μηι With a pitch, the film thickness is about 2·0 μπι. This pattern has a film thickness retention ratio of 91% compared to the thickness of the original soft baked after hard baking, by scanning electron microscopy (scanning electron microscopy) Electron microscope, SEM) The imine pattern has a tapered-angle at the cross section. Example 2 A 1000 ml three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet was used, and 7.6 g (50 mmol) was added. 3,5-DABA, 12.975 grams (30 millimoles) of m_BAPS, 1.54 grams (7.5 millimoles) of ODA, 32.8 grams (80 millimoles) of TMEG and 6.2 grams (20 millimoles) 0 DPA and add 400 grams of NMP solvent. After stirring the above solution at 16 1294559 (TC for 4 hours, add 2.73 g (25 mmol) of the blocking agent % aminobenzaldehyde, and stir at room temperature for another 4 hours, add 8 gram - After toluene, the temperature was raised to 180 ° C and stirred for 3 hours. After cooling, viscous p] [solution PI-2 was obtained. Take 50 g of PI-2 solution, and add 1.875 g of PIC-3, 1 · gram of MTpc, and mix evenly. A photosensitive polyimide coating composition pspi_2 was obtained. The PSPI-2 coating composition was then coated onto the IT glass by spin coating and passed through a hot plate at 11 (TC, 2 minute soft bake procedure). Thereafter, a film having a film thickness of about 1 · 1 μm can be obtained. Then, the coated IT glass is coated with an unfiltered mercury arc lamp (the measured wavelength is between 250 and 400 nm). An energy of about 120 mJ/cm 2 was applied for exposure. Development was carried out with 2 38% by weight of TMAH aqueous developer, and the development time was 35 seconds. Then, in a hot air circulating oven 23 (rc, after 3 minutes of hard baking) Program, you can get a heat-resistant PI graphics. The above ρι graphics have a line width and spacing of 15 μηι, film thickness 〇95 um. The ρι pattern has a film thickness retention of 86% after being hard-baked compared with the original soft-baked thickness. It can also be observed by the SEM image that the polyimine pattern has a tapered shape. Cross section. Example 3 Using a 1000 ml three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet, add 10·8 g (5 Torr) of HAB, 12.975 g (30 mmol) of m_BAps. , 2 公 2 gram (1 〇 millimolar) 〇 da and 41 〇 gram (100 millimolar) of TMEG, and add 400 grams of NMP solvent. Stir the above solution at 0 ^ for 4 hours, then add 218 Gram (2〇17 1294559 mM) of the blocking agent 3-aminophenyl alcohol, and stirred at room temperature for another 4 hours, after adding 80 g of xylene, the temperature was raised to 180 ° C and stirred for 3 hours. A viscous PI solution PI-3 was obtained. 50 g of the PI-3 solution was added, and 1.875 g of PIC-3 and 2.25 g of BIPC-PC were added and mixed uniformly to obtain a photosensitive polyimide coating composition PSPI-3. The PSPI-3 coating composition was coated on the ITO glass by a coating method, and passed through a hot plate at U (rc, after a soft baking process for 2 minutes). A film having a film thickness of about 1.25 μm can be obtained. The coated bismuth glass is then applied to an unfiltered mercury arc lamp (having a wavelength of 250 to 400 nm) for about 120 mj. The energy of /cm2 was exposed. Development was carried out with 2.38% by weight of TMAH aqueous solution developer' development time of 40 seconds. Then, under the hot air circulating oven 23〇〇c, a heat-hardening process can be obtained by a hard baking process for 30 minutes. The above PI pattern has a line width and a pitch of 15 μm, and the film thickness is 1〇5 μιη. The ΡΙ pattern is compared with the thickness of the original pre-baked after hard baking, and has a film thickness retention rate of 87.5% of the original thickness, and the pattern can also be observed by the sem diagram (tapered_angle) At the cr〇ss (10)). Comparative Example 1 A three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet was used to add 36.6 g (1 Torr) of Bis_ApAF, 31.0 g (HH) millimolar. 0DPA 'and add 4 grams of NMp solvent. After the solution was stirred for 4 hours, the solution was heated to 18 (TC scrambled for 3 hours. After cooling, a viscous hydrazine solution PI C1 was obtained. 50 g of ΡΙ-Cl solution was added to add i 8克pic_3 mixed uniform sentence, 18 1294559 A photosensitive polyimide coating composition PSPI-C1 was obtained. The PSPI-C1 coating composition was coated on the ITO glass by spin coating and passed through a heating plate at 110°. After a soft baking process of 2 minutes, a film with a thickness of about u μιη can be obtained. Then the coated IT glass is coated with an unfiltered mercury arc lamp (the wavelength measured) An energy of about 120 mJ/cm 2 was applied for exposure at 250 to 400 nm. Development was carried out with 2.38% by weight of TMAH aqueous developer, and the pattern could not be obtained after the development time exceeded 3 minutes. In this comparative example, the PI was used. For the synthesis, no blocking agent was used. Comparative Example 2 50 g of the PI-1 solution prepared in Example 1 was added, and after adding 1.875 g of PIC_3, the mixture was uniformly mixed to obtain a photosensitive polyimide coating composition pSpi_C2. The lithography process of Example 1, wherein the film thickness after soft baking is i. 〇μπι, to TMAH The development time of the aqueous solution development was 60 seconds, and the line width and pitch of 20 μπι were obtained, and the film thickness was 0·8 μm (the film thickness retention rate was 80%). The cross section of the PI pattern was observed by the seM diagram as a rectangle, and there was no gradation. In this case, the photosensitive polyimide coating composition pSPI_C2 does not use a compound having a phenolic hydroxyl group as component (b). Comparative Example 3 HAB_ODPA_butanol·butanol· The synthesis of p〇lyamic acid ester was carried out using a 25-ml three-necked round bottom flask equipped with a mechanical stirrer and a nitrogen inlet, and 15.50 g (5 mM m) of 〇dpa, 7.4 0 was added. 19 19,294,559 g (100 mmol) of n-butanol (n-butanol) and 115 g of NMP solvent. The mixture was heated to 80 ° C and stirred at this temperature for 4 hours to carry out a crystallization reaction, and the solution was cooled to Below 4 ° C, add 16.63 grams (200 moles) of π pyridine and 19.5 gram gram (1 〇〇 millimoles) of phenvlphosphonic dichlorirlfi, and then room After stirring for 2 hours at room temperature, activation of C00H group After cooling the above solution to 〇~41, add 10.8 g (50 mmol) of HAB, stir at 0 to 4 ° C for 1 hour, and then stir at room temperature for 8 hours. Polymerization of the amine ester) The resulting solution was precipitated using 1 mL of methanol and filtered to collect the polymer therein, and the collected polymer was washed three times with deionized water. Finally, the obtained polylysine S was placed in a vacuum environment of 8 (rC for 24 hours to dry it. 5 g of polyphthalate, 125 g of PIC-3 and 18.75 g of NMP solvent were used. The photosensitive polyamidate coating composition PSPI_C3 was repeated. The lithography process of Example 1 was repeated, wherein the film thickness after soft baking was 1 ·〇μιη, and the development time of developing with TMAH aqueous solution was 60 seconds, which was obtained with 2〇. The line width and pitch pattern of μιη is 〇·9 um. This pattern has a 70% film residual rate after being hard-baked at 35〇cc and its original soft-baked thickness. The pattern is rectangular. Comparative Example 3 is a general photosensitive polyamidate coating composition, which only emphasizes that it needs to be hard baked at 350 ° C and its film thickness retention rate is low. [Simplified illustration] Figure 1 The infrared light 20 1294559 spectrum of the polyimine synthesized in Example 1 of the present invention, wherein the analyzed polyimine has two kinds of reactions of reacting at 180 ° C for 3 hours and at 190 ° C for 3 hours. And 2b are the positive-type photosensitive polyimide coating compositions prepared by using the first embodiment of the present invention, respectively. On view and cross-sectional scanning electron microscope pattern (SEM) photographs.

twenty one

Claims (1)

1294559 Pickup, patent application scope: 1. A positive-type photosensitive polyimide-based coating composition comprising: an organic solvent and (a) polyimine dissolved in the organic solvent, having a main chain end a compound having a phenol group, (b) a compound having a phenol group, and (C) a sulfonium azide sulfonate as a sensitizer, wherein the component (b) is used per 100 parts by weight of the component (a) 1 to 50 parts by weight, and the component (c) is used in an amount of 1 to 50 parts by weight, and the composition of the first aspect of the invention, wherein the polyimine has the following formula (1) or (2) Construction: In the formulae (1) and (2), η is an integer of 1〇_6〇〇, An is a tetravalent organic group ' Ah is a di- to tetravalent organic group, Ar3 is a divalent aryl group, and R1 is a 0H group. Or COOH group. 3 · The composition of claim 2, wherein Ah is 22 1294559 4. A composition as claimed in claim 2 or 3 wherein An is ? /^ /^ ? CH2CH2—〇—' 5_The composition of claim 2 or 3, wherein Ar2 is Lu 23 1294559 -H6C3 1-c3h^ CH〇 Where m is an integer from 1 to 20, and Xi is a Ο-, an S-, a C(CF3)2 _ . _C(CH3)2 - -Cl·^-, -S〇2-, -NHCO-, Or one (CH2)m—^—〇_Si—(CH2)n z z Wherein m is an integer from 1 to 20, and Z is H or a thiol group. 6. The composition of claim 2, wherein the component (b) is used in an amount of 5 to 25 parts by weight per 100 parts by weight of the component (a). </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Wherein R3 to R9 are an anthracene, an 〇H group, a Ci_C2 alkyl group or a C4-C2 anthracene ring group, and z is an integer of 〇-5. 8. The composition of claim 7, wherein the component (b) has a mercapto compound: 25 1294559 9. The composition of claim 1, wherein the photosensitive agent of component (c) has the following structure: 26 1294559 Where D is hydrogen, And D is not all hydrogen. 10. The composition of claim 1, wherein the components (a), (b) and (c) have a weight of from 5 to 50% by weight based on the total weight of the composition. 11. The composition of claim 1, wherein the organic solvent is N-methyl-2-pyrrolidone, γ-butyrolactone, or ethyl lactate. 27