LATENT ACIDS AND THEIR USE

Abstract

Compounds of the formula (I) and (IA) wherein X is —O(CO)—; R.sub.1 is C.sub.1-C.sub.12haloalkyl or C.sub.6-C.sub.10haloaryl; R.sub.2 is located in position 7 of the coumarinyl ring and is OR.sub.8; R.sub.2a, R.sub.2b and R.sub.2C independently of each other are hydrogen; R.sub.3 is C.sub.1-C.sub.8haloalkyl or C.sub.1-C.sub.8haloalkyl; R.sub.4 is hydrogen; and R.sub.8 is C.sub.1-C.sub.6alkyI; are suitable as photosensitive acid donors in the preparation of photoresist compositions such as used for example in the preparation of spacers, insulating layers, interlayer dielectric films, insulation layers, planarization layers, protecting layers, overcoat layers, banks for electroluminescence displays and liquid crystal displays (LCD).

##STR00001##

Claims

1: A compound of the formula (I) ##STR00054## wherein X is —O(CO)—; R.sub.1 is C.sub.1-C.sub.12haloalkyl or C.sub.6-C.sub.10haloaryl; R.sub.2 is located in position 7 of the coumarinyl ring and is OR.sub.8; R.sub.2a, R.sub.2b and R.sub.2c independently of each other are hydrogen; R.sub.3 is C.sub.1-C.sub.8haloalkyl or C.sub.1-C.sub.8alkyl; R.sub.4 is hydrogen; and R.sub.8 is C.sub.1-C.sub.6alkyl.

2: A compound of the formula (I) according to claim 1, wherein the formula (I) is the formula (IA) ##STR00055##

3: A compound of the formula (IA) according to claim 2, wherein R.sub.1 is C.sub.1-C.sub.4haloalkyl; R.sub.2 is OR.sub.8; R.sub.3 is C.sub.1-C.sub.4haloalkyl or C.sub.1-C.sub.4alkyl; and R.sub.8 is C.sub.1-C.sub.4alkyl.

4: A compound of the formula (IA), which is ##STR00056##

5: A chemically amplified photosensitive resin composition, comprising: (a) a compound which cures upon the action of an acid, or a compound whose solubility is increased upon the action of an acid; and (b) as a photosensitive acid donor, the compound of the formula (I) according to claim 1.

6: A chemically amplified photosensitive resin composition according to claim 5, which is positive tone.

7: A chemically amplified positive photosensitive resin composition according to claim 6, comprising: (a1) at least one polymer having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution; and/or (a2) at least one monomeric or oligomeric dissolution inhibitor having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution; and/or (a3) at least one alkali-soluble monomeric, oligomeric or polymeric compound; and (b) as the photosensitive acid donor, the compound of the formula (I).

8: A chemically amplified photosensitive resin composition according to claim 5, which is negative tone.

9: A chemically amplified negative photosensitive resin composition according to claim 8, comprising (a4) an alkali-soluble resin as binder; and/or (a6) a solvent-developable resin as binder; and/or (a5) a component which is cationically or acid-catalytically polymerizable or crosslinkable with itself and/or with the other components; and (b) as the photosensitive acid donor, the compound of the formula (I).

10: A photosensitive resin composition according to claim 5, further comprising: further additive (c), a further photosensitive acid donor compound (b1), other photoinitiator (d), and/or a sensitizer (e).

11: A process for preparing a coating, comprising: (1) applying to a substrate the composition according to claim 5; (2) post apply baking the composition at temperatures between 60° C. and 140° C.; (3) image-wise irradiating with light of wavelengths between 200 nm and 450 nm; (4) optionally post exposure baking the composition at temperatures between 60° C. and 140° C.; (5) developing with a solvent or with an aqueous alkaline developer; (6) optionally flood exposing the coating with light of the wavelengths of between 200 nm and 450 nm; and (7) baking at a temperature between 90° C. and 250° C.

12. (canceled)

13: A method for preparing a cured product, comprising: curing a composition including, as a photosensitive acid donor, the compound of the formula (I) according to claim 1 wherein the cured product is selected from the group consisting of pigmented and non-pigmented coatings, adhesives, laminating adhesives, structural adhesives, pressure-sensitive adhesives, printing inks, printing plates, relief printing plates, planographic printing plates, intaglio printing plates, processless printing plates, screen printing stencils, dental compositions, colour filters, spacers, insulating layers, passivation layers, interlayer dielectric films, planarization layers, protecting layers, overcoat layers, banks, electroluminescence displays and liquid crystal displays (LCD), waveguides, optical switches, color proofing systems, etch resists, photoresists for manufacturing electronic circuits and displays, electroplating resists, solder resist, photoresist materials for UV and visible laser direct imaging system, photoresist materials for forming dielectric layers in a sequential build-up layer of a printed circuit board, image-recording materials, image-recording materials for recording holographic images, optical information storage or holographic data storage, decolorizing materials, decolorizing materials for image recording materials, image recording materials using microcapsules, magnetic recording materials, micromechanical parts, plating masks, etch masks, glass fibre cable coatings, and microelectronic circuits.

14: An electroluminescence display or liquid crystal display, comprising: protective coating or insulating layer or color filter, light shielding layer, black matrix, bank or photo-spacer prepared by the process according to claim 11.

15: An integrated circuit or multilayer circuit, prepared by the process according to claim 11.

16: A photosensitive resin composition, comprising: a resin (A) comprising a structural unit having an acid dissociative group and a structural unit having a functional group capable of forming a covalent bond by reacting with a carboxyl group or a phenolic hydroxyl group; and an acid generator (B) represented by the formula (1) according to claim 1, wherein the resin (A) further comprises at least one structural unit derived from a compound selected from the group consisting of a styrene derivative, a maleimide derivative, (meth)acrylic acid and a hydroxyl group-containing (meth)acrylate.

17: A photosensitive resin composition according to claim 16, wherein the functional group capable of forming a covalent bond by reacting with a carboxyl group or a phenolic hydroxyl group is at least one selected from the group consisting of an epoxy group and an oxetanyl group.

18: A method for forming a cured film, the method comprising (1) applying the photosensitive resin composition according to claim 16 onto a substrate to form a photosensitive resin composition layer; (2) removing a solvent from the photosensitive resin composition layer; (3) exposing the photosensitive resin composition from which the solvent has been removed to actinic rays in a patterned manner; (4) developing the exposed photosensitive resin composition with an aqueous developer; and (5) curing the developed photosensitive resin composition layer after being developed by heating.

19: A cured film formed by the method according to claim 18.

20: A cured film according to claim 19, forming an interlayer dielectric film.

21: An organic EL display device, comprising: cured film and a liquid crystal display device comprising the cured film according to claim 19.

Description

APPLICATION EXAMPLES

[0707] Preparation of the Binder Polymer

[0708] To 175.06 g of poly(p-hydorxystyrene), (VP-8000 produced by Nippon Soda Co., LTD., Japan) and 43.9 g of vinyl ethyl ether in tetrahydrofurane (850 ml) are added 78 mg of p-Toluenesulfonic Acid Monohydrate in THF (50 ml). After stirring 14 hours on water bath, the reaction mixture is passed through DIAION CR20 produced by Mitsubishi Chemical Corporation and the DIAION CR20 is washed by tetrahydrofurane (1 L). The combined organic solution is poured into water (15 L) to generate sticky solid. After removing solvents by decantation, 3 L of water is added. After stirring, a white powder is obtained by filtration. After drying at 65° C. for 3 hours followed by 90° C. for 23 hours, 174.8 g of off white solid is obtained.

[0709] Preparation of 1-Ethoxyethyl Methacrylate (MAEVE)

[0710] To 72.70 g of ethyl vinyl ether are added 0.28 g of phenothiazine and 2.80 g of pyridinium p-toluenesulfonate and 43.70 g of methacrylic acid. After stirring 5.5 hours, 2.50 g of sodium sulfate and 2.83 g of sodium bicarbonate are added to the reaction mixture. The insoluble precipitate is filtered and the mixture is concentrated by evapolator. The crude is purified by distillation under vacuum and 64.42 g of MAEVE is obtained as a colorless oil.

[0711] Preparation of Co-Polymer 1

[0712] To 7.93 g of MAEVE and 7.11 g of glycidyl methacrylate in 12.50 g of PGMEA is added 1.05 g of V-65 (produced by Wako Pure Chemical Industries, Ltd.) in 10.01 g of PGMEA dropwise at 70′C under a flow of nitrogen. The mixture is stirred for 8.5 hours and a solution of co-polymer 1 is obtained (solid content: 40%). It was found by means of gel permeation chromatography (GPC) that the weight-average molecular weight (Mw) of the co-polymer 1 is 56,000.

Example A1

[0713] Photosensitivity is measured in a model photosensitive resin composition under i-line exposure via a bandpass filter (Schott, Germany) with Mask Aligner PLA-501F (Canon, Japan) as an exposure tool. The positive tone resist utilizes the copolymer as prepared above. As for solvent, propylene glycol methyl ether acetate (PGMEA) from Tokyo Kasei Kogyo Co. LTD. is employed. The exact composition of the formulation and the amount of the photoacid generator (PAG) is described in Table 2.

[0714] The resist formulations are spin-coated at 1 μm thickness on silicon wafers on which hexamethyldislazane treatment is applied in advance and prebaked at 100° C. for 1 min. After exposure with various exposure doses, no post exposure bake but post exposure delay for 5 min is applied and the resists are then developed in NMD-3 developer from Tokyo Ohka Kogyo Co. Ltd., which is 2.38% aqueous tetramethyl ammonium hydroxide solution, for 1 min.

TABLE-US-00002 TABLE 2 Binder polymer (parts) 100 PAG (parts) 2 Solvent (parts) 400

[0715] As a measure for photosensitivity, the “Dose to Clear” (E.sub.0), which is the dose just sufficient to completely remove the resist film with 1 min development, is determined. The smaller the required dose, the more sensitive is the resist formulation. The results are collected in Table 4 below and demonstrate that the compositions according to the invention are suitable for the preparation of positive tone resists.

Example A2

[0716] A formulation for transparency evaluation is prepared with the solution of co-polymer 1 mentioned above (solid content: 40%), PAG and solvent, PGMEA. The exact composition of the formulation is described in Table 3.

TABLE-US-00003 TABLE 3 solution of co-polymer 1 (parts) 100 PAG (parts) 0.8 Solvent (parts) 50

[0717] The formulations are spin-coated at 700 rpm on glass plates and prebaked at 80° C. for 10 min. Without exposure process, final bake process is applied at 210° C. for 30 min. Thickness of the final cured film is at 3 μm

[0718] The transparency of the cured film is measured at a wavelength region from 400 to 800 nm with a UV-VIS spectrophotometer, UV-2550 from Shimadzu Corporation. The lowest transmittances as measured are listed in Table 4.

TABLE-US-00004 TABLE 4 Compound of example E.sub.0 [mJ/cm.sup.2] Transparency [%] OS1 20 — OS2 2.6 97.1 OS3 6.2 — OS4 21 — OS11 1.7 92.3 OS16 2.4 94.9 OS17 1.5 98.8 OS24 1.0 90.4 OS25 0.7 96.7 OS26 17 97.7

[0719] The results show, that the compound of the present invention provides a perfect balance between photosensitivity and transparency, which is in particular benevolent for the formation of insulation layers.