JP2005043883A5 - - Google Patents

Description

That is, the present invention contains (a) a polymer mainly composed of the structural unit represented by the general formula (1), (b) two or more photoacid generators, and (c) an alkoxymethyl group-containing compound , (B) Among the two or more photoacid generators, at least one is a quinonediazide compound, and at least one is at least one selected from a sulfonium salt, a phosphonium salt, and a diazonium salt . It is a resin precursor composition.

In the present invention, two or more photoacid generators are used as the component (b). At least one type is used for the purpose of developing positive photosensitivity, and at least one type is used for the purpose of appropriately stabilizing the acid component generated by exposure by the photoacid generator that develops the positive type. As a result, a photosensitive resin composition having excellent post-exposure storage stability can be obtained. Photoacid generator which express positive photosensitivity is Ru der quinonediazide compound. The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound, and a sulfonamide of quinonediazide is bonded to a polyhydroxypolyamino compound and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. If it is less than 50 mol%, the solubility in an alkali developer becomes too high, and a contrast with an unexposed portion cannot be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

Among photo-acid generator to be used as component (b) of the present invention, the photoacid generator to appropriately stabilize the acid component that caused by exposure, Ru compound der selected sulfonium salts, phosphonium salts, diazonium salts . By using these, the standing stability after exposure is remarkably improved. Since the resin composition obtained from the photosensitive resin precursor composition of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus or the like remains, and it is necessary to consider the color tone of the film. Of these, sulfonium salts are preferably used. Of the sulfonium salts, structures represented by the general formulas (14) to (16) are preferably used.

R ^{41 to} R ^{43 in the} general formulas (14) to (16) may be the same as or different from each other, and represent an organic group selected from 1 to 20 carbon atoms. R ⁴⁴ and R ⁴⁵ represent a single bond or an organic group selected from 1 to 20 carbon atoms. Z ⁻ represents an anion moiety selected from R ⁴⁶ SO ₃ ⁻ , R ⁴⁶ COO ⁻ and SbF ₆ ^— . R ⁴⁶ represents an organic group selected from 1 to 20 carbon atoms. Specific examples of the sulfonium salt represented by the general formula (14) are shown below, but are not limited thereto.

Claims (5)

(A) a polymer containing the structural unit represented by the general formula (1) as a main component, (b) two or more photoacid generators, (c) an alkoxymethyl group-containing compound , and (b) two types Among the above photoacid generators, at least one is a quinonediazide compound, and at least one is at least one selected from sulfonium salts, phosphonium salts, and diazonium salts , a photosensitive resin precursor composition .

(Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ³ is hydrogen or carbon. Any one of the organic groups from 1 to 20. n is in the range from 10 to 100,000, m is an integer from 0 to 2, p, q is an integer from 0 to 4, provided that p + q> 0.) (B) Of the two or more photoacid generators, at least one is a quinonediazide compound, and at least one is a sulfonium salt selected from the general formulas (14) to (16). 1. The photosensitive resin precursor composition according to 1.

(In the formula, R ^{41 to} R ⁴² may be the same or different and each represents an organic group selected from 1 to 20 carbon atoms. R ⁴⁴ and R ⁴⁵ represent a single bond and an organic group selected from 1 to 20 carbon atoms. .Z showing a group ^- is _{^{R 46 SO 3 -, R 46}} COO -, SbF 6 - represents an anion portion selected from ^{.R 46} represents an organic group selected from 1 to 20 carbon atoms). (B) The photosensitive resin precursor composition according to claim 1, wherein at least one of the two or more photoacid generators is a quinonediazide compound and at least one is a triarylsulfonium salt. . (C) alkoxymethyl group-containing compound, according to claim 1 to 3, characterized in that the compounds containing urea organic group represented by the compound containing a phenolic hydroxyl group and / or the general formula (2) The photosensitive resin precursor composition in any one.

(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms.) (D) At least 1 sort (s) of the compound chosen from the compound represented by General formula (3), the compound represented by General formula (4), and a vinylsilane compound is included, The any one of Claims 1-4 characterized by the above-mentioned. The photosensitive resin precursor composition as described.

(Ar ¹ and Ar ² represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. R ⁵ , R ⁶ , R ¹² , R ¹⁴ , R ²¹ , R ²² may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms, and R ⁷ , R ¹⁵ , and R ²⁰ may be the same or different and each have 1 to 6 carbon atoms. Represents an organic group, and R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ may be the same or different and are selected from a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group. And at least one of R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms, a, d, f, and h are integers of 1 or more, and b, c, e, and g are Represents an integer greater than or equal to 0. 1 ≦ a + b ≦ 4, 1 ≦ d + e ≦ 4, A ≦ g + h ≦ 4.)