KR20130051402A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE: A positive photosensitive composition is provided to have high sensitivity, make firing after exposure unnecessary and be excellent in forming a transparent film with patterns. CONSTITUTION: A positive photosensitive composition comprises a radical polymer monomer(a1) with alkoxysilyl, a polymer(A) made of a radical polymer monomer(a1,a2) and the other radical polymer monomer(a3), a photo acid generator(B) and an organic solvent(C). The positive photosensitive composition is characterized by a compound such as a radical polymer monomer(a1) represented by chemical formula (I), (II) and (III). The transparent film is formed by the exposure, the development and the firing of the positive photosensitive composition. An insulated layer uses the transparent film. A displaying device comprises the transparent film with patterns.

Description

Positive type photosensitive composition {POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive composition that can be used in the field of resists and the like.

Patterned transparent films are used in many fields of display devices such as spacers, insulating films, protective films, and the like, and many positive photosensitive compositions have been proposed for this purpose (see, for example, Patent Documents 1 to 3).

In general, an electronic component such as a thin film transistor type liquid crystal display element or a solid-state image sensor is provided with an insulating film for insulating between wirings arranged in a layer form. As a material for forming such an insulating film, a positive photosensitive composition having a small number of steps for obtaining an insulating film having a pattern shape required is widely used. The positive photosensitive composition needs to have a wide process margin in the process of forming the insulating film. In addition, the insulating film or display element employing the positive photosensitive composition may be subjected to contact and heat treatment by immersion in a solvent, an acid, an alkali solution, or the like in a post-process (ITO film formation / wet etching, alignment film formation, etc.) after the formation of the insulating film. Because it can be, it needs to be resistant to them. Moreover, high transparency with respect to visible light is calculated | required in the insulating film which can be used for display elements, such as a liquid crystal display.

Moreover, in the use of the photosensitive insulating film which can be used for display elements, such as a liquid crystal display, in recent years, as a mother glass dimension becomes larger, the tact time is performed in a series of processes of the photosensitive material in order to ensure productivity. There is a need for shortening.

High sensitivity positive photosensitive compositions provided for these uses have been proposed. For example, Patent Document 4 discloses a resist containing a polymer having a t-butylester group of carboxylic acid or a t-butylcarbonate group of phenol and a photoacid generator. It is starting. The t-butyl ester group or t-butyl carbonate group in the polymer is deprotected by acid generated during exposure and post exposure bake (PEB), and is converted into an acidic group such as a carboxyl group or a phenolic OH. . As a result, the exposed portion of the resist film is dissolved in the alkaline developer. However, such a system requires a PEB process after exposure, and although there is a high sensitivity in the exposure dose, there is a problem that the overall tact time of the process is not shortened.

On the other hand, Patent Document 5 describes a positive resist composition containing an alkoxysilane-containing vinyl copolymer and a curing catalyst, and contains an alkoxysilane group-containing acrylic acid ester and methacrylic acid ester as a monomer component of the copolymer. Halogen-substituted acrylic acid esters are described, examples of using hydrochloric acid as a curing catalyst.

Prior art literature

Patent Document 1: Japanese Patent Laid-Open No. 51-034711

Patent Document 2: Japanese Patent Laid-Open No. 56-122031

Patent Document 3: Japanese Patent Application Laid-Open No. 05-165214

Patent Document 4: Japanese Patent Application Laid-open No. 02-027660

Patent Document 5: Japanese Patent Laid-Open No. 2002-196494

The present invention provides a positive photosensitive composition capable of forming a patterned transparent film (patterned transparent film) that is highly sensitive and does not require post-exposure baking.

MEANS TO SOLVE THE PROBLEM This inventor is formed by radically copolymerizing radically polymerizable monomer (a3) other than the radically polymerizable monomer (a1) which has an alkoxysilyl, the radically polymerizable monomer (a2) which has an acidic group, (a1), and (a2). It was found that the above-mentioned problems can be solved by the positive photosensitive composition containing (A), the photoacid generator (B), and the organic solvent (C), and completed the present invention on the basis of this viewpoint. The present invention includes the following matters.

(1) A polymer formed by radical copolymerization of a radically polymerizable monomer (a1) having an alkoxysilyl, a radically polymerizable monomer (a2) having an acidic group, and a radically polymerizable monomer (a3) other than (a1) and (a2) ( A positive photosensitive composition containing A), a photo-acid generator (B), and an organic solvent (C).

(2) The positive photosensitive composition as described in said (1) whose radically polymerizable monomer (a1) which has the said alkoxysilyl is one or more of the compounds represented by following General formula (I), general formula (II), and general formula (III).

(I)

≪ RTI ID = 0.0 &

[Formula III]

(In the formulas, R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms, which any hydrogen may be substituted with fluorine, and R ² to R ¹⁰ are each hydrogen, halogen, —CN, —CF ₃ , —OCF ₃ , -OH, linear or branched alkyl of 1 to 20 carbon atoms or alkoxy of 1 to 5 carbon atoms, alkyl in R ² to R ¹⁰ is -CH ₂ -is -COO-, -OCO-, -CO- Or -O- and optionally hydrogen may be substituted with halogen, provided that at least one of R ² to R ⁴ is alkoxy having 1 to 5 carbon atoms and at least one of R ⁵ to R ⁷ has 1 carbon atom. Alkoxy of 5 to 5, and at least one of R ⁸ to R ¹⁰ is alkoxy of 1 to 5. In addition, in formula (I), n is 1 to 5).

(3) The radically polymerizable monomer selected from the radically polymerizable monomer (a2) having the acidic group is a radically polymerizable monomer having a phenolic OH, a radically polymerizable monomer having an unsaturated carboxylic acid, or a radically polymerizable monomer having an unsaturated carboxylic anhydride. The positive photosensitive composition as described in said (1) or said (2) which is 1 or more types in it.

(4) To any one of the above items (1) to (3) containing a radical polymerizable monomer having a acidic group (a2) and a radical polymerizable monomer having a phenolic OH represented by the following general formula (IV). The positive photosensitive composition described.

(IV)

(In formula (IV), R ¹¹ , R ¹² and R ¹³ are each hydrogen or alkyl having 1 to 3 carbon atoms, which any hydrogen may be substituted with fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and Alkyl for R ¹⁸ may be substituted with any —CH ₂ — with —COO—, —OCO—, or —CO—, alkyl for R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ , and Alkoxy may be optionally substituted with hydrogen, provided that at least one of R ¹⁴ to R ¹⁸ is -OH.

(5) The positive photosensitive composition as described in any one of said (1)-(4) whose said radically polymerizable monomer (a3) is a radically polymerizable monomer which has an epoxy.

(6) The positive photosensitive composition according to any one of items (1) to (5), wherein the organic solvent (C) is a solvent having a hydroxyl group.

(7) The pattern-shaped transparent film formed by exposure, image development, and baking of the coating film of the positive photosensitive composition in any one of said (1)-(6).

(8) An insulating film using the patterned transparent film as described in said (7).

(9) The display element which has a transparent film of pattern shape as described in said (7) or (8).

The present invention contains a specific polymer (A), a photoacid generator (B) and an organic solvent (C) as described above, which does not require high-sensitivity and post-exposure baking, and furthermore has a pattern-shaped transparent excellent in transparency. It is possible to provide a positive photosensitive composition capable of forming a film.

1. Photosensitive composition of the present invention

The photosensitive composition of the present invention is a polymer (A) formed by radical polymerization of a radical polymerizable monomer (a1) having an alkoxysilyl, a radical polymerizable monomer (a2) having an acidic group, another radical polymerizable monomer (a3), and photoacid generation. Agent (B) and an organic solvent (C). You may use polymer (A) 1 type or in mixture of 2 or more types of polymers. The photoacid generator (B) may also be used alone or in combination of two or more thereof, and the organic solvent (C) may be used alone or in combination of two or more thereof.

Even in a composition containing only a polymer formed by polymerizing a radically polymerizable monomer (a1) having an alkoxysilyl and a photoacid generator (B), patterning is possible once by exposure and alkali development, but the patterned transparent film In order to impart various functions such as sensitivity, transparency, chemical resistance (acid, alkali, organic solvent), sputter resistance, low dielectric constant, reliability, etc., monomers (a2), (a1), and ( It is also necessary to copolymerize with monomers (a3) other than a2).

1-1. Polymer (A) of the invention

The polymer (A) of the present invention polymerizes a radically polymerizable monomer (a3) other than a radically polymerizable monomer (a1) having an alkoxysilyl, a radically polymerizable monomer (a2) having a acidic group, (a1) and (a2). It is a copolymer obtained.

The polymer (A) may use a single or a plurality of radical polymerizable monomers, respectively, as the radical polymerizable monomers (a1), (a2) and (a3).

In the polymer (A), the radically polymerizable monomer (a1) is preferably used at a ratio of 5% by weight to 50% by weight relative to the total weight of all monomers, and is used at a rate of 10% by weight to 40% by weight. More preferably. When monomer (a1) is contained in such a range, it is preferable in sensitivity, transparency, board | substrate adhesiveness, image development stability, storage stability as a solution, etc.

In addition, in the polymer (A), the radically polymerizable monomer (a2) is preferably used in a ratio of 1% by weight to 20% by weight relative to the total weight of all monomers, and a ratio of 5% by weight to 15% by weight. More preferably used as. It is preferable in the solubility to alkaline developing solution to contain a monomer (a2) in such a range.

Furthermore, in the polymer (A), the radically polymerizable monomer (a3) is preferably used in a ratio of 30% by weight to 94% by weight with respect to the total weight of all monomers, and a ratio of 40% by weight to 80% by weight. More preferably used as.

When monomer (a3) is contained in such a range, it is preferable in developability, low dielectric property, chemical resistance, etc.

1-1-1. Alkoxysilyl  Have Radical Polymerizable  Monomer ( a1 )

The radically polymerizable monomer (a1) having an alkoxysilyl can be selected from compounds represented by the following general formulas (I), (II) and (III).

(I)

≪ RTI ID = 0.0 &

[Formula III]

In the above formulas (I), (II) and (III), R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms which any hydrogen may be substituted with fluorine, and R ² to R ¹⁰ are each hydrogen, Halogen, -CN, -CF ₃ , -OCF ₃ , -OH, straight or branched alkyl of 1 to 20 carbon atoms or alkoxy of 1 to 5 carbon atoms, alkyl in R ² to R ¹⁰ is any -CH ₂ -May be substituted with -COO-, -OCO-, -CO-, or -O-, and any hydrogen may be substituted with halogen, provided that at least one of R ² to R ⁴ has 1 to 5 carbon atoms Alkoxy, at least one of R ⁵ to R ⁷ is alkoxy having 1 to 5 carbon atoms, and at least one of R ⁸ to R ¹⁰ is alkoxy having 1 to 5 carbon atoms. N is 1 to 5 in the formula (I).

It is preferable that alkyl of said R <^1> is methyl in heat resistance, transparency, etc. In addition, the linear or branched alkyl having 1 to 20 carbon atoms of R ² to R ⁴ preferably has 1 to 10 carbon atoms in terms of alkali developability and heat resistance (glass transition point) of the film.

Moreover, it is preferable that C1-C10 is C1-C10 linear alkyl of said R <^5> -R <^8> or branched C1-C20 (optional hydrogen may be substituted by halogen) for the same reason.

In addition, carbon number of the at least 1 alkoxy in R <^2> -R <^4> , the at least 1 alkoxy in R <^5> -R <^7> , and the at least 1 alkoxy in R <^8> -R <^10> is respectively 1 for the reason of hydrolyzability. It is preferable that it is -5.

As a radically polymerizable monomer which has an alkoxysilyl, the quantity in the polymer of the compound (a1) represented by said Formula (I), Formula (II), and Formula (III) is 100 weight part of polymers, Preferably it is 5 weight part Although it is 50 parts by weight, the relative dielectric constant tends to increase when the amount of (a1) is too large. Therefore, 10 parts by weight to 40 parts by weight is preferable in applications where the relative dielectric constant is to be lowered.

Specific examples of the compound (a1) represented by the general formulas (I), (II), and (III) include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-methacryl Oxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. are mentioned. have. When the copolymer using these radically polymerizable monomers is used, it has a high sensitive positive characteristic, has high transparency, hardly deteriorates transparency due to baking at high temperatures, and has high solubility in aqueous alkali solution during development. While developability is high, a pattern-shaped transparent film can be obtained easily, and also solvent resistance, high water resistance, acid resistance, alkali resistance, heat resistance, etc. are exhibited, and also adhesiveness with a base material becomes high.

In the present invention, a radically polymerizable monomer (a1) having an alkoxysilyl is used as a monomer of the polymer (A). The alkoxysilyl in the polymer (A) is hydrolyzed to silanol due to the acid generated by exposure. As a result, the polymer (A) is dissolved in the alkaline developer. Accordingly, in the case of having the positive photosensitive composition of the present invention, it is possible to proceed to the developing step as it is, without needing to fire after exposure (after exposure).

1-1-2. Radically polymerizable monomer (a2)

As a radically polymerizable monomer (a2) which has an acidic group which can be used by this invention, the radically polymerizable monomer which has unsaturated carboxylic acid, the radically polymerizable monomer which has unsaturated carboxylic anhydride, the radically polymerizable monomer which has phenolic OH, phosphorus The radically polymerizable monomer which has an acidic radical, and the radically polymerizable monomer which has a sulfonic acid group is mentioned.

Acrylic acid, methacrylic acid, etc. are mentioned as a specific example of the radically polymerizable monomer which has an unsaturated carboxylic acid, A maleic anhydride is mentioned as a specific example of the radically polymerizable monomer which has an unsaturated carboxylic anhydride.

As a radically polymerizable monomer which has the said phenolic OH, the radically polymerizable monomer which has hydroxy styrene and phenolic OH shown by following General formula (IV) is mentioned, for example.

(IV)

(In the formula (IV), R ¹¹ , R ^12, and R ¹³ are each hydrogen or alkyl having 1 to 3 carbon atoms which any hydrogen may be substituted with fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17. And R ¹⁸ is hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R Alkyl for ¹⁷ and R ¹⁸ may be substituted with any —CH ₂ — with —COO—, —OCO—, or —CO—, and for R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ . Alkyl and alkoxy may be any hydrogen substituted with halogen, provided that at least one of R ¹⁴ to R ¹⁸ is —OH.)

As a specific example of the radically polymerizable monomer which has phenolic OH shown by the said General formula (IV), 4-hydroxyphenyl vinyl ketone is mentioned.

As a radically polymerizable monomer which has a phosphoric acid group, methacrylate phosphate, 2-methacryloyloxyethyl acid phosphate, 2- (methacryloyloxy) ethyl, etc. are mentioned, for example.

As a radically polymerizable monomer which has a sulfonic acid group, vinyl sulfonic acid, acrylamide-tert- butyl sulfonic acid, etc. are mentioned, for example.

It is preferable from the viewpoint of alkali solubility to use a copolymer using the radical polymerizable monomer. These radically polymerizable monomers may be used alone or in combination.

Among the above specific examples, methacrylic acid, hydroxystyrene or 4-hydroxyphenylvinyl ketone are preferred. Methacrylic acid and hydroxy styrene are easily available, and 4-hydroxyphenylvinyl ketone can obtain good characteristics in storage stability such as transparency, heat resistance, and composition.

1-1-3. Radically polymerizable monomer (a3)

Other radically polymerizable monomers (a3) usable in the present invention include radically polymerizable monomers having an epoxy, radically polymerizable monomers having a dicyclopentanyl, radically polymerizable monomers having an N-substituted maleimide, and radically polymerizable having a siloxane. A monomer etc. can be used. One or more monomers may be used. Specific examples of the radical polymerizable monomer having an epoxy include glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, methylglycidyl methacrylate, α-ethylacrylic acid glycidyl ester 3, 4-epoxycyclohexyl acrylate, the (alpha)-ethylacrylic-acid glycidyl ester 3, 4- epoxycyclohexyl methacrylate, etc. are mentioned. When a copolymer using such radically polymerizable monomers is used, sputter resistance is good and chemical resistance is high.

Moreover, as a specific example of the radically polymerizable monomer which has dicyclopentanyl, and the radically polymerizable monomer which has N substituted maleimide, dicyclopentanyl acrylate or dicyclopentanyl methacrylate, N-methyl maleimide, N-ethylmaleimide , N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide , N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl-4) maleimide, N- [4- (2-benzoxazolyl) phenyl] maleic Mid, N- (9-acridinyl) maleimide, etc. are mentioned.

Use of such radically polymerizable monomers is preferable in view of heat resistance and low dielectric constant.

Specific examples of the radically polymerizable monomer having a siloxane used in the present invention include acryloyloxypropyl-tris-trimethylsiloxysilane, methacryloyloxypropyl-tris-trimethylsiloxysilane, and the like.

Furthermore, in the range which does not impair the effect of this invention, the said polymer (A) may use radical polymerizable monomers other than the above-mentioned.

As such a radically polymerizable monomer, benzyl methacrylate and cyclohexyl methacrylate are mentioned, for example.

It is preferable that the said polymer (A) has moderate alkali solubility. In the present invention, alkali-soluble means that a film of about 0.01 μm to 100 μm in thickness formed by applying a solution of polymer (A) formed by radical polymerization to a substrate by spin coating and heating at 100 ° C. for 2 minutes, 25 When immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 5 ° C. for 5 minutes and then rinsed with pure water, it refers to a property that the film dissolves to an extent such that alkali does not remain.

Alkali solubility of the polymer (A) formed by radical polymerization is radical polymerizable monomer having a phenolic OH, a radical polymerizable monomer having an unsaturated carboxylic acid or an unsaturated carboxylic anhydride used for the radical polymerizable monomer (a2). It can adjust with the quantity of a monomer. For example, alkali solubility of the polymer (A) formed by radical polymerization increases the amount of a radically polymerizable monomer having a phenolic OH, a radically polymerizable monomer having an unsaturated carboxylic acid or a radically polymerizable monomer having an unsaturated carboxylic anhydride. It can raise by making it.

Although the synthesis | combining method of a polymer (A) is not specifically limited, It is possible to make it by radical copolymerization of a radically polymerizable monomer. Specifically, it can obtain by polymerizing the mixture of radically polymerizable monomers (a1), (a2), and (a3), and radical polymerization in the solution using a solvent is preferable. In addition, a polymerization initiator can also be used at the time of such radical polymerization.

When using a polymerization initiator, superposition | polymerization temperature will not be specifically limited if it is the temperature which a radical generate | occur | produces sufficiently in the polymerization initiator to be used, but it is usually the range of 50 degreeC-about 150 degreeC. The polymerization time is also not particularly limited, but is usually in the range of about 1 hour to about 24 hours. In addition, this superposition | polymerization can be performed under any pressure of pressurization, reduced pressure, or atmospheric pressure.

The solvent used for the said polymerization reaction dissolves the radically polymerizable monomer to be used, and the polymer (A) to produce | generate. In particular, the solvent which has a hydroxyl is preferable in the storage stability of the polymer superposed | polymerized. However, the hydroxyl-containing solvent may be used as a diluting solvent of the polymer after polymerization in another solvent. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone , Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 3-methoxypropionate, 3-E Ethyl oxypropionate, N, N-dimethylformamide, and the like. One kind of these solvents may be used, or a mixture of two or more kinds thereof may be used.

The polymerization initiator which can be used when synthesize | combining a polymer (A) is azo system, such as a compound which generate | occur | produces a radical by heat, and azobisisobutyronitrile and 2,2'- azobis (2, 4- dimethylvaleronitrile). Peroxide type initiators, such as an initiator and benzoyl peroxide, can be used. In order to adjust molecular weight, you may add an appropriate amount of chain transfer agents, such as thioglycolic acid.

If the polymer (A) has a weight average molecular weight determined by GPC analysis based on polystyrene as the range of about 1,000 to 100,000, the development time until the exposed portion is dissolved in the alkaline developer is appropriate, and the film base is developed at the time of development. It is preferable because it does not become rough easily. In addition, if the weight average molecular weight is in the range of about 1,500 to 50,000, the development time until the unexposed portion is dissolved in the alkaline developer is appropriate, and the base of the film is not easily roughened at the time of development, and the development residue is also very small. More preferred. For the same reason, the weight average molecular weight is particularly preferably in the range of about 2,000 to 20,000.

Polystyrene having a molecular weight of about 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by VARIAN), PLgel MIXED-D (manufactured by VARIAN) for the column, and THF as a mobile phase can do.

The polymer (A) of this invention can be adjusted to a preferable molecular weight according to the monomer concentration at the time of superposition | polymerization, the quantity of a polymerization initiator, and superposition | polymerization temperature. For example, it is preferable that the monomer concentration at the time of superposition | polymerization (concentration of the monomer whole quantity melt | dissolved in the solvent in the solvent used for the said polymerization reaction) is about 5 weight%-60 weight% in the ease of manufacture, and it is 15 weight More preferably, it is about 50% by weight.

Moreover, in the positive photosensitive composition of this invention, it is preferable that content of the said polymer (A) is 1 weight%-60 weight% with respect to the said composition whole quantity, It is more preferable that it is 3 weight%-40 weight%, Particular preference is given to 5% to 35% by weight.

In addition, content of the said polymer (A) can be suitably adjusted in the above-mentioned range according to the application | coating method of the positive photosensitive composition of this invention. For example, the spin coat increases the content of the polymer (A) to increase the viscosity of the composition, while the slit coat decreases the viscosity of the composition by reducing the content of the polymer (A).

2. Photoacid generator (B) of the present invention

Examples of the photoacid generator used in the present invention include onium salt-based photoacid generators such as diphenyl iodinium salt and triphenylsulfonium salt, and sulfonyl imide compound photoacid generators.

Examples of the diphenyl iodonium salt include diphenyl iodide tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoracenate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoro Acetate, diphenyl iodonium-p-toluenesulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, bis (4-t-butylphenyl Iodide tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) Iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Triphenyl sulfonium butyl tris (2, 6- difluorophenyl) borate etc. are mentioned.

Examples of the sulfonylimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyl Oxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmalee Mid, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4- Fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3- Carboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- ( Camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4 -Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2- Trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4- Fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (4 -Methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (Trifluoromethylsulfonyloxy) naphthyldicarboxyimide, N- (camphorsulfonyloxy) naphthyldicarboxyimide, N- (4-methylphenylsulfonyloxy) naphthyldicarboxyimide, N- (phenylsulfonium Ponyloxy) naphthyl dicarboxyl Mead, N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxyimide, N- (pentafluoroethylsulfonyloxy) naphthyldica Foxyimide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxyimide, N- (nonnafluorobutylsulfonyloxy) naphthyldicarboxyimide, N- (ethylsulfonyloxy) naphthyldicarboxyimide, N -(Propylsulfonyloxy) naphthyldicarboxylimide, N- (butylsulfonyloxy) naphthyldicarboxyimide, N- (pentylsulfonyloxy) naphthyldicarboxyimide, N- (hexylsulfonyloxy) nap Tyldicarboxyl imide, N- (heptylsulfonyloxy) naphthyl dicarboxyl imide, N- (octylsulfonyloxy) naphthyl dicarboxyimide, N- (nonylsulfonyloxy) naphthyl dicarboxyimide, etc. are mentioned. have.

In the present invention, in particular, in the case of using the positive photosensitive composition of the present invention for the purpose of producing a transparent film, using the photoacid generator as described above, a post-exposure step for photodegrading all the photoacid generators remaining after development is performed. It is preferable because there is no need.

In the positive photosensitive composition of the present invention, the content of the photoacid generator (B) is preferably 0.1% by weight to 10% by weight, more preferably 0.3% by weight to 5% by weight based on the polymer (A). , 0.5% to 3% by weight is particularly preferred.

3. Organic solvent (C) of this invention

The positive photosensitive composition of the present invention further contains an organic solvent (C) in addition to the polymer (A) and the photoacid generator (B) contained in the composition. The organic solvent used in the present invention is preferably an organic solvent which dissolves the polymer (A) and the photoacid generator (B), and furthermore, the time difference between processes due to storage stability as a composition, trouble during the manufacturing process of the patterned transparent film, and the like. In the case of occurrence of, in the time-lapse stability of the coating film, the organic solvent is more preferably an organic solvent having a hydroxyl. It is preferable that the boiling point of the organic solvent is 100 ° C to 300 ° C. Specific examples of the organic solvent having a boiling point of 100 ° C. to 300 ° C. include butyl acetate, butyl propionate, ethyl lactate, methyl hydroxy acetate, ethyl hydroxy acetate, butyl hydroxy acetate, methyl methoxy acetate, ethyl methoxy acetate, and methoxy Butyl oxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-e Ethyl oxypropionate, 2-hydroxy-2-methyl methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate Ethyl pyruvate, Propyl pyruvate, methyl aceto acetate, ethyl aceto acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl Ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene Glycol monobutyl ether Three Tate, D. may be mentioned ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ- butyrolactone or N, N- dimethylacetamide. These may be used independently and may be used in combination of 2 or more type.

In the positive photosensitive composition of the present invention, the content of the organic solvent (C) is preferably 40 wt% to 99 wt%, more preferably 50 wt% to 90 wt% with respect to the total amount of the composition, and more preferably 60 Particular preference is given to weight percent to 80 weight percent.

4. Other ingredients

Various additives can be added to the photosensitive composition of this invention in order to improve resolution, application | coating uniformity, developability, and adhesiveness. Such additives include anionic, cationic, nonionic, fluorine or silicone leveling agents, surfactants, and silane coupling agents, such as adhesion improving agents, ultraviolet absorbers such as alkoxybenzophenones, epoxy compounds, melamine compounds, or bisazide compounds, and the like. Alkali solubility promoters, such as a crosslinking agent, a polycarboxylic acid, and a phenol compound, antioxidants, such as a hindered phenol type, a hindered amine type, a phosphorus type, and a sulfur type compound, are mentioned mainly.

4-1. Leveling agents, surfactants

In the photosensitive composition of the present invention, polyprop No. 45, polypro KL-245, polypro 75, polyprow no. 90, polyprow no. 95 (above, all brand names, KYOEISHA CHEMICAL CO., LTD), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all, brand names, BIC Chemie) Japan Corporation (BYK Japan KK), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (above, all brand names, Shin-Etsu Chemical Co., Ltd.) (Shin-Etsu Chemicla Co., Ltd)), Safron SC-101, Safron KH-40 (above, all trade names, AGC SEIMI CHEMICAL CO., LTD.), Futagent 222F, Futagent 251, FTX-218 (all, brand name, NEOS COMPANY Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (more, Mitsubishi Materials Corporation (Mitsubishi Materials Corporation), Mega Pack F-171, Mega Pack F-177, Mega Pack F-475, Mega Pack F-556, Mega Pack R-30 (above, all , DIC Corporation), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammo Iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether , Polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene Oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, poly Oxyethylene sorbitan palmitate, poly ox Ciethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, etc. are mentioned. It is preferable to use at least one selected from these for the additive.

Among these additives, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate and diglycerin tetrakis (fluoroalkyl polyoxyethylene ether) Fluorine-based surfactants such as fluoroalkyltrimethylammonium salts and fluoroalkylaminosulfonate salts, and at least one selected from silicon-based surfactants such as BYK306, BYK346, KP-341, KP-358, or KP-368 is added. Since coating uniformity becomes high, it is preferable.

It is preferable that content of the said leveling agent and surfactant in the photosensitive composition of this invention is 0.001 weight%-0.1 weight% with respect to the total amount of a composition, respectively.

4-2. Organic carboxylic acid

Organic carboxylic acid can be used for the said alkali solubility promoter. The organic carboxylic acid may be one kind or two or more kinds. As organic carboxylic acid, polyhydric carboxylic acid is preferable and as such polycarboxylic acid, trimellitic anhydride, a phthalic anhydride, and 4-methylcyclohexane-1, 2- dicarboxylic acid anhydride are mentioned, for example. Among these polycarboxylic acids, trimellitic anhydride is preferable.

When polyhydric carboxylic acid is added to the photosensitive composition of this invention, alkali solubility of a photosensitive composition can be improved. In addition, when the carboxyl of the polycarboxylic acid includes epoxy in the photosensitive composition, the carboxyl may further improve heat resistance, chemical resistance, and the like.

It is preferable that it is 1-30 weight part with respect to 100 weight part of polymers (A), and, as for content of the said organic carboxylic acid in the photosensitive composition of this invention, it is more preferable that it is 2 weight part-20 weight part.

4-3. Phenolic compounds

A phenolic compound can be used for the said alkali solubility promoter. The phenol compound may be one kind or two or more kinds. As a phenolic compound, for example, 2,3,4-trihydroxy benzophenone, 2,4,6-trihydroxy benzophenone, 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3 , 3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, Tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3 , 4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3' -Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, and 2,2,4-trimethyl-7,2 ', 4'-trihydr Roxyflavan is mentioned. Among these phenolic compounds, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol is preferable.

When a phenolic compound is added to the photosensitive composition of this invention, alkali solubility of a photosensitive composition can be improved. In addition, when phenol of the phenol compound includes an epoxy in the photosensitive composition, it can react with these to further improve heat resistance, chemical resistance and the like.

It is preferable that it is 1 weight part-50 weight part with respect to 100 weight part of polymers (A), and, as for content of the phenolic compound in the positive photosensitive composition of this invention, it is more preferable that it is 5 weight part-20 weight part.

4-4. Antioxidant

As said antioxidant, antioxidant of a hindered phenol type, a hindered amine type, a phosphorus type, and a sulfur type compound can be used suitably. The antioxidant may be one kind or two or more kinds. It is preferable from the viewpoint of weather resistance that the said antioxidant is antioxidant of a hindered phenol type compound. As such an antioxidant, for example, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox, 2245, Irganox2,25 Irgan, Irganox, BASF Japan Co., Ltd., ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, and ADK STAB AO-80 (trade name; ADEKA ( Note) can be mentioned. Among these, Irganox1010 is more preferable.

It is preferable that it is 0.1 weight part-15 weight part with respect to 100 weight part of polymers (A), and, as for content of antioxidant in the photosensitive composition of this invention, it is more preferable that it is 1 weight part-10 weight part.

4-5. Adhesion Enhancer

The said adhesion improving agent is used in order to improve the adhesiveness of the photosensitive composition and a board | substrate. A coupling agent can be used suitably for an adhesive improving agent. 1 type or 2 or more types of adhesive improving agents may be sufficient. As the coupling agent, a silane-based, aluminum-based, or titanate-based compound may be used. As such a coupling agent, for example, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, acetalkoxy aluminum diisopropylate, And tetraisopropylbis (dioctylphosphite) titanate. Among these, 3-glycidoxy propyl trimethoxysilane is preferable because the effect of improving adhesiveness is large.

It is preferable that content of the adhesive improvement agent in the photosensitive composition of this invention is 10 weight part or less with respect to 100 weight part of polymers (A).

4-6. Ultraviolet absorber

As said ultraviolet absorber, the component used as a ultraviolet absorber in photosensitive compositions, such as alkoxy benzophenones, can be used. The ultraviolet absorber may be one kind or two or more kinds. As such a ultraviolet absorber, TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, TINUVIN 765 (all are brand names, BASF Japan Co., Ltd., etc.) are mentioned, for example.

It is preferable that it is 0.01 weight part-10 weight part with respect to 100 weight part of polymers (A), and, as for content of the ultraviolet absorber in the photosensitive composition of this invention, it is more preferable that it is 0.1 weight part-5 weight part.

4-7. Cross-linking agent

As a thermal crosslinking agent, the component which raises a crosslinking reaction under the heating conditions in the film-forming which uses a photosensitive composition as a material can be used. The thermal crosslinking agent may be one kind or two or more kinds. As the thermal crosslinking agent, a thermal crosslinking agent such as an epoxy compound can be used. Examples of such thermal crosslinking agents include jER807, jER815, jER825, jER827, jER828, jER190P and jER191P (trade name; emulsified shell epoxy) Note)), jER1004, jER1256, YX8000 (trade name; Mitsubishi Chemical Corporation), Araldite CY177, Araldite CY184 (trade name; Huntsman Japan), Ceroxide 2021P, EHPE- 3150 (brand name; DAICEL CHEMICAL INDUSTRIES, LTD.) And Tekmore VG3101L (brand name; PRINTECH).

It is preferable that it is 1 weight part-50 weight part with respect to 100 weight part of polymers (A), and, as for content of the thermal crosslinking agent in the positive photosensitive composition of this invention, it is more preferable that it is 5 weight part-30 weight part.

In the positive photosensitive composition of the present invention, it is preferable that the temperature of the positive photosensitive composition is shielded and stored in the range of -30 ° C to 25 ° C in terms of time stability of the positive photosensitive composition. If the storage temperature is from -20 deg. C to 10 deg. C, it is more preferable from the viewpoint of preventing the generation of precipitates from the positive photosensitive composition.

The positive photosensitive composition of the present invention is suitable for forming a transparent film, and is also optimal for forming an insulating film having a small hole of 10 μm or less in view of relatively high resolution during patterning. Here, an insulating film means the film | membrane (interlayer insulation film) etc. which are provided in order to insulate between the wiring arrange | positioned in layer shape, for example.

The patterned transparent film of this invention is formed by exposure, image development, and baking of the coating film of the photosensitive composition of this invention mentioned above. For example, the patterned transparent film of the present invention such as the transparent film and the insulating film can be formed by a conventional method of forming a film in the resist field, and is formed as follows, for example.

First, the positive photosensitive composition of this invention is apply | coated on substrates, such as glass, by well-known methods, such as a spin coat, a roll coat, and a slit coat. As a board | substrate, For example, transparent glass substrates, such as a white plate glass, float glass, and a silica-coated float glass, a polycarbonate, a polyether sulfone, polyester, an acryl, a vinyl chloride, an aromatic polyamide, Metal substrates, such as a synthetic resin sheet, a film or a board | substrate, an aluminum plate, copper plate, a nickel plate, and a stainless steel plate, such as a polyamidoimide and a polyimide, In addition, the semiconductor substrate which has a ceramic plate and a photoelectric conversion element is mentioned. If necessary, such substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, and the like.

The coating film of the positive photosensitive composition on the substrate is then dried in a hot plate or oven. Typically, it is dried at 60 ° C to 120 ° C for 1 to 5 minutes. The film on the dried substrate is irradiated with radiation such as ultraviolet rays through a mask having an opening having a desired pattern shape. As for irradiation conditions, about 5 mJ / cm <2> -50mJ / cm <2> is suitable for i line | wire.

The film after irradiation is developed using a developing solution such as an alkaline solution, without requiring post-exposure baking (PEB: a step of firing before developing to remove the protective group present in the polymer after exposure). By this phenomenon, the portion irradiated with radiation in the film quickly dissolves in the developer. The developing method is not particularly limited, and any of dip development, paddle development, shower development, and the like may be employed.

The developing solution is preferably an alkali solution. Examples of the alkali contained in the alkaline solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium hydrogen carbonate and hydroxide. Sodium and potassium hydroxide. Moreover, as a developing solution, these aqueous solutions of alkali can be used suitably. In other words, as a developing solution, organic alkalis, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or 2-hydroxyethyl trimethylammonium hydroxide, and inorganic, such as sodium carbonate, sodium hydroxide, potassium hydroxide, for example. The aqueous solution of alkalis is mentioned.

Methanol, ethanol or surfactant may be added to the developing solution for the purpose of reducing the development residue and aptitude of the pattern shape. As the surfactant, for example, a surfactant selected from anionic, cationic and nonionic systems can be used. Among these, especially the addition of nonionic polyoxyethylene alkyl ether is preferable at the point which improves the resolution.

The developed membrane is sufficiently washed with pure water. Thereafter, it is calcined at 150 ° C to 250 ° C for 10 to 120 minutes. Thus, the patterned transparent film to be obtained can be obtained.

The patterned transparent film thus obtained can also be used as a patterned insulating film. The shape of the hole formed in the insulating film is preferably square, rectangular, circular or elliptical when viewed directly from above. Furthermore, after forming a transparent electrode on the said insulating film and patterning by etching, you may form the film | membrane which performs an orientation process. Since the insulating film has high sputter resistance, even if a transparent electrode is formed, wrinkles do not occur in the insulating film, and high transparency can be maintained.

The transparent film of pattern shape of this invention can be formed in normal thickness according to the desired use in display elements, such as a liquid crystal display element. It is preferable that the film thickness of the patterned transparent film of this invention is about 1 micrometer-about 10 micrometers, and the film thickness of a patterned transparent film is the viscosity of the positive photosensitive composition of this invention, and the solid substance in the positive photosensitive composition of this invention. It can be adjusted according to the concentration.

The patterned transparent film of this invention can be used for the display element using a liquid crystal etc. For example, the display element is formed by pressing the element substrate provided with the patterned transparent film of the present invention obtained as described above and the color filter substrate, which is an opposing substrate, in combination with each other, and then heat-treating and opposing the opposing substrates. It is produced by injecting liquid crystal to seal the injection port.

Or after spreading a liquid crystal on the said element substrate, it can manufacture by overlapping an element substrate and sealing so that a liquid crystal may not leak. The said display element may be a display element produced in this way.

Thus, the insulating film which has the outstanding heat resistance and transparency formed from the positive photosensitive composition of this invention can be used for a liquid crystal display element. In addition, the liquid crystal which can be used for the display element of this invention, that is, a liquid crystal compound and a liquid crystal composition is not specifically limited, You may use any of a liquid crystal compound and a liquid crystal composition.

The positive photosensitive composition according to a preferred embodiment of the present invention is, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, ground, which are generally required for patterned transparent films and insulating films. It has various characteristics, such as adhesiveness with.

Moreover, since the positive photosensitive composition which concerns on a preferable aspect of this invention is excellent in solvent resistance, acid resistance, alkali resistance, heat resistance, transparency, etc., the transparent film, insulating film, display element, etc. using this photosensitive composition form the insulating film. In the subsequent step, even if exposed to a high temperature of 150 ° C to 250 ° C, or immersed, contacted, heat treated, or the like in a solvent, an acid, an alkaline solution, or the like, surface roughness does not easily occur in the film. As a result, the light transmittance of the transparent film using the photosensitive composition which concerns on a preferable aspect of this invention becomes high, and the display quality of products, such as a display element using this, can be improved.

Experimental Example

Hereinafter, the present invention will be described in more detail according to experimental examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Polymer (A1)

Diethylene glycol ethyl methyl ether as a polymerization solvent, glycidyl methacrylate as a monomer, 3-methacryloxypropyl trimethoxysilane, methacryloyloxypropyl-, while bubbling nitrogen in the four neck flask with a stirrer Tris-trimethylsiloxysilane, dicyclopentanyl methacrylate, and 4-vinyl ketone phenol were added at the following weight, and 2,2'-azobis (2,4-dimethylvaleronitrile) was added at the following weight as a polymerization initiator. Was added, and the mixture was heated and polymerized at a polymerization temperature of 90 ° C. for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 2.8 g

2.2 g of 3-methacryloxypropyltrimethoxysilane

2.8 g of methacryloyloxypropyl-tris-trimethylsiloxysilane

1.2 g of dicyclopentanyl methacrylate

4-hydroxyphenyl vinyl ketone 1.0 g

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The solution was cooled to room temperature to obtain a polymer (A1) solution. A portion of the solution was sampled and the weight average molecular weight was determined according to GPC analysis (polystyrene standard). For the weight average molecular weight of the polymer (A1), polystyrene having a molecular weight of 645 to 132,900 (polystyrene calibration kit PL2010-0102 manufactured by VARIAN) is used as a standard polystyrene, and PLgel MIXED-D (manufactured by VARIAN) is used for the column. THF was used as the mobile phase and the column temperature was measured at 35 ° C. using a differential refractive index detector. As a result, the weight average molecular weight of the polymer (A1) was 7,100.

Synthesis Example 2 Synthesis of Polymer (A2)

The following components were added to the following weights as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 4.0 g

3.0 g of 3-methacryloxypropyl trimethoxysilane

Benzyl methacrylate 2.2g

4-hydroxyphenylvinyl ketone 0.8 g

1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight determined by GPC analysis (polystyrene standard) of the obtained polymer (A2) was 4,200.

Synthesis Example 3: Synthesis of Polymer (A3)

The following components were added to the following weights as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 2.8 g

2.2 g of 3-methacryloxypropyltrimethoxysilane

2.8 g of methacryloxypropyl-tris-trimethylsiloxysilane

1.2 g of cyclohexyl methacrylate

4-hydroxyphenyl vinyl ketone 1.0 g

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A3) was 7,500.

Synthesis Example 4 Synthesis of Polymer (A4)

As in Synthesis Example 1, the following components were added at the following weight, and the mixture was heated and polymerized at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 2.8 g

2.2 g of 3-methacryloxypropyltrimethoxysilane

3.0 g of methacryloxypropyl- tris-trimethylsiloxysilane

1.0 g of N-phenylmaleimide

4-hydroxyphenyl vinyl ketone 1.0 g

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A4) was 7,500.

Synthesis Example 5 Synthesis of Polymer (A5)

The following components were charged at the following weight as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 4.0 g

3.0 g of styryl trimethoxysilane

Benzyl methacrylate 1.7g

4-hydroxyphenyl vinyl ketone 1.3 g

1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A5) was 4,100.

Synthesis Example 6 Synthesis of Polymer (A6)

The following components were charged at the following weight as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 4.0 g

2.8 g of vinyl trimethoxysilane

Benzyl methacrylate 2.0 g

1.2 g of 4-hydroxyphenyl vinyl ketone

1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A6) was 3,900.

Synthesis Example 7 Synthesis of Polymer (A7)

The following components were charged at the following weight as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 2.5g

1.5 g of 3-methacryloxypropyltrimethoxysilane

2.0 g of methacryloxypropyl- tris-trimethylsiloxysilane

3.0 g of cyclohexyl methacrylate

1.0 g of methacrylic acid

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (A7) was 6,900.

Comparative Synthesis Example 1 Synthesis of Polymer (B1)

The following component which changed the radically polymerizable monomer (4-hydroxyvinyl ketone) which has an acidic group of the synthesis example 1 into methyl methacrylate which is a non-acid component was thrown in at the following weight, and it polymerized by heating at 90 degreeC polymerization temperature for 2 hours. .

15.0 g of diethylene glycol ethyl methyl ether

Glycidyl methacrylate 2.8 g

2.2 g of 3-methacryloxypropyltrimethoxysilane

2.8 g of methacryloyloxypropyl-tris-trimethylsiloxysilane

1.2 g of dicyclopentanyl methacrylate

1.0 g of methyl methacrylate

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (B1) was 6,800.

Comparative Synthesis Example 2 Synthesis of Polymer (B2)

The following components were charged at the following weight as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

10.0 g of 3-methacryloxypropyltrimethoxysilane

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (B2) was 6,800.

Comparative Synthesis Example 3: Synthesis of Polymer (B3)

The following components were charged at the following weight as in Synthesis example 1, and the polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours.

15.0 g of diethylene glycol ethyl methyl ether

4-hydroxyphenylvinyl ketone 10.0 g

1.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile)

The weight average molecular weight calculated | required by GPC analysis (polystyrene standard) of the obtained polymer (B3) was 7,800.

Experimental Example  1: Preparation of Positive Photosensitive Composition

Polymer (A1) obtained in Synthesis Example 1, Irgacure250 (hereinafter abbreviated as 'Irg250') manufactured by BASF Japan as a photoacid generator, and AnthracureUVS- manufactured by KAWASAKI KASEI CHEMICALS LTD. As a sensitizer. 1331 (hereinafter, abbreviated as 'UVS-1331') was mixed and dissolved in parts by weight shown in Table 1, and further, diethylene glycol ethyl methyl ether (Toho Chemical Industry Co., Ltd.) Solve EDM, hereinafter abbreviated as 'EDM', was diluted as a diluting solvent so that the solid concentration of the composition was 28% by weight. Finally, 500 ppm of KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., a silicone-based surfactant, was added as an additive to obtain a positive photosensitive composition. In addition, the solid content concentration of the polymer (A1) solution obtained by the synthesis example 1 was computed as 40 weight%. And the polymer weight part in following Table 1 and Table 2 shows a weight part as solid content.

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Experimental Example 6 Experimental Example 7 Experimental Example 8 Experimental Example 9



Polymer A1 100 100 100 A2 100 A3 100 A4 100 A5 100 A6 100 A7 100 B1 B2 B3
mine
Generator Irgacure
250 3 3 3 3 3 3 3 HS-1 TF 3 LW-S1 3 Sensitizer UVS-1331 0.25 0.5 0.25 0.25 0.25 0.25 0.25 0.25 Organic solvent EDM EDM EDM PGME PGME DAA EEE EEE EEE Surfactants KP-341 KP-341 KP-341 KP-341 KP-341 KP-341 KP-341 KP-341 KP-341

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4



Polymer A1 A2 A3 A4 A5 A6 A7 B1 100 100 B2 100 B3 100
mine
Generator Irgacure
250 3 3 3 HS-1 TF LW-S1 3 Sensitizer UVS-1331 0.25 Organic solvent EEE EDM EDM EDM Surfactants KP-341 KP-341 KP-341 KP-341

※ HS-1TF... Photo-acid generator of San-Apro Ltd.

LW-S1... Mine generator of San Apro Co., Ltd.

※ PGME…. Propylene glycol monomethyl ether of Tokyo Kasei Kogyo Co., Ltd.

DAA… Diacetone alcohol from Tokyo Kasei Industry Co., Ltd.

※ EEE… 2- (2-ethoxyethoxy) ethanol from Tokyo Kasei Industry Co., Ltd.

Evaluation method of positive photosensitive composition

(1) Formation of patterned transparent film

The positive photosensitive composition synthesize | combined in Example 1 was spin-coated on the glass substrate, and it dried for 2 minutes on 100 degreeC hotplate, and obtained the organic film of 3 micrometers in film thickness. The substrate was exposed to air at 350 nm or less through a wavelength cutoff filter using a mask for forming a hole pattern in air and a proximity exposure machine TME-150PRC manufactured by Topcon Corporation. It cut, g, h, and i line were taken out, and it exposed at 100 micrometers of exposure gaps. The exposure amount was measured by the integrated photometer UIT-102 and the light receiver UVD-365PD manufactured by Ushio Electric Co., Ltd. (USHIO INC.). The glass substrate after exposure was dip-developed for 90 second with 2.38 weight% tetramethylammonium hydroxide aqueous solution, and the composition of the exposure part was removed. The substrate after development was washed with pure water for 60 seconds, and then the substrate was dried by air blow. The substrate was post-baked at 230 ° C. for 30 minutes in an oven to form a patterned transparent film. The film thickness was measured by the tactile film thickness meter α step P15 manufactured by KLA-Tencor Japan Co., Ltd., and three measurement average values were defined as the film thickness.

(2) Film thickness before and after development and remaining film rate after development

The film thickness was measured before and after development. The residual film rate after image development was computed by the following formula.

(Film thickness after development / film thickness before development) × 100 (%)

(3) Sensitivity

Sensitivity was made into the minimum exposure amount which the hole-shaped pattern of the size similar to a photomask size resolves.

(4) Resolution

The board | substrate of the patterned transparent film | membrane after the post-baking obtained by said (1) was observed by the optical microscope by 1,000 times, and the mask size which glass was exposed to the bottom of a hole pattern was confirmed. When the hole pattern was not resolving, it was set as NG (No Good).

(5) transparency

The positive photosensitive composition synthesize | combined by Experimental example 1 was spin-coated on the glass substrate, and it dried for 2 minutes on a 100 degreeC hotplate, and obtained the organic film with a film thickness of 3 micrometers. Thereafter, dip development was carried out for 90 seconds in a 2.38% by weight aqueous tetramethylammonium hydroxide solution. The substrate after development was washed with pure water for 60 seconds, and then the substrate was dried by air blow. The substrate was cut in air using a fluorometer exposure machine TME-150PRC (light source is ultra-high pressure mercury lamp) manufactured by Topcon Corporation, and cut out light of 350 nm or less through a wavelength cutoff filter to take out g, h, and i rays. It exposed to the whole surface. The exposure amount was measured by the integrated photometer UIT-102 and the light-receiver UVD-365PD made by Ushio Electric Co., Ltd. to make 20 mJ / cm 2. The substrate was post-baked at 230 ° C. for 30 minutes in an oven to form a patterned transparent film. Using a UV-visible near-infrared spectrophotometer V-670 manufactured by Nippon Bunko Co., Ltd. (JASCO Co.), the light transmittance at a wavelength of 400 nm was determined with reference to a glass substrate not forming a transparent film. Measured.

(6) Heat resistance

The substrate of the patterned transparent film obtained in the above (1) was further baked in an oven at 230 ° C. for 60 minutes, and the light transmittance was measured as before (4) before and after the additional bake, and the light after the post-baking (before the additional baking) was obtained. The transmittance was set to T1, and the light transmittance after further baking was set to T2. It can be judged that the smaller the decrease in the light transmittance after the post-baking and after the additional baking, the better. In addition, the film thickness was measured before and after the additional bake, and the rate of change of the film thickness was calculated by the following equation.

(Film thickness after additional bake / film thickness after post bake) × 100 (%)

(7) adhesion

The board | substrate of the patterned transparent film obtained by said (1) was evaluated by the board | substrate peeling test (cross cut test). Evaluation showed the residual number after peeling of a tape in 100 1 mm x 1 mm board | substrates.

About the positive photosensitive composition synthesize | combined in Experimental example 1, the result obtained by the said evaluation method is shown in Table 3.

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Experimental Example 6 Experimental Example 7 Experimental Example 8 Experimental Example 9 Film thickness after development
(μm) 2.82
2.61
2.91
2.88
2.97
2.79
2.73
2.82
2.70
Residual rate after development
(%) 98
95
99
97
99
96
98
98
96
Sensitivity
(mJ / cm2) 20
20
20
20
20
20
20
20
20
resolution
(μm) 7
7
7
7
7
7
7
7
7
Film thickness after postbaking
(μm) 2.34
2.32
2.39
2.33
2.41
2.23
2.32
2.31
2.16
Light transmittance T1
(%) 99
98
87
99
99
99
99
99
99
Light transmittance T2
(%) 99
98
85
99
99
99
99
99
99
Film thickness after additional bake
(μm) 2.25
2.21
2.27
2.19
2.33
2.14
2.23
2.22
2.10
Heat resistance
(% Change in film thickness) 96
95
95
94
97
96
96
96
97
Adhesiveness 100 100 100 100 100 100 100 100 100

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Film thickness after development
(μm) 3.00 2.89 - 3.00 Residual rate after development
(%) 100 100 0 99 Sensitivity
(mJ / cm2) - - - - resolution
(μm) NG NG - NG Film thickness after postbaking
(μm) 2.49 2.25 - 2.50 Light transmittance T1
(%) 99 99 - 86 Light transmittance T2
(%) 99 99 - 85 Film thickness after additional bake
(μm) 2.39 2.07 - 2.41 Heat resistance
(% Change in film thickness) 96 92 - 96 Adhesiveness 100 100 - 100

In Comparative Example 3, since the entire film disappeared in the developing step, the subsequent physical properties were not evaluated.

Experimental Examples 2 to 7

Each component was mixed as described in Table 1, and the positive photosensitive composition was prepared and evaluated like Experimental example 1. The ratio of the organic solvent and the surfactant is the same as in Experiment 1. The evaluation results are shown in Table 3.

Comparative Examples 1 to 4

As described in Table 1, each component was mixed to prepare and evaluate a positive photosensitive composition as in Experimental Example 1, but the pattern was not resolved at all. The evaluation results are shown in Table 4.

In Comparative Examples 1, 2, and 4, since the positive photosensitive composition of the exposed portion was not dissolved in the alkaline developer, that is, could not be patterned during the formation of the patterned transparent film, the remaining film ratio after development was high, but the resolution was NG. It was.

In general, a high sensitivity sensitive photosensitive composition tends to have a low residual film ratio after development, while a low sensitivity positive photosensitive composition tends to have a high residual film ratio after development. When the type photosensitive composition is used, it turns out that the film | membrane which is high sensitivity and has a high residual film rate after image development can be obtained.

The photosensitive composition of this invention can be used, for example for a liquid crystal display element.

Claims (9)

A polymer (A) formed by radical copolymerization of a radically polymerizable monomer (a1) having an alkoxysilyl, a radically polymerizable monomer (a2) having an acidic group, a radically polymerizable monomer (a3) other than (a1) and (a2), Positive photosensitive composition containing a photo-acid generator (B) and an organic solvent (C). The positive photosensitive composition according to claim 1, wherein the radically polymerizable monomer (a1) having alkoxysilyl is at least one of the compounds represented by the following formulas (I), (II) and (III).
(I)

[Formula II]

(III)

(In the above formula, R ¹ is hydrogen, or alkyl of 1 to 5 carbon atoms which any hydrogen may be substituted with fluorine, R ² to R ¹⁰ are each hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, linear or branched alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 5 carbon atoms, and the alkyl at R ² to R ¹⁰ is -CH ₂ -is -COO-, -OCO-,- May be substituted with CO— or —O— and any hydrogen may be substituted with halogen, provided that at least one of R ² to R ⁴ is alkoxy having 1 to 5 carbon atoms and at least one of R ⁵ to R ⁷ Is alkoxy having 1 to 5 carbon atoms, and at least one of R ⁸ to R ¹⁰ is alkoxy having 1 to 5 carbon atoms, in formula (I), n is 1 to 5). The radically polymerizable monomer (a2) which has the said acidic group is a radically polymerizable monomer which has phenolic OH, the radically polymerizable monomer which has unsaturated carboxylic acid, and the unsaturated carboxylic anhydride of Claim 1 or 2. Positive type photosensitive composition characterized by the above-mentioned at least 1 sort (s) of the radically polymerizable monomer chosen from monomer. The radically polymerizable monomer (a2) which has the said acidic group contains the radically polymerizable monomer which has phenolic OH represented by following General formula (IV), The said radical radical polymerizable monomer as described in any one of Claims 1-3 characterized by the above-mentioned. Positive photosensitive composition.
[Formula IV]

(In the formula (IV), R ¹¹ , R ^12, and R ¹³ are each hydrogen or alkyl having 1 to 3 carbon atoms which any hydrogen may be substituted with fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^17. And R ¹⁸ is hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl having 1 to 5 carbon atoms, or alkoxy having 1 to 5 carbon atoms, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R Alkyl for ¹⁷ and R ¹⁸ may be substituted with any -CH ₂ -with -COO-, -OCO-, or -CO-, and in R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ Alkyl and alkoxy may be any hydrogen substituted with halogen, provided that at least one of R ¹⁴ to R ¹⁸ is —OH.) The positive photosensitive composition as described in any one of Claims 1-4 whose said radically polymerizable monomer (a3) is a radically polymerizable monomer which has an epoxy. The positive photosensitive composition as described in any one of Claims 1-5 whose said organic solvent (C) is a solvent which has a hydroxyl. The patterned transparent film formed by exposure, image development, and baking of the coating film of the positive photosensitive composition in any one of Claims 1-6. The insulating film using the patterned transparent film of Claim 7. The display element which has a patterned transparent film of Claim 7 or 8.