KR20150011311A - Positive type photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive type photosensitive resin composition, which comprises (A) a polymer manufactured by radical-co-polymerizing (a1) a radical polymerizable monomer represented by formula (I), (a2) a radical polymerizable monomer having an acidic group, (a3) a radical polymerizable monomer having alkoxysilyl, and (a4) a radical polymerizable monomer other than (a1), (a2) and (a3); (B) a photo acid generator; and (C) an organic solvent. The positive type photosensitive resin composition of the present invention is high sensitive, and does not require sintering after exposure. By using the positive type photosensitive resin composition, a patterned transparent film with excellent pattern adhesion in development, and post exposure delay stability can be formed. In formula I, R1 is hydrogen, or C1-5 alkyl having any hydrogen possibly substituted with fluorine; R2 is hydrogen or a functional group with 1-3-dioxopropane-1,3-diyl (-COCH2CO-); and n is an integer of 1-6.

Description

[0001] POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a positive photosensitive composition usable in the field of resists and the like.

A patterned transparent film has been used in many fields such as spacers, insulating films, and protective films, and many positive photosensitive compositions have heretofore been proposed for this application (see, for example, Patent Documents 1 to 3).

2. Description of the Related Art In general, an insulating film is formed in an electronic part such as a thin film transistor liquid crystal display element or a solid-state imaging element or a display element such as a liquid crystal display in order to insulate wirings. As a material for forming the insulating film, a positive photosensitive composition having few steps for obtaining an insulating film having a required pattern shape is widely used. It is necessary for the positive photosensitive composition to have a wide process margin in the process of forming the insulating film.

In recent years, in the use of a photosensitive insulating film used in a display device such as a liquid crystal display or the like, as the size of the mother glass becomes even larger, in order to secure productivity, the time taken for a series of processes Time is required to be shortened.

For example, Patent Document 4 discloses a positive photosensitive composition which is provided with a high sensitivity for these uses. The following Patent Document 4 discloses a positive photosensitive composition comprising a polymer having a t-butyl ester group of a carboxylic acid or a t- And a resist composition containing the same. The t-butyl ester group or t-butyl carbonic acid group in the polymer is deprotected by post-exposure baking (PEB) with an acid generated at the time of exposure, and converted into an acid group such as a carboxyl group or phenolic OH. As a result, the exposed portion of the resist film is dissolved in the alkali developing solution. However, in such a system, a PEB process is required after exposure, and the exposure amount is low because of high sensitivity, but there is a problem that the overall process time is not shortened. Further, in the case of using the above-described method, there is a problem that the pattern shape and size are changed because the post exposure delay stability becomes poor if the time from exposure to PEB to development becomes long.

Japanese Laid-Open Patent Publication No. 51-34711 Japanese Patent Application Laid-Open No. 56-122031 Japanese Unexamined Patent Publication No. 5-165214 Japanese Patent Publication No. 2-27660

The present invention provides a positive photosensitive composition capable of forming a patterned transparent film having high sensitivity and not requiring post-exposure baking, pattern adhesion at the time of development, and post-exposure delay stability.

The present inventors have intensively studied in order to achieve the above object and as a result have found that a positive photosensitive composition containing a polymer (A), a photo acid generator (B) and an organic solvent (C) The present invention has been completed on the basis of this finding. The present invention includes the following items.

[1] A thermoplastic resin composition comprising a radically polymerizable monomer (a1) represented by the following formula (I)

The radically polymerizable monomer (a2) having an acidic group,

A radically polymerizable monomer (a3) having alkoxysilyl, and

(A) containing a radically polymerizable monomer (a4) other than (a1), (a2) and (a3), a photoacid generator (B) and an organic solvent (C) :

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine and R ² is hydrogen or 1,3-dioxopropane-1,3-diyl (-COCH ₂ CO- ), And n is an integer of 1 to 6.

[2] The positive photosensitive composition according to [1], wherein the radically polymerizable monomer (a1) is at least one selected from the group consisting of a compound represented by the following formula (II)

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;

R ³ is alkyl having 1 to 6 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;

n is an integer of 1 to 6;

[3] The method according to any one of [1] to [3], wherein the radically polymerizable monomer (a2) having an acidic group is selected from the group consisting of a radically polymerizable monomer having a phenolic OH, a radically polymerizable monomer having an unsaturated carboxylic acid and a radically polymerizable monomer having an unsaturated carboxylic acid anhydride The positive photosensitive composition according to [1] or [2], which is at least one selected.

[4] The thermosetting resin composition according to any one of [1] to [3], wherein the radically polymerizable monomer (a2) having an acidic group comprises at least one radically polymerizable monomer having a phenolic OH represented by the following formula (IV) Positive type photosensitive composition:

Wherein R ⁴ , R ⁵ And R < ⁶ > are each independently hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms , At least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ is -OH,

^{R 7, R 8, R 9} , R 10, and R ¹¹ is alkyl in any of the -CH ₂ - is optionally substituted by -COO-, -OCO-, or -CO-, and, R ^7, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ , alkyl and alkoxy may be substituted with any hydrogen by halogen.

[5] Any one of [1] to [4], wherein the radically polymerizable monomer (a3) having an alkoxysilyl is at least one selected from the group consisting of a compound represented by the following formula (V) The positive photosensitive composition described in item

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;

n is an integer from 1 to 6;

R ¹² to R ¹⁷ each independently represent hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 5 carbon atoms,

At least one of R ¹² to R ¹⁴ is alkoxy of 1 to 5 carbon atoms,

At least one of R ¹⁵ to R ¹⁷ is alkoxy having 1 to 5 carbon atoms,

R ¹² ~ R ¹⁷ is alkyl in the -CH ₂ that connects to the silicon-arbitrary -CH ₂ except - - -CH ₂ and the terminal is -COO-, -OCO-, -CO-, or -O- , And any hydrogen may be substituted with halogen.

[6] The positive photosensitive composition according to any one of [1] to [5], wherein the radically polymerizable monomer (a4) comprises at least one radically polymerizable monomer having an epoxy.

[7] The positive photosensitive composition as described in any one of [1] to [6], wherein the organic solvent (C) is a compound having a hydroxyl group (-OH).

[8] A patterned transparent film formed by exposing, developing, and firing a coating film of the positive photosensitive composition described in any one of [1] to [7].

[9] An insulating film using the patterned transparent film according to [8].

The present invention also includes a display element having a patterned transparent film, for example, a liquid crystal display element.

The present invention is a positive photosensitive composition containing the above-mentioned specific polymer (A), photo acid generator (B) and organic solvent (C). By using the positive photosensitive composition of the present invention, it is possible to form a patterned transparent film having high sensitivity, which does not require post-exposure baking, and which is excellent in pattern adhesion upon development and post exposure delay stability .

<1. Photosensitive composition of the present invention>

The photosensitive composition of the present invention comprises a radically polymerizable monomer (a1) represented by the following formula (I), a radically polymerizable monomer (a2) having an acidic group, a radically polymerizable monomer (a3) (A), photoacid generator (B), and organic solvent (C) obtained by radical copolymerization of the radical polymerizable monomer (a4) other than the monomer (a2) The polymer (A) may be one type, or two or more kinds of polymers may be used in combination. The photo acid generator (B) may be a single type or a mixture of two or more types. The organic solvent (C) may be one type or a mixture of two or more kinds.

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine and R ² is hydrogen or 1,3-dioxopropane-1,3-diyl (-COCH ₂ CO- ), And n is an integer of 1 to 6.

<1-1. The polymer (A) of the present invention>

The polymer (A) of the present invention can be obtained by copolymerizing the radical polymerizable monomer (a1) represented by the above formula (I), the radically polymerizable monomer (a2) having an acidic group, the radically polymerizable monomer (a3) ), (a2), and (a3) other than the above-mentioned radical polymerizable monomer (a4).

Each of the radically polymerizable monomers (a1), (a2), (a3) and (a4) which are raw materials of the polymer (A) may be used alone or in combination of two or more.

<1-1-1. The radically polymerizable monomer (a1) represented by the formula (I)

The radically polymerizable monomer (a1) represented by the formula (I) can be selected from the compounds represented by the following formulas (II) and (III).

In the formulas (II) and (III), R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine, and n is an integer of 1 to 6. In the formula (III), R ³ is alkyl having 1 to 6 carbon atoms in which arbitrary hydrogen may be substituted with fluorine.

The alkyl in R ¹ is preferably methyl in view of heat resistance and transparency. The alkyl of R ³ preferably has 1 to 6 carbon atoms in view of alkali developability and heat resistance (glass transition point) of the film.

The radical polymerizable monomer (a1) is preferably used in a proportion of 0.1 to 10% by weight based on the total weight of the total monomers from the viewpoints of substrate adhesion, stability of post exposure delay, and storage stability as a solution , And more preferably 0.1 to 5 wt%. In order to suppress the decrease of the residual film ratio, the amount of the radical polymerizable monomer (a1) is more preferably 0.1 to 3 parts by weight. However, this does not mean that use of more than 3% by weight of the radical polymerizable monomer (a1) is not problematic.

 Specific examples of the compounds represented by the general formulas (II) and (III) include hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, Ethoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, and acetoacetoxybutyl acrylate. When a copolymer using these radical polymerizable monomers is used, it has a positive characteristic of high sensitivity, and the base adhesion and the post exposure delay stability are improved.

<1-1-2. Radical polymerizable monomer (a2) &gt;

The radically polymerizable monomer (a2) having an acidic group which can be used in the present invention may be a radically polymerizable monomer having a phenolic OH, a radically polymerizable monomer having an unsaturated carboxylic acid, a radically polymerizable monomer having an unsaturated carboxylic acid anhydride, A radically polymerizable monomer having a phosphoric acid group, and a radically polymerizable monomer having a sulfonic acid group. Use of the radically polymerizable monomer (a2) as a raw material of the copolymer (A) is preferable from the viewpoint of alkali solubility. These radically polymerizable monomers (a2) may be used alone or in combination of two or more.

Examples of radically polymerizable monomers having phenolic OH are hydroxystyrene and radically polymerizable monomers having a phenolic OH represented by the following formula (IV).

In formula (IV), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be substituted with fluorine. R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl of 1 to 5 carbon atoms, or alkoxy of 1 to 5 carbon atoms, At least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is -OH. ^{R 7, R 8, R 9} , R 10 and R ¹¹ are alkyl in any of the -CH ₂ - that may be substituted by -COO-, -OCO-, or -CO-. The alkyl and alkoxy in R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be substituted with any hydrogen by halogen.

A specific example of a radically polymerizable monomer having a phenolic OH represented by the formula (IV) is 4-hydroxyphenylvinyl ketone.

Specific examples of the radically polymerizable monomer having an unsaturated carboxylic acid are acrylic acid and methacrylic acid. A specific example of a radically polymerizable monomer having an unsaturated carboxylic acid anhydride is maleic anhydride.

Specific examples of the radically polymerizable monomer having a phosphoric acid group are 2-hydroxyethyl methacrylate phosphate, 2-hydroxypropyl methacrylate phosphate, and bis (2-hydroxyethyl methacrylate) phosphate.

Specific examples of the radically polymerizable monomer having a sulfonic acid group are vinylsulfonic acid and acrylamide-tert-butylsulfonic acid.

Among the above-mentioned specific examples, the radical polymerizable monomer (a2) is preferably methacrylic acid, hydroxystyrene, or 4-hydroxyphenyl vinyl ketone. Methacrylic acid and hydroxystyrene are readily available. 4-hydroxyphenylvinyl ketone can obtain good properties in terms of storage stability of the composition.

In the polymer (A), the radical polymerizable monomer (a2) is preferably used in a proportion of 1 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of all monomers . Including the monomer (a2) in such a range is preferable from the viewpoint of solubility in an alkali developing solution.

<1-1-3. Radical Polymerizable Monomer (a3) &gt;

Examples of the radically polymerizable monomer (a3) having an alkoxysilyl which can be used in the present invention include the compounds represented by the following formulas (V) and (VI). When these compounds are used, positive characteristics with high sensitivity can be obtained.

In the formulas (V) and (VI), R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine, and n is an integer of 1 to 6. R ¹² ~ R ¹⁷ are each independently hydrogen, _{halogen, -CN, -CF 3, -OCF 3} , -OH, alkoxy of 1 to 20 carbon atoms but alkyl, or 1 to 5 carbon atoms of, R ¹² ~ R of at least ¹⁴ One is an alkoxy of 1 to 5 carbon atoms, and at least one of R ¹⁵ to R ¹⁷ is an alkoxy of 1 to 5 carbon atoms. Alkyl and alkoxy may be linear or branched. However, R ¹² ~ R ¹⁷ the alkyl is -CH ₂ connecting to the silicon in the - and ends of the -CH ₂ - -CH ₂ except any - is -COO-, -OCO-, -CO-, or - O-, and arbitrary hydrogen may be substituted with halogen.

The alkyl in R ¹ is preferably methyl in view of heat resistance and transparency. The alkyl group in R ¹² to R ¹⁴ preferably has 1 to 10 carbon atoms in view of alkali developability and heat resistance (glass transition point) of the film. The alkyl (any hydrogen may be substituted with halogen) in the above-mentioned R ¹⁵ to R ¹⁷ also preferably has 1 to 10 carbon atoms for the same reason. At least one alkoxy of R ¹² to R ¹⁴ and at least one alkoxy of R ¹⁵ to R ¹⁷ each have 1 to 5 carbon atoms, but for reasons of hydrolysis, it is preferably 1 to 3 .

The radical polymerizable monomer (a3) is preferably used in a proportion of 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total weight of all the monomers. The incorporation of the monomer (a3) in such a range is preferable from the viewpoints of sensitivity and transparency.

Specific examples of the compounds represented by the formulas (V) and (VI) include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- P-styryltrimethoxysilane, p-styryltriethoxysilane, and vinyltrimethoxysilane, and vinyltriethoxysilane.

<1-1-4. Radical Polymerizable Monomer (a4) &gt;

The radically polymerizable monomers (a4) other than (a1), (a2) and (a3) which can be used in the present invention include radically polymerizable monomers having epoxy, radically polymerizable monomers having dicyclopentanyl, A radically polymerizable monomer having a siloxane, and the like can be used. The number of the monomers to be used may be one or plural. By using the copolymer of the present invention using these radical polymerizable monomers, the sputtering resistance is good and the chemical resistance is high.

Specific examples of radically polymerizable monomers having an epoxy include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 4- Hydroxybutyl acrylate glycidyl ether. When these radically polymerizable monomers are used, the sputtering resistance is good and the chemical resistance is high.

Specific examples of radically polymerizable monomers having dicyclopentanyl are dicyclopentanyl acrylate and dicyclopentanyl methacrylate. Specific examples of the radically polymerizable monomer having an N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, , N- (4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino- - (2-benzoxazolyl) phenyl] maleimide. Use of these radically polymerizable monomers is preferable from the standpoint of heat resistance and low dielectric constant.

Specific examples of radically polymerizable monomers having siloxane are acryloxypropyl-tris-trimethylsiloxysilane and methacryloyloxypropyl-tris-trimethylsiloxysilane. When a copolymer using these radical polymerizable monomers is used, it has a high sensitivity, a positive property, a high transparency, a little deterioration of transparency due to firing at a high temperature, and a post-exposure baking (post-exposure baking) It is possible to carry out the development without needing to carry out, that is, a patterned transparent film can be easily obtained, and also exhibits a solvent resistance, a high water resistance, an acid resistance, an alkali resistance and a heat resistance,

The polymer (A) of the present invention may further contain a radically polymerizable monomer other than the above insofar as the effect of the present invention is not impaired. Specific examples of such radically polymerizable monomers include benzyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, butyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentyl acrylate, Pentenyl methacrylate, and dicyclopentenyl oxyethyl methacrylate.

<1-1-5. Polymer (A)>

Polymer (A) has suitable alkali solubility. In the present invention, alkali solubility refers to the alkali solubility, which means that a solution of the polymer (A) obtained by radical polymerization is applied to a substrate by a spin coat, and a coating having a thickness of 0.01 to 100 탆 formed by heating at 90 캜 for 2 minutes is coated at 2.38 Refers to a property of dissolving in alkaline to such an extent that the coating does not remain when immersed in an aqueous solution of tetramethylammonium hydroxide in weight% for 5 minutes and then washed with pure water.

The alkali solubility of the polymer (A) is preferably selected from the group consisting of radical polymerizable monomers having a phenolic OH, radically polymerizable monomers having an unsaturated carboxylic acid, or radical polymerizable monomers having an unsaturated carboxylic acid anhydride, which are used for the radical polymerizable monomer (a2) It can be adjusted according to the amount of monomer. That is, the alkali solubility of the polymer (A) can be increased by increasing 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 acid anhydride have.

The method of synthesizing the polymer (A) is not particularly limited, but it is possible to make the radical polymerizable monomer by radical copolymerization. Specifically, it can be obtained by polymerizing a mixture of the radically polymerizable monomers (a1), (a2), (a3) and (a4), and radical polymerization in a solution using a solvent is preferable. In this radical polymerization, a polymerization initiator may be used.

In the case of using a polymerization initiator, the polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. The polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent to be used in the polymerization reaction is preferably a solvent which dissolves the radical polymerizable monomer to be used and the polymer (A) to be produced. A solvent having a hydroxyl group is preferable in terms of storage stability of the polymerized polymer. After polymerization with another solvent, a solvent having hydroxyl may be used as a diluting solvent for the polymer (A). Specific examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, 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, methyl 3-methoxypropionate, 3- Ethyl propionate, and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more.

Polymerization initiators which can be used in the synthesis of the polymer (A) include compounds which generate radicals by heat, azo compounds such as azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) Peroxide initiators such as initiators and benzoyl peroxide can be used. To adjust the molecular weight, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount.

When the weight average molecular weight of the polymer (A) determined by GPC analysis using polystyrene as a standard is in the range of 1,000 to 100,000, the developing time until the exposed portion is dissolved in the alkaline developing solution is appropriate, Is not well roughened. When the weight average molecular weight is in the range of 1,500 to 50,000, the developing time until the unexposed portion is dissolved in the alkaline developing solution is appropriate. Further, the surface of the film is not well roughened at the time of development, , More preferable. It is more preferable that the weight average molecular weight is in the range of 2,000 to 20,000.

In the measurement of the weight average molecular weight, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by VARIAN) and PLgel MIXED-D (manufactured by VARIAN) were used as standard polystyrene , And THF may be used as the mobile phase.

The polymer (A) of the present invention can be adjusted to a preferable molecular weight according to the monomer concentration at the time of polymerization, the amount of the polymerization initiator, and the polymerization temperature. For example, from the viewpoints of production time, polymerization reproducibility and handling of the product, the monomer concentration at the time of polymerization (the weight of the solvent used in the polymerization and the total weight of the monomers) %, More preferably 15 to 50 wt%.

In the positive photosensitive composition of the present invention, the content of the polymer (A) is preferably 1 to 60% by weight, more preferably 3 to 5% by weight based on the total amount of the positive photosensitive composition, By weight to 40% by weight, and particularly preferably 5 to 35% by weight. The content of the polymer (A) can be appropriately adjusted within the above range according to the application method of the positive photosensitive composition of the present invention. For example, in the case of spin coating, the content of the polymer (A) is increased to increase the viscosity of the composition. On the other hand, for example, in the slit coat, the content of the polymer (A) is decreased to lower the viscosity of the composition.

<2. The photoacid generator (B) of the present invention>

Examples of the photoacid generator used in the present invention include photoacid generators based on onium salts such as diphenyliodonium salts and triphenylsulfonium salts, photo acid generators based on sulfonylimide compounds, and the like.

Specific examples of the diphenyliodonium salt include diphenyl iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyl iodide Diphenyl iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, (4-methoxyphenylphenyliodonium tetrafluoroborate), diphenyl iodonium (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium- p-toluenesulfonate, and bis (4-t-butylphenyl) Eau titanium is camphor sulfonic acid.

Specific examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p -Toluenesulfonate, triphenylsulfonium hexafluorophosphate, and triphenylsulfonium butyltris (2,6-difluorophenyl) borate.

Specific examples of the sulfonylimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (Camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- Maleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2 -2,1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept- , N - (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] -2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5- (Trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2. 1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- 2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide 2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane- Heptane-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) ), Naphthyldicarboxylate, N- (camphorsulfonyloxy) naphthyldicarboxylide, N- (4-methylphenylsulfonyloxy) naphthyldicarboxyimide, N- Dicarboxylic imide, N- (2-tert (4-fluorophenylsulfonyloxy) naphthyldicarboxylic acid, N- (pentafluoroethylsulfonyloxy) naphthyldicarboxylic acid, N- (Heptafluoropropylsulfonyloxy) naphthyldicarboxylide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboxyimide, N- (ethylsulfonyloxy) naphthyldicarboxylate, N- (Butylsulfonyloxy) naphthyldicarboxylide, N- (pentylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxylate, N- (Hexylsulfonyloxy) naphthyldicarboxylic imide, N- (heptylsulfonyloxy) naphthyldicarboxyimide, N- (octylsulfonyloxy) naphthyldicarboxyimide and N- (nonylsulfonyl) Oxy) naphthyl dicarboxylic imide.

In particular, when the positive photosensitive composition of the present invention is used for the purpose of producing a transparent film, if the above-described photo acid generator is used, a post exposure process for photodecomposing all of the photo acid generator remaining after development is performed So that it is unnecessary.

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

<3. The organic solvent (C) of the present invention>

The positive photosensitive composition of the present invention further contains an organic solvent (C) in addition to the polymer (A) and the photo acid 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 stability of the composition as a composition or the trouble during the manufacturing process of the patterned transparent film It is more preferable that the organic solvent is an organic solvent having hydroxyl in view of the time-course stability of the coated film when the time is short.

The organic solvent preferably has a boiling point of 100 占 폚 to 300 占 폚. Specific examples of the organic solvent having a boiling point of 100 占 폚 to 300 占 폚 include butyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, methoxyacetate, methoxy Ethoxyacetonate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxypropionate, methyl 2-hydroxypropionate, methyl 2-hydroxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy- And examples thereof include ethyl lactate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, methyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl 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 Propylene glycol monomethyl ether, recoloxyl monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene,? -Butyrolactone, Lt; / RTI &gt; These may be used alone or in combination of two or more.

In the positive photosensitive composition of the present invention, the content of the organic solvent (C) is preferably 40 to 99% by weight, more preferably 50 to 90% by weight, and more preferably 60 to 80% %.

<4. Other components>

To the positive photosensitive composition of the present invention, various additives may be added to improve resolution, uniformity of coating, developability, and adhesion. The additive may be an adhesion promoter such as an anionic, cationic, nonionic, fluorine or silicon leveling agent / surfactant or a silane coupling agent, an ultraviolet absorber such as an alkoxybenzophenone, an epoxy compound, a melamine compound or a bisazide compound , Alkali-solubility accelerators such as polycarboxylic acids and phenol compounds, antioxidants such as hindered phenol-based compounds, hindered amine-based compounds, phosphorus-based compounds and sulfur-based compounds.

<4-1. Leveling agents, Surfactants>

The leveling agent and the surfactant that can be used in the positive photosensitive composition of the present invention include polyphosphoric acid, 45, Polyflow KL-245, Polyflow No. 35, 75, Polyflow No. &quot; 90, poly flow No. BYK300, BYK306, BYK310, BYK320, BYK330, BYK342 and BYK346 (all trade names, Vick Chemical Japan Co., Ltd.), KP-341, KP-358 and KP-368 (all trade names, all trade names, all trade names, Kyocera Chemical Industries, , KF-96-50CS, KF-50-100CS (all trade names, Shin-Etsu Chemical Co., Ltd.), Surfron S-611, Surfron SC-101 and Surfron KH-40 EFTOP EF-351, EFTOP EF-601, EFTOP EF-801 and EFTOP EF-802 (all of which are trade names, all of which are incorporated herein by reference in their entirety), phthalate 222F, phytagent 251 and FTX- (All trade names, manufactured by DIC Corporation), fluoroalkylbenzenesulfonic acid (manufactured by Mitsubishi Materials Corporation), Megafac F-171, Megafac F-177, Megafac F-475, Megafac F- Salts, fluoroalkylcarboxylic acid salts, fluoroalkyl polyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl betaines, fluoroalkyl sulfonic acids (Fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene stearate, polyoxyethylene stearyl ether, Polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan palaurate, polyoxyethylene sorbitan palmitate, polyoxyethylene Ethylene sorbitan stearate, polyoxyethylene sorbitan Les benzoate, a polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonic acid salts. At least one selected from these is preferably used as an additive.

Among these additives, preferred are fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkyl polyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl betaines, fluoroalkylsulfonic acid salts, diglycerin tetrakis ( BYK306, BYK346, KP-341, KP-358, KP-368, etc., which are fluorine-based surfactants such as fluoroalkyltrimethylammonium salts, fluoroalkylaminosulfonate salts and Surplon S- Based silicone surfactant is added, it is preferable that the coating uniformity of the photosensitive composition is increased.

The content of the leveling agent and the surfactant in the photosensitive composition of the present invention is preferably 0.001 to 0.1% by weight based on the total amount of the composition.

<4-2. Organic carboxylic acid>

As the alkali solubility promoter, an organic carboxylic acid can be used. The organic carboxylic acid may be used singly or in combination of two or more kinds. The organic carboxylic acid is preferably a polycarboxylic acid. Specific examples of the polycarboxylic acid are anhydrous trimellitic acid, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic acid anhydride. Among these polycarboxylic acids, trimellitic anhydride is preferred.

When the polycarboxylic acid is added to the positive photosensitive composition of the present invention, the alkali solubility of the organic film formed using the composition can be increased. The carboxyl group of the polyvalent carboxylic acid can further improve the heat resistance and chemical resistance of the cured film obtained by reacting with the epoxy resin in the photosensitive composition and exposing the formed organic film to exposure and development and firing .

The content of the organic carboxylic acid in the photosensitive composition of the present invention is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, per 100 parts by weight of the polymer (A).

<4-3. Phenol compounds>

As the alkali solubility promoter, a phenol compound can be used. The phenol compounds may be used singly or in a mixture of two or more. Specific examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3, (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (4-hydroxybenzophenone) (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2- 4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- -Tetramethyl-1,1'-spirobindene-5,6,7,5 ', 6', 7'-hexanol, and 2,2,4-trimethyl-7,2 ', 4'- It is Roxy Flambana. Among these phenol compounds, 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

When the phenolic compound is added to the photosensitive composition of the present invention, the alkali solubility of the organic film formed using the composition can be increased. Further, phenol as the phenolic compound can further improve the heat resistance and chemical resistance of the cured film obtained by reacting with the photosensitive organic compound when the photosensitive composition contains epoxy and exposing the formed organic film to development and firing.

The content of the phenolic compound in the positive photosensitive composition of the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the polymer (A).

<4-4. Antioxidants>

As the antioxidant, antioxidants of hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds can be preferably used. The antioxidant may be used alone or in combination of two or more. The antioxidant is preferably an antioxidant of a hindered phenol-based compound from the viewpoint of weather resistance. Specific examples of such antioxidants include, but are not limited to, Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox 1076, Irganox 1066D, Irganox 1076DWJ, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, , 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 (product name: BASF Japan) ; ADEKA Co., Ltd.). Of these, Irganox 1010 is more preferable.

The content of the antioxidant in the photosensitive composition of the present invention is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer (A).

<4-5. Adhesion improving agent>

As described above, the photosensitive composition of the present invention is characterized by being able to improve adhesion with a substrate by using a radically polymerizable monomer represented by the formula (I) as a raw material of the polymer (A). However, it is also possible to further use an adhesion improver. As the adhesion improver, a coupling agent can be preferably used. One kind of the adhesion improver may be used alone, or two or more kinds may be mixed and used. As the coupling agent, a silane-based, aluminum-based or titanate-based compound may be used. Specific examples of the coupling agent include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, and tetraisobutyl Propyl bis (dioctylphosphite) titanate. Among these, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

The content of the adhesion improver in the photosensitive composition of the present invention is preferably 10 parts by weight or less based on 100 parts by weight of the polymer (A).

<4-6. UV absorbers>

As the ultraviolet absorber, a component used as an ultraviolet absorber in a photosensitive composition, such as alkoxybenzophenones, can be used. The ultraviolet absorber may be used singly or in combination of two or more. Specific examples of such ultraviolet absorbers are Tinuvin P, Tinuvin 120, Tinuvin 144, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 571 and Tinuvin 765 (all trade names, ) to be.

The content of the ultraviolet absorber in the photosensitive composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polymer (A).

<4-7. Cross-linking agent>

As the thermal cross-linking agent, a component which causes a cross-linking reaction under the heating condition in the film formation using the photosensitive composition may be used. The thermal crosslinking agent may be used alone or in combination of two or more. As the thermal crosslinking agent, a thermal crosslinking agent such as an epoxy compound can be used. Specific examples of such a thermal cross-linking agent are jER 807, jER 815, jER 825, jER 827, jER 828, jER 190P and jER 191P (trade name; Yuka Shell Epoxy Co.), jER1004, jER1256, YX8000 (trade name, Mitsubishi Chemical Corporation) CY177, Araldite CY184 (trade name: Huntsman 占 Japan Co.), Celloxide 2021P, EHPE-3150 (trade name; manufactured by Daicel Chemical Industries Ltd.), Techmoa VG3101L (trade name, HP-4700, and EPICLON HP-7200 (trade name, DIC Co., Ltd.).

The content of the heat crosslinking agent in the positive photosensitive composition of the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the polymer (A).

The positive photosensitive composition of the present invention is preferably shielded from light in the range of -30 캜 to 25 캜 from the viewpoint of stability over time of the positive photosensitive composition. A storage temperature of -20 캜 to 10 캜 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 optimal for forming an insulating film having a small pore size of 10 占 퐉 or less because of a relatively high resolution at the time of patterning. Here, the insulating film is, for example, a film (interlayer insulating film) or the like formed to insulate between wirings arranged in layers.

The patterned transparent film of the present invention is formed by exposure, development, and firing of a coating film of the photosensitive composition. 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 for forming a film in the field of resist, and is formed, for example, as follows.

First, the positive photosensitive composition of the present invention is applied to a substrate such as glass by a known method such as spin coating, roll coating, slit coating or the like. The substrate on which the positive photosensitive composition of the present invention can be used is a transparent glass substrate such as a white plate glass, a chelate glass or a silica-coated chelate glass, a polycarbonate, a polyether sulfone, a polyester, an acryl, a vinyl chloride, an aromatic polyamide, Film or substrate, a metal plate such as an aluminum plate, a copper plate, a nickel plate, or a stainless steel plate, a ceramic plate, and a semiconductor substrate having a photoelectric conversion element. These substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, etc., as desired.

Next, the coating film of the positive photosensitive composition on the substrate is dried by a hot plate or an oven. It is usually dried at 60 to 120 ° C for 1 to 5 minutes. The organic film on the dried substrate is irradiated with radiation such as ultraviolet rays through a mask having an opening with a desired pattern shape. The irradiation conditions are suitably 5 to 50 mJ / cm 2 by i-line.

The organic film after irradiation is developed by using a developer such as an alkali solution without the need of post-exposure baking (PEB: after baking, baking is carried out before development to remove a protecting group present in the polymer) . The portion irradiated with the radiation in the organic film by the development is quickly dissolved in the developer. The developing method is not particularly limited, and a dip phenomenon, a puddle phenomenon, and a shower phenomenon can all be used.

The developer is preferably an alkali solution. Specific examples of the alkali included in the alkali solution include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, 2-hydroxyethyl trimethyl ammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, And potassium hydroxide. An aqueous solution of these alkalis is preferably used as the developer. Specifically, examples of the developer include organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or 2-hydroxyethyltrimethylammonium hydroxide, inorganic alkalis such as sodium carbonate, sodium hydroxide, or potassium hydroxide &Lt; / RTI &gt;

Methanol, ethanol, or a surfactant may be added to the developer for the purpose of reducing the development residue and improving the pattern shape. As the surfactant, for example, a surfactant selected from anionic, cationic, and nonionic surfactants can be used. Among them, it is particularly preferable to add a nonionic type polyoxyethylene alkyl ether from the viewpoint of increasing the resolution.

The developed film is sufficiently cleaned with pure water. Thereafter, it is baked at 150 to 250 DEG C for 10 to 120 minutes. Thus, a desired patterned transparent film can be obtained.

The patterned transparent film thus obtained may be used as a patterned insulating film. Further, a transparent electrode may be formed on the insulating film, patterned by etching, and then a film to be subjected to the alignment treatment may be formed. Since the insulating film has high sputtering resistance, wrinkles do not occur in the insulating film even if a transparent electrode is formed, and high transparency can be maintained.

The patterned transparent film of the present invention can be formed to have a usual thickness in accordance with a desired use in a display device such as a liquid crystal display device. The film thickness of the patterned transparent film is preferably in the range of 1 m to 10 m, and the film thickness of the patterned transparent film of the present invention is preferably in the range of 1 m to 10 m, and the film thickness of the patterned transparent film is preferably set in accordance with the viscosity of the positive photosensitive composition of the present invention, .

The patterned transparent film of the present invention is used in a display device using liquid crystal or the like. For example, the liquid crystal display element may be manufactured by pressing the element substrate on which the patterned transparent film of the present invention is formed and the color filter substrate serving as the counter substrate in such a manner as described above, , And sealing the injection port.

Alternatively, liquid crystal may be sprayed on the element substrate, then the element substrate may be overlapped and the liquid crystal may be sealed so as not to leak. The display element may be a display element manufactured in this way.

In this way, an insulating film formed from the positive photosensitive composition of the present invention and having excellent heat resistance and transparency can be used for the liquid crystal display element. The liquid crystal used in the display device of the present invention, that is, the liquid crystal compound and the liquid crystal composition, is not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

The cured film formed by exposing a coating film of the positive photosensitive composition of the present invention and then baking after development can be used as a film having a high solvent resistance, high water resistance, high acid resistance, high alkali resistance, High heat resistance, high transparency, adhesion to the base, and the like.

Since the cured film formed by exposing the coating film of the positive photosensitive composition of the present invention and baking after development is excellent in solvent resistance, acid resistance, alkali resistance, heat resistance and transparency, the transparent film, The surface roughness of the film does not occur even when the display element is exposed to a high temperature of 150 to 250 ° C. in a post-process after the formation of the insulating film, or when it is immersed in a solvent, an acid, or an alkali solution or the like. As a result, the transmittance of light such as a transparent film using the photosensitive composition according to the preferred embodiment of the present invention is increased, and the display quality of a product such as a display device using the same can be increased.

Example

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto.

[Polymerization Example 1] Synthesis of polymer (A1)

In a four-necked flask equipped with a stirrer, 1-methoxy-2-propyl acetate was used as a polymerization solvent while 2-acetoacetoxyethyl methacrylate (a1) and 4-hydroxyphenyl vinyl ketone (a4), glycidyl methacrylate (a4), and methacryloxypropyl-tris-trimethylsiloxysilane (a4), as well as methacryloxypropyltrimethoxysilane (a3) Azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator (hereinafter abbreviated as an initiator) at the following weights, and 2 g of 2,2'-azobis The polymerization was carried out by heating for a time.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.2 g of 2-acetoacetoxyethyl methacrylate (a1)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.6 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

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 by GPC analysis (polystyrene standard). The polystyrene (PL2010-0102 manufactured by VARIAN) having a molecular weight of 645 to 132,900 was used as the standard polystyrene and the PLgel MIXED-D (manufactured by VARIAN) was used as the weight average molecular weight of the polymer (A1) , THF was used as the mobile phase, the column temperature was set to 35 占 폚, and the measurement was carried out using a differential refractive index detector. As a result, the weight average molecular weight of the polymer (A1) was 7,600.

[Polymerization Example 2] Synthesis of polymer (A2)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at a temperature of 87 캜 for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.2 g of 2-acetoacetoxyethyl methacrylate (a1)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.6 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The polymer (A2) thus obtained had a weight average molecular weight determined by GPC analysis (polystyrene standard) of 8,100.

[Polymerization Example 3] Synthesis of polymer (A3)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.5 g of 2-acetoacetoxyethyl methacrylate (a1)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.3 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The polymer (A3) obtained had a weight average molecular weight determined by GPC analysis (polystyrene standard) of 10,500.

[Polymerization Example 4] Synthesis of polymer (A4)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

2-Acetoacetoxyethyl methacrylate (a1) 0.8 g

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The polymer (A4) thus obtained had a weight average molecular weight determined by GPC analysis (polystyrene standard) of 10,200.

[Polymerization Example 5] Synthesis of polymer (A5)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

2-Acetoacetoxyethyl methacrylate (a1) 0.3 g

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.6 g

6.0 g of glycidyl methacrylate (a4)

Methacryloxypropyl-tris-trimethylsiloxysilane (a4) 4.1 g

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The polymer (A5) obtained had a weight average molecular weight determined by GPC analysis (polystyrene standard) of 9,700.

[Polymerization Example 6] Synthesis of polymer (A6)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.02 g of hydroxyethyl methacrylate (a1)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.6 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The polymer (A6) obtained had a weight average molecular weight determined by GPC analysis (polystyrene standard) of 8,800.

[Comparative Polymerization Example 1] Synthesis of polymer (B1)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.8 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The weight average molecular weight of the obtained polymer (B1) determined by GPC analysis (polystyrene standard) was 8,100.

[Comparative Polymerization Example 2] Synthesis of polymer (B2)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.2 g of 2-acetoacetoxyethyl methacrylate (a1)

1.8 g of methacrylic acid (a2)

2.3 g of 3-methacryloxypropyltrimethoxysilane (a3)

Benzyl methacrylate (a4) 0.6 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The weight average molecular weight of the polymer (B2) obtained by GPC analysis (polystyrene standard) was 88,300.

[Comparative Polymerization Example 3] Synthesis of polymer (B3)

In the same manner as in Polymerization Example 1, the following components were added in the following weights and polymerization was carried out by heating at 90 DEG C for 2 hours.

22.5 g of 1-methoxy-2-propyl acetate (solvent)

0.2 g of 2-acetoacetoxyethyl methacrylate (a1)

1.8 g of 4-hydroxyphenyl vinyl ketone (a2)

Benzyl methacrylate (a4) in an amount of 2.8 g

6.0 g of glycidyl methacrylate (a4)

4.2 g of methacryloxypropyl-tris-trimethylsiloxysilane (a4)

Azobis (2,4-dimethylvaleronitrile) (initiator) 1.5 g

The weight average molecular weight of the polymer (B3) obtained by GPC analysis (polystyrene standard) was 9,750.

[Example 1]

[Preparation of positive photosensitive composition]

Irgacure 250 (hereinafter abbreviated as "Irg250" hereinafter) manufactured by BASF Japan Co., Ltd. as a photo acid generator and Anthracure UVS-1331 (hereinafter abbreviated as "DBA" hereinafter) manufactured by Kawasaki Kasei Kogyo Co., ) And EPICLON HP-4700 (hereinafter referred to as &quot; HP-4700 &quot;) as a crosslinking agent were mixed and dissolved in the parts by weight shown in Table 1, and further ethyldiglycol (hereinafter abbreviated as "ECa" And diluted so that the solid content concentration of the composition became 35% by weight. Lastly, 1100 ppm of Surfron S-611, a fluorine-based surfactant, AGC Semi-Chemical Co., Ltd., was added as an additive to obtain a positive photosensitive composition. The solid content concentration of the polymer (A1) solution obtained in Polymerization Example 1 was calculated as 40% by weight. The parts by weight of the polymer in Table 1 are parts by weight as solids.

[Evaluation method of positive photosensitive composition]

1) Formation of a transparent film on a pattern

The positive photosensitive composition prepared in Example 1 was spin-coated on a glass substrate and dried on a hot plate at 90 占 폚 for 2 minutes to obtain an organic film having a thickness of 3 占 퐉. This substrate was passed through a wavelength cut filter using a TME-150PRC (light source: ultra-high pressure mercury lamp) manufactured by Topcon manufactured by Sumitomo Chemical Co., Ltd., through a hole / dot pattern formation mask to cut light of 350 nm or less g, h and i lines were taken out and exposed at an exposure gap of 100 mu m. The exposure dose was measured by UIT-102 manufactured by Ushio Electric Co., Ltd., and UVD-365PD using a photoreceptor. The exposed glass substrate was subjected to dip development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 70 seconds to remove the organic film from the exposed portion. The developed substrate was washed with pure water for 60 seconds, and then the substrate was dried with air blow. The substrate was post-baked in an oven at 230 캜 for 30 minutes to form a patterned transparent film. The film thickness was measured by a total of the contact-assisted film thickness alpha phase P15 manufactured by KLA-Tencor Japan Co.,

2) Sensitivity

The minimum exposure amount at which a holographic pattern having the same size as the size of the photomask resolves is taken as sensitivity.

3) PED

After drying the hot plate in the above step 1), when a predetermined gap time is taken from exposure to development, the maximum gap time

4) Film thickness before and after development and residual film ratio after development

The film thickness was measured before and after development. The residual film ratio after development was calculated from the following formula.

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

5) Developing adhesion

When the air blow was performed after the dip development in 1) above, the dot pattern was confirmed to be missing, and the developing adhesion was evaluated by the presence or absence of the pattern. ?: No peeling,? Partial peeling, x no dot pattern.

Table 2 shows the results obtained by the above evaluation method for the patterned transparent film formed using the positive photosensitive composition prepared in Example 1.

[Examples 2 to 6]

A positive photosensitive composition was prepared in the same manner as in Example 1 by mixing each component as shown in Table 1, and a patterned transparent film was formed and evaluated. The evaluation results are shown in Table 2.

[Comparative Example 1]

A positive photosensitive composition was prepared and evaluated in the same manner as in Example 1 except that the components were mixed as described in Table 1, but the pattern did not completely resolve or the pattern deteriorated, and the PED was very poor and there was no development adhesion. The evaluation results are shown in Table 2.

[Comparative Examples 2 and 3]

In the process of forming the patterned transparent film, the organic film of the unexposed portion was completely dissolved in Comparative Example 2, and the organic film of the exposed portion in Comparative Example 3 was not dissolved in the alkaline developer, that is, patterning could not be performed.

In Comparative Examples 2 and 3, the fact that the sensitivity was &quot; NG &quot; indicates that the evaluation was impossible. In addition, the numerical values of the residual film ratios of Comparative Examples 2 and 3 were recorded for reference.

In general, the residual film ratio after development in an organic film formed using a positive photosensitive composition having a high sensitivity tends to be poor and the PED tends to be very bad. From the results of the above examples, it can be seen that when the positive photosensitive composition of the present invention is used , It can be seen that a film having high sensitivity, high residual film ratio after development, and high PED and developing adhesion can be obtained.

Industrial availability

The patterned transparent film using the photosensitive composition of the present invention can be used, for example, in a liquid crystal display device.

Claims (9)

The radically polymerizable monomer (a1) represented by the following formula (I)
The radically polymerizable monomer (a2) having an acidic group,
A radically polymerizable monomer (a3) having alkoxysilyl, and
(A) containing a radically polymerizable monomer (a4) other than (a1), (a2) and (a3), a photoacid generator (B) and an organic solvent (C) :

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine and R ² is hydrogen or 1,3-dioxopropane-1,3-diyl (-COCH ₂ CO- ), And n is an integer of 1 to 6. The method according to claim 1,
Wherein the radical polymerizable monomer (a1) is at least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the following formula (III):

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;
R ³ is alkyl having 1 to 6 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;
n is an integer of 1 to 6; 3. The method according to claim 1 or 2,
Wherein the radically polymerizable monomer (a2) having an acidic group is at least one selected from the group consisting of a radically polymerizable monomer having a phenolic OH, a radically polymerizable monomer having an unsaturated carboxylic acid and a radically polymerizable monomer having an unsaturated carboxylic acid anhydride Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; 4. The method according to any one of claims 1 to 3,
A positive photosensitive composition comprising a radically polymerizable monomer (a2) having an acidic group and at least one of radically polymerizable monomers having a phenolic OH represented by the following formula (IV): &lt; EMI ID =

Wherein R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently selected from the group consisting of hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms , At least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ is -OH,
^{R 7, R 8, R 9} , R 10, and R ¹¹ is alkyl in any of the -CH ₂ - is optionally substituted by -COO-, -OCO-, or -CO-, and, R ^7, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ , alkyl and alkoxy may be substituted with any hydrogen by halogen. 5. The method according to any one of claims 1 to 4,
Wherein the radical polymerizable monomer (a3) having alkoxysilyl is at least one selected from the group consisting of a compound represented by the following formula (V) and a compound represented by the following formula (VI):

Wherein R ¹ is hydrogen or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted with fluorine;
n is an integer from 1 to 6;
R ¹² to R ¹⁷ each independently represent hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH, alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 5 carbon atoms,
At least one of R ¹² to R ¹⁴ is alkoxy of 1 to 5 carbon atoms,
At least one of R ¹⁵ to R ¹⁷ is alkoxy having 1 to 5 carbon atoms,
R ¹² ~ R ¹⁷ is alkyl in the -CH ₂ that connects to the silicon-arbitrary -CH ₂ except - - -CH ₂ and the terminal is -COO-, -OCO-, -CO-, or -O- , And any hydrogen may be substituted with halogen. 6. The method according to any one of claims 1 to 5,
Wherein the radical polymerizable monomer (a4) comprises at least one of radically polymerizable monomers having an epoxy. 7. The method according to any one of claims 1 to 6,
Wherein the organic solvent (C) is a compound having a hydroxyl group (-OH). A patterned transparent film formed by exposure, development, and firing of a coating film of the positive photosensitive composition according to any one of claims 1 to 7. An insulating film using the patterned transparent film according to claim 8.