TW201321899A - Positive photosensitive composition - Google Patents

Abstract

A positive photosensitive composition, which has high sensitivity and does not require baking after exposure, is provided and is useful for forming a patterned transparent film obtained through developing by an alkali aqueous solution. The positive photosensitive composition contains a polymer (A), a photo-acid generator (B), and an organic solvent (C), wherein the polymer (A) is formed by radical polymerizing a radical polymerizable monomer having an alkoxysilyl group (a1), a radical polymerizable monomer having an acidic group (a2), and a radical polymerizable monomer (a3) other than (a2) and (a1).

Description

Positive photosensitive composition

The present invention relates to a positive photosensitive composition which can be utilized in the field of a resist or the like.

The patterned transparent film is used in many fields of display elements such as spacers, insulating films, protective films, etc. Up to now, a large number of positive photosensitive compositions have been proposed in this application (for example, reference patents) Document 1 to Patent Document 3).

In general, in an electronic component such as a thin film transistor type liquid crystal display element or a solid-state image sensor, an insulating film is provided in order to insulate wirings arranged in a layer. As a material for forming an insulating film, a positive photosensitive composition is widely used, and the number of steps of obtaining an insulating film having a necessary pattern shape of the positive photosensitive composition is small. The positive photosensitive composition must have a wide process margin in the process of forming the insulating film. Further, the insulating film or the display element using the positive photosensitive composition may be in a subsequent step after the formation of the insulating film (indium tin oxide (ITO) film formation, wet etching, alignment film formation, etc.) It is necessary to have resistance to these treatments by contact with a solvent, an acid, an alkaline solution or the like by immersion or the like and heat treatment. Further, for an insulating film used in a display element such as a liquid crystal display, high transparency to visible light is required.

In addition, in the use of the photosensitive insulating film used for a display element such as a liquid crystal display in recent years, the size of the mother glass is further increased, and in order to ensure productivity, it is urgent to shorten the photosensitive material. Time spent on series process (production time (tack Time)).

A high-sensitivity positive photosensitive composition for use in such applications has been proposed. For example, Patent Document 4 discloses a resist containing a third butyl ester group having a carboxylic acid or a phenol. Tributyl carbonate based polymer with photoacid generator. The third butyl ester group or the third butyl carbonate group in the polymer is deprotected by the acid generated during exposure and the post-exposure firing (Post Exposure Bake (PEB)). An acidic group such as a carboxyl group or a phenolic OH. As a result, the exposed portion of the resist film was dissolved in the alkaline developing solution. However, in the case of such a system, there is a problem that the PEB step is necessary after the exposure, and although it is high in sensitivity in terms of the amount of exposure, the total production time of the resulting process is not shortened.

On the other hand, Patent Document 5 describes a positive resist composition containing an alkoxydecane-containing vinyl-based copolymer and a curing catalyst, and an example of the following is described: The alkoxyalkyl group-containing acrylate, methacrylate or α-halogen-substituted acrylate is described as a body component, and hydrochloric acid is used as a curing catalyst.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 51-34711

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 56-122031

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-165214

[Patent Document 4] Japanese Patent Special Fair No. 2-27660

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2002-196494

The present invention provides a positive photosensitive composition which is highly sensitive and has no After exposure and firing, a patterned transparent film (patterned transparent film) can be formed.

The inventors of the present invention have found that the above problems can be solved by the following positive photosensitive composition, and the positive photosensitive composition contains the polymer (A) and the photoacid generator (B). And the organic solvent (C), the polymer (A) is a radical polymerizable monomer (a1) having an alkoxysilyl group, a radical polymerizable monomer (a2) having an acidic group, and (a1) is a radical copolymerization of the radically polymerizable monomer (a3) other than (a2). The invention includes the following items.

<1> A positive photosensitive composition comprising a polymer (A), a photoacid generator (B), and an organic solvent (C), wherein the polymer (A) is a radical having an alkoxyalkyl group The polymerizable monomer (a1), the radically polymerizable monomer (a2) having an acidic group, and the radically polymerizable monomer (a3) other than (a2) (a1) are radically copolymerized.

<2> The positive photosensitive composition of the above-mentioned <1>, wherein the radically polymerizable monomer (a1) having an alkoxyalkylalkyl group is represented by the following formula (I), formula (II) and One or more compounds represented by the formula (III), [Chemical 2] (wherein R ¹ is hydrogen or any hydrogen having 1 to 5 carbon atoms which may be substituted by fluorine, and R ² to R ¹⁰ are each independently hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH a straight or branched carbon number of 1 to 20 or an alkoxy group having 1 to 5 carbon atoms, and any -CH ₂ - of the alkyl group of R ² to R ¹⁰ may be -COO-, -OCO- And -CO- or -O-substituted, and any hydrogen may be substituted by halogen, wherein at least one of R ² to R ⁴ is an alkoxy group having 1 to 5 carbon atoms, and at least one of R ⁵ to R ⁷ is carbon The alkoxy group having 1 to 5 atoms, at least one of R ⁸ to R ¹⁰ is an alkoxy group having 1 to 5 carbon atoms; and in the formula (I), n is 1 to 5).

<3> The positive photosensitive composition as described in <1>, wherein the radically polymerizable monomer (a2) having an acidic group is selected from a radically polymerizable monomer having a phenolic OH. One or more kinds of radical polymerizable monomers having a radically polymerizable monomer having an unsaturated carboxylic acid and a radical polymerizable monomer having an unsaturated carboxylic acid anhydride.

The positive photosensitive composition as described in any one of <1> to <3>, wherein the radically polymerizable monomer (a2) having an acidic group is represented by the following formula (IV) a radically polymerizable monomer having a phenolic OH, (wherein R ¹¹ , R ¹² and R ¹³ are each hydrogen or an arbitrary alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each hydrogen; , halogen, -CN, -CF ₃ , -OCF ₃ , -OH, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ Any of -CH ₂ - in the alkyl group may be substituted by -COO-, -OCO- or -CO-, any of alkyl and alkoxy groups of R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ The hydrogen may be substituted by a halogen, wherein at least one of R ¹⁴ to R ¹⁸ is -OH).

The positive-type photosensitive composition of any one of the above-mentioned radically polymerizable monomers (a3) is a radically polymerizable monomer which has an epoxy group.

The positive photosensitive composition as described in any one of <1> to <5>, wherein the said organic solvent (C) is a solvent which has a hydroxyl group.

<7> A pattern-like transparent film which is formed by exposure, development, and baking of a coating film of a positive photosensitive composition as described in any one of <1> to <6>.

<8> An insulating film which uses a pattern as described in <7> Bright film.

<9> A display element having a patterned transparent film as described in <7> or <8>.

The present invention provides a positive photosensitive composition comprising the above specific polymer (A), photoacid generator (B) and organic solvent (C), so that it is highly sensitive and does not need to be fired after exposure, and can be formed. A pattern-like transparent film excellent in transparency.

<1. Photosensitive composition of the present invention>

The photosensitive composition of the present invention contains a polymer (A), a photoacid generator (B), and an organic solvent (C), and the polymer (A) is a radical polymerizable monomer having an alkoxyalkyl group ( A1) A radically polymerizable monomer (a2) having an acidic group and a radical polymerizable monomer (a3) are radically polymerized. One type of polymer may be used for the polymer (A), or two or more types of polymers may be used in combination. In addition, the photo-acid generator (B) may be used singly or in combination of two or more kinds, and the organic solvent (C) may be used alone or in combination of two or more.

The composition containing only the polymer obtained by polymerizing the radically polymerizable monomer (a1) having an alkoxyalkyl group and the photoacid generator (B) can be substantially patterned by exposure or alkali development. However, in order to impart various functions such as sensitivity, transparency, chemical resistance (acid, alkali, organic solvent), sputtering resistance, low dielectric constant, and reliability to the formed pattern-like transparent film, actually It is also necessary to copolymerize the monomer (a2) having an acidic group and the monomer (a3) other than (a1) and (a2).

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

The polymer (A) of the present invention is a radical polymerizable monomer (a1) having an alkoxyalkyl group, a radical polymerizable monomer (a2) having an acidic group, and (a1) and (a2). A copolymer obtained by polymerizing a radical polymerizable monomer (a3).

In the polymer (A), as the radical polymerizable monomer (a1), the radical polymerizable monomer (a2), and the radical polymerizable monomer (a3), a single radical polymerizable single can be used. A plurality of radical polymerizable monomers can also be used separately.

In the above polymer (A), the radical polymerizable monomer (a1) is preferably used in a proportion of 5% by weight to 50% by weight, more preferably 10% by weight based on the total weight of all the monomers. Use at a ratio of ~40% by weight. When the monomer (a1) is contained in such a range, it is preferable from the viewpoints of sensitivity, transparency, substrate adhesion, development stability, and storage stability of the solution.

Further, in the above polymer (A), the radical polymerizable monomer (a2) is preferably used in a proportion of from 1% by weight to 20% by weight based on the total weight of all the monomers, more preferably 5 parts by weight. It is used in a ratio of % by weight to 15% by weight. When the monomer (a2) is contained in such a range, it is preferable from the viewpoint of the solubility of the alkaline developer.

Further, in the polymer (A), the radical polymerizable monomer (a3) is preferably used in a proportion of 30% by weight to 94% by weight, more preferably 40%, based on the total weight of all the monomers. It is used in a ratio of % by weight to 80% by weight.

When the monomer (a3) is contained in such a range, developability, low dielectric property, It is preferable from the viewpoint of chemical resistance.

<1-1-1. Radical Polymerizable Monomer (a1) having an alkoxyalkylalkyl group>

The radically polymerizable monomer (a1) having an alkoxyalkyl group may be selected from the compounds represented by the following formula (I), formula (II) and formula (III).

In the general formula (I), the general formula (II) and the general formula (III), R ¹ is hydrogen or any hydrogen having 1 to 5 carbon atoms which may be substituted by fluorine, and R ² to R ¹⁰ are each hydrogen, Halogen, -CN, -CF ₃ , -OCF ₃ , -OH, a linear or branched alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, in an alkyl group of R ² to R ¹⁰ Any -CH ₂ - may be substituted by -COO-, -OCO-, -CO- or -O-, and any hydrogen may be substituted by halogen, wherein at least one of R ² to R ⁴ is a carbon number of 1 to 5 The alkoxy group, at least one of R ⁵ to R ⁷ is an alkoxy group having 1 to 5 carbon atoms, and at least one of R ⁸ to R ¹⁰ is an alkoxy group having 1 to 5 carbon atoms. In the formula (I), n is from 1 to 5.

The alkyl group of the above R ¹ is preferably a methyl group from the viewpoint of heat resistance and transparency. Further, from the viewpoint of alkali developability and heat resistance (glass transition point) of the film, the linear or branched alkyl group having 1 to 20 carbon atoms of R ² to R ⁴ preferably has a carbon number of 1 to 10 .

Further, for the same reason, the linear or branched alkyl group having 1 to 20 carbon atoms (arbitrarily hydrogen may be substituted by halogen) of R ⁵ to R ⁸ is preferably a carbon number of 1 to 10.

Further, for the reason of the hydrolysis property, at least one alkoxy group of R ² to R ⁴ , at least one alkoxy group of R ⁵ to R ⁷ , and carbon number of at least one alkoxy group of R ⁸ to R ¹⁰ Preferably, they are 1 to 5, respectively.

The radically polymerizable monomer having an alkoxyalkylene group is polymerized in the above compound (I), the formula (II), and the compound (a1) represented by the formula (III) in 100 parts by weight of the polymer. The amount of the substance is preferably from 5 parts by weight to 50 parts by weight. If the amount of the above (a1) is too large, the relative dielectric constant tends to increase, so that it is preferably 10 parts for use in the application for lowering the relative dielectric constant. Parts ~ 40 parts by weight.

Specific examples of the compound (a1) represented by the formula (I), the formula (II) and the formula (III) include 3-methylpropenyloxypropyltrimethoxydecane and 3-propenyloxyl Propyl trimethoxy decane, 3-methyl propylene oxime Propyl triethoxy decane, 3-propenyl methoxypropyl triethoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, vinyl trimethoxy decane, ethylene Triethoxy decane and the like. When a copolymer using these radically polymerizable monomers is used, it has a positive property of high sensitivity, high transparency, and almost no deterioration in transparency due to firing at a high temperature, and The solubility in the alkaline aqueous solution during development is high, that is, the developability is high, and the pattern-like transparent film can be easily obtained, and exhibits solvent resistance, high water resistance, acid resistance, alkali resistance, heat resistance, and further, with the underlayer. The adhesion is high.

Further, in the present invention, by using a radical polymerizable monomer (a1) having an alkoxyalkylalkyl group as a monomer of the polymer (A), the alkoxyalkyl group in the polymer (A) is used by The acid generated by the exposure is hydrolyzed to a silanol, whereby the polymer (A) is dissolved in an alkaline developing solution. Thereby, in the case of using the positive photosensitive composition of the present invention, it is not necessary to perform firing (exposure after exposure) after exposure, and it is possible to directly enter the developing step.

<1-1-2. Radical Polymerizable Monomer (a2)>

The radically polymerizable monomer (a2) having an acidic group which can be used in the invention includes a radical polymerizable monomer having an unsaturated carboxylic acid, a radical polymerizable monomer having an unsaturated carboxylic anhydride, and a phenol. A radical polymerizable monomer having an OH group, a radical polymerizable monomer having a phosphoric acid group, and a radical polymerizable monomer having a sulfonic acid group.

Specific examples of the radically polymerizable monomer having an unsaturated carboxylic acid include acrylic acid and methacrylic acid, and specific examples of the radical polymerizable monomer having an unsaturated carboxylic acid anhydride include maleic anhydride.

The radically polymerizable monomer having a phenolic OH is, for example, a hydroxystyrene or a radically polymerizable monomer having a phenolic OH represented by the following formula (IV).

(wherein R ¹¹ , R ¹² and R ¹³ are each hydrogen or an arbitrary alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each hydrogen; , halogen, -CN, -CF ₃ , -OCF ₃ , -OH, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ Any of -CH ₂ - in the alkyl group may be substituted by -COO-, -OCO- or -CO-, any of alkyl and alkoxy groups of R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ The hydrogen may be substituted by a halogen, wherein at least one of R ¹⁴ to R ¹⁸ is -OH.

Specific examples of the radically polymerizable monomer having a phenolic OH represented by the above formula (IV) include 4-hydroxyphenyl vinyl ketone.

Examples of the radical polymerizable monomer having a phosphoric acid group include phosphoric acid methacrylate, 2-methylpropenyloxyethyl acid phosphate, and 2-(methacryloxy)ethyl phosphate.

Examples of the radical polymerizable monomer having a sulfonic acid group include vinylsulfonic acid and acrylamide-t-butylsulfonic acid.

If a copolymer using the above radical polymerizable monomer is used, the base is used. It is preferred from the viewpoint of solubility. These radical polymerizable monomers may be used singly or in combination of two or more.

In the above specific examples, methacrylic acid, hydroxystyrene or 4-hydroxyphenyl vinyl ketone is preferred. Methacrylic acid and hydroxystyrene are easily available, and 4-hydroxyphenyl vinyl ketone can obtain good characteristics in terms of transparency, heat resistance, and storage stability of the composition.

<1-1-3. Radical polymerizable monomer (a3)>

Other radical polymerizable monomers (a3) which can be used in the present invention can be used: a radical polymerizable monomer having an epoxy group, a radical polymerizable monomer having a dicyclopentyl group, and an N-substituted male fluorene. A radically polymerizable monomer of an imine, a radically polymerizable monomer having a deuterium oxide, or the like. The monomers to be used may be one type or plural types. Specific examples of the radical polymerizable monomer having an epoxy group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, and α-ethyl acrylate. Glycidyl acrylate 3,4-epoxycyclohexyl acrylate, α-ethyl methacrylate glycidyl methacrylate 3,4-epoxycyclohexyl ester, and the like. When a copolymer using these radically polymerizable monomers is used, the sputtering resistance is good and the chemical resistance is high.

Further, specific examples of the radically polymerizable monomer having a dicyclopentyl group and a radically polymerizable monomer having an N-substituted maleimide include dicyclopentanyl acrylate or dicyclopentan methacrylate. N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(4-ethylmercaptophenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(4 -dimethylamino-3,5-dinitrophenyl)maleimide, N-(1-anilinophthalene Base-4) Maleidimine, N-[4-(2-benzoxazolyl)phenyl]maleimide or N-(9-acridinyl)maleimide.

When these radically polymerizable monomers are used, it is preferable from the viewpoint of heat resistance and low dielectric constant.

Specific examples of the radically polymerizable monomer having a decane used in the present invention include acryloxypropyl-tris-trimethyldecyloxydecane and methacryloxypropyl-tri- Trimethylnonyloxydecane, and the like.

Further, the polymer (A) may be a radical polymerizable monomer other than the above, insofar as the effects of the present invention are not impaired.

Examples of such a radical polymerizable monomer include benzyl methacrylate and cyclohexyl methacrylate.

The above polymer (A) preferably has an appropriate alkali solubility. In the present invention, the term "base solubility" refers to a property in which a solution of a polymer (A) which is subjected to radical polymerization by spin coating is applied onto a substrate and heated at 100 ° C for 2 minutes to form a solution. The film having a thickness of 0.01 μm to 100 μm was immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 5 minutes, and then rinsed with pure water. At this time, the film was dissolved in the alkali to the extent that it did not remain.

The alkali solubility of the polymer (A) which is subjected to radical polymerization can be adjusted by the amount of the monomer: a radically polymerizable monomer having a phenolic OH used in the radical polymerizable monomer (a2), Or a radically polymerizable monomer having an unsaturated carboxylic acid or a radically polymerizable monomer having an unsaturated carboxylic anhydride. For example, the alkali solubility of the polymer (A) which is subjected to radical polymerization can be increased by increasing the amount of a monomer having a phenolic OH or a radical having an unsaturated carboxylic acid. Polymeric monomer Or a radically polymerizable monomer having an unsaturated carboxylic anhydride.

The method for synthesizing the polymer (A) is not particularly limited, and a radically polymerizable monomer can be produced by radical copolymerization. Specifically, a mixture of the radical polymerizable monomer (a1), the radical polymerizable monomer (a2), and the radical polymerizable monomer (a3) can be obtained by polymerization, preferably a solution using a solvent. Free radical polymerization in. Further, a polymerization initiator may also be used in the radical polymerization.

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

The solvent used in the above polymerization reaction is preferably a solvent which dissolves the radically polymerizable monomer to be used and the polymer (A) to be produced. In particular, in terms of storage stability of the polymer obtained by polymerization, a solvent having a hydroxyl group is preferred. Among them, a solvent having a hydroxyl group can also be used as a diluent solvent for the polymer after being polymerized 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, and the like. 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 ether, 3-methoxy Methyl propyl propionate, ethyl 3-ethoxypropionate, N,N-dimethylformamide, and the like. The solvent may be one of these or a mixture of two or more of these.

A polymerization initiator which can be used in the synthesis of the polymer (A) can be used: a compound which generates a radical by heat, an azobisisobutyronitrile or an azo initiator such as 2,2'-azobis(2,4-dimethylvaleronitrile) or benzoyl peroxide A peroxide-based initiator. In order 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 determined by gel permeation chromatography (GPC) analysis using a polystyrene standard is in the range of 1,000 to 100,000, the polymer (A) is used until an alkaline developer The development time until the exposed portion is dissolved is appropriate, and the surface of the film during development is less likely to be roughened, which is preferable. Further, when the weight average molecular weight is in the range of 1,500 to 50,000, the development time until the unexposed portion is dissolved in the alkaline developing solution is appropriate, and the surface of the film is hardly roughened during development, and the development residue is extremely small, which is more preferable. For the same reason, it is particularly preferable if the weight average molecular weight is in the range of 2,000 to 20,000.

Polystyrene having a molecular weight of 645 to 132,900 (for example, a polystyrene calibration kit PL2010-0102 manufactured by VARIAN) can be used as the standard polystyrene, using PLgel MIXED-D (Watt) VARIAN (manufactured by VARIAN) was used as a column and measured using Tetrahydrofuran (THF) as a mobile phase.

The polymer (A) of the present invention can be adjusted to a preferred molecular weight by the monomer concentration at the time of polymerization, the amount of the polymerization initiator, and the polymerization temperature. For example, from the viewpoint of easiness of production, the monomer concentration at the time of polymerization (the concentration of the total amount of the monomers dissolved in the solvent in the solvent used in the polymerization reaction) is preferably 5% by weight to 60%. The weight% is more preferably 15% by weight to 50% by weight.

Further, in the positive photosensitive composition of the present invention, the content of the polymer (A) is preferably from 1% by weight to 60% by weight, more preferably from 3% by weight to 40% by weight based on the total mass of the composition. %, particularly preferably from 5% by weight to 35% by weight.

Further, the content of the above polymer (A) can be appropriately adjusted within the above range according to the coating 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, if the slit is applied, the content of the polymer (A) is decreased to lower the viscosity of the composition.

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

The photoacid generator used in the present invention may, for example, be a sulfonium salt-based photoacid generator such as a diphenylsulfonium salt or a triphenylsulfonium salt, or a sulfonimide compound-based photoacid generator.

Examples of the diphenyl phosphonium salt include diiodonium tetrafluoroborate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroarsenate, and diphenylphosphonium. Trifluoromethanesulfonate, diphenylsulfonium trifluoroacetate, diphenylphosphonium-p-toluenesulfonate, diphenylphosphonium butyl tris(2,6-difluorophenyl)borate , 4-methoxyphenylphenylphosphonium tetrafluoroborate, bis(4-t-butylphenyl)phosphonium tetrafluoroborate, bis(4-t-butylphenyl)phosphonium hexafluorophosphate Arsenate, bis(4-t-butylphenyl)phosphonium triflate, bis(4-t-butylphenyl)phosphonium trifluoroacetate, bis(4-tert-butyl Phenyl) fluorene-p-toluenesulfonate, bis(4-t-butylphenyl) camphorsulfonic acid, and the like.

Examples of the triphenyl sulfonium include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium trifluoroacetate. , triphenylsulfonium-p-toluenesulfonate, Triphenylphosphonium butyl tris(2,6-difluorophenyl)borate, and the like.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy) succinimide, N-(camphorsulfonyloxy) succinimide, and N-(4-methylphenyl). Sulfomethoxy) succinimide, N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) succinimide, N -(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoromethylphenylsulfonate) Ethylene phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy) diphenyl malayan Amine, N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylbenzene Sulfosulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy) Diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-methylphenyl Sulfomethoxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1] -5-ene-2,3-dicarboxy quinone imine, N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(4-methylphenylsulfonate醯oxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy) double ring [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine, N -( camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)bicyclo[ 2.2.1] heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5 ,6-oxy-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-di Carboxylimine, N-(trifluoromethylsulfonyloxy)naphthyldicarboxy quinone imine, N-(camphorsulfonyloxy)naphthyldicarboxy quinone imine, N-(4-methylbenzene Alkyl sulfonyloxy)naphthyldicarboxy quinone imine, N-(phenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)naphthyl Dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(pentafluoroethylsulfonyloxy)naphthyl dicarboxy quinone imine, N-( Heptafluoropropyl sulfonyloxy)naphthyldicarboxy quinone imine, N-(nonafluorobutane Sulfomethoxy)naphthyldicarboxy quinone imine, N-(ethylsulfonyloxy)naphthyldicarboxy quinone imine, N-(propylsulfonyloxy)naphthyldicarboxy quinone imine, N -(butylsulfonyloxy)naphthyldicarboxy quinone imine, N-(pentylsulfonyloxy)naphthyldicarboxy quinone imine, N-(hexylsulfonyloxy)naphthyldicarboxy fluorene Amine, N-(heptylsulfonyloxy)naphthyldicarboxy quinone imine, N-(octylsulfonyloxy)naphthyldicarboxy quinone imine, N-(decylsulfonyloxy)naphthyl Dicarboxy quinone imine and the like.

In the present invention, particularly in the case of using the positive photosensitive composition of the present invention in order to produce a transparent film, if the photoacid generator as described above is used, it is not necessary to pass the photoacid remaining after development. It is preferred that the generating agent is subjected to a post-exposure step in which all of the light is decomposed.

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

<3. 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 photoacid generator (B) contained in the composition. The organic solvent used in the present invention is preferably an organic solvent in which the polymer (A) and the photoacid generator (B) are dissolved, and is used as a storage stability of the composition or in a process for producing a patterned transparent film. In terms of the temporal stability of the coating film in the case where there is a pause between steps, the organic solvent is more preferably an organic solvent having a hydroxyl group. A compound having a boiling point of an organic solvent of from 100 ° C to 300 ° C is preferred. Specific examples of the above organic solvent having a boiling point of 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, and methoxy group. Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropane Acid propyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxyl Ethyl 2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-oxo Butyric acid Ethyl ester, 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, diethyl 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 Acid ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, toluene, xylene, γ-butyrolactone or N,N-dimethylacetamide. These may be used singly 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 from 40% by weight to 99% by weight, more preferably from 50% by weight to 90% by weight, based on the total amount of the composition. It is particularly preferably from 60% by weight to 80% by weight.

<4. Other ingredients>

In the photosensitive composition of the present invention, various additives may be added in order to improve resolution, coating uniformity, developability, and adhesion. Examples of the additives include anionic, cationic, nonionic, fluorine or ketone ketone leveling agents/surfactants, decane coupling agents and the like, and alkoxy benzophenones. A UV absorber such as a ketone, a crosslinking agent such as an epoxy compound, a melamine compound or a bisazide compound, an alkali solubility promoter such as a polyvalent carboxylic acid or a phenol compound, a hindered phenol system, a hindered amine system, a phosphorus system or a sulfur compound. Such as antioxidants.

<4-1.> Leveling agent, surfactant

In the photosensitive composition of the present invention, Polifloli can be cited. (Polyflow) No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (All of the above are trade names, Kyoeisha Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all of which are trade names, BYK Chemie Japan Co., Ltd.) , KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of the above are trade names, Shin-Etsu Chemical Co., Ltd.), Shaflon (Surflon) SC-101, sand Surflon KH-40 (all of which are trade names, AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names) , Neos Co., Ltd., EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF- 801, EFTOP EF-802 (all of which are trade names, Mitsubishi Materials Co., Ltd.), Megaface F-171, Megaface F-177, Megaface F- 475, Megaface F-556, Megaface R-30 (all of which are trade names, Di Ai Sheng (DIC) Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethyl ether, Fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra(fluoroalkyl polyoxyethyl ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amine sulfonate Acid salt, polyoxyethylene ethyl phenyl ether, polyoxyethyl octyl phenyl ether, polyoxyethylene ethyl ether, polyoxyethylene ethyl laurate, polyoxyethylene ethyl ether Polyoxyethylene ethyltridecyl ether, polyoxyethylene ethyl cetyl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl laurate, Polyoxyethylene ethyl oleate, polyoxyethylene ethyl stearate, polyoxyethylene ethyl laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearin Acid ester, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene ethyl sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethyl ether Sorbitol stearate, polyoxyethylene sorbitan oleate, polyoxyethylene ethyl naphthyl ether, alkyl benzene sulfonate or alkyl diphenyl ether disulfonate. It is preferred to use at least one selected from the above for the above additives.

Among these additives, if added, it is selected from a fluoroalkylbenzenesulfonate, a fluoroalkylcarboxylate, a fluoroalkyl polyoxyethyl ether, a fluoroalkylammonium iodide, a fluoroalkyl betaine, a fluoroalkyl group. Fluorinated surfactants such as sulfonate, diglycerol tetrakis(fluoroalkyl polyoxyethyl ether), fluoroalkyltrimethylammonium salt or fluoroalkylamine sulfonate, and BYK306, BYK346, KP-341 At least one of an anthrone-based surfactant such as KP-358 or KP-368 is preferred because the coating uniformity of the photosensitive composition is high.

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

<4-2. Organic carboxylic acid>

Among the above alkali solubility promoters, organic carboxylic acids can be used. The organic carboxylic acid may be one type or two or more types. The organic carboxylic acid is preferably a polyvalent carboxylic acid, and examples of such a polyvalent carboxylic acid include trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride. Among these polycarboxylic acids, trimellitic anhydride is also preferred.

If a polyvalent carboxylic acid is added to the photosensitive composition of the present invention, it can be mentioned The alkali solubility of the highly photosensitive composition. Further, when the photosensitive composition contains an epoxy group, the carboxyl group of the polyvalent carboxylic acid can react with the above to further improve heat resistance and chemical resistance.

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

<4-3. Phenol compound>

A phenol compound can be used for the said alkali solubility promoter. The phenol compound may be one type or two or more types. Examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2 ,3,3',4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl) Methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-dual (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]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyl Phenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobindene-5,6,7,5',6',7'-hexanol and 2, 2,4-Trimethyl-7,2',4'-trihydroxy flavan. Among these phenol compounds, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol is preferred.

When a phenol compound is added to the photosensitive composition of the present invention, the alkali solubility of the photosensitive composition can be improved. Further, when the photosensitive composition contains an epoxy group, the phenol of the phenol compound can react with these to further improve heat resistance and chemical resistance.

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

<4-4. Antioxidant>

Among the above antioxidants, an antioxidant of a hindered phenol type, a hindered amine type, a phosphorus type, and a sulfur type compound can be preferably used. The antioxidant may be one type or two or more types. From the viewpoint of weather resistance, the antioxidant is preferably an antioxidant of a hindered phenol compound. Such antioxidants include, for example, Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox ) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Irganox 1330, Easy Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox ) 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD, Irganox 295 (trade name) ; Japan BASF (shares)), ADIK STAB AO-20, ADK STAB AO-30, ADX STAB AO-50, Addicus ADB STAB AO-60, ADK STAB AO-70 and ADK STAB AO-80 (trade name; ADEKA). Among them, it is better to be Irganox 1010.

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

<4-5. Adhesion enhancer>

The adhesion improving agent is used to improve the adhesion between the photosensitive composition and the substrate. Among the adhesion promoters, a coupling agent can be preferably used. The adhesion improving agent may be one type or two or more types. Among the above coupling agents, a decane-based, aluminum-based or titanate-based compound can be used. Examples of such a coupling agent include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy. Base decane, acetonitrile alkoxy aluminum diisopropoxide and tetraisopropyl bis(dioctylphosphonium oxy) titanate. Among these, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving adhesion.

The content of the adhesion improving agent 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 absorber>

Among the above ultraviolet absorbers, a component such as an alkoxybenzophenone used as a UV absorber in a photosensitive composition can be used. The ultraviolet absorber may be one type or two or more types. Such ultraviolet absorbers include, for example, Tinuvin P, Tinuvin 120, Tinuvin 144, Tinuvin 213, Tinuvin 234, Emperor Tinuvin 326, Tinuvin 571, Tinuvin 765 (all of which are trade names, Japan BASF).

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

<4-7. Crosslinking agent>

In the thermal crosslinking agent, a component which causes a crosslinking reaction under heating conditions of film formation using a photosensitive composition as a material can be used. The thermal crosslinking agent may be used alone or in combination of two or more. A thermal crosslinking agent such as an epoxy compound may be used in the thermal crosslinking agent, and examples of such a thermal crosslinking agent include: jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (trade name; oiled shell epoxy) )), jER1004, jER1256, YX8000 (trade name; Mitsubishi Chemical (share)), Araldite CY177, Araldite CY184 (trade name; Japan Huntsman Japan (share)), match Celloxide 2021P, EHPE-3150 (trade name; Daicel Chemical Industry), Techmore VG3101L (trade name; Printec).

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

The positive photosensitive composition of the present invention is preferably stored in the dark at a temperature of from -30 ° C to 25 ° C from the viewpoint of stability over time of the positive photosensitive composition. When the storage temperature is -20 ° C to 10 ° C, it is more preferable from the viewpoint of preventing the occurrence of precipitates from the positive photosensitive composition.

The positive photosensitive composition of the present invention is suitable for forming a transparent film, and since it has a relatively high resolution at the time of patterning, it is most suitable for forming an insulating film having a small hole of 10 μm or less. Here, the insulating film is, for example, a film (interlayer insulating film) or the like provided to insulate between wirings arranged in a layer.

The patterned transparent film of the present invention is the photosensitive group of the present invention The coating film of the object is formed by exposure, development, and firing. For example, the pattern-like transparent film of the present invention such as the above-mentioned transparent film and insulating film can be formed by a usual method of forming a film in the field of a resist, and is formed, for example, as follows.

First, the positive photosensitive composition of the present invention is applied onto a substrate such as glass by a known method such as spin coating, roll coating or slit coating. Examples of the substrate include a transparent glass substrate such as white plate glass, blue plate glass, and ceria coated blue plate glass, polycarbonate, polyether oxime, polyester, Acryl, vinyl chloride, and aromatic polyfluorene. A synthetic resin sheet such as an amine, a polyamidimide or a polyimide, a film or a substrate, a metal substrate 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. For these substrates, a chemical treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition may be performed as needed.

Then, 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 ° C ~ 120 ° C for 1 minute ~ 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. The irradiation conditions are preferably i-line and 5 mJ/cm ² to 50 mJ/cm ² .

The film after the radiation irradiation is not fired after exposure (PEB: after exposure, in order to remove the protective group present in the polymer and is fired before development), development is carried out using a developing solution such as an alkaline solution. By the development, the portion irradiated with radiation in the above film is rapidly dissolved in the developer. The development method is not particularly limited, and any of immersion development, immersion development, and shower development can be used.

The above developing solution is preferably an alkaline solution. Alkali case contained in alkaline solution Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydroxide, and hydrogen. Potassium oxide. Further, as the developer, an aqueous solution of the base can be preferably used. That is, examples of the developer include organic bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or 2-hydroxyethyltrimethylammonium hydroxide, or sodium carbonate, sodium hydroxide or potassium hydroxide. An aqueous solution of an inorganic base.

In the developer, methanol, ethanol or a surfactant may be added for the purpose of reducing the development residue or optimizing the shape of the pattern. Among the surfactants, for example, a surfactant selected from the group consisting of an anionic system, a cationic system, and a nonionic system can be used. Among these, in particular, when a nonionic polyoxyethylidene ether is added, it is preferable from the viewpoint of improving the resolution.

The above-mentioned film developed as described above was sufficiently washed with pure water. Thereafter, it is fired at 150 ° C to 250 ° C for 10 minutes to 120 minutes. The desired patterned transparent film is thus obtained.

The pattern-like transparent film thus obtained can also be used as a pattern-like insulating film. The shape of the hole formed in the insulating film is preferably square, rectangular, circular or elliptical when viewed from directly above. Further, a film may be formed by forming a transparent electrode on the insulating film, patterning by etching, and performing an alignment treatment. Since the insulating film has high sputtering resistance, even if a transparent electrode is formed, wrinkles are not formed in the insulating film, and high transparency can be ensured.

The pattern-like transparent film of the present invention can be formed in a usual thickness corresponding to a desired use in a display element such as a liquid crystal display element. The film thickness of the pattern-like transparent film of the present invention is preferably from 1 μm to 10 μm, and the film thickness of the pattern-like transparent film can be obtained by the viscosity of the positive-type photosensitive composition of the present invention or the positive-type photosensitive composition of the present invention. The concentration of the solid component is adjusted.

The pattern-like transparent film of the present invention can be used in a display element using a liquid crystal or the like. For example, the display element is produced by arranging and crimping an element substrate provided with the pattern-like transparent film of the present invention as described above, and a color filter substrate as a counter substrate, followed by heat treatment. Liquid crystal is injected between the opposing substrates to seal the injection port.

Alternatively, it may be produced by dispersing liquid crystal on the element substrate, superimposing the element substrate, and sealing the liquid crystal so as not to be exposed, and the display element may be a display element produced in this manner.

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

The positive photosensitive composition of the preferred embodiment of the present invention has, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance which are generally required for the patterned transparent film and the insulating film. Various characteristics such as high transparency and adhesion to the underlying layer.

Further, since the positive photosensitive composition of the preferred embodiment of the present invention is excellent in solvent resistance, acid resistance, alkali resistance, heat resistance, and transparency, a transparent film, an insulating film, and a display using the photosensitive composition are used. The element or the like is exposed to a high temperature of 150 ° C to 250 ° C in the subsequent step after the formation of the insulating film, or the film is less likely to cause surface roughness even if it is immersed, contacted, heat-treated or the like in a solvent, an acid, an alkaline solution or the like. As a result, the transmittance of light such as a transparent film using the photosensitive composition of the preferred embodiment of the present invention is improved, and the display quality of a product such as a display element using the same can be improved.

[Example]

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

[Synthesis Example 1] Synthesis of Polymer (A1)

In a four-necked flask equipped with a stirrer, nitrogen gas foaming was carried out while adding diethylene glycol ethyl methyl ether as a polymerization solvent and glycidyl methacrylate as a monomer, 3-methyl group. Propylene methoxypropyltrimethoxydecane, methacryloxypropyl-tris-trimethyldecaneoxydecane, dicyclopentanyl methacrylate, 4-vinylketophenol, added as weight below The polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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 weight average molecular weight of the polymer (A1) is a polystyrene having a molecular weight of 645 to 132,900 (a calibration kit PL2010-0102 manufactured by VARIAN Co., Ltd.) is used as a standard polystyrene. And the column uses PLgel MIXED-D (manufactured by VARIAN Co., Ltd.), using THF as a mobile phase, the column temperature was set to 35 ° C, and measurement was performed 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)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Synthesis Example 3] Synthesis of Polymer (A3)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Synthesis Example 4] Synthesis of Polymer (A4)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Synthesis Example 5] Synthesis of Polymer (A5)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Synthesis Example 6] Synthesis of Polymer (A6)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Synthesis Example 7] Synthesis of Polymer (A7)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Comparative Synthesis Example 1] Synthesis of Polymer (B1)

The following components obtained by replacing the radically polymerizable monomer (4-hydroxyvinylketone) having an acidic group of Synthesis Example 1 with methyl methacrylate as a non-acidic component were added at a polymerization temperature of 90 ° C under the following weight: The polymerization was carried out by heating for 2 hours.

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

[Comparative Synthesis Example 2] Synthesis of Polymer (B2)

In the same manner as in Synthesis Example 1, the following components were added under the following weight, and the mixture was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization.

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

[Comparative Synthesis Example 3] Synthesis of Polymer (B3)

The following components were added in the same manner as in Synthesis Example 1 at the following weight, at 90 ° C The polymerization was carried out by heating at a polymerization temperature for 2 hours.

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

[Example 1] [Manufacture of positive photosensitive composition]

The polymer (A1) obtained in Synthesis Example 1, the Irgacure 250 (hereinafter referred to as "Irg250") manufactured by Japan BASF Co., Ltd. as a photoacid generator, and the Kawasaki Chemical Industry as a sensitizer Anthracure UVS-1331 (hereinafter referred to as "UVS-1331") manufactured by Co., Ltd. is mixed and dissolved in the parts shown in Table 1, and then diethylene glycol ethyl methyl ether (Dongbang Chemical Industry Co., Ltd.) Hisolve EDM manufactured by the company, hereinafter referred to as "EDM", is diluted as a dilution solvent so that the solid content concentration of the composition is 28% by weight. Finally, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., which is an anthrone-based surfactant which is an additive of 500 ppm based on the weight of the composition, was added to obtain a positive-type photosensitive composition. Further, the solid content concentration of the polymer (A1) solution obtained in Synthesis Example 1 was calculated to be 40% by weight. In addition, the weight part of the polymer in Table 1 and Table 2 below shows the weight part as a solid component.

[Evaluation method of positive photosensitive composition] 1) Formation of patterned transparent film

The positive photosensitive composition synthesized in Example 1 was spin-coated on a glass substrate, and dried on a hot plate at 100 ° C for 2 minutes to obtain an organic film having a film thickness of 3 μm. A mask for forming a substrate with a hole pattern in the air is used, and a proximity exposure machine TME-150PRC (light source is an ultrahigh pressure mercury lamp) manufactured by Topcon Co., Ltd. is used, and 350 is passed through a wavelength cut filter. The light below nm was cut off, and the g line, the h line, and the i line were taken out, and exposure was performed under the condition that the exposure gap was 100 μm. The exposure amount was measured using an integrated photometer UIT-102 manufactured by Oxtail Electric Co., Ltd. and a light receiver UVD-365PD. The exposed glass substrate was immersed and developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 90 seconds to remove the composition of the exposed portion. The developed substrate was washed with pure water for 60 seconds, and then the substrate was dried by a blower. The substrate was post-baked in an oven at 230 ° C for 30 minutes to form a patterned transparent film. The film thickness was measured by a stylus type film thickness meter α step meter (α step) P15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the three measurements was taken as the film thickness.

2) Film thickness before and after development and residual film rate after development

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

(film thickness after development / film thickness before development) × 100 (%) 3) Sensitivity

The minimum exposure amount of the hole pattern having the same size as that of the reticle is analyzed as the sensitivity.

4) Resolution

The substrate of the post-baking pattern-shaped transparent film obtained in the above 1) was observed by an optical microscope at 1,000 times, and it was confirmed that the mask size of the glass was exposed at the bottom of the hole pattern.

The case where the hole pattern was not analyzed was evaluated as poor (NG, No Good).

5) Transparency

The positive photosensitive composition synthesized in Example 1 was spin-coated on a glass substrate, and dried on a hot plate at 100 ° C for 2 minutes to obtain an organic film having a film thickness of 3 μm. Thereafter, it was immersed and developed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 90 seconds. The developed substrate was washed with pure water for 60 seconds, and then the substrate was dried by a blower. The substrate is used in the air using a proximity exposure machine TME-150PRC (the light source is an ultrahigh pressure mercury lamp) manufactured by Topcon Co., Ltd., and the light of 350 nm or less is cut off by a wavelength cut filter to take out the g line. The h line and the i line are used to fully expose the substrate. The exposure amount was measured using an integrated photometer UIT-102 manufactured by Oxtail Electric Co., Ltd. and a light receiver UVD-365PD, and was set to 20 mJ/cm ² . The substrate was post-baked in an oven at 230 ° C for 30 minutes to form a patterned transparent film. The light transmittance at a wavelength of 400 nm was measured using a UV-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation, based on a glass substrate on which a transparent film was not formed.

6) Heat resistance

The pattern-like transparent film obtained in the above 1) was placed in an oven at 230 ° C The substrate was additionally baked for 60 minutes, and the light transmittance was measured in the same manner as in the above 4) before and after the additional baking, and the light transmittance after post-baking (before the additional baking) was set to T1, and the light transmittance after baking was added. Set T2. The light transmittance after the additional baking is lower than that after the post-baking, and the smaller the decrease, the better the determination. Further, the film thickness was measured before and after the additional baking, and the rate of change in film thickness was calculated from the following formula.

(additional film thickness after baking / film thickness after post-baking) × 100 (%)

7) Adhesion

The substrate of the patterned transparent film obtained in the above 1) was evaluated by a mesh peeling test (cross-cut test). In the evaluation, the number of remaining meshes after peeling off the tape in 100 meshes of 1 mm square was shown.

The results obtained by the above evaluation method for the positive photosensitive composition synthesized in Example 1 are shown in Table 3.

[Example 2 to Example 7]

Each component was mixed as described in Table 1, and a positive photosensitive composition was prepared and evaluated in the same manner as in Example 1. The ratio of the organic solvent to the surfactant was the same as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 1 to Comparative Example 4]

Each component was mixed as described in Table 1, and a positive photosensitive composition was prepared and evaluated in the same manner as in Example 1, but the pattern was not analyzed at all. The evaluation results are shown in Table 4.

In Comparative Example 1, Comparative Example 2, and Comparative Example 4, during the formation of the pattern-like transparent film, the positive photosensitive composition of the exposed portion was not dissolved in the alkaline developing solution, that is, it could not be patterned, so development was performed. After the residual film rate becomes A high value, but the resolution is NG.

In general, the positive photosensitive composition having a high sensitivity has a low residual film ratio after development, and the positive photosensitive composition having a low sensitivity has a high residual film ratio after development, and the result of the above example is obtained. It is known that when the positive photosensitive composition of the present invention is used, a film having high sensitivity and a high residual film ratio after development can be obtained.

[Industrial availability]

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

Claims (9)

A positive photosensitive composition comprising: a polymer (A) which is a radical polymerizable monomer (a1) having an alkoxyalkyl group, and a radical polymerizable monomer having an acidic group (a2) And (a1) and the radically polymerizable monomer (a3) other than (a2) are subjected to radical copolymerization; a photoacid generator (B); and an organic solvent (C). The positive photosensitive composition according to claim 1, wherein the radically polymerizable monomer (a1) having an alkoxyalkyl group is represented by the following formula (I), formula (II) and One or more compounds represented by the formula (III), [Chemical 3] (wherein R ¹ is hydrogen or any hydrogen having 1 to 5 carbon atoms which may be substituted by fluorine, and R ² to R ¹⁰ are each independently hydrogen, halogen, -CN, -CF ₃ , -OCF ₃ , -OH a straight or branched carbon number of 1 to 20 or an alkoxy group having 1 to 5 carbon atoms, and any -CH ₂ - of the alkyl group of R ² to R ¹⁰ may be -COO-, -OCO- And -CO- or -O-substituted, and any hydrogen may be substituted by halogen, wherein at least one of R ² to R ⁴ is an alkoxy group having 1 to 5 carbon atoms, and at least one of R ⁵ to R ⁷ is carbon The alkoxy group having 1 to 5 atoms, at least one of R ⁸ to R ¹⁰ is an alkoxy group having 1 to 5 carbon atoms; and in the formula (I), n is 1 to 5). The positive photosensitive composition according to the first or second aspect of the invention, wherein the radical polymerizable monomer (a2) having an acidic group is selected from a radically polymerizable monomer having a phenolic OH. One or more kinds of radical polymerizable monomers having a radically polymerizable monomer having an unsaturated carboxylic acid and a radical polymerizable monomer having an unsaturated carboxylic acid anhydride. The positive photosensitive composition according to any one of claims 1 to 3, wherein the radically polymerizable monomer (a2) having an acidic group is represented by the following formula (IV) Radical polymerizable monomer having phenolic OH, [Chemical 4] (wherein R ¹¹ , R ¹² and R ¹³ are each hydrogen or an arbitrary alkyl group having 1 to 3 carbon atoms which may be substituted by fluorine, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each hydrogen; , halogen, -CN, -CF ₃ , -OCF ₃ , -OH, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ Any of -CH ₂ - in the alkyl group may be substituted by -COO-, -OCO- or -CO-, any of alkyl and alkoxy groups of R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ The hydrogen may be substituted by a halogen, wherein at least one of R ¹⁴ to R ¹⁸ is -OH). The positive photosensitive composition according to any one of claims 1 to 4, wherein the radical polymerizable monomer (a3) is a radical polymerizable monomer having an epoxy group. The positive photosensitive composition according to any one of claims 1 to 5, wherein the organic solvent (C) is a solvent having a hydroxyl group. A pattern-like transparent film which is formed by exposure, development, and firing of a coating film of a positive photosensitive composition according to any one of claims 1 to 6. An insulating film using the patterned transparent film as described in claim 7 of the patent application. A display element having a patterned transparent film as described in claim 7 or item 8.