JP2014062978A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition used for producing an alkali-developable transparent film excellent in adhesion to an inorganic base material, sensitivity, transparency, and heat resistance.SOLUTION: The positive photosensitive composition contains: an organic-inorganic hybrid polymer (A) obtained by reacting a radically polymerizable compound (a1) having an alkoxysilane structure, a radically polymerizable compound (a2) having carboxyl or hydroxyphenyl, other radically polymerizable compounds (a3), and a compound (a4) represented by general formula (III); naphthoquinone diazide (B); and an organic solvent (C).

Description

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

  Patterned transparent films are used in many fields of display elements such as spacers, insulating films, protective films, etc., and many positive photosensitive compositions have been proposed for this purpose (for example, patents). References 1-3).

  In general, an electronic component such as a thin film transistor type liquid crystal display element or a solid-state imaging element is provided with an insulating film for insulating between wirings arranged in layers. As a material for forming the insulating film, positive photosensitive compositions are widely used. The positive photosensitive composition needs to have a wide process margin in the process of forming the insulating film. Furthermore, an insulating film or a display element using a positive photosensitive composition may be subjected to contact with a solvent, an acid, an alkaline solution or the like by immersion in a post-manufacturing process and may be heat-treated. It is important to have In addition, when used in a liquid crystal display element, it is important that an organic film formed of a positive insulating film maintain high transparency in the visible light region in order to avoid attenuation of light from a backlight. On the other hand, it is also important that the film has a low dielectric property in order to reduce the parasitic capacitance between the wirings.

In recent years, when forming a transparent film (patterned transparent film) used for a thin film transistor type liquid crystal display element, the length of processing time due to an increase in substrate size has been a problem. In order to shorten the processing time, it is important to shorten the time required for the exposure process. For this reason, a highly sensitive positive photosensitive composition has been required. However, when the sensitivity of the positive photosensitive composition is improved, the developing solution penetrates into the interface between the substrate and the transparent film in the development process, and a problem that a part of the pattern is peeled off from the substrate occurs. This is because the intermolecular interaction between the transparent film made of an organic component and the substrate made of an inorganic component is weak.
In order to avoid this problem, conventionally, a method for hydrophobizing the surface of an inorganic substrate using a surface treatment agent such as hexamethyldisilazane to improve the adhesion with an organic component is known. However, this method requires a new step of hydrophobizing the substrate with the surface treatment agent, and as a result, there is a problem that the processing time becomes long. For this reason, a positive photosensitive composition having high sensitivity and high adhesion to an inorganic substrate has been desired.

JP 51-34711 A JP 56-122031 A JP-A-5-165214

  Under such circumstances, there is a demand for a positive photosensitive composition having high sensitivity and high substrate adhesion and having other characteristics (transparency and heat resistance) compatible.

As a result of intensive studies, the present inventor has found that the radical polymerizable compound (a1) represented by the following general formula (I) and / or (II) described later, a radical polymerizable compound having carboxyl or hydroxyphenyl (a2) ), Other radical polymerizable compounds (a3) and organic-inorganic hybrid polymer (A), naphthoquinone diazide (B) and organic solvent (C) obtained by reacting compound (a4) represented by the following general formula (III) ) Was found, and the present invention was completed based on this finding. The present invention includes the following items.

[1] Radical polymerizable compound (a1) represented by the following general formula (I) and / or (II), radical polymerizable compound (a2) having carboxyl or hydroxyphenyl, other radical polymerizable compound (a3) And a positive photosensitive composition comprising an organic-inorganic hybrid polymer (A) obtained by reacting the compound (a4) represented by the following general formula (III), a naphthoquinone diazide (B), and an organic solvent (C) object.

（式中、Ｒ¹は水素、又は任意の水素がフッ素で置き換えられてもよい炭素数１〜５のア
ルキルであり、Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、水酸基、炭素数１〜５のアルコキ
シまたはアセトキシであり、Ｒ²、Ｒ³およびＲ⁴の少なくとも一つが加水分解性基であり
、ｎは１以上の整数である。）

(In the formula, R ¹ is hydrogen, or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ² , R ³ and R ⁴ are each independently a hydroxyl group, 5 is alkoxy or acetoxy, at least one of R ² , R ³ and R ⁴ is a hydrolyzable group, and n is an integer of 1 or more.)

（式中、Ｒ⁵〜Ｒ⁷はそれぞれ独立に、水酸基、炭素数１〜５のアルコキシまたはアセトキシであり、Ｒ⁵、Ｒ⁶およびＲ⁷の少なくとも一つが加水分解性基である。）

(In the formula, R ^{5 to} R ⁷ are each independently a hydroxyl group, alkoxy having 1 to 5 carbon atoms or acetoxy, and at least one of R ⁵ , R ⁶ and R ⁷ is a hydrolyzable group.)

（式中、Ｒ⁸〜Ｒ¹¹はそれぞれ独立に、水素、フッ素、ヒドロキシル、炭素数１〜５のア
ルコキシ、アセトキシ、または一価の有機基であるが、少なくとも一つの加水分解性基を含む。）

(In the formula, R ^{8 to} R ¹¹ are each independently hydrogen, fluorine, hydroxyl, C 1-5 alkoxy, acetoxy, or a monovalent organic group, and include at least one hydrolyzable group. )

[2] The radical polymerizable compound (a1) is 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, or p. -The positive photosensitive composition as described in [1] which is styryltrimethoxysilane.

[3] In the above [1] or [2], the radical polymerizable compound (a2) is a compound selected from acrylic acid, methacrylic acid, 4-hydroxystyrene, and a compound represented by the following general formula (IV). The positive photosensitive composition as described.

（式中、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、それぞれ水素、又は任意の水素がフッ素で置き換えられてもよい炭素数１〜３のアルキルであり、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸及びＲ¹⁹は、それぞれ水素、ハロゲン、−ＣＮ、−ＣＦ₃、−ＯＣＦ₃、−ＯＨ、任意の−ＣＨ₂−が−ＣＯＯ−
、−ＯＣＯ−、−ＣＯ−で置き換えられてもよく、また任意の水素がハロゲンで置き換えられてもよい炭素数１〜５のアルキル、又は任意の水素がハロゲンで置き換えられてもよい炭素数１〜５のアルコキシである。但し、Ｒ¹⁵〜Ｒ¹⁹のうち少なくとも１つは−ＯＨである。）

(In the formula, R ¹² , R ¹³ and R ¹⁴ are each hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^18. And R ¹⁹ are each hydrogen, halogen, —CN, —CF ₃ , —OCF ₃ , —OH, or —CH ₂ — is —COO—.
, —OCO—, —CO— may be substituted, and any hydrogen may be substituted with halogen, alkyl having 1 to 5 carbon atoms, or any hydrogen may be substituted with halogen. ~ 5 alkoxy. However, at least one of R ^{15 to} R ¹⁹ is —OH. )

[4] The positive photosensitive composition according to any one of [1] to [3], including a radical polymerizable compound having epoxy or oxetanyl as the other radical polymerizable compound (a3).

[5] The compound (a4) represented by the general formula (III) is tetraethyl orthosilicate, tetramethyl orthosilicate, trimethoxymethylsilane, triethoxymethylsilane, trimethoxypropylsilane, triethoxypropylsilane, trimethoxy. Hexylsilane, Triethoxyhexylsilane, Allyltriethoxysilane, Allyltrimethoxysilane, Triethoxyvinylsilane, Trimethoxyvinylsilane, Triethoxyphenylsilane, Trimethoxyphenylsilane, 3-Glycidyloxypropyltrimethoxysilane, Trimethoxysilane, Di Selected from ethoxydimethylsilane, dimethoxydimethylsilane, diphenyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, and diphenylsilanediol A compound [1] to positive photosensitive composition according to any one of [4].

[6] The positive photosensitive composition as described in any one of [1] to [5], further comprising an antioxidant.

[7] The organic-inorganic hybrid polymer (A) is obtained by copolymerizing the radical polymerizable compounds (a1), (a2) and (a3), and the obtained copolymer is represented by the formula (III). The positive photosensitive composition according to any one of [1] to [6], which is obtained by hydrolytic condensation in the presence of the compound (a4).

[8] The organic-inorganic hybrid polymer (A) is copolymerized after mixing the radical polymerizable compounds (a1), (a2) and (a3) and the compound (a4) represented by the formula (III). And the positive photosensitive composition according to any one of [1] to [6], which is obtained by simultaneously performing hydrolytic condensation.

[9] Exposure to a coating film formed using the positive photosensitive composition according to any one of [1] to [8], development through a mask having an opening corresponding to a desired pattern, development, And a patterned transparent film obtained by firing.

  The positive photosensitive composition of the present invention is excellent in sensitivity, substrate adhesion, and resolution, and a film such as a transparent film, an insulating film, and a display element using the positive photosensitive composition has a small exposure amount. When the pattern is resolved and the pattern is not peeled off from the substrate during the development process, the film deteriorates even if it is exposed to high temperatures in the subsequent post-manufacturing process or after-treatment such as heat treatment. It is hard to do. As a result, the display quality of a display element using a film such as a transparent film using the positive photosensitive composition of the present invention is enhanced.

  The positive photosensitive composition of the present invention contains an organic-inorganic hybrid polymer (A) described later, naphthoquinone diazide (B), and an organic solvent (C).

<1. Organic Inorganic Hybrid Polymer (A)>
The organic-inorganic hybrid polymer (A) in the present invention includes a radical polymerizable compound (a1) represented by the following general formula (I) or (II), a radical polymerizable compound (a2) having carboxyl or hydroxyphenyl, and the following general formula It is a polymer obtained by reacting the compound (a4) represented by the formula (III).

（式中、Ｒ¹は水素、又は任意の水素がフッ素で置き換えられてもよい炭素数１〜５のア
ルキルであり、Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、水酸基、炭素数１〜５のアルコキ
シまたはアセトキシであり、Ｒ²、Ｒ³およびＲ⁴の少なくとも一つが加水分解性基であり
、ｎは１以上の整数である。）

(In the formula, R ¹ is hydrogen, or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ² , R ³ and R ⁴ are each independently a hydroxyl group, 5 is alkoxy or acetoxy, at least one of R ² , R ³ and R ⁴ is a hydrolyzable group, and n is an integer of 1 or more.)

（式中、Ｒ⁵、Ｒ⁶及びＲ⁷はそれぞれ独立に、水酸基、炭素数１〜５のアルコキシまたは
アセトキシであり、Ｒ⁵、Ｒ⁶およびＲ⁷の少なくとも一つが加水分解性基である。）

Wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydroxyl group, alkoxy having 1 to 5 carbon atoms or acetoxy, and at least one of R ⁵ , R ⁶ and R ⁷ is a hydrolyzable group. )

（式中、Ｒ⁸〜Ｒ¹¹はそれぞれ独立に、水素、フッ素、ヒドロキシル、炭素数１〜５のア
ルコキシ、アセトキシ、または一価の有機基であるが、少なくとも一つの加水分解性基を含む。）

(In the formula, R ^{8 to} R ¹¹ are each independently hydrogen, fluorine, hydroxyl, C 1-5 alkoxy, acetoxy, or a monovalent organic group, and include at least one hydrolyzable group. )

<1-1. Radical polymerizable compound (a1) represented by general formula (I) and (II) and compound (a4) represented by general formula (III)>
In the compound represented by the general formula (I), as a specific example of the substituent in the formula, R ¹ is preferably hydrogen or alkyl having 1 to 3 carbon atoms, and more preferably methyl. Each of R ² , R ³ and R ⁴ is preferably alkoxy having 1 to 5 carbon atoms, and each of R ² , R ³ and R ⁴ is more preferably methoxy or ethoxy.
In the formula (I), n is more preferably 3 or more. On the other hand, n is usually 5 or less.

In the compound represented by the general formula (II), as specific examples of the substituent in the formula, R ⁵ ,
Each of R ⁶ and R ⁷ is preferably alkoxy having 1 to 5 carbon atoms, and each of R ⁵ , R ⁶ and R ⁷ is more preferably methoxy or ethoxy.

Specific examples of the radical polymerizable compound (a1) represented by the general formula (I) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Acryloxypropyltriethoxysilane is mentioned, As a specific example of the radically polymerizable monomer (a1) represented by the general formula (II), p-styryltrimethoxysilane is mentioned.
By using these compounds, the radical copolymerization of the vinyl group of the radical polymerizable compound represented by the general formula (I) and / or (II) and the general formula (I) and / or (II) Hydrolysis condensation of the hydrolyzable group of the radically polymerizable compound represented can be combined, and the organic-inorganic hybrid polymer (A) can be synthesized.

  In the compound (a4) represented by the general formula (III), as specific examples of the monovalent organic group mentioned as the substituent in the formula, any hydrogen is bromine, chlorine, fluorine, mercapto, cyano, amino C1-C18 alkyl, allyl, vinyl, benzyl, phenyl, tolyl which may be substituted with ethylamino, epoxycyclohexyl, isocyanate, amino, glycidyloxy, ureido or phenylamino and may have a cyclic structure , Bicyclo [2.2.1] hept-5-en-2-yl or alkylureido having 1 to 3 carbon atoms. Examples of the at least one hydrolyzable group include C1-C5 alkoxyl.

Examples of the silane compound represented by the general formula (III) are shown below. Examples of the tetrafunctional alkoxysilane compound having four alkoxyl groups include tetrabutyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetraethyl orthosilicate, and tetramethyl orthosilicate. Examples of the trifunctional alkoxysilane compound having three alkoxyl groups include (3-bromopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, and chloromethyl. Triethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3- (2-aminoethylamino) propyl Triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltri Ethoxy 3-glycidyloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl chloride, 3-ureidopropyltriethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, benzyltriethoxysilane, Cyclohexyltrimethoxysilane, dodecyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, pentyltriethoxysilane, triethoxyphenylsilane, Trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, trimethoxymethylsilane, triethoxymethylsilane , Trimethoxypropylsilane, triethoxypropylsilane, trimethoxyhexylsilane, triethoxyhexylsilane, [bicyclo [2.2.1] hept-5-en-2-yl] triethoxysilane, triethoxy-1H, 1H , 2H, 2H-tridecafluoro-n-octylsilane, triethoxyethylsilane, triethoxyfluorosilane, triethoxysilane, trimethoxysilane, and trimethoxy [3- (phenylamino) propyl] silane. Examples of the bifunctional alkoxysilane compound having two alkoxyl groups include diethoxydimethylsilane, dimethoxydimethylsilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-glycidyloxypropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, diethoxymethylphenylsilane, dimethoxymethylphenylsilane , Diethoxydiphenylsilane, dimethoxydiphenylsilane, diethoxymethylsilane, dimethoxymethylsilane, diethoxymethylvinylsilane Dimethoxymethyl vinyl silane, and Jimetokishiji -p- tolylsilane the like. Examples of the monofunctional alkoxysilane compound having one alkoxyl group include ethoxytriethylsilane, methoxytrimethylsilane, and trimethylethoxysilane.
Examples of compounds other than the above include diphenylsilanediol.

  The organic-inorganic hybrid polymer using the compound represented by the general formula (III) has high initial transparency, almost no deterioration of transparency due to baking at high temperature, and solubility in an aqueous alkali solution during development. High, i.e., high developability, a pattern-like transparent film can be easily obtained, pattern peeling during development does not occur, and solvent resistance, high water resistance, acid resistance, alkali resistance, heat resistance are exhibited, and Increases adhesion to the substrate.

  Two or more kinds of the compounds represented by the general formula (III) may be mixed for use.

  Among the above specific examples, tetraethyl orthosilicate, tetramethyl orthosilicate, allyltriethoxysilane, allyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, triethoxyphenylsilane, trimethoxyphenylsilane, triethoxysilane, trimethoxysilane , Diethoxydimethylsilane, dimethoxydimethylsilane, diphenyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, diphenylsilanediol are easily available, and the resulting pattern-like transparent film has solvent resistance, water resistance, acid resistance From the viewpoint of enhancing alkali resistance, heat resistance, and transparency.

<1-2. Radical polymerizable compound having carboxyl or hydroxyphenyl (a2)>
The radical polymerizable compound (a2) having carboxyl or hydroxyphenyl used for the polymerization of the organic-inorganic hybrid polymer of the present invention is not particularly limited as long as it is a compound having carboxyl or hydroxyphenyl in the molecule, but specific examples of (a2) Examples thereof include acrylic acid, methacrylic acid, 4-hydroxystyrene, and compounds represented by the following general formula (IV).

（式中、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、それぞれ水素、又は任意の水素がフッ素で置き換えられてもよい炭素数１〜３のアルキルであり、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸及びＲ¹⁹は、それぞれ水素、ハロゲン、−ＣＮ、−ＣＦ₃、−ＯＣＦ₃、−ＯＨ、任意の−ＣＨ₂−が−ＣＯＯ−
、−ＯＣＯ−、−ＣＯ−で置き換えられてもよく、また任意の水素がハロゲンで置き換えられてもよい炭素数１〜５のアルキル、又は任意の水素がハロゲンで置き換えられてもよい炭素数１〜５のアルコキシである。但し、Ｒ¹⁵〜Ｒ¹⁹のうち少なくとも１つは−ＯＨである。）

(In the formula, R ¹² , R ¹³ and R ¹⁴ are each hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^18. And R ¹⁹ are each hydrogen, halogen, —CN, —CF ₃ , —OCF ₃ , —OH, or —CH ₂ — is —COO—.
, —OCO—, —CO— may be substituted, and any hydrogen may be substituted with halogen, alkyl having 1 to 5 carbon atoms, or any hydrogen may be substituted with halogen. ~ 5 alkoxy. However, at least one of R ^{15 to} R ¹⁹ is —OH. )

  Specific examples of the compound represented by the general formula (IV) include, for example, 4-hydroxyphenyl vinyl ketone.

  In addition to radically polymerizable compounds (a1) and (a2), other radically polymerizable compounds (a3) are used for polymerization in the organic-inorganic hybrid polymer (A) in the present invention. An example is shown below.

<1-3. Other radical polymerizable compound (a3)>
Examples of the other radical polymerizable compound (a3) include a radical polymerizable compound having epoxy or oxetanyl. Specifically, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, α-ethylacrylic acid glycidyl ester 3,4-epoxycyclohexyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, and the like can be given. When these radically polymerizable monomers (a3) are used, the chemical resistance is good and the transparency is high.
Among the above specific examples, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3-ethyl-3- (meth) acryloxymethyl oxetane are easily available. Yes, from the viewpoint of improving the solvent resistance, water resistance, acid resistance, alkali resistance, heat resistance, and transparency of the obtained patterned transparent film.

  Moreover, said other radically polymerizable compound (a3) may be used alone or in combination.

  In addition to the above, a radical polymerizable monomer containing N-substituted maleimide or dicyclopentanyl can be used as the radical polymerizable compound (a3). Use of these radical polymerizable monomers is preferable from the viewpoints of heat resistance and low dielectric constant.

  Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N -(2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N- (1-anilinonaphthyl-4) maleimide, N- [4- (2-benz And oxazolyl) phenyl] maleimide or N- (9-acridinyl) maleimide.

  Specific examples of the radical polymerizable monomer containing dicyclopentanyl include dicyclopentanyl acrylate and dicyclopentanyl methacrylate.

  When the above organic-inorganic hybrid polymer (A) is used, the solubility in an alkaline aqueous solution is high, that is, the developability is high, and a patterned transparent film can be easily obtained by combining with a naphthoquinone photosensitizer. Furthermore, pattern peeling during development does not occur, and a patterned transparent film having high adhesion can be obtained. Moreover, it has low dielectric properties, solvent resistance, high water resistance, high acid resistance, high alkali resistance, and high heat resistance. Of these, the low dielectric properties are considered to be due to the presence of both the organic polymer portion and the siloxane portion in the organic-inorganic hybrid polymer (A).

  The amount of the radical polymerizable compound (a1) in the raw material when synthesizing the organic-inorganic hybrid polymer (A) is preferably 1 to 50% by weight from the viewpoint of development adhesion and substrate adhesion. It is more preferably ˜40% by weight, and further preferably 15-30% by weight.

  In addition, the amount of the radical polymerizable compound (a2) in the raw material when synthesizing the organic-inorganic hybrid polymer (A) is from 1 to 30 from the viewpoint of solubility of the polymer in an alkaline developer and improvement in sensitivity during patterning. % By weight is preferable, 3 to 20% by weight is more preferable, and 3 to 15% by weight is even more preferable.

  Further, the amount of the radical polymerizable compound (a3) in the raw material when synthesizing the organic-inorganic hybrid polymer (A) is 5 to 50% by weight from the viewpoint of improving developability and substrate adhesion. Preferably, it is 5 to 40% by weight, more preferably 10 to 30% by weight.

  When the organic-inorganic hybrid polymer (A) is synthesized, the weight ratio of the compound (a4) represented by the general formula (I) to the radically polymerizable compound (a1) is adhesiveness, developability, and transparency. When the weight of the radically polymerizable compound (a1) is 1, it is usually 0.1 to 10, preferably 0.5 to 10, and preferably 1.0 to 5. More preferably 0.

<1-4. Polymerization Method of Organic-Inorganic Hybrid Polymer (A)>
The reaction during the polymerization of the organic-inorganic hybrid polymer (A), that is, the polymerization method is not particularly limited, but the radically polymerizable compounds (a1), (a2) and (a3) are copolymerized in the presence of a polymerization initiator, Thereafter, (a4) may be added and hydrolytic condensation may be performed in the presence of an acid catalyst and water, or (a1), (a2), (a3) and (a4) are mixed and a polymerization initiator is mixed. Radical polymerization and hydrolytic condensation may be carried out simultaneously in the presence of water and an acid catalyst and / or water.
The polymerization temperature is not particularly limited as long as radical polymerization is a temperature at which radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C 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 pressure, reduced pressure, or atmospheric pressure. The hydrolysis condensation is not particularly limited as long as the hydrolysis reaction and the condensation reaction proceed, but it is usually in the range of 50 ° C to 150 ° C. In order to advance the hydrolysis and condensation efficiently, it is preferable to distill off the alcohol and water produced by the reaction.

  The solvent used for the above polymerization reaction is not particularly limited as long as it is a solvent that dissolves the raw materials used and the organic-inorganic hybrid polymer (A) to be generated. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene. Examples include glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and N, N-dimethylformamide. The solvent may be one of these, or a mixture of two or more of these.

  The polymerization initiator used when synthesizing the organic-inorganic hybrid polymer (A) is a compound that generates radicals by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide initiator such as benzoyl peroxide. Agents can be used. In order to adjust the molecular weight, a suitable amount of a chain transfer agent such as thioglycolic acid may be added.

  When the organic-inorganic hybrid polymer (A) has a weight average molecular weight in the range of 1,000 to 100,000 determined by GPC analysis using polystyrene as a standard, the development time until the exposed portion is dissolved with an alkaline developer. Is preferable, and the film surface is less likely to be rough during development. Furthermore, when the weight average molecular weight is in the range of 1,500 to 50,000, the development time until the unexposed part is dissolved with an alkaline developer is appropriate, and the surface of the film is hardly roughened during development. Since the development residue is also extremely small, it is more preferable. For the same reason, the weight average molecular weight is particularly preferably in the range of 2,000 to 20,000.

  The weight average molecular weight of the organic-inorganic hybrid polymer (A) is, for example, polystyrene having a molecular weight of 645 to 132,900 as standard polystyrene (eg, polystyrene calibration kit PL2010-0102 from VARIAN), and PLgel MIXED-D (as a column). VARIAN) and THF as a mobile phase.

  The content of the organic-inorganic hybrid polymer (A) in the positive photosensitive composition of the present invention is usually 5 to 60% by weight with respect to the total amount of the positive photosensitive composition.

<2. Positive photosensitive composition of the present invention>
The positive photosensitive composition of the present invention contains an organic-inorganic hybrid polymer (A), naphthoquinone diazide (B), and an organic solvent (C).

<2-1. Naphthoquinonediazide (B)>
For the naphthoquinone diazide (B), for example, a compound used as a photosensitizer in the resist field can be used. As naphthoquinone diazide (B), an ester of a phenol compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a phenol compound and 1,2-naphthoquinonediazide-4- Esters with sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid, compounds in which the hydroxyl group of the phenolic compound is replaced with an amino group, and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5 -Sulfonamide with sulfonic acid, sulfonamide with compound in which hydroxyl group of phenol compound is replaced with amino group and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid It is done. These may be used alone or in combination of two or more.
About said ester, the average esterification rate uses what is 30-100% normally.

  Specific examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,3 ′, 4- Tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1, 1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-Dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-H, Roxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1, 1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol or 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan.

  Naphthoquinonediazide (B) is an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5 -Esters with sulfonic acids, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid Or 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid Use of ester or the like is preferable from the viewpoint of increasing the transparency of the positive photosensitive composition. These may be used alone or in combination of two or more.

  Moreover, in the positive photosensitive composition of this invention, it is preferable that a naphthoquinone diazide (B) is 5-50 weight part with respect to 100 weight part of an organic inorganic hybrid polymer (A).

<2-2. Organic solvent (C)>
The positive photosensitive composition of the present invention further contains an organic solvent (C) in addition to the organic-inorganic hybrid polymer (A) and the naphthoquinone diazide (B). The organic solvent used in this case is an organic solvent that dissolves the organic-inorganic hybrid polymer (A) and the naphthoquinone diazide (B).

In addition, the organic solvent (C) used in the present invention is preferably a compound having a boiling point of 100 ° C to 300 ° C. Specific examples of the organic solvent having a boiling point of 100 ° C. to 300 ° C. include butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate 2 Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono Chill ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, or N, N-dimethylacetate Bromide, and the like. These may be used alone or in combination of two or more.

  The organic solvent used in the present invention may be a mixed solvent containing 20% by weight or more of the organic solvent having a boiling point of 100 to 300 ° C. As the solvent other than the organic solvent having a boiling point of 100 to 300 ° C. in the mixed solvent, one or more known solvents can be used.

  As the organic solvent (C) contained in the positive photosensitive composition, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl Use of at least one selected from ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate is more preferable because the coating uniformity is increased. Further, when at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate is used, the positive photosensitive composition is applied. It is even more preferable from the viewpoint of enhancing uniformity and safety to the human body.

  In addition, in the positive photosensitive composition of the present invention, the organic-inorganic hybrid polymer (A) and the photosensitive material, which are solids, with respect to the total amount of the organic-inorganic hybrid polymer (A), naphthoquinonediazide (B), and organic solvent (C). The organic solvent (C) is preferably blended so that the total amount of naphthoquinonediazide (B), which is an agent, is 5 to 50% by weight.

<2-3. Other ingredients>
<2-3-1. Antioxidant>
In the present invention, it is preferable to further contain an antioxidant from the viewpoint of weather resistance. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds. Among them, the hindered phenol type is more preferable as the antioxidant.
Specific examples of the antioxidant, e.g., IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox 295 (trade name; BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB O-60, ADK STAB AO-70, ADK STAB AO-80 (trade name; Ltd ADEKA) and the like. Among these, ADK STAB AO-60 is more preferable from the viewpoint of transparency and heat resistance.
When adding the said antioxidant to the positive photosensitive composition of this invention, 0.1-5 weight part is normally added with respect to 100 weight part of the said organic inorganic hybrid polymer (A).

<2-3-2. Additives>
Various additives other than the antioxidant can be added to the positive photosensitive composition of the present invention in order to improve resolution, coating uniformity, developability, and adhesion. Additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, silicone resin coating improvers, silane couplings Adhesion improvers such as adhesives, ultraviolet absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, thermal cross-linking agents such as epoxy compounds, melamine compounds or bisazide compounds, and alkali solubility promotion such as organic carboxylic acids Agents and the like.

  Specific examples of the additive include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disperse Bake 162, Disperse Bake 163, Disperse Bake 164, Disperse Bake 166, Disperse Bake 170, Disperse Bake 180, Disperse Bake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (all of which are trade names, Big Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS , KF-50-100CS (all are trade names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all are trade names, Seimichemica) Inc.), Aftergent 222F, Aftergent 251, FTX-218 (all are trade names, Neos Inc.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF- 802 (all are trade names, Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck R-08, Megafuck R-30 (all are trade names, DIC Corporation), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxy Ethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate , Sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid Examples include stealth, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, or alkyl diphenyl ether disulfonate. It is done. At least one selected from these is preferably used for the additive.

Among these additives, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene) Oxyethylene ether), fluorosurfactants such as fluoroalkyltrimethylammonium salts, or fluoroalkylaminosulfonates, silicon such as BYK306, BYK342, BYK344, BYK346, KP-341, KP-358, or KP-368 It is preferable to add at least one selected from resin-based coatability improvers because the coating uniformity of the positive photosensitive composition is increased.
When adding the said additive to the positive photosensitive composition of this invention, 0.001-5 weight part is normally added with respect to 100 weight part of the said organic-inorganic hybrid polymer (A).

<2-3-3. Polyvalent carboxylic acid>
A polyvalent carboxylic acid such as trimellitic anhydride, phthalic anhydride, or 4-methylcyclohexane-1,2-dicarboxylic anhydride may be added to the positive photosensitive composition of the present invention. Of these polyvalent carboxylic acids, trimellitic anhydride is preferable.

  When the polyvalent carboxylic acid is added to the positive photosensitive composition of the present invention and heated, the carboxyl of the polyvalent carboxylic acid reacts with the epoxy when the positive photosensitive composition contains epoxy. Thus, the heat resistance and chemical resistance can be further improved.

  In the positive photosensitive composition of the present invention, when the polyvalent carboxylic acid is added, the polyvalent carboxylic acid may be 1 to 30 parts by weight with respect to 100 parts by weight of the organic-inorganic hybrid polymer (A). Preferably, it is 2 to 20 parts by weight.

<2-4. Preservation of positive photosensitive composition>
When the positive photosensitive composition of the present invention is stored in the light-shielded state at a temperature in the range of -30 ° C to 25 ° C, the composition is preferable because the stability over time is good. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

<3. Resin Film Formed from Positive Photosensitive Composition of the Present Invention>
The positive photosensitive composition of the present invention is suitable for forming a transparent resin film, and has a relatively high resolution at the time of patterning, so that an insulating film having a small hole of 10 μm or less is formed. Is optimal. Here, the insulating film refers to, for example, a film (interlayer insulating film) provided to insulate the wirings arranged in layers.

  The resin film such as the transparent film and the insulating film can be formed by an ordinary method of forming a resin film in the resist field, and is formed as follows, for example.

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 substrates include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass, synthetic resins such as polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide. Examples thereof include a metal sheet such as a sheet, a film or a substrate, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. If necessary, 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 method, and vacuum deposition.

Next, the film of the positive photosensitive composition on the substrate is dried by a hot plate or an oven. Usually, it is dried at 60 to 120 ° C for 1 to 5 minutes. The film on the dried substrate is irradiated with radiation such as ultraviolet rays through a mask having a desired pattern shape. The irradiation condition is suitably 5 to 1,000 mJ / cm ^{2 for} i-line. The naphthoquinone diazide in the portion exposed to ultraviolet rays becomes indenecarboxylic acid and dissolves quickly in the developer.

  The film after irradiation with radiation is developed using a developer such as an alkaline solution. By this development, the portion of the film irradiated with radiation is quickly dissolved in the developer. The development method is not particularly limited, and any of dip development, paddle development, and shower development can be used.

  The developer is preferably an alkaline solution. Specific examples of the alkali contained in the alkaline solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, or A potassium hydroxide etc. are mentioned. As the developer, an aqueous solution of these alkalis is preferably used. That is, as a developer, organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or 2-hydroxyethyltrimethylammonium hydroxide, inorganic alkalis such as sodium carbonate, sodium hydroxide, or potassium hydroxide are used. An aqueous solution can be mentioned.

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

The developed film is sufficiently rinsed with pure water, and then radiation is again irradiated on the entire surface of the film on the substrate. For example, when the radiation is ultraviolet, the film is irradiated with an intensity of 100 to 1,000 mJ / cm ² . The film on the substrate which has been re-irradiated with radiation is finally baked at 180 to 250 ° C. for 10 to 120 minutes. Thus, a desired patterned transparent film can be obtained.

  The patterned transparent film thus obtained can also be used as a patterned insulating film. The shape of the hole formed in the insulating film is preferably a square, a rectangle, a circle or an ellipse when viewed from directly above. Furthermore, a transparent electrode may be formed over the insulating film, and after patterning by etching, a film for performing an alignment process may be formed. Since the insulating film has high sputtering resistance, wrinkles are not generated in the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

  The positive photosensitive composition according to a preferred embodiment of the present invention has high substrate adhesion to an inorganic substrate typified by silicon dioxide, silicon nitride, silicon, molybdenum, aluminum, chromium, tungsten, etc., and sensitivity. And high resolution, high heat resistance, high transparency, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, low dielectric properties, etc. Transparent films, insulating films, display elements, etc. using positive photosensitive compositions will deteriorate even if they are immersed, contacted, or heat-treated in solvents, acids, alkali solutions, etc. in the manufacturing process. Hard to do. As a result, the display quality of a product such as a display element using the positive photosensitive composition according to a preferred embodiment of the present invention can be improved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Synthesis Example 1] Synthesis of organic-inorganic hybrid polymer (A1) In a four-necked flask equipped with a stirrer, diethylene glycol ethyl methyl ether as a polymerization solvent, 3-methacryloxypropyltrimethoxysilane as a radical polymerizable compound (a1), radical polymerization 4-hydroxyphenyl vinyl ketone as the functional compound (a2), glycidyl methacrylate as the other radical polymerizable compound (a3), and 2,2′-azobis (2,4-dimethylvaleronitrile) as the radical polymerization initiator Charged by weight (preparation 1-1) and heated at 90 ° C. for 2 hours for radical polymerization.

(Preparation 1-1)
Diethylene glycol ethyl methyl ether 12.00g
3.62 g of 3-methacryloxypropyltrimethoxysilane
4-hydroxyphenyl vinyl ketone 0.7280 g
Glycidyl methacrylate 2.912 g
2,280'-azobis (2,4-dimethylvaleronitrile) 0.7280 g

  Thereafter, diacetone alcohol, 3-glycidyloxypropyltrimethoxysilane and trimethylmethoxysilane as (a4) were charged into the four-necked flask containing the above polymer solution with the following weight (preparation 1-2) and stirred. . Further, a mixed solution of formic acid and pure water as an acid catalyst was added dropwise to a four-necked flask with the following weight. The four-necked flask was heated at an internal temperature of 100 ° C. for 1 hour, and then the internal temperature was further increased to 130 ° C., and low molecular components produced by hydrolysis were removed by distillation for 3 hours. The total amount of low boiling point components removed by distillation was 26.1 g.

(Preparation 1-2)
Diacetone alcohol 12.00g
3-Glycidoxypropyltrimethoxysilane 8.000 g
Trimethylmethoxysilane 4.0000g
Formic acid 1.810 g
8.480 g of water

  Thereafter, the reaction solution was cooled to room temperature to obtain a transparent polymer solution. The solid content concentration of the polymer solution was calculated from the remaining weight after applying 0.3 g of the polymer solution on a glass substrate and drying it on a hot plate at 100 ° C. for 5 minutes. The solid content concentration of the polymer solution was 37%. A part of the polymer solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 16,000.

[Synthesis Example 2] Synthesis of Organic-Inorganic Hybrid Polymer (A2) In the same manner as in Synthesis Example 1, raw materials were charged with the following weight (preparation 2-1), and radical polymerization was performed at 110 ° C for 2 hours.

(Preparation 2-1)
Diethylene glycol ethyl methyl ether 20.00g
3.000 g of 3-methacryloxypropyltrimethoxysilane
Dicyclopentanyl methacrylate 3000g
N-cyclohexylmaleimide 2.500 g
Methacrylic acid 1.500 g
2,2'-azobis (2,4-dimethylvaleronitrile) 1.000 g

  Thereafter, diacetone alcohol, 3-glycidyloxypropyltrimethoxysilane, and trimethylmethoxylane were charged into the four-necked flask containing the above polymer solution at the following weight (charge 2-2) and stirred. Further, pure water was added dropwise to the four-necked flask at the following weight. The four-necked flask was heated at an internal temperature of 100 ° C. for 1 hour, and then the internal temperature was further increased to 130 ° C., and low molecular components produced by hydrolysis were removed by distillation for 3 hours. The total of low-boiling components removed by distillation was 28.9 g.

(Preparation 2-2)
Diacetone alcohol 20.00g
3-glycidoxypropyltrimethoxysilane 10.00 g
Trimethylmethoxysilane 5.000g
8.480 g of water

  Thereafter, the reaction solution was cooled to room temperature, and the solid content concentration was calculated in the same manner as in Synthesis Example 1. The solid concentration was 35%. A part of this solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 14,000.

[Synthesis Example 3] Synthesis of Organic-Inorganic Hybrid Polymer (A3) In the same manner as in Synthesis Example 1, raw materials were charged with the following weight (preparation 3-1), and radical polymerization was performed at 110 ° C for 2 hours.

(Preparation 3-1)
Diethylene glycol ethyl methyl ether 20.00g
p-styryltrimethoxysilane 3.500 g
Dicyclopentanyl methacrylate 4.00 g
Methacrylic acid 2.500 g
2,2'-azobis (2,4-dimethylvaleronitrile) 1.000 g

  Thereafter, diacetone alcohol, 3-glycidoxypropyltrimethoxysilane, and phenyltrimethoxysilane were charged into the four-necked flask containing the polymer solution with the following weight (preparation 3-2) and stirred. Further, pure water was added dropwise to the four-necked flask at the following weight. The four-necked flask was heated at an internal temperature of 100 ° C. for 1 hour, and then the internal temperature was further increased to 130 ° C., and low molecular components produced by hydrolysis were removed by distillation for 3 hours. The low boiling point components removed by distillation were 29.1 g in total.

(Preparation 3-2)
Diacetone alcohol 20.00g
3-00 g of 3-glycidoxypropyltrimethoxysilane
Phenyltrimethoxysilane 5.000g
8.480 g of water

  Thereafter, the reaction solution was cooled to room temperature, and the solid content concentration was calculated in the same manner as in Synthesis Example 1. The solid concentration was 38%. A part of this solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 11,000.

[Synthesis Example 4] Synthesis of Organic-Inorganic Hybrid Polymer (A4) Instead of 3-glycidoxypropyltrimethoxysilane (8 g) used in Synthesis Example 1, phenyltrimethoxysilane (6.4 g) and dimethyldimethoxysilane ( An organic-inorganic hybrid polymer (A4) was synthesized in the same manner as in Synthesis Example 1 except that 1.6 g) was used. A part of the polymer solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 10,000.

[Comparative Synthesis Example 1]
The acrylic polymer (D1) was polymerized in the same manner as in Synthesis Example 1 with the composition used in (Preparation 1-1) of Synthesis Example 1.
Diethylene glycol ethyl methyl ether 12.00g
3.62 g of 3-methacryloxypropyltrimethoxysilane
4-hydroxyphenyl vinyl ketone 0.7280 g
Glycidyl methacrylate 2.912 g
2,280'-azobis (2,4-dimethylvaleronitrile) 0.7280 g

  Thereafter, the reaction solution was cooled to room temperature, a part of this solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 8,100.

[Comparative Synthesis Example 2]
The acrylic polymer (D2) was polymerized with the composition used in (Preparation 2-1) of Synthesis Example 2.
Diethylene glycol ethyl methyl ether 20.000 g
3.000 g of 3-methacryloxypropyltrimethoxysilane
Dicyclopentanyl methacrylate 3000g
N-cyclohexylmaleimide 2.500 g
Methacrylic acid 1.500 g
2,2'-azobis (2,4-dimethylvaleronitrile) 0.1000 g

  Thereafter, the reaction solution was cooled to room temperature, a part of this solution was sampled, and the weight average molecular weight was measured by the GPC analysis (polystyrene standard) described above. As a result, the weight average molecular weight was 7,800.

[Example 1]
[Production of positive photosensitive composition]
Organic-inorganic hybrid polymer (A1) obtained in Synthesis Example 1, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, which is naphthoquinonediazide And 1,2-naphthoquinonediazide-5-sulfonic acid chloride condensate (average esterification rate 58%, hereinafter also referred to as “PAD”), surfactant BYK-342 (trade name; Big Chemie Japan Co., Ltd.) Then, diethylene glycol methyl ethyl ether was mixed and dissolved so that the solid content concentration was 30% by weight (excluding the surfactant) to obtain a positive photosensitive composition. In terms of solid content, the organic-inorganic hybrid polymer (A1) component is 100 parts by weight, and the PAD is 20 parts by weight. The surfactant was added at 1000 ppm with respect to the total of components other than the surfactant. Table 1 shows the composition.

Diethylene glycol ethyl methyl ether 0.8130g
Organic-inorganic hybrid polymer (A1) 2.000 g
PAD 0.1500g
BYK-342 0.0028g

[Method for evaluating positive photosensitive composition]
1) Formation of patterned transparent film The positive photosensitive composition synthesized in Example 1 was spin-coated at 500 rpm for 10 seconds on a glass substrate, and dried on a hot plate at 100 ° C. for 2 minutes. Using this substrate in air, a mask for hole pattern formation, Topcon Proximity Exposure Machine TME-150PRC (light source is ultra-high pressure mercury lamp) cuts light below 350nm through a wavelength cut filter. , H, i lines were taken out and exposed with an exposure gap of 100 μm. The exposure amount was 100 mJ / cm ^{2 as} measured by Ushio Electric Co., Ltd. integrated light meter UIT-102 and photoreceiver UVD-365PD. The exposed glass substrate was dip-developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds to remove the composition in the exposed area. The substrate after development was washed with pure water for 60 seconds and then dried on a hot plate at 100 ° C. for 2 minutes. The entire surface of the substrate was exposed at an exposure amount of 300 mJ / cm ² without using a mask with the exposure machine, and then post-baked in an oven at 300 ° C. for 30 minutes to form a patterned transparent film having a thickness of about 3 μm. The film thickness was an average value of three measurements using a stylus type film thickness meter P15, KLA-Tencor Japan Co., Ltd.

2) Residual film ratio after development The film thickness was measured before and after development, and the residual film ratio after development was calculated from the following equation.
(Film thickness after development / film thickness before development) x 100 (%)

3) Resolution The post-baked patterned transparent film substrate obtained in 1) above was observed with an optical microscope at a magnification of 1,000 to confirm the mask size at which the glass was exposed at the bottom of the hole pattern.

4) Development adhesion After development, the mask size of the smallest dot pattern formed was defined as development adhesion. The development adhesiveness is better when the dots remain up to a small mask size pattern.

5) Transparency Using JASCO Corporation V-670, light transmittance at a wavelength of 400 nm was measured using a glass substrate on which a transparent film was not formed as a reference. The result was expressed as light transmittance T1 (same as T1 obtained in the evaluation of heat resistance below).

6) Heat resistance The substrate of the patterned transparent film obtained in 1) above was additionally baked in an oven at 230 ° C. for 60 minutes, the light transmittance was measured in the same manner as 5) before and after the additional baking, and after post-baking ( The light transmittance before the additional baking was T1, and the light transmittance after the additional baking was T2. It can be determined that the smaller the decrease in light transmittance after post-baking and after additional baking, the better. Moreover, the film thickness was measured before and after the additional baking, and the rate of change of the film thickness was calculated from the following equation.
(Film thickness after additional baking / film thickness after post-baking) x 100 (%)
The smaller the rate of change in film thickness after post-baking and after additional baking, the better the heat resistance.

7) Substrate adhesion A cured film that has been subjected to post-baking treatment on a glass substrate, a substrate obtained by sputtering ITO on the glass, and a substrate on which Al is deposited on the glass is prepared, and a cross-cut peel test (cross cut test) It was evaluated by. The evaluation represents the number of remaining grids after tape peeling in 100 1 mm square grids. The greater the number of remaining substrates, the better the adhesion.

  The evaluation results are shown in Table 2.

[Examples 2 to 4]
In the same manner as in Example 1, a positive photosensitive composition was prepared with a solid content of 30% by weight. The composition is shown in Table 1. The evaluation results are shown in Table 2.

[Comparative Examples 1-2]
In the same manner as in Example 1, a positive photosensitive composition was prepared with a solid content of 30% by weight. The composition is shown in Table 1. The evaluation results are shown in Table 2.

Claims (9)

Radical polymerizable compound (a1) represented by the following general formula (I) and / or (II), radical polymerizable compound (a2) having carboxyl or hydroxyphenyl, other radical polymerizable compound (a3) and the following general A positive photosensitive composition comprising an organic-inorganic hybrid polymer (A) obtained by reacting the compound (a4) represented by formula (III), naphthoquinonediazide (B), and an organic solvent (C).

(In the formula, R ¹ is hydrogen, or alkyl having 1 to 5 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ² , R ³ and R ⁴ are each independently a hydroxyl group, 5 is alkoxy or acetoxy, at least one of R ² , R ³ and R ⁴ is a hydrolyzable group, and n is an integer of 1 or more.)

(In the formula, R ^{5 to} R ⁷ are each independently a hydroxyl group, alkoxy having 1 to 5 carbon atoms or acetoxy, and at least one of R ⁵ , R ⁶ and R ⁷ is a hydrolyzable group.)

(In the formula, R ^{8 to} R ¹¹ are each independently hydrogen, fluorine, hydroxyl, C 1-5 alkoxy, acetoxy, or a monovalent organic group, and include at least one hydrolyzable group. )   The radical polymerizable compound (a1) is 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane or p-styryltri. The positive photosensitive composition according to claim 1, which is methoxysilane. 3. The positive photosensitive compound according to claim 1, wherein the radical polymerizable compound (a2) is a compound selected from acrylic acid, methacrylic acid, 4-hydroxystyrene, and a compound represented by the following general formula (IV). Sex composition.

(In the formula, R ¹² , R ¹³ and R ¹⁴ are each hydrogen or alkyl having 1 to 3 carbon atoms in which arbitrary hydrogen may be replaced by fluorine, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^18. And R ¹⁹ are each hydrogen, halogen, —CN, —CF ₃ , —OCF ₃ , —OH, or —CH ₂ — is —COO—.
, —OCO—, —CO— may be substituted, and any hydrogen may be substituted with halogen, alkyl having 1 to 5 carbon atoms, or any hydrogen may be substituted with halogen. ~ 5 alkoxy. However, at least one of R ^{15 to} R ¹⁹ is —OH. )   The positive photosensitive composition as described in any one of Claims 1-3 containing the radically polymerizable compound which has an epoxy or oxetanyl as said other radically polymerizable compound (a3).   Compound (a4) represented by the general formula (III) is tetraethyl orthosilicate, tetramethyl orthosilicate, trimethoxymethylsilane, triethoxymethylsilane, trimethoxypropylsilane, triethoxypropylsilane, trimethoxyhexylsilane, Triethoxyhexylsilane, allyltriethoxysilane, allyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, triethoxyphenylsilane, trimethoxyphenylsilane, 3-glycidyloxypropyltrimethoxysilane, trimethoxysilane, diethoxydimethylsilane , Dimethoxydimethylsilane, diphenyldiethoxysilane, ethoxytrimethylsilane, methoxytrimethylsilane, and diphenylsilanediol There, positive photosensitive composition according to any one of claims 1-4.   The positive photosensitive composition according to any one of claims 1 to 5, further comprising an antioxidant.   The organic-inorganic hybrid polymer (A) is copolymerized with the radical polymerizable compounds (a1), (a2) and (a3), and the resulting copolymer is represented by the compound (a4) represented by the formula (III). The positive photosensitive composition according to any one of claims 1 to 6, which is obtained by hydrolytic condensation in the presence of.   After the organic-inorganic hybrid polymer (A) is mixed with the radical polymerizable compounds (a1), (a2) and (a3) and the compound (a4) represented by the formula (III), copolymerization and hydrolysis The positive photosensitive composition as described in any one of Claims 1-6 obtained by performing condensation simultaneously.   By exposure, development, and baking through a mask having an opening corresponding to a desired pattern to a coating film formed using the positive photosensitive composition according to any one of claims 1 to 8. Patterned transparent film obtained.