JP2007137800A - Photosensitive compound, compound for addition, positive type photosensitive composition comprising the same and display element having film of the same positive type photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a quinonediazidosulfonic acid ester derivative having a new silsesquioxane skeleton useful as a photosensitizer component of a positive type photosensitive composition and to provide a phenol derivative which is a precursor thereof as an additive in the composition. <P>SOLUTION: A photosensitive compound or a compound for addition in the positive type photosensitive composition is obtained as follows. A specific group containing a specified quinonediazidosulfonic acid group or a hydroxy group is introduced into at least one of R of a silsequioxane derivative containing a basic structure composed of 4-12 silicons, an oxygen bonded to each silicon and a monovalent R. The basic structure is a structure in which three oxygens and one R are bonded to one silicon and one oxygen is interposed between the two silicons. The silsesquioxane derivative may have the oxygen at the end or R may be bonded to the oxygen at the end or one silicon bonded to two Rs may be bonded to the two oxygens at the end. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel silsesquioxane derivative from the viewpoint of application to the resist field and its application to the resist field.

  In general, it is known to convert a compound having a phenolic hydroxyl group into a quinonediazide sulfonate ester and use it as a photosensitive agent in a photosensitive resin composition for semiconductor microfabrication (see, for example, Patent Document 1).

  That is, when a positive photosensitive composition containing a compound having a quinonediazide group and an alkali-soluble resin soluble in alkali is applied on a metal substrate and irradiated with light having a wavelength of 300 to 500 nm, After the quinonediazide group is decomposed, it reacts with the coexisting water or the water of the developer to generate carboxyl. Thereby, the said compound changes from an alkali-insoluble state to an alkali-soluble state. By utilizing this change in state caused by light irradiation, such a composition is used for the production of a transparent film or an insulating film on which a pattern of a positive resist is formed. A positive resist has a feature of being excellent in resolving power as compared with a negative resist, and is therefore used for manufacturing various integrated circuits for semiconductors.

  In recent years, integrated circuits in the semiconductor industry have been miniaturized due to high integration, and in this technical field, submicron pattern formation is now required. Among them, the lithography process occupies an important position at the time of manufacturing an integrated circuit, and even a positive resist is required to have a higher resolution, that is, a higher γ value.

  For positive photosensitive compositions containing a quinonediazide compound and an alkali-soluble resin, many proposals have been made for combinations of components. For example, Patent Document 1 describes that a compound obtained by converting a triphenylmethane-based compound having at least two phenolic hydroxyl groups into a quinonediazide sulfonic acid ester is used as a photosensitive agent.

  However, these known photosensitizers are still subject to investigation from the viewpoint of the production of finer circuits as photosensitizers for ultra-fine processing for the production of ultra-high integrated circuits, so-called submicron lithography. Yes.

  For example, when a transparent electrode is formed on an insulating film, further reduction in the resistance value of the transparent electrode is required. In order to reduce the resistance value of the transparent electrode on the insulating film, it is desired to form the transparent electrode on the patterned insulating film by sputtering at a higher temperature. If the heat resistance of the positive photosensitive composition is insufficient, the sputtering may cause wrinkles in the insulating film, thereby reducing the quality of the product. Therefore, a low-resistance transparent electrode is formed on the insulating film. The photosensitizer used in this case is required to have further heat resistance.

  For this reason, various studies for improving the resist performance such as sensitivity, resolving power, heat resistance and the like have been conducted on the photosensitive agent.

On the other hand, a compound having a phenolic hydroxyl group is used as an alkali-soluble low molecular weight additive in a photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin.
Studies are also being conducted to increase the sensitivity of resists (see, for example, Patent Document 1).
JP-A-9-194413

  An object of the present invention is to provide a novel quinonediazide sulfonic acid compound having a silsesquioxane skeleton that is useful as a photosensitive agent component of a photosensitive resin composition, and a compound having a hydroxyl group as a precursor thereof. It is to be provided as an additive in the composition.

  Another object of the present invention is to use such a hydroxyl group-containing compound or its quinonediazide sulfonic acid compound to provide resists such as high sensitivity, high resolution, high heat resistance, good profile, good focus tolerance, and small development residue. The object is to provide a photosensitive composition having a balanced performance.

  As a result of intensive research, the present inventors have found a phenol derivative having a specific structure having two phenolic hydroxyl groups, and this compound is useful as an alkali-soluble low molecular weight additive in a photosensitive resin composition. It has been found that excellent results can be obtained even when a compound obtained by converting a compound into a quinonediazide sulfonic acid ester is used as a photosensitizer, and the present invention has been completed.

The present invention is a compound comprising a silsesquioxane derivative containing a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R, wherein the basic structure is In this structure, three oxygen atoms and one R atom are bonded to one silicon, and one oxygen is interposed between the two silicons. The silsesquioxane derivative has oxygen at the end. In the compound in which R may be bonded to the oxygen at the end, and one silicon having two R bonded to the two oxygen at the end may be bonded to R Is independently hydrogen, alkyl, aryl, aralkyl, a group represented by the following formula (1) (hereinafter also referred to as “group of formula (1)”), or a group represented by the following formula (2) (hereinafter “ The carbon number in alkyl is also referred to as “group of formula (2)” -30, the carbon number in aryl is 6-30, the carbon number of alkylene in aralkyl is 1-12, and in each of the alkyl and aralkyl alkylene, any hydrogen may be replaced with a halogen, Arbitrary —CH ₂ — is —O—, —S—, —CO—, —NH—, —SiR ^a ₂ — (R ^a is independently alkyl having 1 to 8 carbons, phenyl, cyclopentyl or cyclohexyl. ), —CH═CH—, —C≡C—, —CF═CF—, cycloalkylene or cycloalkenylene, and in each of aryl and aralkyl, any hydrogen in the ring is halogen, cyano , An alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons or an alkenyl having 2 to 12 carbons may be substituted. Both one compound is a group represented by the formula (1) (hereinafter, the compound referred to as "photosensitive compound") to provide. In the following formula (1), a is an integer of 0 to 8, and b is 0 or 1. Moreover, in following formula (2), c is an integer of 0-8, d is 0 or 1.

  In the silsesquioxane compound, the present invention provides a compound wherein the quinonediazide sulfonic acid group is not present, and at least one of the R is a group represented by the formula (2) (hereinafter, this compound is referred to as “ "Additive compound").

  The present invention also provides a positive photosensitive composition containing the photosensitive compound of the present invention and an alkali-soluble resin, and a positive photosensitive composition containing the photosensitive compound, the additive compound of the present invention, and an alkali-soluble resin. A composition is provided.

  Moreover, this invention provides the display element which has an element substrate and the film | membrane of the said positive photosensitive composition formed on the said element substrate.

  The photosensitive compound of the present invention is a silsesquioxane derivative comprising a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R, wherein the R Since at least one of the groups is a group of the formula (1), it is possible to provide a quinonediazide sulfone compound having a novel silsesquioxane skeleton that is useful as a photosensitizer component of a photosensitive composition.

  The additive compound of the present invention is a silsesquioxane derivative containing a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R, Since at least one of the R is a group of the formula (2), a hydroxyl group that is a precursor of a quinonediazide sulfonic acid compound having a novel silsesquioxane skeleton that is useful as a photosensitizer component of a photosensitive composition The containing compound can be provided as an additive in the composition.

  Moreover, since the positive photosensitive composition of the present invention contains the photosensitive compound of the present invention and an alkali-soluble resin (hereinafter referred to as alkali-soluble resin), it has high sensitivity and high resolution. Thus, it is possible to provide a photosensitive composition in which the resist performances such as high heat resistance, good profile, good focus tolerance, and small development residue are balanced.

  Further, since the positive photosensitive composition of the present invention contains a photosensitive compound, the additive compound of the present invention, and an alkali-soluble resin, resist performance such as heat resistance and sputtering resistance can be achieved. A particularly excellent photosensitive composition can be provided.

  In addition, since the display element of the present invention has an element substrate and the film of the positive photosensitive composition of the present invention formed on the element substrate, the display element according to various processes in the process of manufacturing the element. The influence on the film can be suppressed, and the deterioration of the quality of the element due to this influence can be prevented.

Further, the photosensitive compound and additive compound of the present invention are silsesquioxane derivatives represented by the following formula (3) (wherein at least one of R ¹ to R ⁴ is a group represented by the formula (1)): This is more effective from the viewpoint of improving the chemical resistance of the film.

Moreover, the photosensitive compound and additive compound of the present invention are even more effective from the viewpoint of improving compatibility with a polymer containing phenyl when all R ⁵ in the formula (3) are phenyl.

In the photosensitive compound of the present invention, when R ² in the formula (3) is a group of the formula (1) and R ³ is a group of the formula (1) or a group of the formula (2), This is even more effective from the viewpoint of improving heat resistance. Similarly, the additive compound of the present invention is more effective from the viewpoint of improving the heat resistance of the film when R ² and R ³ in the formula (3) are a group of the formula (2).

  In addition, when the positive photosensitive composition of the present invention further contains the compound for addition, the solubility of the exposed portion in the alkaline developer during development of the photosensitive compound in the positive photosensitive composition of the present invention. And it is much more effective from the viewpoint of enhancing the dissolution inhibition of the unexposed portion in the alkaline developer.

In the present invention, in each of alkyl and aralkyl alkylene, any —CH ₂ — represents —O—, —S—, —CO—, —NH—, —SiR ^a ₂ — (R ^a independently represents the number of carbon atoms. 1-8 alkyl, phenyl, cyclopentyl or cyclohexyl.), —CH═CH—, —C≡C—, —CF═CF—, cycloalkylene or cycloalkenylene may be substituted. It means that —CH ₂ — at any position such as etc. may be substituted with —O—, —S—, —CO— or the like. However, it is not desirable that two or more —O— are continuous. Thus, for example _{-CH 2 -O-O-CH 2} - -CH 2 -O-CH 2 -O- is preferred over.

  The photosensitive compound of the present invention reacts with visible light in the blue region from near ultraviolet light, and the light in these regions is sometimes collectively referred to as ultraviolet light.

<Photosensitive compound>
The photosensitive compound in the present invention is a compound whose solubility in alkali changes upon exposure to light. The photosensitivity of the photosensitive compound in the present invention can be confirmed by the following method.

1 g of the photosensitive compound is dissolved in 10 g of dioxane or tetrahydrofuran, the obtained solution is spin-coated on a 4 cm square glass substrate at 1,000 rpm, and the obtained coating film is heated at 80 ° C. for 30 minutes. Two of these are prepared. The film thicknesses of the two are made the same as much as possible so that the film thickness after heating is about 4 μm. One of the samples is poured into 100 mL of dioxane to dissolve the film, and the absorbance of light having a wavelength of 405 nm is measured with an ultraviolet-visible spectrophotometer (the absorbance is referred to as A ₀ ). The other sample is irradiated with light from an ultra-high pressure mercury lamp through a cut filter so that g, h, and i rays can be selectively and simultaneously irradiated, corresponding to an energy of 150 mJ / cm ² . The sample after irradiation is put into 100 mL of dioxane to dissolve the film, and the absorbance of light having a wavelength of 405 nm is measured with an ultraviolet-visible spectrophotometer (the absorbance is referred to as A ₁ ). If A ₁ / A ₀ <0.5, the effect of being useful as a photosensitive compound can be expected.

  The photosensitive compound of the present invention is a silsesquioxane derivative containing a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R. Here, the basic structure is a structure in which three oxygens and one R are bonded to one silicon, and one oxygen is interposed between two silicons.

  The silsesquioxane derivative may have the basic structure (that is, all of oxygen may be bonded to two silicons) or may have the oxygen at an end (that is, a part thereof). May be bonded to only one silicon), R may be bonded to the oxygen at the end, and the silsesquioxane derivative may have two of the ends described above. One silicon having two R bonded thereto may be bonded to oxygen. Further, the silsesquioxane derivative may be a compound having a structure in which these structures are combined.

  Examples of the silsesquioxane derivative include various known derivatives of silsesquioxane including the basic structure. Examples of the silsesquioxane derivative having the basic structure include silsesquioxane derivatives represented by the following formulas (4) to (6). Examples of the silsesquioxane derivative having oxygen at the end and R bonded to the oxygen include silsesquioxane derivatives represented by the following formulas (7) and (8). The silsesquioxane derivative having oxygen at the end and one silicon having two R bonded to the two oxygens at the end is a silsesquioxane derivative of the following formula (9). Oxane derivatives are mentioned.

  The silsesquioxane derivative is preferably a compound having a structure in which a ring formed by alternately bonding silicon and oxygen is formed, as shown in formulas (4) to (9). As shown in formulas (4) to (6) and (9), the silsesquioxane derivative has two rings which are in a positional relationship overlapping each other when viewed in the direction penetrating the ring, A compound having a structure in which part or all of silicon in one ring is bonded to part or all of silicon in the other ring through oxygen (hereinafter also referred to as “double-decker structure” or “DD”). It is more preferable.

  Furthermore, the silsesquioxane derivative has the basic structure containing eight silicon, the four ends to which the oxygen is bonded, and two ends of each set when the two ends are combined. The compound represented by the formula (9) having two R bonded end silicons bonded to each of the two groups in the DD is different from R in the DD. It is particularly preferable from the viewpoint of introduction as R of the two end silicons.

  At least one R is a group of the formula (1) shown below. Other Rs can be independently selected from hydrogen, alkyl, aryl, aralkyl, and the group of formula (2) shown below. The other R can be selected from the viewpoints of compatibility in the composition, three-dimensional structure of the molecule, and improvement in exposure property and developability in the manufacturing process of the display element.

In the formula (1), a is an integer of 0 to 8 and b is 0 or 1 in the formula (1). In the formula (2), c is an integer of 0 to 8 and d is 0 or 1 in the formula (2). The values of a and b in the group of the formula (1) and the values of c and d in the group of the formula (2) are the solubility of the obtained photosensitive compound and the ease of synthesis of the target photosensitive compound, etc. It can be determined as appropriate based on the viewpoint.

  For example, in the group of formula (1) or formula (2), when b or d is 1, increasing a or c improves the solubility. Moreover, the photosensitive compound of this invention is easily compoundable by introduce | transducing these groups by the hydrosilylation mentioned later. From the viewpoint of easy availability of raw materials and ease of synthesis, a, b, c and d can be appropriately determined.

  More specifically, the group of formula (1) includes, for example, a group in which a and b in formula (1) are 0, a group in which a in formula (1) is 0 and b is 1, ) In which a is an integer of 1 to 8 and b is 0, and a in formula (1) is an integer of 1 to 8 and b is 1.

  Further, the group of formula (2) includes, for example, a group in which c and d in formula (2) are 0, a group in which c in formula (2) is 0 and d is 1, and c in formula (2) And a group in which d is an integer of 1 to 8 and d is 0, and a group in which c is an integer of 1 to 8 and d is 1 in formula (2).

Moreover, as for the group of Formula (1) and Formula (2), the alkylene of these groups may contain structures other than a bivalent hydrocarbon. In such groups of formula (1) and formula (2), for example, any —CH ₂ — of — (CH ₂ ) _a — and — (CH ₂ ) _c — in these groups is replaced by —O—. And a group in which any —CH ₂ CH ₂ — of — (CH ₂ ) _a — and — (CH ₂ ) _c — is replaced by —COO—.

In R other than the group of formula (1), alkyl is alkyl having 1 to 30 carbon atoms, aryl is aryl having 6 to 30 carbon atoms, and aralkyl is aralkyl having 1 to 12 carbon atoms of alkylene. . In each of the alkyl and aralkyl alkylenes, any hydrogen may be replaced by a halogen, and any —CH ₂ — may be —O—, —S—, —CO—, —NH—, —SiR ^a ₂ — ( R ^a is independently alkyl having 1 to 8 carbons, phenyl, cyclopentyl or cyclohexyl.), —CH═CH—, —C≡C—, —CF═CF—, cycloalkylene or cycloalkenylene. May be.

  In R other than the group of formula (1), in each of aryl and aralkyl, any hydrogen of the ring is halogen, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or carbon 2 May be substituted with ~ 12 alkenyl.

In the case where the silsesquioxane derivative is a compound represented by the formula (9), as shown in the following formula (3), the R is bonded to one of the end silicons, R ¹ and R ^2. And R ³ and R ⁴ bonded to the other end silicon and a plurality of R ⁵ bonded to silicon of the basic structure, at least one of R ¹ to R ⁴ is represented by the formula ( The group 1) is preferable from the viewpoint of obtaining a compound having a specific structure in which the group of the formula (1) is introduced at an arbitrary position at the end of DD. Among R ¹ to R ⁴ , groups other than the group of the formula (1) are appropriately selected from R.

In the present invention, the number of groups of the formula (1) in R ¹ to R ⁴ is not particularly limited, but two of R ¹ to R ⁴ are groups of the formula (1). It is more preferable from the viewpoint of increasing the contrast in exposure and development.

In the present invention, the group of the formula (2) reacts with the epoxy or oxetanyl of the alkali-soluble resin during post-baking after development in the display element to be described later, thereby forming a crosslink. In one preferred embodiment, at least one of R ¹ to R ⁴ is a group of the formula (2). The number of groups of formula (2) in R ¹ to R ⁴ is not particularly limited as long as it is 3 or less.

In the present invention, in particular, among R ¹ to R ⁴ , one is a group of the formula (1) and the other is a group of the formula (2). This is one of the more preferred embodiments from the viewpoint of enhancing the heat resistance and sputtering resistance of the film.

In the present invention, when R ¹ to R ⁴ include both groups of formula (1) and formula (2), the individual structures of these groups are particularly within the scope of the concept described above. Although not limited, the fact that the number of alkylene carbons and the presence or absence of phenylene in these groups are the same makes it possible to easily prepare photosensitive compounds containing both groups of formula (1) and formula (2) in R ¹ to R ^4. It is preferable from the viewpoint of synthesis.

R ⁵ is appropriately selected from the above-mentioned R independently, depending on conditions such as the structure of the group of formula (1) and the type of group other than the group of formula (1) in R ¹ to R ⁴ . It is. R ⁵ includes, for example, independently, alkyl, aryl, and arylalkyl.

In the alkyl in R ⁵ , any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O—, —CH═CH—, or a cycloalkylene having 4 to 8 carbon atoms. Examples thereof include alkyl having 1 to 20 carbon atoms.

The aryl in R ^{5 includes} aryl in which any hydrogen in the ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons.

The arylalkyl in R ^{5 includes} arylalkyl in which any hydrogen in the ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons. .

More specifically, R ⁵ includes, for example, alkyl, phenyl, phenylalkyl, or naphthyl independently.

In such alkyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O—, —CH═CH—, or cycloalkylene having 4 to 8 carbon atoms. Examples thereof include alkyl having 1 to 8 carbon atoms.

The phenyl in R ^{5 includes} phenyl in which any hydrogen in the benzene ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons. .

In addition, phenylalkyl in R ^{5 includes} phenylalkyl in which any hydrogen in the benzene ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons. Can be mentioned.

R ⁵ may be a different type of group or the same type of group, but from the viewpoint of easily synthesizing a photosensitive compound, it is preferable that all R ⁵ are the same. . R ⁵ is preferably phenyl from which arbitrary hydrogen may be replaced by fluorine, methyl, or methoxy from the viewpoint of ease of synthesis of the photosensitive compound. Further, phenyl is particularly preferable.

The photosensitive compound represented by the formula (3) is the above-mentioned R ¹ to R from the viewpoint of easy availability of raw materials, ease of synthesis, solubility of the obtained compound, unity of the obtained compound, and the like. ⁵ is configured by appropriately combining.

As such a photosensitive compound, for example, R ⁵ is phenyl in which arbitrary hydrogen may be replaced by fluorine, methyl, or methoxy, and all R ⁵ are the same, and R ¹ to R ⁴ , the groups of formula (1) and formula (2) are substituted with —O— in which any —CH ₂ — of — (CH ₂ ) _a — and — (CH ₂ ) _c — is replaced by —O—. Or _a photosensitive compound in which any —CH ₂ CH ₂ — in — (CH ₂ ) _a — and — (CH ₂ ) _c — may be replaced by —COO—, particularly R ⁵ is phenyl. The photosensitive compound which is is mentioned.

As the photosensitive compound, for example, R ¹ and R ⁴ are alkyl having 1 to 8 carbon atoms, R ² and R ³ are each an integer of 1 to 8 and b is 1. And a photosensitive compound in which R ⁵ is at least one selected from the aforementioned groups.

In addition, as the photosensitive compound, for example, R ¹ and R ⁴ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ³ is A photosensitive compound in which a is a group of formula (1) in which b is 1 and b is 1 and R ⁵ is at least one selected from the aforementioned groups.

In addition, as the photosensitive compound, for example, R ¹ and R ⁴ are methyl, R ² and R ³ are groups of the formula (1) in which a is an integer of 1 to 8 and b is 1. R ⁵ is a photosensitive compound that is at least one selected from the aforementioned groups.

Examples of the photosensitive compound include, for example, R ¹ and R ⁴ are methyl, R ² and R ³ are groups of the formula (1) in which a is 2 and b is 1, and R ⁵ is the above-mentioned group. And a photosensitive compound that is at least one selected from the above groups.

In addition, as the photosensitive compound, for example, R ¹ and R ⁴ are alkyl having 1 to 8 carbon atoms, R ² is an integer of 1 to 8 and b is 1. R ³ is a group of the formula (2) in which c is an integer of 1 to 8 and d is 1, and R ⁵ is a photosensitive compound that is at least one selected from the aforementioned groups. .

In addition, as the photosensitive compound, for example, R ¹ and R ⁴ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ³ is Examples thereof include a photosensitive compound in which c is 2 and d is 1 in formula (2), and R ⁵ is at least one selected from the aforementioned groups.

In addition, as the photosensitive compound, for example, R ¹ and R ⁴ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ³ is Examples thereof include a photosensitive compound in which c is an integer of 1 to 8 and d is 1, and R ⁵ is at least one selected from the groups described above.

Further, as the photosensitive compound, for example, R ¹ and R ⁴ are methyl, R ² is a group of the formula (1) in which a is 2 and b is 1, and R ³ is c in 2. A photosensitive compound in which d is a group of the formula (2) in which 1 is 1 and R ⁵ is at least one selected from the groups described above;

Further, as the photosensitive compound, e.g., R ¹ and R ³ are alkyl of 1 to 8 carbon atoms, R ² and R ⁴ are 1 a is an integer from 1 to 8 b formula ( And a photosensitive compound in which R ⁵ is at least one selected from the groups described above.

In addition, as the photosensitive compound, for example, R ¹ and R ³ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ⁴ is A photosensitive compound in which a is a group of formula (1) in which b is 1 and b is 1 and R ⁵ is at least one selected from the aforementioned groups.

In addition, as the photosensitive compound, for example, R ¹ and R ³ are methyl, R ² and R ⁴ are groups of the formula (1) in which a is an integer of 1 to 8 and b is 1. R ⁵ is a photosensitive compound that is at least one selected from the aforementioned groups.

Further, as the photosensitive compound, for example, R ¹ and R ³ are methyl, R ² and R ⁴ are groups of the formula (1) in which a is 2 and b is 1, and R ⁵ is the above-mentioned group. And a photosensitive compound that is at least one selected from the above groups.

As the photosensitive compound, for example, R ¹ and R ³ are alkyl having 1 to 8 carbon atoms, R ² is an integer of 1 to 8 and b is 1. R ⁴ is a group of the formula (2) in which c is an integer of 1 to 8 and d is 1, and R ⁵ is a photosensitive compound that is at least one selected from the aforementioned groups. .

In addition, as the photosensitive compound, for example, R ¹ and R ³ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ⁴ is Examples thereof include a photosensitive compound in which c is 2 and d is 1 in formula (2), and R ⁵ is at least one selected from the aforementioned groups.

In addition, as the photosensitive compound, for example, R ¹ and R ³ are methyl, R ² is a group of the formula (1) in which a is an integer of 1 to 8 and b is 1, and R ⁴ is Examples thereof include a photosensitive compound in which c is an integer of 1 to 8 and d is 1, and R ⁵ is at least one selected from the groups described above.

In addition, as the photosensitive compound, for example, R ¹ and R ³ are methyl, and R ² is ² in a.
And b is 1, a group of formula (1), R ⁴ is a group of formula (2), wherein c is 2 and d is 1, and R ⁵ is at least one selected from the aforementioned groups The photosensitive compound which is is mentioned.

The photosensitive compound is not limited to the specific structure described above, but R ¹ and R ⁴ are methyl, and R ² is a compound of the formula (1). From the viewpoint of improving the heat resistance and sputtering resistance of the film of the active composition, R ¹ and R ⁴ are methyl, and R ² and R ³ are compounds which are groups of the formula (1). It is more preferable from the viewpoints of availability, easiness of synthesis, and heat resistance and sputtering resistance of a film of a positive photosensitive composition in a display element to be described later.

For example, R ¹ and R ⁴ are methyl, R ² is a group of formula (1) in which a is 2 and b is 1, R ³ is a group of formula (1) in which a is 2 and b is 1. A photosensitive compound in which c is 2 and d is 1 and d is 1 and R ⁵ is at least one selected from the aforementioned groups; From the viewpoints of easiness of synthesis and improving the heat resistance and sputtering resistance of the film of the positive photosensitive composition in the display element described later, among them, R ³ is a formula (1 where a is 2 and b is 1). ) Is more preferable from the viewpoint of ease of synthesis.

The photosensitive compound is not limited to the specific structure described above, but R ¹ and R ³ are methyl, and R ² is a compound represented by the formula (1). From the viewpoint of enhancing the heat resistance and sputtering resistance of the film of the photosensitive type composition, R ¹ and R ³ are methyl, and R ² and R ⁴ are compounds that are groups of the formula (1), It is more preferable from the viewpoints of easy availability of raw materials, ease of synthesis, and enhancing heat resistance and sputtering resistance of a film of a positive photosensitive composition in a display element described later.

For example, R ¹ and R ³ are methyl, R ² is a group of formula (1) wherein a is 2 and b is 1, R ⁴ is a group of formula (1) where a is 2 and b is 1. Or a photosensitive compound in which c is 2 and d is 1 and R ⁵ is at least one selected from the above-described groups. From the viewpoint of enhancing the heat resistance and sputtering resistance of the film of the conductive composition, among them, the photosensitive compound in which R ⁴ is a group of the formula (1) in which a is 2 and b is 1 is easy to synthesize. More preferable from the viewpoint.

  The said photosensitive compound can be manufactured based on well-known techniques as described, for example in Japanese translations of PCT publication No. 2003-24870 and Unexamined-Japanese-Patent No. 9-194413. For example, the photosensitive compound can be produced by producing a basic structure having the basic structure and introducing the group of the formula (1) directly or indirectly into the obtained basic structure.

  The basic structure is formed by hydrolyzing and condensing, for example, trichlorosilane or trialkoxysilane having a guiding group for deriving R or R in the presence of a monovalent alkali metal hydroxide and water. Depending on R, it can be produced by condensing R or dichlorosilane or dialkoxysilane having the aforementioned induction group. Examples of the inducing group include chloro, alkoxy, hydrogen, carboxyl, and hydroxyl group.

  The group of the formula (1) may be introduced as the R in the production of the basic structure with an appropriate protective group as necessary. From the viewpoint of controlling the introduction position, the basic structure After the production, it is preferably introduced by substituting the inducing group.

The group of formula (1) can be directly bonded to the basic structure by reacting the derivatizing group with quinonediazidesulfonic acid or its acid chloride. Also, the formula (1
Group) is indirectly bonded to the basic structure by reacting the other group with quinonediazidosulfonic acid or its acid chloride after binding the derivatizing group and the other group. It is possible.

  Specific examples of the production of the photosensitive compound of the present invention include, for example, a trialkoxysilane having R and a monovalent alkali such as sodium hydroxide, as described in JP-T-2003-24870. By reacting in the presence of a metal hydroxide, water, and alcohol, and reacting the resulting reaction product with dichlorosilane having R in tetrahydrofuran in the presence of triethylamine, the following formula (10) is obtained. The compound shown is obtained.

  Hydrosilylation reaction of the compound represented by the formula (10) and the olefinic compound having a protected hydroxyphenyl group represented by the following formula (11) in the presence of a platinum catalyst, followed by deprotection. Gives a compound represented by the following formula (12).

“PG” in the formula (11) represents a protecting group. This protecting group may be a protecting group that can be removed by acid, such as acetyl, benzoyl, methoxymethyl, methyl, benzyloxymethyl, methoxyethoxymethyl, tetrahydropyranyl, isopropyl, tert-butyl, 4 -Methoxybenzyl, trimethylsilyl, tert-butyldimethylsilyl and the like. R ⁶ in the formulas (11) and (12) represents a divalent hydrocarbon group having 1 or more carbon atoms, but may not be present.

  In the hydrosilylation reaction, the compound of formula (11) is preferably used in a molar ratio of 2.0 to 10.0 with respect to the compound of formula (10), and used in a molar ratio of 2.2 to 5.0. It is more preferable.

The hydrosilyl reaction is usually performed in the presence of a platinum catalyst. Examples of the platinum catalyst include inorganic compounds such as chloroplatinic acid and complexes such as tris (divinyldisiloxane) diplatinum (0). The amount of the platinum catalyst used is usually 5 mol% or less, preferably 0.01 to 0.1 mol%, based on the compound of the formula (10).

  The hydrosilyl reaction is preferably performed in a solvent. In this case, an aprotic organic solvent can be used as the reaction solvent, and the reaction solvent is preferably a solvent in which the raw materials and the product are dissolved. Examples of the reaction solvent include benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, N, N-dimethylformamide, and dioxane. Of these organic solvents, toluene is preferably used. The amount of the reaction solvent used is generally in the range of 0.5 to 10 times by weight, preferably 1 to 5 times by weight, more preferably 2 to 3 times the compound of the formula (10). Weight times.

  The hydrosilyl reaction is usually performed at a temperature in the range of 40 to 120 ° C, preferably in the range of 60 to 100 ° C for about 2 to 10 hours. This reaction usually proceeds under atmospheric pressure.

  By removing the protecting group of the phenolic hydroxyl group in the hydrosilylation product obtained by the hydrosilyl reaction, a compound of the formula (12) is obtained. This deprotection reaction is carried out under acidic conditions, and commonly used acids are used. Examples of the acid used for the deprotection reaction include inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid. The usage-amount of the acid in the said deprotection reaction is 0.5-10 mol times normally with respect to the compound of Formula (12), Preferably it is 2-5 mol times.

  The deprotection reaction is usually carried out in a solvent. The reaction solvent used for the deprotection reaction is water, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, N, N-dimethylformamide, dioxane, ethanol, methanol. Etc. Among these reaction solvents, a mixed solvent of water and another solvent is preferable. The usage-amount of the said reaction solvent is 1-10 weight times normally with respect to the compound of Formula (12), Preferably it is 2-6 weight times. The deprotection reaction is usually performed in the range of 30 ° C. to the reflux temperature of the reaction solvent, and preferably in the range of 50 ° C. to the reflux temperature of the reaction solvent.

  The present invention, which is a compound represented by the above formula (3) by subjecting the compound represented by the above formula (12) to an esterification reaction using various sulfonic acid derivatives having a 1,2-quinonediazide skeleton as an esterifying agent. The photosensitive compound is obtained. As the esterifying agent, 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide is preferably used.

  Examples of the halogen constituting the sulfonyl halide include chlorine and bromine, but it is usually preferable to use chlorine. Therefore, 1,2-naphthoquinonediazide-4- or -5-sulfonyl chloride is preferably used as the esterifying agent. A mixture of 1,2-naphthoquinonediazide-4-sulfonyl halide and 1,2-naphthoquinonediazide-5-sulfonyl halide can also be used as the esterifying agent.

  In the esterification reaction, the amount of 1,2-naphthoquinonediazide-4- and / or -5-sulfonyl halide used is usually in a molar ratio of 1.0 to 5.0 with respect to the compound of formula (12). Yes, preferably a molar ratio of 1.1 to 2.5.

The esterification reaction is usually performed in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, a basic compound is generally used. For example, an inorganic base such as sodium carbonate or sodium hydrogen carbonate, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, N, N-dimethylaniline. And amines such as N, N-diethylaniline. The amount of the dehydrohalogenating agent used is usually a molar ratio of 1.05 to 1.5, preferably 1.05 to 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. 1.2, more preferably a molar ratio of 1.1 to 1.2.

  The esterification reaction is usually performed in a solvent. Examples of the reaction solvent in the esterification reaction include ethers, lactones, and aliphatic ketones. Among these reaction solvents, a solvent selected from dioxolane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, acetone and 2-heptanone is preferable. These solvents can be used alone or in combination of two or more as the reaction solvent. As the reaction solvent, 1,4-dioxane is particularly preferable. The amount of the reaction solvent used is usually 2 to 6 times by weight, preferably 3 to 5 times by weight, more preferably 4 times the total amount of the compound of formula (12) and quinonediazidesulfonyl halide. ~ 5 times by weight.

  The esterification reaction proceeds sufficiently even under normal pressure and near room temperature, and is generally performed at a temperature in the range of 20 to 30 ° C. and is performed for about 2 to 10 hours.

  After completion of the reaction, neutralization is performed with a known acid such as acetic acid, the solid matter is filtered, and then the filtrate is washed, dried and concentrated, whereby the target quinonediazide sulfonic acid ester can be taken out. If necessary, the filtrate may be mixed with a thin acid aqueous solution, for example, an acetic acid aqueous solution having a concentration of about 0.1 to 2% by weight.

In the esterification reaction, although depending on the molar ratio of 1,2-naphthoquinonediazidesulfonyl halide used, ^one of R ¹ , R ² , R ³ , and R ⁴ in formula (3) is usually quinonediazidesulfonyl. by now, the compound (monoester), a compound in which two any of R ¹ to R ⁴ is a quinone diazide sulfonyl (diester), a compound of three one of R ¹ through R ⁴ is a quinone diazide sulfonyl (triester), And a mixture of two or more of the compounds (tetraesters) in which all ^four of R ¹ to R ⁴ are quinonediazidosulfonyl. This mixture can usually be used as it is as the photosensitive compound of the present invention.

  In addition, individual esters obtained by separating and purifying the mixture can also be used as the photosensitive compound of the present invention. The separation and purification of the mixture can be performed by a known separation and purification technique such as column chromatography or recrystallization, although it depends on the composition in the mixture.

  The photosensitive compound of the present invention thus obtained can be advantageously used as a photosensitive agent sensitive to ultraviolet rays. This photosensitive agent exhibits a particularly high effect when it is used as a photosensitive composition for a positive resist in combination with an alkali-soluble resin such as an acrylic resin or a novolac resin.

  Since the photosensitive compound of the present invention has a silsesquioxane derivative containing 4 to 12 silicon as a basic structure and has R containing a group of the formula (1) described above for each silicon, an organic group, silicon, Is moderately included. For this reason, the photosensitive compound of this invention is excellent in compatibility with a silicone type polymer compared with the organic photosensitive compound which does not contain silicon, and shows equivalent compatibility with an organic type polymer.

<Compound for addition>
The additive compound of the present invention is an additive compound further blended in a positive photosensitive composition containing a photosensitive compound and an alkali-soluble resin soluble in alkali. The additive compound of the present invention has the same structure as that of the photosensitive compound of the present invention described above, except that the group of formula (1) in the photosensitive compound of the present invention described above is replaced by a group represented by the following formula (2). It is a compound of this. In the following formula (2), c is an integer of 0 to 8, and d is 0 or 1.

  As the basic structure of the additive compound, the same basic structure as that of the photosensitive compound described above can be used. R other than the group of the formula (2) in the compound for addition can use the same group as the photosensitive compound described above. These are appropriately selected from the structures and groups described above for the same reason as the photosensitive compounds described above.

  The values of c and d in the group of the formula (2) are the same as those of the photosensitive compound described above, the solubility of the obtained additive compound, the ease of synthesis of the target additive compound, and the availability of raw materials. It can be determined as appropriate based on such viewpoints.

  For example, in the group of formula (2), when d is 1, if c is small, the solubility of the obtained compound for addition in a solvent may be low. Increasing c improves solubility. Further, the additive compound of the present invention can be easily synthesized by introducing these groups by the hydrosilylation described above, similarly to the photosensitive compound described above. From the viewpoint of easy availability of raw materials and ease of synthesis, c and d can be appropriately determined.

  Specifically, in the additive compound, at least one of R is a compound of the formula (2) in which c and d are 0, and at least one of R is 0 in which c is 0 and d is 1. A compound of the formula (2), at least one of R is a compound of the formula (2) in which c is an integer of 1 to 8 and d is 0, and at least one of R is c = 1 A compound of the formula (2) which is an integer of ˜8 and d is 1.

In the group of the formula (2), the alkylene of this group may contain a structure other than the divalent hydrocarbon. Such a group of the formula (2) includes, for example, a group in which any —CH ₂ — of — (CH ₂ ) _c — in this group is replaced by —O—, and — (CH ₂ ) _c — A group in which arbitrary —CH ₂ CH ₂ — is replaced by —COO— is exemplified.

As in the case of the photosensitive compound described above, the additive compound of the present invention is a silsesquioxane compound represented by the above formula (3), and an arbitrary group different from R ⁵ in DD is represented by DD. It is preferable from the viewpoint of introducing from R ¹ to R ⁴ which two silicons at the end have. In the additive compound of the present invention, at least one of R ¹ to R ⁴ is a group of the formula (2). In the additive compound of the present invention, the above-mentioned R is appropriately selected as R ¹ to R ⁴ other than the group of the formula (2) as in the above-described photosensitive compound. Also, R ⁵ in addition compounds of the present invention can be used the same group as R ⁵ of the photosensitive compound described above.

  The group of formula (2) reacts with the epoxy group or oxetanyl group of the alkali-soluble resin to form a crosslink during post-baking after development of the display element described later. Therefore, the additive compound of the present invention is effective from the viewpoint of improving the heat resistance and sputtering resistance of the film in the display element by blending with the positive photosensitive composition.

The additive compound represented by the formula (3) is similar to the photosensitive compound described above, such as the availability of raw materials, the ease of synthesis, the solubility of the resulting compound, and the unity of the resulting compound. From the viewpoint, R ¹ to R ⁵ described above are appropriately combined.

As such a compound for addition, for example, R ⁵ is phenyl in which arbitrary hydrogen may be replaced by fluorine, methyl, or methoxy, and all R ⁵ are the same, and R ¹ to R ⁴ , in the group of the formula (2), any —CH ₂ — of — (CH ₂ ) _c — in this group may be replaced by —O—, or any of — (CH ₂ ) _c — The compound in which —CH ₂ CH ₂ — may be replaced by —COO—, and particularly the additive compound in which R ⁵ is phenyl.

In addition, as the compound for addition, for example, R ¹ and R ³ are alkyl having 1 to 8 carbon atoms, R ² and R ⁴ are an integer of 1 to 8 and c is 1 (2) And a compound in which R ⁵ is at least one selected from the aforementioned groups.

In addition, as the compound for addition, for example, R ¹ and R ⁴ are alkyls having 1 to 8 carbon atoms, R ² and R ³ are those in which c is an integer of 1 to 8 and d is 1. And a compound in which R ⁵ is at least one selected from the aforementioned groups.

Further, as the compound for addition, for example, R ¹ and R ³ are methyl, R ² and R ⁴ are groups of the formula (2) in which c is 2 and d is 1, and R ⁵ is as described above. The compound which is at least one chosen from group is mentioned.

Further, as the compound for addition, for example, R ¹ and R ⁴ are methyl, R ² and R ³ are groups of the formula (2) in which c is 2 and d is 1, and R ⁵ is as described above. The compound which is at least one chosen from group is mentioned.

The additive compound is not limited to the specific structure described above, but R ¹ and R ³ are methyl, R ² and R ⁴ are groups of formula (2) in which c is 2 and d is 1. A certain compound is preferable from the viewpoint of easy availability of raw materials, ease of synthesis, and enhancing heat resistance and sputtering resistance of a film in a display element by formation of a bridge, and R ¹ and R ⁴ are methyl. From the above viewpoint, R ² and R ³ are preferably compounds of the formula (2) in which c is 2 and d is 1.

  The additive compound of the present invention can be obtained as an intermediate product of the photosensitive compound of the present invention. For example, the compound for addition of the present invention can be obtained as a reaction product in the deprotection reaction in the production of the photosensitive compound of the present invention.

  Similar to the photosensitive compound of the present invention, the additive compound of the present invention is obtained as a compound having the structure of the formula (2) of mono, di, tri, tetra, and higher, and is one of these. It may be a mixture of two or more. Moreover, each said ester can be isolate | separated and refine | purified by well-known separation purification techniques, such as column chromatography and recrystallization, according to the composition of a mixture similarly to the photosensitive compound of this invention.

  When the additive compound of the present invention is combined with the photosensitive compound of the present invention in a positive photosensitive composition, the photosensitivity of the photosensitive compound of the present invention, insolubility in unexposed areas, and solubility in exposed areas Improve various physical properties. Therefore, the compound for addition of the present invention is blended with the positive photosensitive composition containing the photosensitive compound of the present invention, so that products such as display elements manufactured using this positive photosensitive composition can be obtained. May increase quality and productivity.

  The additive compound of the present invention has, as in the case of the photosensitive compound of the present invention, a silsesquioxane derivative containing 4 to 12 silicon as a basic structure, and R containing the group of the formula (2) described above for each silicon. Therefore, it contains an organic group and silicon moderately. For this reason, the compound for addition of the present invention is superior in compatibility with the silicone-based polymer as compared with the organic photosensitive compound not containing silicon, and exhibits the same compatibility with the organic polymer.

<Positive photosensitive composition>
The first positive photosensitive composition of the present invention contains one or more of the photosensitive compounds of the present invention described above and an alkali-soluble resin (hereinafter referred to as an alkali-soluble resin).

  The alkali-soluble resin is not particularly limited as long as it is soluble in alkali and is usually used in the resist field. The solubility in alkali in the alkali-soluble resin can be confirmed by the method shown below.

  A resin solution was spin-coated on the substrate, heated at 80 ° C. for 30 minutes to form a film having a thickness of 3 to 5 μm, and this was then applied to a 0.4% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Soak and rinse with pure water. If no film remains at this time, it can be confirmed that the resin is an alkali-soluble resin in the present invention.

  Examples of the alkali-soluble resin include a radical polymerization polymer obtained by polymerizing a plurality of types of radical polymerizable monomers having an appropriate group, a compound having at least one phenolic hydroxyl group, and an aldehyde in the presence of an acid catalyst. Examples thereof include novolak resins obtained by condensation. The novolac resin can be produced by a known method.

  Various polymers can be used as the radical polymerization polymer, such as a radical polymerizable monomer having oxetanyl, a radical polymerizable monomer having carboxyl, a radical polymerizable monomer having an acid anhydride group, a radical polymerizable monomer having an epoxy group, etc. A polymer obtained by polymerizing a mixture of a plurality of monomers selected from the above is preferable from the viewpoint of enhancing the properties of the film formed using the first positive photosensitive composition. The radical polymerization polymer may be a polymer obtained by polymerizing these single monomers.

  The radical polymerizable monomer having oxetanyl is not particularly limited as long as it is a compound having oxetanyl and radical polymerization. Examples of such monomers include 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3 -(Meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, and the like.

  The radical polymerizable monomer having oxetanyl can be used alone or in admixture of two or more. Using at least one of the above-mentioned radical polymerizable monomers having oxetanyl as a raw material for the alkali-soluble resin makes it possible to obtain transparency, heat resistance, chemical resistance, and resistance of the film obtained from the first positive photosensitive composition. This is preferable from the viewpoint of increasing the sputtering property.

The amount of the radically polymerizable monomer having oxetanyl in the polymerization of the alkali-soluble resin is preferably 50 to 95% by weight with respect to the total monomers from the viewpoint of improving the sputtering resistance of the film. It is more preferable from the viewpoint of increasing the transparency of the film that the amount of the monomer used is 61 to 95% by weight. The amount of the monomer used is preferably 70 to 95% by weight from the viewpoint of improving the heat resistance of the film.

  The radical polymerizable monomer having carboxyl is not particularly limited as long as it is a compound having carboxyl and radical polymerization. Examples of such monomers include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) ) Acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl] and the like.

  The above-mentioned radically polymerizable monomer having carboxyl can be used alone or in admixture of two or more. Among the above-mentioned radical-polymerizable monomers having carboxyl, (meth) acrylic acid and itaconic acid are preferred. In particular, (meth) acrylic acid is the first from the viewpoint of enhancing the storage stability of the first positive photosensitive composition. It is more preferable from the viewpoint of increasing the transparency of the film obtained from the positive photosensitive composition and from the viewpoint of reducing the development residue during exposure and development of the film.

  Development of the first positive photosensitive composition with an alkaline aqueous solution is that the amount of the carboxyl-containing radical polymerizable monomer used in the polymerization of the alkali-soluble resin is 5 to 50% by weight based on the total monomers. From the viewpoint of enhancing the properties. The amount of the monomer used is preferably 6 to 25% by weight from the viewpoint of increasing the resolution during development, and the amount of the monomer used is 7 to 15% by weight from the viewpoint of increasing the sensitivity during development. preferable.

  The radical polymerizable monomer having an acid anhydride group is not particularly limited as long as it is a compound having an acid anhydride group and radical polymerization. Examples of such monomers include maleic anhydride and itaconic anhydride. The radical polymerizable monomer having an acid anhydride group may be used alone or in combination of two or more. Among the radical polymerizable monomers having an acid anhydride group described above, itaconic anhydride is preferable from the viewpoint of increasing the sputtering resistance and transparency of the film obtained from the first positive photosensitive composition.

  The use amount of the radical polymerizable monomer having an acid anhydride group in the polymerization of the alkali-soluble resin is 1 to 44% by weight with respect to the total monomers, and the developability of the first positive photosensitive composition. From the viewpoint of increasing The amount of the monomer used is preferably 2 to 30% by weight from the viewpoint of enhancing the sputtering resistance of the film, and more preferably 5 to 20% by weight.

  The radical polymerizable monomer having an epoxy is not particularly limited as long as it is a compound having an epoxy and having radical polymerization. Examples of such a monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. The radically polymerizable monomer having an epoxy can be used alone or in admixture of two or more. Among the radical polymerizable monomers having an epoxy as described above, 3,4-epoxycyclohexyl (meth) acrylate is preferable from the viewpoint of improving the sputtering resistance and transparency of a film obtained from the first positive photosensitive composition.

  The amount of the radically polymerizable monomer having an epoxy in the polymerization of the alkali-soluble resin is preferably 1 to 45% by weight based on the total monomers, from the viewpoint of increasing the sputtering resistance of the film, and 5 to 30 More preferably, it is 10% by weight.

In the polymerization of the radical polymerization polymer, another monomer other than the above-described monomers may be further used. Examples of such monomers include styrene, methyl styrene, vinyl toluene, chloromethyl styrene, (meth) acrylamide, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer, poly Chill methacrylate macromonomer, N- acryloyl morpholine, indene, manufactured by Nippon Kayaku Co., Ltd. KAYARAD (trademark) TC110S, and the like.

The other monomers can be used alone or in admixture of two or more. Among the other monomers mentioned above, styrene, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^{2 , 6} ] Decanyl (meth) acrylate, N-phenylmaleimide, KAYARAD (trademark) TC110S manufactured by Nippon Kayaku Co., Ltd., and polystyrene macromonomer are preferable from the viewpoint of enhancing the developability of the first positive photosensitive composition. .

  The amount of the other monomer used in the polymerization of the alkali-soluble resin is not particularly limited as long as it does not impair the characteristics of the first positive photosensitive composition. For example, the viewpoint of not reducing the sputtering resistance of the film Therefore, the content is preferably 9% by weight or less based on the total monomers.

  The radical polymerization polymer can be produced by mixing the aforementioned various monomers and polymerizing them in the presence of a polymerization initiator. The method for polymerizing the various monomers is not particularly limited, but is preferably radical polymerization in a solution using a solvent. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator, but is usually in the range of 50 to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 3 to 24 hours. Further, this polymerization can be carried out under pressure, reduced pressure, or atmospheric pressure.

  The solvent used for the polymerization reaction is preferably a solvent that dissolves the monomer as a raw material and the radical polymerization polymer as a reaction product. Such a solvent can be appropriately selected from known solvents. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene glycol. Examples include monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid, water and the like. The said solvent can be used individually or in mixture of 2 or more types.

  As the polymerization initiator, a known polymerization initiator such as a compound that generates a radical by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide initiator such as benzoyl peroxide is used. be able to. In the polymerization of the monomer, an appropriate amount of a chain transfer agent such as thioglycolic acid may be used in order to adjust the molecular weight of the polymer produced.

  The alkali-soluble resin preferably has an acid value of 20 to 200 mgKOH / g from the viewpoint of controlling the exposure area development time, which is the time during which the exposed area of the film is dissolved in an alkali developer, to an appropriate time. The acid value is preferably from 25 to 150 mgKOH / g, more preferably from the viewpoint of optimizing the exposed area development time and the suppression of film roughness during development, and even more preferably from 30 to 100 mgKOH / g. The acid value of the alkali-soluble resin can be measured by a known method, and can be adjusted by, for example, the composition of raw material monomers.

  The alkali-soluble resin has a weight average molecular weight of 1,000 to 10,000 determined by GPC analysis using polyethylene oxide as a standard, in view of optimizing the exposure area development time and film roughness during development. It is preferable from the viewpoint of prevention. When the weight average molecular weight is 1,500 to 50,000, the viewpoint of appropriately controlling the non-exposed portion development time, which is the time until the non-exposed portion of the film is dissolved with an alkaline developer, and the development residue From the viewpoint of reducing the weight, the weight average molecular weight is more preferably 2,000 to 20,000.

  The first positive photosensitive composition may further contain one kind or two or more kinds of the compound for addition of the present invention described above.

  The content of the photosensitive compound and the compound for addition in the first positive photosensitive composition depends on the quality of a product such as a display element manufactured using the first positive photosensitive composition. It can be determined as appropriate. The content of the photosensitive compound in the positive photosensitive composition is preferably 1 to 50% by weight with respect to the alkali-soluble resin. Moreover, it is preferable that content of the said compound for addition in the said positive photosensitive composition is 30 weight% or less with respect to the said alkali-soluble resin.

  The structures of the photosensitive compound and the additive compound in the first positive photosensitive composition are not particularly limited, but the basic structure in the photosensitive compound, the type and position of the group, and the basic in the additive compound It is preferable that the structure, the kind and position of the group are similar from the viewpoint of enhancing advantages such as improvement of solubility by the group and improvement of thermal specification by the position of the group, and the same is more preferable. Here, the same type of group means that the chain structure in the group is the same. For example, a and b of the group of the formula (1) in the photosensitive compound and the formula ( It means that c and d of the group of 2) are the same.

  The first positive photosensitive composition includes the above-described photosensitivity from the viewpoint of improving the resolution during development of the positive photosensitive composition, the coating uniformity of the positive photosensitive composition, the developability, and the adhesiveness. Additives other than the compound, the alkali-soluble resin, and the additive compound may be contained. Examples of such additives include acrylic, styrene, polyethyleneimine, or urethane polymer dispersants; anionic, cationic, nonionic, or fluorine surfactants; improved coating properties such as silicone resins Agents; Adhesion improvers such as silane coupling agents; Ultraviolet absorbers such as alkoxybenzophenones; Anti-aggregation agents such as sodium polyacrylate; Thermal crosslinking agents such as epoxy compounds, melamine compounds or bisazide compounds; Organic carboxylic acids, etc. And an alkali solubility promoter.

In addition, the first positive photosensitive composition includes an epoxy-containing polymer having no carboxyl and a carboxyl from the viewpoint of improving the heat resistance and chemical resistance of the film obtained from the first positive photosensitive composition. An oxetanyl-containing polymer that does not have any may be added. Examples of these polymers include homopolymers of glycidyl methacrylate, copolymers of glycidyl methacrylate and other monofunctional monomers capable of radical polymerization, homopolymers of 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3 -A copolymer of methacryloxymethyl oxetane and other radically polymerizable monofunctional monomers. These polymers are preferable from the viewpoint of improving the heat resistance, chemical resistance, and developability of the film.

  Among the polymers, glycidyl methacrylate homopolymer, glycidyl methacrylate and methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane homopolymer, glycidyl methacrylate and N-phenylmaleimide copolymer, glycidyl A copolymer of methacrylate and 3-ethyl-3-methacryloxymethyloxetane is more preferable from the viewpoint of improving the heat resistance, chemical resistance, and developability of the film.

  The epoxy-containing polymer and the oxetanyl-containing polymer have a weight average molecular weight of 2,000 to 70,000 determined by GPC analysis using polyethylene oxide as a standard, to improve the heat resistance and chemical resistance of the film. To preferred. Furthermore, when the weight average molecular weight is 3,000 to 30,000, it is more preferable from the viewpoint of enhancing the heat resistance and chemical resistance of the film and optimizing the developing time of the exposed or non-exposed area.

  A solvent can be further added to the first positive photosensitive composition. A known solvent can be used as the solvent. The solvent is preferably a compound having a boiling point of 100 to 200 ° C. or a mixed solvent containing 20% by weight or more of this compound.

  Examples of the solvent having a boiling point of 100 to 200 ° C. include water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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, N, N-dimethylacetamide And the like.

Among the solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether At least one selected from diethylene glycol methyl ethyl ether and ethyl lactate is preferable from the viewpoint of improving the coating uniformity of the first positive photosensitive composition.

  In particular, among the solvents, at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, and ethyl lactate is a first positive photosensitive composition. It is more preferable from the viewpoint of increasing the coating uniformity of the coating and the viewpoint of increasing the safety to the human body.

  Although the usage-amount of the said solvent is not specifically limited, It is preferable that it is the quantity from which the solid content concentration in a 1st positive photosensitive composition will be 10 to 50 weight%.

  The first positive photosensitive composition is preferably stored in the light-shielded state at -5 to 25 ° C from the viewpoint of stabilization with time, and more preferably the storage temperature is 0 to 10 ° C.

  The first positive photosensitive composition is used in the same manner as an ordinary positive photosensitive composition, for example, in the production of a transparent film or an insulating film produced in the process of producing a liquid crystal display element. be able to.

  The first positive photosensitive composition uses the monomer of the silsesquioxane derivative into which the group of the formula (1) is introduced as the photosensitive compound, and as described above, the photosensitive compound of the present invention. Has good compatibility with the polymer. Therefore, the first positive photosensitive composition has a formula (1) in the positive photosensitive composition as compared with the photosensitive composition containing polysilsesquioxane in which the group of formula (1) is introduced. The group of 1) can be more uniformly dispersed.

  The second positive photosensitive composition of the present invention contains a photosensitive compound whose solubility in alkali is changed by photosensitivity, the aforementioned additive compound of the present invention, and the aforementioned alkali-soluble resin.

  The photosensitive compound is not particularly limited as long as it is a compound whose solubility in alkali changes upon exposure to light. As such a photosensitive compound, a known photosensitive compound can be used, and its photosensitivity can be confirmed by the same method as that of the photosensitive compound of the present invention described above.

  Examples of the photosensitive compound include a quinone diazide sulfonate ester of a pentaphenol compound described in JP-A-9-194413, 1,2-benzoquinone diazide sulfonate, 1,2-naphthoquinone diazide sulfonate. Examples thereof include esters, 1,2-benzoquinone diazide sulfonic acid amide, and 1,2-naphthoquinone diazide sulfonic acid amide. More specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Esters, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, and 4, And 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester. These photosensitive compounds can be used alone or in admixture of two or more.

  The second positive photosensitive composition is the same as the first positive photosensitive composition described above except that it contains an additive compound and the photosensitive compound contains a known photosensitive compound. Can be configured and handled. The second positive photosensitive composition can be constituted by mixing the aforementioned additive compound of the present invention with a composition containing a known photosensitive compound and an alkali-soluble resin. Moreover, when a monomer is used for the photosensitive compound, it is effective from the viewpoint of uniformly dispersing the photosensitive functional group in the composition, as in the first positive photosensitive composition.

<Display element>
The display element of the present invention has an element substrate and a film of a positive photosensitive composition formed on the element substrate. As the positive photosensitive composition for forming the film, the above-described first or second photosensitive composition of the present invention is used. The display element of the present invention is manufactured using a known technique for manufacturing a display element, except that the positive photosensitive composition of the present invention is used for the positive photosensitive composition for forming the film. can do.

  If the display element of this invention is an element which has an element substrate and the film | membrane of the positive photosensitive composition of this invention, the form will not be specifically limited. The form of the display element of the present invention may be a form in which the film is uniformly formed on the entire surface of the element substrate, or the film having a predetermined shape on a part of the surface of the element substrate. May be formed, or may be a form in which development for forming the film from which the image portion of the electrode and the wiring pattern is removed is performed on one surface of the element substrate. Other members such as a polarizing filter, a transparent electrode, an alignment film, a spacer, a liquid crystal, and a color filter may be provided.

  The element substrate can be appropriately selected from known substrates according to the use of the display element. Examples of the element substrate include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass; synthetic resin sheets and films such as polycarbonate, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide. Or a substrate; a metal substrate such as an aluminum plate, a copper plate, a nickel plate, or a stainless plate; a ceramic plate; a semiconductor substrate having a photoelectric conversion element; The element substrate can be subjected to a pretreatment such as a chemical treatment using a chemical such as a silane coupling agent, plasma treatment, ion plating, sputtering, a gas phase reaction method, or vacuum deposition, if desired.

  The film of the positive photosensitive composition of the present invention is a film formed using the positive photosensitive composition of the present invention, and is a film containing at least a photosensitive compound and an alkali-soluble resin. A film that further contains a compound for addition, a film that may further contain other additives, and a film in which any component such as a solvent may be removed from the positive photosensitive composition. is there.

  The film of the positive photosensitive composition of the present invention can be formed by applying and drying the positive photosensitive composition of the present invention on the surface of the element substrate by a known technique. Examples of the method for applying the positive photosensitive composition of the present invention to the element substrate include known methods such as spin coating, roll coating, and dipping. The drying conditions are not particularly limited, but are, for example, about 60 to 120 ° C. for about 1 to 5 minutes in a hot plate or oven.

  The film having a predetermined shape on the element substrate may be formed by removing a film of a part other than the predetermined shape from the uniformly formed film, or in the positive photosensitive composition of the present invention. Depending on the type of the solvent, a hydrophilic portion or a hydrophobic portion surrounding the predetermined shape may be formed on the element substrate, and then formed by applying the positive photosensitive composition of the present invention.

  The removal (development) of the image portion of the electrode or wiring pattern from the film is performed by exposing the film through a mask having a window having a shape corresponding to the shape of the electrode or wiring pattern, and using an alkaline alkaline developer. This can be done by a known method in which the film is washed away to develop the image.

The light beam applied to the film through the mask in exposure of the film is preferably ultraviolet light, and the amount of ultraviolet light irradiation at the time of exposure is 5 to 1,000 mJ / cm ² for i-line. Is appropriate.

  The photosensitive compound of the present invention at a portion irradiated with ultraviolet rays at the time of exposure becomes an indenecarboxylic acid derivative by contacting with an alkaline developer. Moreover, the well-known photosensitive compound used for this invention is also solubilized with respect to an alkali developing solution by ultraviolet irradiation. Therefore, the alkaline developer used for the development does not substantially elute the photosensitive compound used in the present invention from the film, and elutes the indenecarboxylic acid derivative and the alkali-soluble resin from the film. The liquid is not particularly limited as long as it can be used.

  Examples of the alkaline developer include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide; and organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. The alkaline developer may further contain an appropriate amount of components other than the aforementioned alkaline compounds such as methanol, ethanol, and surfactant.

The development method using the alkali developer can be performed by a known technique such as shower development, spray development, paddle development, dip development, or the like. Further, the film after development is sufficiently rinsed with pure water, and the whole surface of the film is again irradiated with an irradiation amount of 100 to 1,000 mJ / cm ² and baked at 180 to 250 ° C. for 10 to 120 minutes. A transparent film on which a desired pattern is formed is obtained.

  Further installation of the other members such as a polarizing filter, a transparent electrode, a spacer, a liquid crystal, and a color filter on the element substrate and the film may be performed by using known materials and methods according to various conditions such as the structure and application of the display element. It can be done using it.

  As described above, in the display element of the present invention, the group of formula (1) which is a photosensitive functional group is uniformly dispersed in the first positive photosensitive composition of the present invention. The concentration of the group of formula (1) in the film becomes constant, and a constant resolution can be obtained in the film. In the second positive photosensitive composition of the present invention, the same effect can be obtained even when a monomeric photosensitive compound is used.

  Further, in the display element of the present invention, when the photosensitive compound in the film is the aforementioned silsesquioxane derivative, the photosensitivity of a ladder type silsesquioxane derivative having a plurality of cyclic structures connected in a plane is obtained. Excellent chemical resistance, especially alkali resistance, compared to the functional compound. For this reason, damage to the film caused by the manufacturing process of the display element, such as damage to the film during development, can be suppressed.

<Synthesis of photosensitive compound>
As shown in the following reaction formula, compound III was prepared from compound I.

  First, Compound I was synthesized according to the method described in JP-T-2003-024870.

  That is, phenyltrimethoxysilane, sodium hydroxide, water, and 2-propyl alcohol were refluxed for 4 hours with stirring, the resulting reaction solution was allowed to stand overnight at room temperature, and the deposited precipitate was filtered. Washing and drying gave a white powdery solid.

  Next, while stirring the solid, tetrahydrofuran, and triethylamine, methyldichlorosilane was added dropwise at room temperature, and the mixture was stirred at room temperature for 1 hour. Sodium chloride produced by adding water to the obtained reaction solution was dissolved, and unreacted methyldichlorosilane was hydrolyzed. The reaction mixture thus obtained was separated, and the resulting organic layer was washed, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure using a rotary evaporator to obtain Compound I as a white powdery solid. It was.

  Next, 57.7 g (50 mmol) of Compound I and 17.0 g (105 mmol) of 4-acetoxystyrene were suspended in 200 mL of toluene under a nitrogen stream, heated to 80 ° C., and tris (divinyldisiloxane) diplatinum ( 0) 185 μL (xylene solution having a platinum content of 3% by weight) was added, and the mixture was heated to 100 ° C. and stirred for 3 hours. The obtained reaction liquid was cooled to room temperature, 16.7 mL of concentrated hydrochloric acid and 200 mL of ethanol were added, and the mixture was stirred at room temperature for 19 hours. Toluene and water were added to the reaction solution until the two layers were separated, and after separation, the organic layer was repeatedly washed with water until neutrality. Anhydrous magnesium sulfate was added to the organic layer for drying, magnesium sulfate was filtered off, and the obtained filtrate was concentrated under reduced pressure to obtain 96.4 g of a crude product of Compound II (mixture of structural isomers).

  This was separated by silica gel column chromatography (toluene: ethyl acetate = 10: 1), and 8.6 g of cis isomer of Compound II (cis-II, melting point 236.5-238.0 ° C.) and 25. 6 g of the trans isomer of compound II (trans-II) was obtained.

  Regarding trans-II, recrystallization (mixed solvent of n-hexane and ethyl acetate) was repeated three times to obtain 8.6 g of white crystals (melting point: 237.0-238.0 ° C.). In both cases, the yield was 12%. The NMR data of the cis- and trans-isomers of Compound II are shown below.

cis-II NMR (deuterated chloroform solvent) data
¹ H-NMR: δ 0.27, 6H (s), Si—CH ₃ ; δ 1.06, 4H (m), Si—CH ₂ —CH ₂ , d2.65, 4H (m), Si—CH ₂ — _{CH 2; d6.53-7.52,48H (m),} aromatic
²⁹ Si-NMR: d-79.58, −78.62, −18.10.

trans-II NMR (deuterated chloroform solvent) data
¹ H-NMR: δ 0.26, 6H (s), Si—CH ₃ ; δ 1.06, 4H (m), Si—CH ₂ —CH ₂ , d2.65, 4H (m), Si—CH ₂ — _{CH 2; d6.53-7.52,48H (m),} aromatic
²⁹ Si-NMR: d-79.56, -78.56, -18.05

  Next, 8.6 g (6.2 mmol) of compound trans-II and 3.8 g (14 mmol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride are dissolved in 85 mL of 1,4-dioxane under a nitrogen stream. Then, a solution of 1.4 g (14 mmol) of triethylamine in 1,4-dioxane (15 mL) was added in a water bath at about 15 ° C. After confirming that the exotherm had subsided, the water bath was removed, and after stirring at room temperature for 20 hours, the reaction was stopped by adding water and toluene to the resulting reaction solution.

After liquid separation, liquid separation with the obtained aqueous layer and toluene was performed three times. The obtained organic layers were combined and dried over anhydrous magnesium sulfate, magnesium sulfate was filtered off, and the obtained filtrate was concentrated. 18.1 g of crude product was obtained. This was purified by silica gel column chromatography to obtain 10.4 g of an orange crystal (melting point: 149.0 to 150.5 ° C., decomposition) of compound III in a trans form (trans-III, the following structural formula 13). The yield was 90%. The NMR data of the trans isomer of Compound III are shown below.

NMR (deuterated chloroform solvent) data
¹ H-NMR: δ0.21, 6H (s), Si—CH ₃ ; δ0.99, 4H (m), Si—CH ₂ —CH ₂ , d2.60, 4H (m), Si—CH ₂ — _{CH 2; d6.63-7.55,48H (m),} aromatic; d8.08,2H (dd, J = 1.26and7.57Hz), 8-H on NQD; d8.62,2H (d, J = 8.01 Hz), 6-H on NQD
²⁹ Si-NMR: -79.54, -78.56, -18.57

Further, in the same manner as trans-III, a cis isomer of compound III (cis-III, the following structural formula 14) was obtained.

<Synthesis of alkali-soluble resin (A)>
An alkali-soluble resin (A) was produced using Synthesis Example 2 described in JP-A No. 2001-330953.

That is, the following materials were charged into a four-necked flask equipped with a stirrer and heated at the reflux temperature of 2-butanone for 4 hours.
2-butanone 200.0g
17.5 g of 3-ethyl-3-methacryloxymethyloxetane
Methacrylic acid 12.5g
Styrene 10.0g
N-Phenylmaleimide 10.0g
2,2′-azobis (2,4-dimethylvaleronitrile) 2.0 g

The resulting reaction solution was cooled to room temperature and poured into a large amount of hexane. The produced precipitate was dissolved in methyl 3-methoxypropionate (hereinafter abbreviated as MMP), hexane was distilled off at 100 ° C. under a reduced pressure of 1.33 × 10 ⁴ Pa, and an MMP solution of the alkali-soluble resin (A) was obtained. Obtained.

  A part of the solution was sampled and dried at 220 ° C. for 30 minutes to determine the weight loss. Based on the result, MMP was added so that the resin concentration was 30% by weight to prepare a solution. The yield of alkali-soluble resin (A) was 81%. The acid value of the obtained alkali-soluble resin (A) was 48 mgKOH / g, and the weight average molecular weight determined by GPC analysis (polyethylene oxide standard) was 4,400.

<Example 1>
Alkali-soluble resin (A), photo-sensitive compound trans-III, fluorine-based surfactant Neos Co., Ltd. Frantent (trademark) DFX-18 (hereinafter abbreviated as DFX-18), MMP as a solvent, Epicoat 827 as an epoxy resin was mixed and dissolved in the following composition to obtain a positive photosensitive composition.
MMP 2.47g
trans-III 0.63 g
Epicoat 827 0.60g
DFX-18 0.008g

This positive photosensitive composition was spin-coated on a glass substrate at 800 rpm for 10 seconds, and dried on a hot plate at 100 ° C. for 2 minutes to form a film of the positive photosensitive composition on the glass substrate. The film of the glass substrate was irradiated with a predetermined light beam in the air through a hole pattern forming mask and exposed with an exposure gap of 100 μm. The irradiated light is g, h, i line extracted by using a proximity exposure machine TME-150PRC manufactured by Topcon Co., Ltd. and cutting light of 350 nm or less through a wavelength cut filter. The amount of irradiation was 150 mJ / cm ^{2 as} measured by Ushio Corporation 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 film on the exposed portion. 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 to produce a display element. The residual film ratio after development (film thickness after development × 100 / film thickness before development) is 84.1%, the hole pattern with a mask size of 8 μm is resolved, and it has sufficient sensitivity. confirmed.

The entire surface of the substrate was exposed at an irradiation amount of 300 mJ / cm ² without using a mask with the exposure machine, and then post-baked at 220 ° C. for 30 minutes in an oven. The film thickness was 3.03 μm. The transmittance at 400 nm was 97.3%, and it was confirmed that the transparency was high. The film thickness after additional baking at 230 ° C. for 60 minutes in the oven was 2.93 μm, the transmittance at 400 nm was 97.0%, and it was confirmed that high transparency was maintained.

  When a transparent electrode of ITO (indium tin oxide) was formed on this substrate by sputtering at 200 ° C., no wrinkles were observed. Table 1 shows the results.

<Example 2>
Except having changed the photosensitive compound into cis-III (0.63g), the positive photosensitive composition and the display element were produced like Example 1, and the obtained display element was evaluated. The results are shown in Table 1.

<Example 3>
A positive photosensitive composition and a display device were produced in the same manner as in Example 1 except that the photosensitive compound was changed to a mixture of trans-III (0.315 g) and cis-III (0.315 g). The obtained display element was evaluated. The results are shown in Table 1.

<Comparative example>
The photosensitive compound was converted to 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester (P100 The positive photosensitive composition and the display element were produced in the same manner as in Example 1 except that the display element was changed to), and the obtained display element was evaluated. The results are shown in Table 1.

<Example 4>
A positive photosensitive composition and a display element were produced in the same manner as in Example 1 except that 0.15 g of trans-II was further added, and the obtained display element was evaluated. The results are shown in Table 1.

<Example 5>
A positive photosensitive composition and a display device were produced in the same manner as in the comparative example except that 0.15 g of cis-II was further added, and the obtained display device was evaluated. The results are shown in Table 1.

  As is clear from the above results, the film of the photosensitive composition of this example has sufficient sensitivity and resolving power to resolve a hole pattern having a mask size of 8 μm.

In addition, the film of the photosensitive composition of this example is different from the film thickness after post-baking and the film thickness after additional baking in that the film of the photosensitive composition of the comparative example containing the organic photosensitive composition. Compared to the above, it is about 2/3, and wrinkles due to sputtering of the ITO transparent electrode are not confirmed, so that it is excellent in sputtering resistance and heat resistance.

  Furthermore, the film | membrane of the photosensitive composition of the present Examples 1-4 has the very small reduction of the transmittance | permeability after post-baking, and has shown high transparency.

  In addition, the film of the photosensitive composition of Example 4 shows a higher remaining film ratio after baking compared to the film of the photosensitive composition of Example 1. Similarly, the film of the photosensitive composition of Example 5 has a higher film remaining ratio after baking compared to the film of the photosensitive composition of the comparative example. As is clear from Examples 4 and 5, the film of the positive photosensitive composition containing the additive compound of the present invention is more effective for improving the sputtering resistance and heat resistance.

Claims (41)

A compound comprising a silsesquioxane derivative containing a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R,
The basic structure is a structure in which three oxygens and one R are bonded to one silicon, and one oxygen is interposed between two silicons.
The silsesquioxane derivative may have oxygen at the end, R may be bonded to the oxygen at the end, and two R may be bonded to the two oxygen at the end. In the compound that one silicon may be bonded,
R is independently hydrogen, alkyl, aryl, aralkyl, a group represented by the following formula (1), or a group represented by the following formula (2);
The alkyl has 1 to 30 carbon atoms, the aryl has 6 to 30 carbon atoms, the aralkyl alkylene has 1 to 12 carbon atoms, and in each of the alkyl and aralkyl alkylenes, any hydrogen is a halogen. Any —CH ₂ — may be replaced by —O—, —S—, —CO—, —NH—, —SiR ^a ₂ — (R ^a is independently an alkyl having 1 to 8 carbon atoms, phenyl, , Cyclopentyl or cyclohexyl), -CH = CH-, -C≡C-, -CF = CF-, cycloalkylene or cycloalkenylene, each of the aryl and aralkyl having any ring Hydrogen is replaced by halogen, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. You may be able to
A compound, wherein at least one of R is a group represented by the formula (1).

(In the formula, a is an integer of 0 to 8, and b is 0 or 1.)

(In the formula, c is an integer of 0 to 8, and d is 0 or 1.) Silsesquioxane derivative is composed of eight silicon-containing basic structures, four ends to which oxygen is bonded, and two R-bonded silicon bonded to two sets of two ends. And a compound represented by the following formula (3):
R is represented by R ¹ and R ² bonded to ^one silicon at the end, R ³ and R ⁴ bonded to the other silicon at the end, and a plurality of R ⁵ bonded to silicon of the basic structure. sometimes,
The compound according to claim 1, wherein at least one of R ¹ to R ⁴ is a group represented by the formula (1).

The compound according to claim 2, wherein at least one of R ¹ to R ⁴ is a group in which a and b in the formula (1) are 0. The compound according to claim 2, wherein at least one of R ¹ to R ⁴ is a group in which a is 0 and b is 1 in formula (1). The compound according to claim 2, wherein at least one of R ¹ to R ⁴ is a group in which a in formula (1) is an integer of 1 to 8 and b is 0. The compound according to claim 2, wherein at least one of R ¹ to R ⁴ is a group in which a in formula (1) is an integer of 1 to 8 and b is 1. R ⁵ is independently alkyl, aryl, or arylalkyl;
Alkyl, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, —CH═CH—, or cycloalkylene having 4 to 8 carbon atoms, 1-20 alkyl,
Aryl is aryl in which any hydrogen of the ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons;
Arylalkyl is characterized in that any hydrogen in the ring is an arylalkyl which may be replaced by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms The compound according to any one of claims 2 to 6. R ⁵ is independently alkyl, phenyl, phenylalkyl, or naphthyl;
Alkyl, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, —CH═CH—, or cycloalkylene having 4 to 8 carbon atoms, 1-8 alkyl,
Phenyl is phenyl in which any hydrogen of the benzene ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons;
The phenylalkyl is characterized in that any hydrogen of the benzene ring is phenylalkyl which may be replaced by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms. The compound according to claim 7. R ⁵ is phenyl where any hydrogen may be replaced by fluorine, methyl or methoxy, and all R ⁵ are the same;
In R ¹ to R ⁴ , the group represented by the formula (1) and the group represented by the formula (2) are an arbitrary —CH of — (CH ₂ ) _a — and — (CH ₂ ) _c — in these groups. ₂ — may be replaced by —O—, and any —CH ₂ CH ₂ — of — (CH ₂ ) _a — and — (CH ₂ ) _c — may be —CO
9. A compound according to claim 8, which may be replaced by O-. A compound according to claim 9 wherein R ⁵ is characterized in that it is a phenyl. 11. The compound according to claim 2, wherein at least one of R ¹ to R ⁴ other than the group represented by the formula (1) is a group represented by the formula (2). The compound according to claim 11, wherein at least one of R ¹ to R ⁴ other than the group represented by the formula (1) is a group in which c and d in the formula (2) are 0. The compound according to claim 11, wherein at least one of R ¹ to R ⁴ other than the group represented by the formula (1) is a group in which c is 0 and d is 1 in the formula (2). 12. At least one of R ¹ to R ⁴ other than the group represented by the formula (1) is a group in which c is an integer of 1 to 8 and d is 0 in the formula (2). The described compound. 12. At least one of R ¹ to R ⁴ other than the group represented by the formula (1) is a group in which c is an integer of 1 to 8 and d is 1 in the formula (2). The described compound. R ¹ is alkyl having 1 to 8 carbon atoms,
R ² is a group in which a in formula (1) is an integer of 1 to 8 and b is 1.
R ³ and R ⁴ are each an alkyl having 1 to 8 carbon atoms and a in formula (1) where a is an integer of 1 to 8 and b is 1, or a in formula (1) is 1 to 1 An integer of 8 and b is 1 and alkyl having 1 to 8 carbons, or alkyl having 1 to 8 carbons and c in formula (2) are integers of 1 to 8 and d is 1 Or a group in which c in formula (2) is an integer of 1 to 8 and d is 1, and an alkyl having 1 to 8 carbon atoms. The compound according to any one of 2 to 15. R ¹ is methyl, R ³ and R ⁴ are each methyl and a group in which a is 2 and b is 1 in formula (1), or a in formula (1) is 2 and b is 1 Or a group in which c is 2 and d is 1 in formula (2), or a group in which c is 2 and d is 1 in formula (2) 17. A compound according to claim 16 which is any of methyl. R ³ is a group in which a is 2 and b is 1 in formula (1) or a group in which c is 2 and d is 1 in formula (2), and R ⁴ is methyl 18. A compound according to claim 17. The compound according to claim 18, wherein R ³ is a group in which a is 2 and b is 1 in formula (1). R ³ is methyl and R ⁴ is a group in which a is 2 and b is 1 in the formula (1) or a group in which c is 2 and d is 1 in the formula (2) 18. A compound according to claim 17. R ⁴ is The compound of claim 20 wherein a is 2 b is characterized in that it is a group which is 1 in the formula (1). A compound comprising a silsesquioxane derivative containing a basic structure composed of 4 to 12 silicon, oxygen bonded to each silicon, and monovalent R,
The basic structure is a structure in which three oxygens and one R are bonded to one silicon, and one oxygen is interposed between two silicons.
The silsesquioxane derivative may have oxygen at the end, R may be bonded to the oxygen at the end, and two R may be bonded to the two oxygen at the end. In the compound that one silicon may be bonded,
R is independently hydrogen, alkyl, aryl, aralkyl, or a group represented by the following formula (2);
The alkyl has 1 to 30 carbon atoms, the aryl has 6 to 30 carbon atoms, the aralkyl alkylene has 1 to 12 carbon atoms, and in each of the alkyl and aralkyl alkylenes, any hydrogen is a halogen. Any —CH ₂ — may be replaced by —O—, —S—, —CO—, —NH—, —SiR ^a ₂ — (R ^a is independently an alkyl having 1 to 8 carbon atoms, phenyl, , Cyclopentyl or cyclohexyl), -CH = CH-, -C≡C-, -CF = CF-, cycloalkylene or cycloalkenylene, each of the aryl and aralkyl having any ring Hydrogen is replaced by halogen, cyano, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. You may be able to
A compound, wherein at least one of R is a group represented by the formula (2).

(In the formula, c is an integer of 0 to 8, and d is 0 or 1.) Silsesquioxane derivative is composed of eight silicon-containing basic structures, four ends to which oxygen is bonded, and two R-bonded silicon bonded to two sets of two ends. And a compound represented by the following formula (3):
R is represented by R ¹ and R ² bonded to ^one silicon at the end, R ³ and R ⁴ bonded to the other silicon at the end, and a plurality of R ⁵ bonded to silicon of the basic structure. sometimes,
The compound according to claim 22, wherein at least one of R ¹ to R ⁴ is a group represented by the formula (2).

At least one of the R ¹ R ⁴ is The compound of claim 23 wherein c and d is equal to or is a group which is 0 in the formula (2). At least one of the R ¹ R ⁴ is The compound of claim 23 wherein c is 0 d is characterized in that it is a group which is 1 in the formula (2). At least one of the R ¹ R ⁴ is The compound of claim 23, wherein c is equal to or d is an integer from 1 to 8 are groups is 0 of the formula (2). At least one of the R ¹ R ⁴ is The compound of claim 23 wherein c is is d an integer from 1 to 8, characterized in that a group is one of formula (2). R ⁵ is independently alkyl, aryl, or arylalkyl;
Alkyl, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, —CH═CH—, or cycloalkylene having 4 to 8 carbon atoms, 1-20 alkyl,
Aryl is aryl in which any hydrogen of the ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons;
Arylalkyl is characterized in that any hydrogen in the ring is an arylalkyl which may be replaced by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms 28. A compound according to any one of claims 23 to 27. R ⁵ is independently alkyl, phenyl, phenylalkyl, or naphthyl;
Alkyl, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, —CH═CH—, or cycloalkylene having 4 to 8 carbon atoms, 1-8 alkyl,
Phenyl is phenyl in which any hydrogen of the benzene ring may be replaced by halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons or alkenyl having 2 to 4 carbons;
The phenylalkyl is characterized in that any hydrogen of the benzene ring is phenylalkyl which may be replaced by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms. 29. The compound of claim 28. R ⁵ is phenyl where any hydrogen may be replaced by fluorine, methyl or methoxy, and all R ⁵ are the same;
In R ¹ to R ⁴ , in the group represented by the formula (2), any —CH ₂ — of — (CH ₂ ) _c — in this group may be replaced by —O—, and — (CH ₂ ) The compound according to claim 29, wherein any —CH ₂ CH ₂ — in _c — may be replaced by —COO—. The compound of claim 30, wherein R ⁵ is characterized in that it is a phenyl. R ¹ is alkyl having 1 to 8 carbon atoms,
R ² is a group in which c in formula (2) is an integer of 1 to 8 and d is 1.
R ³ and R ⁴ are each an alkyl having 1 to 8 carbon atoms and c in the formula (2) is an integer having 1 to 8 and d is 1, or c in the formula (2) is The compound according to any one of claims 23 to 31, wherein the compound is any one of an integer of 1 to 8 and d of 1 and an alkyl having 1 to 8 carbon atoms. R ¹ is methyl, R ² is a group in which c in formula (2) is 2 and d is 1.
R ³ and R ⁴ are each methyl and a group in which c in formula (2) is 2 and d is 1, or a group in which c in formula (2) is 2 and d is 1 and methyl The compound according to claim 32, wherein the compound is any one of the following: R ³ is a group which is c, is 2 d 1 of the formula (2), R ⁴ is A compound according claim 33 which is a methyl. The compound according to claim 33, wherein R ³ is methyl, and R ⁴ is a group in which c in formula (2) is 2 and d is 1.   A positive photosensitive composition comprising the compound according to any one of claims 1 to 21 and an alkali-soluble resin soluble in an alkali.   37. The positive photosensitive composition according to claim 36, further comprising the compound according to any one of claims 22 to 35.   37. A positive photosensitive composition comprising a photosensitive compound whose solubility in alkali is changed by light exposure, the compound according to any one of claims 22 to 35, and an alkali-soluble resin soluble in alkali.   The content of the compound according to any one of claims 1 to 21 or the photosensitive compound in the composition is 1 to 50% by weight with respect to the alkali-soluble resin. The positive photosensitive composition as described in any one of Claims.   The positive photosensitive composition according to claim 37 or 38, wherein the content of the compound according to any one of claims 22 to 35 in the composition is 30% by weight or less based on the alkali-soluble resin. Sex composition. In a display element having an element substrate and a film of a positive photosensitive composition formed on the element substrate,
41. A display element, wherein the positive photosensitive composition is the positive photosensitive composition according to any one of claims 36 to 40.