Positive photosensitive resin composition, cured product thereof, and display device provided with same

Abstract

This invention addresses the problem of providing a positive photosensitive composition having both characteristics of high heat resistance and high transparency as well as high sensitivity, high residual film ratio patterning ability and high storage stability, and as a solution therefor, proposes a positive photosensitive resin composition containing (a) a polysiloxane and (b) a naphthoquinone diazide compound represented by formula (1). [Chem 1] (In formula (1), R1 represents a 1-8 carbon alkyl group. Q represents a naphthoquinone diazide sulfonyl group represented by the following structures or a hydrogen atom. Of all of the Qs in formula (1), at least one Q is a naphthoquinone diazide sulfonyl group. n represents an integer 0-4 and m represents an integer 4-8. X represents a 4-30 carbon tetravalent to octavalent organic group.) [Chem 2] (In the above structures, ＊ represents a bonding site.)

Description

Positive photosensitive resin composition, cured product thereof, and display device including the same

[0001] The present invention relates to a photosensitive composition that can be suitably used for planarizing films and interlayer insulating films for thin film transistor (TFT) substrates in liquid crystal display devices, organic EL display devices, and the like, a cured product formed from the composition, and a display device having the cured product.

[0002] In recent years, a method for increasing the aperture ratio of a display device has been known as a method for achieving higher definition and resolution in liquid crystal displays and organic EL displays (see Patent Document 1). This method involves providing a transparent planarizing film as a protective film on top of a TFT substrate, thereby enabling the data lines and pixel electrodes to overlap, thereby increasing the aperture ratio compared to conventional techniques.

[0003] The material for such a planarization film for a TFT substrate must have high heat resistance and high transparency, and must be capable of forming a hole pattern of about several μm to ensure electrical continuity between the TFT substrate electrode and the ITO electrode. Therefore, a positive-type photosensitive material is generally used. A typical example of such a material is a combination of an acrylic resin and a naphthoquinone diazide compound (hereinafter sometimes referred to as NQD) (see Patent Documents 2 to 4). However, these materials have insufficient heat resistance, and the cured product is subject to strong coloration upon high-temperature treatment of the substrate.

[0004] Positive-type materials using polyimide are also known as materials with high heat resistance (see Patent Document 5). However, these materials do not have sufficient transparency due to the large light absorption in the polymer, and there is also room for improvement in sensitivity.

[0005] On the other hand, polysiloxane is known as another material having high heat resistance and high transparency, and materials in which NQDs are combined with polysiloxane to impart positive photosensitivity are known (see Patent Documents 6 and 7). These materials have high transparency, and the transparency does not decrease even when the substrate is treated at high temperatures, making it possible to obtain a cured product with high transparency.

[0006] In recent years, efforts to improve throughput in the production of liquid crystal displays and organic electroluminescent displays have led to a demand for higher sensitivity in positive-tone photosensitive compositions used as materials. In photosensitive systems using naphthoquinone diazide, such as those mentioned above, the addition of an NQD-based photosensitizer reduces the composition's alkaline solubility (dissolution inhibition), thereby increasing developer resistance in unexposed areas. Meanwhile, in exposed areas, naphthoquinone diazide is converted to indene carboxylic acid, increasing developer solubility. This difference in solubility between exposed and unexposed areas in alkaline developer is utilized for patterning. To achieve high sensitivity and high film retention, it is essential to select a photosensitizer that can adequately balance the solubility of the exposed and unexposed areas. In other words, a highly sensitive photosensitizer must be used that exhibits sufficient dissolution inhibition in alkaline developer in unexposed areas due to the interaction between the photosensitizer and resin, while efficiently decomposing even with low light exposure in exposed areas and exhibiting sufficient alkaline solubility in exposed areas.

[0007] To solve this problem, photosensitizers in which the hydroxyl groups of hydroxybenzophenone-based or bisphenol-based compounds are esterified with naphthoquinone diazide sulfonic acid halides or the like have been investigated (see Patent Documents 8 and 9). When siloxane materials are combined with these photosensitizers, the alkali dissolution inhibitory properties of the composition are enhanced compared to other materials, resulting in a greater difference in solubility between unexposed and exposed areas, and higher sensitivity can be expected. However, these photosensitizers have not yet achieved the demand for higher sensitivity that has arisen in recent years due to the increasing size of substrates used in the manufacture of liquid crystal displays and organic EL displays and the need to reduce manufacturing costs.

[0008] Furthermore, due to the characteristics of polysiloxane, there is a problem in that the molecular weight of the polymer changes due to a bias in the equilibrium reaction of condensation between Si-OH groups or cleavage of Si-O-Si bonds, which affects the storage stability of the composition.

[0009] In other words, it can be said that a positive-working photosensitive material containing polysiloxane is required to have a photosensitizer that is excellent in the ability to inhibit dissolution of unexposed areas and also improves the storage stability of polysiloxane.

[0010] Japanese Patent Laid-Open No. 9-152625 Japanese Patent Laid-Open No. 2001-281853 Japanese Patent Laid-Open No. 5-165214 Japanese Patent Laid-Open No. 2002-341521 Japanese Patent Laid-Open No. 2001-5179 Japanese Patent Laid-Open No. 2006-178436 Japanese Patent Laid-Open No. 2009-211033 Japanese Patent Laid-Open No. 64-6947 Japanese Patent Laid-Open No. 3-20743

[0011] The present invention has been made in view of the above circumstances, and provides a positive photosensitive composition which has high sensitivity, patterning performance with a high film remaining rate, and also has high storage stability.

[0012] Another object of the present invention is to provide a cured product formed from the above-mentioned photosensitive composition and usable as a planarizing film for a TFT substrate, an interlayer insulating film, a core or clad material, etc., and to provide devices such as a display device, a semiconductor device, and an optical waveguide that have the cured product.

[0013] That is, the present invention is a positive photosensitive resin composition containing (a) a polysiloxane and (b) a naphthoquinone diazide compound represented by formula (1).

[0014]

[0015] (In the formula, R １ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazide sulfonyl group represented by the following structure or a hydrogen atom. In formula (1), at least one Q among all Qs is a naphthoquinone diazide sulfonyl group. n represents an integer of 0 to 4, and m represents an integer of 4 to 8. X represents a tetravalent to octavalent organic group having 4 to 30 carbon atoms.

[0016]

[0017] (In the above structure, * represents the binding site.)

[0018] The positive photosensitive resin composition of the present invention has patterning performance with high sensitivity and high film retention rate, and also has high storage stability.

[0019] The present invention provides a positive-type photosensitive resin composition containing (a) a polysiloxane (hereinafter, may be referred to as “component (a)”) and (b) a naphthoquinone diazide compound represented by formula (1) (hereinafter, may be referred to as “component (b)”).

[0020]

[0021] (In formula (1), R １ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazide sulfonyl group represented by the following structure or a hydrogen atom. In formula (1), at least one Q among all Qs is a naphthoquinone diazide sulfonyl group. n represents an integer of 0 to 4, and m represents an integer of 4 to 8. X represents a tetravalent to octavalent organic group having 4 to 30 carbon atoms.

[0022]

[0023] (In the above structure, * represents a bonding site.) A positive-type photosensitive resin composition containing component (b) has positive photosensitivity such that exposed areas are removed by a developer. Furthermore, the interaction between component (b) and component (a) inhibits dissolution in unexposed areas.

[0024] The photosensitive composition of the present invention contains (a) a polysiloxane. Known polysiloxanes can be used as component (a).

[0025] Specifically, (a) polysiloxane may have one or more repeating structural units selected from the group consisting of repeating structural units represented by formulas (2) to (7). Such structures are incorporated into the polymer structure by mixing and reacting with one or more silanes represented by formula (8).

[0026]

[0027]

[0028] R ２ R each independently represents a hydrogen atom, a monovalent saturated aliphatic group having 1 to 10 carbon atoms, a monovalent unsaturated aliphatic group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. ３each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. p represents an integer of 0 to 2.

[0029] R in formula (8) ２ The monovalent saturated aliphatic groups having 1 to 10 carbon atoms, the monovalent unsaturated aliphatic groups having 2 to 10 carbon atoms, and the aryl groups having 6 to 15 carbon atoms mentioned above may all have a substituent, or may be unsubstituted. Furthermore, in the case of a monovalent saturated aliphatic group or a monovalent unsaturated aliphatic group, an ether group, a thioether group, an ester group, an amide group, or the like may be inserted into the structure, and this can be selected depending on the properties of the composition.

[0030] Specific examples of the monovalent saturated aliphatic group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, an n-decyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a (3-alkyloxetan-3-yl)methoxyalkyl group, an aminopropyl group, a 3-mercaptopropyl group, and a 3-isocyanatopropyl group.

[0031] Specific examples of the monovalent unsaturated aliphatic group having 2 to 10 carbon atoms include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.

[0032] Specific examples of the aryl group having 6 to 15 carbon atoms include a phenyl group, a tolyl group, a p-styryl group, a p-methoxyphenyl group, a p-hydroxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group, a 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group, and a naphthyl group.

[0033] R in formula (8) ３The alkyl groups and acyl groups mentioned above may have a substituent or may be unsubstituted, and can be selected depending on the properties of the composition. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, and n-butyl groups. Specific examples of acyl groups include acetyl groups. Specific examples of aryl groups include phenyl groups.

[0034] In formula (8), p represents an integer of 0 to 2. When p=0, it is a tetrafunctional silane, when p=1, it is a trifunctional silane, and when p=2, it is a difunctional silane.

[0035] Specific examples of silanes that can be used in the synthesis of component (a) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane. silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,Examples of such silanes include trifunctional silanes such as (4-epoxycyclohexyl)ethyltrimethoxysilane, (3-ethyl-3-((3-(trimethoxysilyl)propoxy)methyl)oxetane, (oxetan-3-yl)methyltrimethoxysilane, (oxetan-3-yl)methyltriethoxysilane, (oxetan-3-yl)methyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, phenyltrimethoxysilane, p-styryltrimethoxysilane, and p-methoxyphenyltrimethoxysilane; and bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, and diphenyldimethoxysilane.

[0036] Among these silanes, trifunctional silanes are preferred in terms of crack resistance and hardness of the cured product. These silanes may be used alone or in combination of two or more. Monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane may also be used as end-capping agents.

[0037] From the viewpoint of improving storage stability, component (a) has either or both of a repeating structural unit having an epoxy group and a repeating structural unit having an oxetane group, and the total amount of the repeating structural unit having an epoxy group and the repeating structural unit having an oxetane group relative to 100 mol % of all repeating structural units of component (a) is preferably 1 to 8 mol %, and more preferably 3 to 6 mol %.

[0038] Preferred examples of the repeating structural unit having an epoxy group and the repeating structural unit having an oxetane group include structures represented by the following general formulas (9) to (11).

[0039]

[0040] In the above general formulas (9) to (11), q １ ~q ３ represents an integer of 1 to 5. From the viewpoint of increasing sensitivity, q １ ~q ３ is preferably an integer of 1 to 3.

[0041] In the above general formula (11), R ４ represents hydrogen or a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. ４ is preferably hydrogen, a methyl group, or an ethyl group.

[0042] Specific examples of silanes that can be used in the synthesis of component (a) to incorporate these structural units include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-ethyl-3-((3-(trimethoxysilyl)propoxy)methyl)oxetane), (oxetan-3-yl)methyltrimethoxysilane, (oxetan-3-yl)methyltriethoxysilane, and (oxetan-3-yl)methyltriacetoxysilane.

[0043] Furthermore, from the viewpoint of expecting an improved dissolution suppression effect through π-π stacking with the photosensitizer and achieving high sensitivity, the (a) polysiloxane has a repeating structural unit having an aromatic group, and the (a) polysiloxane preferably has 60 mol% or more of the repeating structural units having the aromatic group relative to 100 mol% of all repeating structural units constituting the (a) polysiloxane. More preferably, it is 70 mol% or more. Furthermore, it is even more preferably 90 mol% or less. There is no particular upper limit to the proportion of the repeating structural units having the aromatic group, and it may account for 100 mol%.

[0044] Specific examples of the repeating structural unit having an aromatic group include repeating structural units having a phenyl group, a tolyl group, a p-styryl group, a p-methoxyphenyl group, a p-hydroxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group, a 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group, a naphthyl group, and the like. Specific examples of silanes for incorporating the repeating structural unit into (a) polysiloxane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, p-hydroxyphenyltrimethoxysilane, p-hydroxyphenyltriethoxysilane, 2-(p-hydroxyphenyl)trimethoxysilane, 2-(p-hydroxyphenyl)triethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltriethoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, p-styryltrimethoxysilane, and p-methoxyphenyltrimethoxysilane.

[0045] From the viewpoint of enhancing sensitivity by promoting crosslinking between polysiloxanes, three-dimensionally interacting with the photosensitizer, and enhancing the dissolution suppression effect in the unexposed areas, the (a) polysiloxane has a repeating structural unit having an ethylenically unsaturated group, and the (a) polysiloxane preferably has the repeating structural unit having the ethylenically unsaturated group in a range of 10 mol% to 70 mol%, more preferably 20 mol% to 70 mol%, relative to 100 mol% of all repeating structural units constituting the (a) polysiloxane. When the content of the repeating structural unit having an ethylenically unsaturated group is 70 mol% or less, it is possible to suppress the generation of residues in the removal pattern during development, and when the ethylenically unsaturated group is 10 mol% or more, a sufficient dissolution suppression effect is obtained.

[0046] Specific examples of the repeating structural unit having an ethylenically unsaturated group include a vinyl group, a methacryl group, and an acrylic group. To incorporate the repeating structural unit into (a) polysiloxane, the following silanes or the like may be polymerized. Examples of silanes having an ethylenically unsaturated group include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, with vinyltrimethoxysilane, vinyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane being preferred.

[0047] In particular, from the viewpoint of three-dimensionally interacting with the photosensitizer and further improving the dissolution-inhibiting effect through π-π stacking with the photosensitizer to thereby achieve high sensitivity, the (a) polysiloxane has a repeating structural unit having a styryl group, and the (a) polysiloxane preferably has the repeating structural unit having the styryl group in a range of 10 mol% to 70 mol%, and more preferably in a range of 30 mol% to 70 mol%, relative to 100 mol% of all repeating structural units constituting the (a) polysiloxane. When the content of the repeating structural unit having a styryl group is 70 mol% or less, it is possible to suppress the generation of residues in the removal pattern during development, and when the styryl group is 10 mol% or more, a sufficient dissolution-inhibiting effect is obtained.

[0048] Specific examples of the partial structure containing a styryl group in the repeating structural unit having a styryl group include a 4-vinylphenyl group (p-styryl group), a 3-vinylphenyl group (m-styryl group), a 2-vinylphenyl group (o-styryl group), and a 4-vinylphenylmethylene group.

[0049] (a) Specific examples of silanes for incorporating the repeating structural unit having a styryl group into polysiloxane by polymerization include styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane, styryltri(propoxy)silane, styryltri(butoxy)silane, styrylmethyldimethoxysilane, styrylethyldimethoxysilane, styrylmethyldiethoxysilane, and styrylmethyldi(methoxyethoxy)silane, with styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, and styrylethyldimethoxysilane being preferred.

[0050] In addition, when one repeating unit in component (a) contains two or more of an "aromatic group," an "ethylenically unsaturated group," a "styryl group," an "epoxy group," an "oxetane group," or a "dicarboxylic acid group" described below, the amount of the structural unit relative to 100 mol% of all repeating structural units in component (a) is counted independently as a structural unit containing the above groups. For example, a structural unit containing a styryl group is counted as a structural unit containing an aromatic group, a structural unit containing an ethylenically unsaturated group, or a structural unit containing a styryl group.

[0051] From the viewpoint of increasing the dissolution rate of the polysiloxane and further increasing the sensitivity, the polysiloxane (a) has a repeating structural unit having a dicarboxylic acid group, and the amount of the repeating structural unit having a dicarboxylic acid group relative to 100 mol% of all repeating structural units in component (a) is preferably 1 mol% or more, more preferably 1.5 mol% or more, more preferably 20 mol% or less, and most preferably 7 mol% or less.

[0052] Here, the term "dicarboxylic acid group" refers to a partial structure in which a carboxyl group is bonded to each of two adjacent carbon atoms, such as the structure shown below. The bond between the two adjacent carbon atoms may be a single bond, a double bond, or part of an aromatic ring.

[0053]

[0054] (a) Specific examples of silanes for incorporating a repeating structural unit having a dicarboxylic acid group into a polysiloxane by polymerization include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, and 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride. 3-trimethoxysilylpropyl succinic anhydride and 3-triethoxysilylpropyl succinic anhydride are preferred. These acid anhydrides undergo ring-opening during polymerization, making it possible to easily incorporate a dicarboxylic acid group into the polysiloxane.

[0055] The weight average molecular weight (Mw) of the polysiloxane (a) used in the present invention is not particularly limited, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, in terms of polystyrene, as measured by GPC (gel permeation chromatography). If the Mw is less than 1,000, the coating properties will be poor, and if it is more than 100,000, the solubility in the developer during pattern formation will be poor.

[0056] The polysiloxane (a) of the present invention can be obtained by hydrolyzing and partially condensing the above-mentioned silane. Conventional methods can be used for the hydrolysis and partial condensation. For example, a solvent, water, and optionally a catalyst are added to the mixture, followed by heating and stirring. During stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) can be removed by distillation, if necessary.

[0057] The reaction solvent is not particularly limited, but typically the same solvent as used in the composition is used. The amount of solvent added is preferably 10 to 1000% by weight per 100% by weight of the total amount of silane or silane and silica particles. The amount of water added in the hydrolysis reaction is preferably 0.5 to 2 mol per 1 mol of hydrolyzable group.

[0058] The catalyst added as needed is not particularly limited, but acid catalysts and base catalysts are preferably used. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Specific examples of base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having amino groups, and ion exchange resins. The amount of catalyst added is preferably 0.01 to 10% by weight based on 100% by weight of silane.

[0059] Furthermore, from the viewpoint of coating properties and storage stability, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain by-product alcohol, water, or catalyst. These may be removed as needed. The removal method is not particularly limited. A preferred method for removing alcohol and water is to dilute the polysiloxane solution with an appropriate hydrophobic solvent, wash the solution with water several times, and then concentrate the resulting organic layer using an evaporator. Furthermore, a method for removing the catalyst can be used in addition to the above-mentioned water washing, or separately, by treating the solution with an ion exchange resin.

[0060] The positive photosensitive resin composition of the present invention contains a naphthoquinone diazide compound (component (b)) represented by formula (1).

[0061]

[0062] (In formula (1), R １ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazide sulfonyl group represented by the following structure or a hydrogen atom. In formula (1), at least one Q out of all Qs is a naphthoquinone diazide sulfonyl group. n represents an integer of 0 to 4, and m represents an integer of 4 to 8. X represents a tetravalent to octavalent organic group having 4 to 30 carbon atoms.

[0063]

[0064] (In the above structure, * represents a bonding site.) Component (b) has a structure represented by formula (1). When component (b) contains at least one naphthoquinone diazide sulfonyl group in formula (1), component (b) and the silanol groups in polysiloxane (a) interact with each other, making it possible to improve the effect of inhibiting dissolution of unexposed areas. As a result, the difference in solubility between unexposed and exposed areas increases, enabling pattern processing with higher sensitivity and a higher film retention rate. Furthermore, by interacting with Si-OH groups in the polysiloxane, condensation of silanol groups is inhibited, suppressing changes in molecular weight and improving storage stability.

[0065] The naphthoquinone diazide sulfonyl group for Q in formula (1) represents a basic skeleton, and is permitted to have a substituent, such as a saturated aliphatic group having 1 to 2 carbon atoms, such as a methyl group, an ethyl group, or a methoxy group, to the extent that it does not inhibit the development of alkali solubility in the composition after exposure or inhibit the interaction with component (a).

[0066] In formula (1), R １ represents an alkyl group having 1 to 8 carbon atoms. １ However, when the compound has an alkyl group having 1 to 8 carbon atoms, it becomes moderately hydrophilic, and the solubility of the exposed area in an alkaline developer is improved, thereby improving the sensitivity. １ is preferably an alkyl group having 1 to 3 carbon atoms. From the viewpoint of further improving sensitivity, in formula (1), n ​​is 1 or 2, and R １ is preferably attached at the ortho position relative to the -OQ group.

[0067] Furthermore, from the viewpoint of improving storage stability, it is preferable that the average esterification rate of component (b) is 75% or more, that is, when all of Q in formula (1) contained in component (b) is taken as 100 mol %, 75 mol % or more of Q are naphthoquinone diazide sulfonyl groups.

[0068] In the formula (1), the value of m is preferably 4 to 6, and more preferably 4, from the viewpoint of improving the sensitivity and storage stability due to the improved dissolution inhibiting effect.

[0069] As specific examples of the component (b) that satisfy these requirements, the following can be given as examples.

[0070]

[0071] In the compound represented by the above structure, 75 mol % or more of Q are groups represented by the following formula, and the remaining Q are hydrogen atoms.

[0072]

[0073] (In the above structure, * represents a bonding site.) Furthermore, from the viewpoint of improving sensitivity and storage stability due to an improved dissolution inhibiting effect, it is more preferable that X in the formula (1) contains an alicyclic skeleton.

[0074] In the positive-type photosensitive resin composition of the present invention, the content of component (b) is not particularly limited, but is preferably 1 to 85 parts by weight, more preferably 1 to 60 parts by weight, and even more preferably 1 to 30 parts by weight, per 100 parts by weight of component (a). When the content of component (b) is 1 part by weight or more, the residual film rate of the unexposed area increases. On the other hand, when the content of component (b) is 85 parts by weight or less, the light transmittance of the cured product can be maintained at a high level.

[0075] In particular, when component (a) has a repeating structural unit having a dicarboxylic acid group, from the viewpoint of achieving high sensitivity, when the number of moles of dicarboxylic acid groups in component (a) is M1 (mol) and the number of moles of naphthoquinone diazide groups contained in component (b) is M2 (mol), the ratio M1 / M2 is preferably 0.2 to 2.5, and more preferably 0.5 to 2.5.

[0076] The values ​​of M1 and M2 can be determined from the amount of the silane compound blended when synthesizing component (a), and the amounts of the solution of component (a) and component (b) blended when preparing a positive photosensitive resin composition. For example, a positive photosensitive resin composition containing a solution (weight of polysiloxane solids equivalent to Z5×T2 / 100(g)) extracted from a polysiloxane solution (total weight Z4(g), solid concentration T2(%)) synthesized by adding Z1, Z2, and Z3 moles of methyltrimethoxysilane, phenyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride, respectively, and having a ring-opening rate of 3-trimethoxysilylpropylsuccinic anhydride of T1(%), and a naphthoquinone diazide compound Y(g) of general formula (1) in which m=4, the proportion of naphthoquinone diazide sulfonyl groups in Q is T3 (mol %), and molecular weight M, can be determined as follows: M1 = Z3 x T1 / 100 x Z5 / Z4 M2 = Y / M x m x T3 / 100.

[0077] Specifically, in the case of a positive photosensitive resin composition containing 10 g of a polysiloxane solution having a total weight of 406 g, a solids concentration of 52 wt%, and a ring-opening rate of the succinic anhydride structure of 95%, synthesized by adding 0.672 mol of methyltrimethoxysilane, 0.672 mol of phenyltrimethoxysilane, and 0.336 mol of 3-trimethoxysilylsuccinic anhydride in a solvent, and 0.5 g of a naphthoquinone diazide compound (molecular weight 1328.5) having the following structure, the following relationships are obtained: M1 = 0.336 × 95 / 100 × 10 / 406 = 0.00786 M2 = 0.5 / 1328.5 × 4 × 75 / 100 = 0.00113 M1 / M2 = 6.96

[0078]

[0079] The cured product of the present invention will now be described. The cured product of the present invention is a cured product obtained by heat-treating the photosensitive resin composition of the present invention.

[0080] A specific example will be given to explain a method for forming a cured product using the positive photosensitive composition of the present invention. The positive photosensitive composition of the present invention is applied to a substrate such as a glass substrate, SiO substrate, SiN substrate, or ITO substrate by a known method such as spinning, dipping, or slitting, and then prebaked using a heating device such as a hot plate or oven. Prebaking is carried out at a temperature in the range of 50 to 150°C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 μm.

[0081] After pre-baking, a UV-visible exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA) is used to expose the film to 10 to 200 mJ / cm. ２ (equivalent to an exposure dose at a wavelength of 405 nm) is subjected to patterning exposure through a desired mask.

[0082] After patterning exposure, the exposed areas are dissolved by development, yielding a pattern. Development is preferably performed by immersion in a developer for 5 seconds to 10 minutes using methods such as showering, dipping, or puddling. Known alkaline developers can be used as the developer. Specific examples include aqueous solutions containing one or more of inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and quaternary ammonium salts such as TMAH (tetramethylammonium hydroxide) and choline. Among these, an aqueous TMAH solution is preferred, as it is an organic alkali that is free from the risk of metal ion contamination and is a strong alkali. A TMAH solution is generally preferably used at a concentration of 0.20 to 2.38 wt % in view of the solubility of phenolic hydroxyl groups, silanol groups, and carboxyl groups in alkalis.

[0083] After development, it is preferable to rinse with water, and then dry bake may be carried out at a temperature in the range of 50 to 150°C.

[0084] The film is then thermally cured for approximately 1 hour at a temperature in the range of 150 to 300°C using a heating device such as a hot plate or oven. The resolution is preferably 10 µm or less. The cured product of the present invention can be used as a planarizing film for TFTs in display devices, an interlayer insulating film in semiconductor devices, or a core or clad material in optical waveguides.

[0085] The display device of the present invention includes a first electrode formed on a substrate, an insulating layer formed on the first electrode so as to partially expose the first electrode, and a second electrode provided opposite the first electrode, wherein the insulating layer includes the above-described cured product. In particular, the display device is preferably a display device including a planarizing film provided in a state of covering irregularities on a substrate on which thin film transistors (TFTs) are formed.

[0086] The present invention will be described below using examples, but the present invention is not limited to these examples. Among the compounds used in the examples, those using abbreviations are shown below. DAA: diacetone alcohol PGME: propylene glycol monomethyl ether The solids concentration of the polysiloxane solution and the ring-opening rate of succinic acid were determined as follows.

[0087] (1) Measurement of solids concentration of polysiloxane solution 1 g of the polysiloxane solution was weighed out in an aluminum cup and heated on a hot plate at 250° C. for 30 minutes to evaporate the liquid. The solids remaining in the aluminum cup after heating were weighed to determine the solids concentration of the polysiloxane solution.

[0088] (2) Succinic Acid Ring Opening Rate This was determined by measuring the proton NMR of the polysiloxane solution.

[0089] Synthesis Example 1 Synthesis of Polysiloxane (PS-1) Solution 91.53 g (0.672 mol) of methyltrimethoxysilane, 166.57 g (0.840 mol) of phenyltrimethoxysilane, 41.40 g (0.168 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 183.57 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous solution of phosphoric acid prepared by dissolving 0.599 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and then heated and stirred for 2 hours (internal temperature: 100-110 ° C.), to obtain a polysiloxane (PS-1) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 L / min. A total of 203 g of by-products, methanol and water, was distilled off during the reaction. The solids concentration of the resulting polysiloxane (PS-1) solution was 52 wt %.

[0090] Synthesis Example 2 Synthesis of Polysiloxane (PS-2) Solution 68.64 g (0.504 mol) of methyltrimethoxysilane, 199.89 g (1.01 mol) of phenyltrimethoxysilane, 41.40 g (0.168 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 194.01 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous solution of phosphoric acid prepared by dissolving 0.620 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature: 100-110 ° C.), to obtain a polysiloxane (PS-2) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 L / min. A total of 197 g of by-products, methanol and water, was distilled off during the reaction. The solids concentration of the resulting polysiloxane (PS-2) solution was 53 wt %.

[0091] Synthesis Example 3 Synthesis of Polysiloxane (PS-3) Solution Into a 1000 ml three-neck flask, 68.64 g (0.504 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.1 g (0.504 mol) of p-styryltrimethoxysilane, 41.40 g (0.168 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were added. －３ mol), 207.11 g of DAA was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.323 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-3) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 208.1 g of by-products, methanol and water, was distilled during the reaction. The solids concentration of the resulting polysiloxane (PS-3) solution was 50 wt%.

[0092] Synthesis Example 4 Synthesis of Polysiloxane (PS-4) Solution Into a 1000 ml three-neck flask, 86.95 g (0.638 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.1 g (0.504 mol) of p-styryltrimethoxysilane, 8.81 g (0.0336 mol) of 3-trimethoxysilylsuccinic anhydride, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were placed. －３mol), 193.44 g of DAA was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.309 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-4) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 188.89 g of by-products, methanol and water, were distilled during the reaction. The ring-opening rate of the succinic anhydride structure of the resulting polysiloxane (PS-4) solution was 95%, the total weight of the solution was 404.94 g, and the solids concentration was 52 wt%.

[0093] Synthesis Example 5 Synthesis of Polysiloxane (PS-5) Solution 114.42 g (0.840 mol) of methyltrimethoxysilane, 166.56 g (0.840 mol) of phenyltrimethoxysilane, and 171.42 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous phosphoric acid solution prepared by dissolving 0.556 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40 ° C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110 ° C), yielding a polysiloxane (PS-5) solution. During heating and stirring, dry nitrogen was flowed at 0.070 L / min. A total of 199 g of by-product methanol and water was distilled during the reaction. The solids concentration of the resulting polysiloxane (PS-5) solution was 52% by weight.

[0094] Synthesis Example 6 Synthesis of Polysiloxane (PS-6) Solution 109.85 g (0.806 mol) of methyltrimethoxysilane, 166.57 g (0.840 mol) of phenyltrimethoxysilane, 8.28 g (0.0336 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 174.10 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous phosphoric acid solution prepared by dissolving 0.564 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature: 100-110 ° C.), yielding a polysiloxane (PS-6) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 L / min. A total of 200 g of by-products, methanol and water, were distilled off during the reaction. The solids concentration of the resulting polysiloxane (PS-6) solution was 52 wt %.

[0095] Synthesis Example 7 Synthesis of Polysiloxane (PS-7) Solution 96.12 g (0.706 mol) of methyltrimethoxysilane, 166.57 g (0.840 mol) of phenyltrimethoxysilane, 33.11 g (0.134 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 187.11 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous phosphoric acid solution prepared by dissolving 0.607 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature: 100-110 ° C.), yielding a polysiloxane (PS-7) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 L / min. A total of 198 g of by-products, methanol and water, was distilled off during the reaction. The solids concentration of the resulting polysiloxane (PS-7) solution was 52 wt %.

[0096] Synthesis Example 8 Synthesis of Polysiloxane (PS-8) Solution 80.10 g (0.588 mol) of methyltrimethoxysilane, 199.88 g (1.008 mol) of phenyltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 186.99 g of DAA were charged into a 1000 ml three-neck flask, and an aqueous solution of phosphoric acid prepared by dissolving 0.606 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature: 100-110 ° C.), yielding a polysiloxane (PS-8) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 L / min. A total of 203 g of by-products, methanol and water, was distilled off during the reaction. The solids concentration of the resulting polysiloxane (PS-8) solution was 52 wt %.

[0097] Synthesis Example 9 Synthesis of Polysiloxane (PS-9) Solution Into a 1000 ml three-neck flask, 80.10 g (0.588 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.06 g (0.504 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were added. －３ mol), 189.71 g of DAA was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.309 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-9) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 199 g of by-products, methanol and water, was distilled during the reaction. The solids concentration of the resulting polysiloxane (PS-3) solution was 52 wt%.

[0098] Synthesis Example 10 Synthesis of Polysiloxane (PS-10) Solution Into a 1000 ml three-neck flask, 57.21 g (0.420 mol) of methyltrimethoxysilane, 33.31 g (0.168 mol) of phenyltrimethoxysilane, 226.12 g (1.01 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 1.130 g (5.14 × 10) of dibutylhydroxytoluene were added. －３ mol), and 213.29 g of DAA were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.348 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-10) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 197 g of by-products, methanol and water, were distilled during the reaction. The solids concentration of the resulting polysiloxane (PS-10) solution was 52 wt%.

[0099] Synthesis Example 11 Synthesis of Polysiloxane (PS-11) Solution Into a 1000 ml three-neck flask, 11.44 g (0.084 mol) of methyltrimethoxysilane, 33.31 g (0.168 mol) of phenyltrimethoxysilane, 301.50 g (1.344 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 1.507 g (6.85 × 10) of dibutylhydroxytoluene were added. －３mol), and 236.00 g of DAA were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.385 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-11) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 202 g of by-products, methanol and water, were distilled during the reaction. The solids concentration of the resulting polysiloxane (PS-11) solution was 52 wt%.

[0100] Synthesis Example 12 Synthesis of Polysiloxane (PS-12) Solution Into a 1000 ml three-neck flask, 75.52 g (0.554 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.1 g (0.504 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 8.81 g (0.0336 mol) of 3-trimethoxysilylsuccinic anhydride, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were added. －３ mol), 197.77 g of DAA was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.322 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-12) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 195.43 g of by-products, methanol and water, was distilled out during the reaction. The ring-opening rate of the succinic anhydride structure in the resulting polysiloxane (PS-12) solution was 95%, the total weight of the solution was 412.02 g, and the solids concentration was 52 wt%.

[0101] Synthesis Example 13 Synthesis of Polysiloxane (PS-13) Solution Into a 1000 ml three-neck flask, 68.65 g (0.504 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.1 g (0.504 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 22.04 g (0.084 mol) of 3-trimethoxysilylsuccinic anhydride, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were added. －３ mol), and 205.95 g of DAA were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.336 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-13) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 192.95 g of by-products, methanol and water, were distilled during the reaction. The ring-opening rate of the succinic anhydride structure in the resulting polysiloxane (PS-13) solution was 95%, the total weight of the solution was 429.05 g, and the solids concentration was 52 wt%.

[0102] Synthesis Example 14 Synthesis of polysiloxane (PS-14) solution Into a 1000 ml three-neck flask, 57.21 g (0.420 mol) of methyltrimethoxysilane, 99.94 g (0.504 mol) of phenyltrimethoxysilane, 113.1 g (0.504 mol) of p-styryltrimethoxysilane, 20.70 g (0.084 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 44.07 g (0.168 mol) of 3-trimethoxysilylsuccinic anhydride, and 0.5652 g (2.57 × 10) of dibutylhydroxytoluene were added. －３mol), 208.34 g of DAA was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.340 g of phosphoric acid in 90.72 g of water was added over 15 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 120°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature: 100-110°C), yielding a polysiloxane (PS-14) solution. During heating and stirring, air was flowed at 0.070 L / min. A total of 200.95 g of by-products, methanol and water, was distilled out during the reaction. The resulting polysiloxane (PS-14) solution had a ring-opening rate of 95% for the succinic anhydride structure, a total solution weight of 434.04 g, and a solids concentration of 52 wt%.

[0103] Synthesis Example 15: Synthesis of naphthoquinone diazide compound (QD-1) Under a dry nitrogen stream, 8.65 g (0.015 mol) of TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 10.48 g (0.039 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 66.5 g of acetone and the solution was allowed to reach room temperature. 9.11 g (0.09 mol) of triethylamine mixed with 10 g of acetone was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 23°C for 30 minutes. 5.32 g of 35% HCl was added to neutralize the mixture. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain naphthoquinone diazide compound (QD-1) having the following structure.

[0104]

[0105] In the above structure, * represents the binding site.

[0106] Synthesis Example 16: Synthesis of naphthoquinone diazide compound (QD-2) Under a dry nitrogen stream, 9.49 g (0.015 mol) of TEOC-BOCP (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.) and 10.48 g (0.039 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 69.9 g of acetone and the solution was allowed to reach room temperature. 9.11 g (0.09 mol) of triethylamine mixed with 10 g of acetone was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 23°C for 30 minutes. 5.32 g of 35% HCl was added to neutralize the mixture. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-2) having the following structure.

[0107]

[0108] In the above structure, * represents the binding site.

[0109] Synthesis Example 17 Synthesis of naphthoquinone diazide compound (QD-3) Under a dry nitrogen stream, 9.49 g (0.015 mol) of TEOC-BOCP (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.) and 12.09 g (0.045 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 67.3 g of acetone and the solution was allowed to reach room temperature. 9.11 g (0.090 mol) of triethylamine mixed with 10 g of acetone was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 23°C for 30 minutes. 6.26 g of 35% HCl was added to neutralize the mixture. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-3) having the following structure.

[0110]

[0111] In the above structure, * represents the binding site.

[0112] Synthesis Example 18 Synthesis of naphthoquinone diazide compound (QD-4) Under a dry nitrogen stream, 15.32 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 23.11 g (0.086 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. To this solution, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain naphthoquinone diazide compound (QD-4) having the following structure.

[0113]

[0114] In the above structure, * represents the binding site.

[0115] Synthesis Example 19: Synthesis of naphthoquinone diazide compound (QD-5) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 29.56 g (0.11 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. To this solution, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain naphthoquinone diazide compound (QD-5) having the following structure.

[0116]

[0117] In the above structure, * represents the binding site.

[0118] Example 1 Under yellow light, 0.671 g of naphthoquinone diazide compound (QD-1) (10 parts by weight relative to 100 parts by weight of polysiloxane solids) was dissolved in 4.84 g of DAA and 10.9 g of PGME, and then 12.9 g of polysiloxane (PS-1) solution was added and stirred. The mixture was then filtered through a 0.45 μm filter to obtain a positive photosensitive composition (PP-1). The prepared positive photosensitive composition (PP-1) was spin-coated onto a glass substrate (OA-10 manufactured by Nippon Electronic Glass Co., Ltd.) at an arbitrary rotation speed using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then pre-baked at 100 ° C. for 3 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film with a film thickness of 1.5 μm. The prepared prebaked film was irradiated with 200, 300, and 400 mJ / cm using a parallel light mask aligner (PLA-501F manufactured by Canon Inc., hereinafter referred to as PLA) and a gray scale mask. ２ The film was irradiated with a 405 nm wavelength equivalent exposure dose. The grayscale mask is a mask that allows exposure from above the mask to a range of 1% to 100% in a single step. The film was then shower-developed with a 2.38 wt % TMAH aqueous solution for 90 seconds using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), and then rinsed with water for 30 seconds. Next, the entire film was exposed to a 200, 300, and 400 mJ / cm ultra-high pressure mercury lamp using PLA. ２ The coating was then exposed to light (equivalent to an exposure dose at a wavelength of 405 nm) and then cured in air at 230° C. for 1 hour using an oven (IHPS-222, manufactured by Espec Corporation) to produce a cured product.

[0119] The following measurements were carried out on this cured product.

[0120] (1) Film Thickness Measurement Using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the thickness of the prebaked film and the cured product was measured at a refractive index of 1.55.

[0121] (2) Film Remaining Rate The film remaining rate is calculated by applying a composition to a glass substrate, pre-baking it on a hot plate at 100°C for 180 seconds, and then developing it. The film remaining rate is calculated by the following formula: Film remaining rate (%) = (ii) × 100 / (i), where i is the film thickness after pre-baking (µm) and ii is the film thickness of the unexposed portion after development (µm).

[0122] (3) Sensitivity The film is shower developed with a 2.38 wt % TMAH aqueous solution for 90 seconds, rinsed with water for 30 seconds, and baked in an oven at 230° C. for 1 hour. After baking, the exposure dose at which a 20 μm line and space pattern is resolved at a 1:1 width (hereinafter referred to as the optimum exposure dose) is determined as the sensitivity.

[0123] (4) Storage Stability A positive-type photosensitive composition was prepared, and the initial sensitivity (Eop(0)) was measured. The composition was then stored for 3 days in an incubator (Cool Incubator KMH-050 (AS ONE Corporation)) at 25°C. Thereafter, the sensitivity (Eop(3)) was measured again to evaluate the storage stability of the composition. The change in sensitivity x (%) was calculated using the following formula, and the evaluation criteria were determined as follows:

[0124] Sensitivity change x (%) = Eop(3) / Eop(0) × 100 A: 120 ≥ x B: 150 ≥ x > 120 C: x > 150 In the above measurement, the initial sensitivity (Eop(0)) was 120 mJ / cm ２ The test piece was judged to be acceptable if the sensitivity change x was B or higher and the test piece was judged to be acceptable if the sensitivity change x was B or higher.

[0125] The details of the composition of Example 1 are shown in Table 1, and the evaluation results are shown in Table 2.

[0126] Examples 2 to 24, Comparative Examples 1 and 2 Positive-type photosensitive compositions (PP-2 to PP-26) were obtained in the same manner as in Example 1, except that the polysiloxane (PS-1 to PS-14) solutions and naphthoquinone diazide compounds (QD-1 to QD-5) were added in the amounts shown in Table 1. Details of the compositions are also shown in Table 1. Each of the obtained compositions was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0127]

[0128]

[0129] In Table 1, the meanings of the terms are as follows:

[0130] Explanation 1: The content (mol %) of repeating structural units having an aromatic group relative to 100 mol % of all repeating structural units constituting the component (a). Explanation 2: The content (mol %) of repeating structural units having an epoxy group relative to 100 mol % of all repeating structural units constituting the component (a). Explanation 3: The content (mol %) of repeating structural units having an ethylenically unsaturated group relative to 100 mol % of all repeating structural units constituting the component (a). Explanation 4: The content (mol %) of repeating structural units having a styryl group relative to 100 mol % of all repeating structural units constituting the component (a). Explanation 5: The content (mol %) of repeating structural units having a dicarboxylic acid group relative to 100 mol % of all repeating structural units constituting the component (a). Explanation 6: The ratio of R to -OQ groups. １ Explanation 7: The content (mol %) of naphthoquinone diazide sulfonyl groups when all of Q in formula (1) contained in component (b) is taken as 100 mol %. Explanation 8: The content (parts by weight) relative to 100 parts by weight of component (a).

[0131]

Claims

1. A positive-type photosensitive resin composition containing (a) a polysiloxane (hereinafter referred to as "component (a)") and (b) a naphthoquinone diazide compound represented by formula (1) (hereinafter referred to as "component (b)"), wherein component (a) has a repeating structural unit having an ethylenically unsaturated group, and the amount of the repeating structural unit having the ethylenically unsaturated group relative to 100 mol % of all repeating structural units of component (a) is 10 mol % or more and 70 mol % or less, and wherein component (b) is a positive-type photosensitive resin composition in which, in formula (1), R 1 is bonded at an ortho position relative to an -OQ group. 【Chemistry 1】 (In formula (1), R １ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazide sulfonyl group represented by the following structure or a hydrogen atom. In formula (1), at least one Q out of all Qs is a naphthoquinone diazide sulfonyl group. n is 1 or 2, and m represents an integer of 4 to 8. X represents a tetravalent to octavalent organic group having 4 to 30 carbon atoms. 【Chemistry 2】 (In the above structure, * represents the binding site.)

2. 2. The positive photosensitive resin composition according to claim 1, wherein the average esterification rate of component (b) is 75% or more.

3. 2. The positive photosensitive resin composition according to claim 1, wherein component (b) contains an alicyclic skeleton in X in formula (1).

4. the component (a) has either or both of a repeating structural unit having an epoxy group and a repeating structural unit having an oxetane group; 2. The positive photosensitive resin composition according to claim 1, wherein the total amount of the repeating structural units having an epoxy group and the repeating structural units having an oxetane group is 1 to 8 mol % relative to 100 mol % of all repeating structural units of component (a).

5. The component (a) has a repeating structural unit having an aromatic group, 2. The positive photosensitive resin composition according to claim 1, wherein the amount of repeating structural units having an aromatic group in component (a) is 60 mol % or more relative to 100 mol % of all repeating structural units in component (a).

6. The component (a) has a repeating structural unit having a styryl group, 6. The positive photosensitive resin composition according to claim 5, wherein the amount of repeating structural units having a styryl group in component (a) is 10 to 70 mol % relative to 100 mol % of all repeating structural units in component (a).

7. The component (a) has a repeating structural unit having a dicarboxylic acid group, 2. The positive photosensitive resin composition according to claim 1, wherein the amount of the repeating structural unit having a dicarboxylic acid group in component (a) is 1 mol % or more relative to 100 mol % of all repeating structural units in component (a).

8. 8. The positive photosensitive resin composition according to claim 7, wherein the ratio M1 / M2 is 0.2 to 2.5, where M1 (mol) is the number of moles of dicarboxylic acid groups in component (a) and M2 (mol) is the number of moles of naphthoquinone diazide groups contained in component (b).

9. A cured product obtained by heat-treating the positive photosensitive resin composition according to claim 1.

10. A display device including a first electrode formed on a substrate, an insulating layer formed on the first electrode so as to partially expose the first electrode, a display function section provided between the partially exposed first electrode and a second electrode described later, which causes an optical change when a voltage is applied, and a second electrode provided opposite the first electrode, A display device, wherein the insulating layer comprises the cured product according to claim 9.

11. A display device comprising a planarization film provided in a state of covering irregularities on a substrate on which thin film transistors (TFTs) are formed, wherein the planarization film comprises the cured product according to claim 9.

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