Positive-type photosensitive resin composition, cured product thereof, and display device comprising the 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

[Technical Field]

[0001] The present invention relates to a photosensitive composition that can be suitably used as a planarizing film and interlayer insulating film for thin-film transistor (TFT) substrates such as liquid crystal displays and organic EL displays, a cured product formed therefrom, and a display device having the cured product. [Background technology]

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

[0003] Materials for planarization films used on TFT substrates generally possess high heat resistance and high transparency, and require the formation of a hole pattern of several micrometers in size to ensure conductivity between the TFT substrate electrodes and the ITO electrodes. Generally, positive-type photosensitive materials are used. Typical materials include those combining acrylic resin with naphthoquinone diazide compounds (hereinafter sometimes referred to as NQD) (see Patent Documents 2-4). However, these materials have insufficient heat resistance, and the cured product becomes strongly discolored when the substrate is subjected to high-temperature treatment.

[0004] Furthermore, 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 high light absorption in the polymer, and there is room for improvement in terms of sensitivity as well.

[0005] On the other hand, polysiloxane is known as another material that possesses high heat resistance and high transparency, and materials that combine it with NQD to impart positive-type photosensitivity (see Patent Documents 6 and 7) are known. These materials have high transparency, and even with high-temperature treatment of the substrate, the transparency does not decrease, and a cured product with high transparency can be obtained.

[0006] In recent years, there has been a demand for higher sensitivity in positive-type photosensitive compositions used as materials, in order to improve throughput in the manufacturing of liquid crystal displays and organic EL displays. In photosensitive systems using naphthoquinone diazide as mentioned above, the addition of NQD-type photosensitive agents reduces the alkali solubility of the composition (dissolution inhibition), resulting in developer resistance in the unexposed areas. On the other hand, in the exposed areas, the naphthoquinone diazide is converted to indene carboxylic acid, increasing solubility in the developer. Patterning is performed by utilizing this difference in solubility in the alkaline developer between the exposed and unexposed areas. To obtain patterning performance with high sensitivity and high residual film rate, the selection of a photosensitive agent that can sufficiently accommodate the difference in solubility between the two is absolutely essential. In other words, a highly sensitive photosensitive agent must be used that, through the interaction between the photosensitive agent and the resin, provides sufficient dissolution inhibition in the unexposed areas against the alkaline developer, while efficiently decomposing even with slight light in the exposed areas, resulting in sufficient alkali solubility.

[0007] To address this problem, photosensitive materials have been investigated in which the hydroxyl groups of hydroxybenzophenone-based or bisphenol-based compounds are esterified with naphthoquinone diazidesulfonic acid halides, etc. (See Patent Documents 8 and 9). When siloxane materials are combined with these photosensitive materials, the alkali dissolution inhibitory ability of the composition works compared to other materials, resulting in a larger difference in solubility between unexposed and exposed areas, and thus higher sensitivity can be expected. However, this has not yet met the demands for higher sensitivity aimed at increasing the size of substrates used in the manufacture of liquid crystal displays and organic EL displays in recent years, and at reducing manufacturing costs.

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

[0009] That is, it can be said that a positive photosensitive material containing polysiloxane requires a photosensitizer that has excellent ability to suppress dissolution in the unexposed area and further improves the storage stability of polysiloxane.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0011] The present invention has been made based on the above circumstances, and provides a positive photosensitive composition having high-sensitivity and high-residual film rate patterning performance and high storage stability.

[0012] Another object of the present invention is to provide a planarization film for a TFT substrate, an interlayer insulating film, a cured product that can be used for a core, a cladding material, etc. formed from the above photosensitive composition, and devices such as a display device, a semiconductor device, and an optical waveguide having the cured product. **Means for Solving the Problems**

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

[0014] **[Chemical Formula]**

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

[0016] **[Chemical Formula]**

[0017] (In the above structure, * represents a bonding site.) **[Advantages of the Invention]**

[0018] The positive photosensitive resin composition of the present invention has patterning performance with high sensitivity and high residual film rate, and also has high storage stability. **[Modes for Carrying Out the Invention]**

[0019] The present invention is a positive-type photosensitive resin composition containing (a) a polysiloxane (hereinafter sometimes referred to as "component (a)") and (b) a naphthoquinone diazide compound represented by formula (1) (hereinafter sometimes referred to as "component (b)").

[0020] [ka]

[0021] (In formula (1), R 1 ¹ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazidosulfonyl group or a hydrogen atom represented by the structure shown below. In formula (1), at least one of the Qs is a naphthoquinone diazidosulfonyl group. n represents an integer from 0 to 4, and m represents an integer from 4 to 8. X represents a 4- to 8 valent organic group having 4 to 30 carbon atoms.

[0022] [ka]

[0023] (In the above structure, * represents a bonding site.) A positive-type photosensitive resin composition containing component (b) has positive-type photosensitivity, where the exposed area is removed by the developer. In addition, the interaction between component (b) and component (a) results in a dissolution-inhibiting effect in the unexposed area.

[0024] The photosensitive composition of the present invention contains (a) a polysiloxane. Component (a) may be one of known types.

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

[0026] [ka]

[0027] [ka]

[0028] R 2 Each of these independently represents one of the following: a hydrogen atom, a monovalent saturated aliphatic group with 1 to 10 carbon atoms, a monovalent unsaturated aliphatic group with 2 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. 3 Each of these independently represents one of the following: a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an acyl group with 1 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms. p represents an integer from 0 to 2.

[0029] R in equation (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 listed above may have substituents, or they may be unsubstituted. Furthermore, in the case of monovalent saturated aliphatic groups or monovalent unsaturated aliphatic groups, ether groups, thioether groups, ester groups, amide groups, etc., may be inserted into the structure, and can be selected according to the properties of the composition.

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

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

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

[0033] R in equation (8) 3 The alkyl and acyl groups listed above may have substituents or may be unsubstituted, and can be selected according to the characteristics 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 equation (8), p represents an integer from 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 bifunctional silane.

[0035] (a)Specific examples of silanes that can be used in the synthesis of the component 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. Lan, 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 trifunctional silanes include 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, p-methoxyphenyltrimethoxysilane, and other trifunctional silanes, as well as difunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, and diphenyldimethoxysilane.

[0036] Of these silanes, trifunctional silanes are preferred due to their crack resistance and hardness in the cured product. These silanes may be used individually or in combination of two or more. Monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane may also be used as end-cap encapsulants.

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

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

[0039] [ka]

[0040] In the general formulas (9) to (11) above, q1 to q3 represent integers from 1 to 5. From the viewpoint of increasing sensitivity, it is preferable that q1 to q3 be integers from 1 to 3.

[0041] In the above general formula (11), R 4 This represents hydrogen or a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. From the perspective of increasing sensitivity, R 4 The preferred component is hydrogen, a methyl group, or an ethyl group.

[0042] Specific examples of silanes that can be used in the synthesis of component (a) for incorporating 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 improving the dissolution inhibition effect through π-π stacking with the photosensitive agent and thereby increasing sensitivity, it is preferable that the (a) polysiloxane has repeating structural units having aromatic groups, and that the (a) polysiloxane has 60 mol% or more of the repeating structural units having aromatic groups relative to 100 mol% of the total repeating structural units constituting the (a) polysiloxane. More preferably, it is 70 mol% or more. It is even more preferable that it is 90 mol% or less. There is no particular upper limit to the proportion of repeating structural units having aromatic groups, and it may account for 100 mol%.

[0044] Specific examples of repeating structural units having the aforementioned 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 above repeating structural units 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 increasing sensitivity by promoting crosslinking between polysiloxanes, interacting with the photosensitive agent in three dimensions, and enhancing the dissolution inhibition effect of unexposed areas, the (a) polysiloxane has repeating structural units having ethylenically unsaturated groups, and it is preferable that the (a) polysiloxane contains 10 mol% to 70 mol% of the repeating structural units having ethylenically unsaturated groups, and more preferably 20 mol% to 70 mol%, based on 100 mol% of the total repeating structural units constituting the (a) polysiloxane. If the content of repeating structural units having ethylenically unsaturated groups is 70 mol% or less, the generation of residue in the development pattern can be suppressed, and if the ethylenically unsaturated groups are 10 mol% or more, a sufficient dissolution inhibition effect can be obtained.

[0046] Specific examples of repeating structural units having an ethylenically unsaturated group include vinyl groups, methacrylic groups, and acrylic groups. To incorporate the above repeating structural units into (a) polysiloxane, the following silanes can 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 further improving the dissolution inhibitory effect and increasing sensitivity by interacting with the photosensitive agent in three dimensions and via π-π stacking with the photosensitive agent, (a) polysiloxane has repeating structural units having a styryl group, and it is preferable that the (a) polysiloxane contains 10 mol% or more and 70 mol% or less of the repeating structural units having a styryl group, and more preferably 30 mol% or more and 70 mol% or less, based on 100 mol% of the total repeating structural units constituting the (a) polysiloxane. If the content of repeating structural units having a styryl group is 70 mol% or less, the generation of residue in the development pattern can be suppressed, and if the styryl group is 10 mol% or more, a sufficient dissolution inhibitory effect can be obtained.

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

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

[0050] Furthermore, in component (a), if a single repeating unit contains two or more of the following: "aromatic group," "ethylenically unsaturated group," "styryl group," "epoxy group," "oxetane group," and "dicarboxylic acid group" (described later), the amount of structural units relative to 100 mol% of all repeating structural units of component (a) shall be counted independently as structural units containing each of the above groups, if such structural units contain each of the above groups. For example, a structural unit containing a styryl group shall be counted as a structural unit containing an aromatic group, a structural unit containing an ethylenically unsaturated group, and a structural unit containing a styryl group.

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

[0052] Here, "dicarboxylic acid group" refers to a substructure 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 can be a single bond, a double bond, or part of an aromatic ring.

[0053] [ka]

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

[0055] Furthermore, 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 in polystyrene equivalent as measured by GPC (gel permeation chromatography), and more preferably 2,000 to 50,000. If Mw is less than 1,000, the coating properties will be poor, and if it is greater than 100,000, the solubility in the developer during pattern formation will be poor.

[0056] (a) The polysiloxane in the present invention is obtained by hydrolysis and partial condensation of the silane described above. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water, and optionally a catalyst are added to the mixture and heated and stirred. During stirring, hydrolysis byproducts (alcohols such as methanol) and condensation byproducts (water) may be removed by distillation as needed.

[0057] There are no particular restrictions on the reaction solvent used, but usually the same solvent used in the composition is used. The amount of solvent added is preferably 10 to 1000% by weight relative to 100% by weight of the total amount of silane or silane and silica particles. The amount of water added for the hydrolysis reaction is preferably 0.5 to 2 moles per mole of hydrolyzable group.

[0058] There are no particular restrictions on the catalyst added as needed, 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 per 100% by weight of silane.

[0059] Furthermore, from the viewpoint of film-forming properties and storage stability, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain by-products such as alcohol, water, and catalyst. These may be removed as needed. The method of removal is not particularly limited. Preferably, as a method for removing alcohol and water, the polysiloxane solution can be diluted with a suitable hydrophobic solvent, and the organic layer obtained by washing it several times with water can be concentrated in an evaporator. As a method for removing the catalyst, treatment with an ion exchange resin can be used in addition to or alone to the above-mentioned water washing.

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

[0061] [ka]

[0062] (In formula (1), R 1 represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinonediazidosulfonyl group represented by the following structure or a hydrogen atom. At least one of all Qs in formula (1) is a naphthoquinonediazidosulfonyl group. n represents an integer of 0 to 4, and m represents an integer of 4 to 8. X represents a 4- to 8-valent organic group having 4 to 30 carbon atoms.)

[0063] [Chemical formula]

[0064] (In the above structure, * represents a bonding site.) Component (b) has a structure represented by formula (1). Since component (b) has at least one naphthoquinonediazidosulfonyl group in formula (1), the silanol groups of component (b) and (a) polysiloxane can interact with each other, and the dissolution inhibition effect of the unexposed part can be improved. As a result, the solubility difference between the unexposed part and the exposed part becomes large, and pattern processing can be performed with higher sensitivity and higher residual film rate. Also, by interacting with the Si-OH groups in the polysiloxane, the condensation of the silanol groups is inhibited, the change in molecular weight is suppressed, and it is also effective in improving the storage stability.)

[0065] Note that the naphthoquinonediazidosulfonyl group of Q in formula (1) represents the basic skeleton, does not inhibit the expression of alkali solubility in the composition after exposure, and is allowed to have a substituent such as a methyl group, an ethyl group, a methoxy group, etc., which is a saturated aliphatic group having 1 to 2 carbon atoms, that does not inhibit the interaction with component (a).

[0066] In formula (1), R 1 represents an alkyl group having 1 to 8 carbon atoms. When R 1 has an alkyl group having 1 to 8 carbon atoms, it has appropriate hydrophilicity, the solubility of the exposed part in an alkaline developer is improved, and the sensitivity is improved. From the viewpoint of further improving the sensitivity, R 1A C1-C3 alkyl group is preferred. Furthermore, from the viewpoint of improving sensitivity, in formula (1), n ​​is 1 or 2, and R 1 It is preferable that the -OQ group is bonded in an ortho position.

[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 the Q in formula (1) contained in component (b) is taken as 100 mol%, 75 mol% or more of Q is a naphthoquinone diazidosulfonyl group.

[0068] Furthermore, in formula (1) above, from the viewpoint of improving sensitivity by enhancing the dissolution inhibitory effect and improving storage stability, the value of m is preferably 4 to 6, and more preferably 4.

[0069] The following are examples of preferred specific examples of component (b) that satisfy these conditions.

[0070] [ka]

[0071] In the compound represented by the above structure, at least 75 mol% of Q is the group shown below, and the remaining Q is a hydrogen atom.

[0072] [ka]

[0073] (In the above structure, * represents a bonding site.) Furthermore, from the viewpoint of improving sensitivity by enhancing the dissolution inhibitory effect and improving storage stability, it is even more preferable that X in formula (1) includes 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, a state in which the light transmittance of the cured product is high can be maintained.

[0075] In particular, when component (a) has repeating structural units having dicarboxylic acid groups, from the viewpoint of increasing sensitivity, it is preferable that 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). More preferably, it is 0.5 to 2.5.

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

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

[0078] [ka]

[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 of a method for forming a cured product using the positive-type photosensitive composition of the present invention will be described. The positive-type photosensitive composition of the present invention is applied to a substrate such as a glass substrate, SiO substrate, SiN substrate, or ITO substrate by known methods such as spinning, dipping, or slitting, and then pre-baked using a heating device such as a hot plate or oven. Pre-baking is performed at a temperature in the range of 50 to 150°C for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

[0081] After pre-baking, UV-Vis exposure is performed using a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., at a rate of 10-200 mJ / cm². 2 Patterning exposure (equivalent to exposure amount at a wavelength of 405 nm) is performed through the desired mask.

[0082] After patterning exposure, the exposed areas dissolve during development, allowing a pattern to be obtained. For development, immersion in the developer solution for 5 seconds to 10 minutes using methods such as showering, dipping, or paddle is preferred. As the developer, a known alkaline developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and aqueous solutions containing one or more quaternary ammonium salts such as TMAH (tetramethylammonium hydroxide) and choline. Among these, an aqueous TMAH solution is preferred because it is an organic alkali that does not pose a risk of metal ion contamination and is strongly alkaline. The TMAH aqueous solution is generally preferred at a concentration of 0.20 to 2.38 wt% from the viewpoint of the solubility of phenolic hydroxyl groups, silanol groups, and carboxyl groups in alkali.

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

[0084] Next, this film is heat-cured for about one hour at a temperature of 150-300°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 applied to planarization films for TFTs in display devices, interlayer insulating films in semiconductor devices, or cores and cladding materials in optical waveguides, etc.

[0085] The present invention relates to a display device comprising 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 comprises the above-mentioned cured material. In particular, it is preferable that the display device includes a planarization film provided in a manner that covers the irregularities on a substrate on which thin-film transistors (TFTs) are formed. [Examples]

[0086] The present invention will be described below using examples, but the embodiments of the present invention are not limited to these examples. Furthermore, abbreviations used for the compounds in the examples are listed below. DAA: Diacetone alcohol PGME: Propylene glycol monomethyl ether Furthermore, the solid content concentration of the polysiloxane solution and the ring-opening rate of succinic acid were determined as follows.

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

[0088] (2) Ring-opening rate of succinic acid 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-necked flask. An aqueous phosphoric acid solution, 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. 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 heating, the internal temperature of the solution reached 100°C, and it was 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 liters / min. During the reaction, a total of 203 g of methanol and water were distilled off as by-products. The solid content concentration of the resulting polysiloxane (PS-1) solution was 52% by weight.

[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-necked flask. An aqueous phosphoric acid solution, 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. 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 heating, the internal temperature of the solution reached 100°C, and it 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 liters / min. During the reaction, a total of 197 g of by-products, methanol and water, were distilled off. The solid content of the resulting polysiloxane (PS-2) solution was 53% by weight.

[0091] Synthesis Example 3: Synthesis of Polysiloxane (PS-3) Solution In a 1000 ml three-necked flask, combine 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. -3207.11 g of DAA (mol) was charged, and a phosphoric acid aqueous solution (0.323 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-3) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 208.1 g of methanol and water, which were by-products, distilled off. The solid content concentration of the obtained polysiloxane (PS-3) solution was 50% by weight.

[0092] Synthesis Example 4: Synthesis of Polysiloxane (PS-4) Solution In a 1000 ml three-necked flask, combine 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 × 10⁻¹⁵) of dibutylhydroxytoluene. -3 193.44 g of DAA (mol) was charged, and an aqueous phosphoric acid solution (0.309 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-4) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 188.89 g of by-products methanol and water distilled off. The ring-opening rate of the succinic anhydride structure of the obtained polysiloxane (PS-4) solution was 95%, the total weight of the solution was 404.94 g, and the solid content concentration was 52% by weight.

[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-necked flask. A phosphoric acid aqueous 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 heating, the internal temperature of the solution reached 100°C. The mixture was then heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-5) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 liters / min. During the reaction, a total of 199 g of methanol and water were distilled off as by-products. The solid content concentration of the obtained 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-necked flask. 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. 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-6) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 liters / min. During the reaction, a total of 200 g of methanol and water were distilled off as by-products. The solid content of the resulting polysiloxane (PS-6) solution was 52% by weight.

[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-necked flask. A phosphoric acid aqueous 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. 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-7) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 liters / min. During the reaction, a total of 198 g of by-products, methanol and water, were distilled off. The solid content of the resulting polysiloxane (PS-7) solution was 52% by weight.

[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-necked flask. An aqueous phosphoric acid solution, 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. 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-8) solution. During heating and stirring, dry nitrogen was flowed at a rate of 0.070 liters / min. During the reaction, a total of 203 g of by-products methanol and water were distilled off. The solid content concentration of the resulting polysiloxane (PS-8) solution was 52% by weight.

[0097] Synthesis Example 9: Synthesis of Polysiloxane (PS-9) Solution In a 1000 ml three-necked flask, combine 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. -3 189.71 g of DAA (mol) was charged, and a phosphoric acid aqueous solution (0.309 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain the polysiloxane (PS-9) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 199 g of methanol and water, which were by-products, distilled off. The solid content concentration of the obtained polysiloxane (PS-3) solution was 52% by weight.

[0098] Synthesis Example 10: Synthesis of Polysiloxane (PS-10) Solution In a 1000 ml three-necked flask, combine 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. -3213.29 g of DAA (mol) was charged, and a phosphoric acid aqueous solution (0.348 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain the polysiloxane (PS-10) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 197 g of methanol and water were distilled off as by-products. The solid content concentration of the obtained polysiloxane (PS-10) solution was 52% by weight.

[0099] Synthesis Example 11: Synthesis of Polysiloxane (PS-11) Solution In a 1000 ml three-necked flask, combine 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. -3 236.00 g of DAA (mol) was charged, and a phosphoric acid aqueous solution (0.385 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain the polysiloxane (PS-11) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 202 g of methanol and water were distilled off as by-products. The solid content concentration of the obtained polysiloxane (PS-11) solution was 52% by weight.

[0100] Synthesis Example 12: Synthesis of Polysiloxane (PS-12) Solution In a 1000 ml three-necked flask, combine 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 × 10⁻¹⁵) of dibutylhydroxytoluene. -3 197.77 g of DAA (mol) was charged, and an aqueous phosphoric acid solution (0.322 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-12) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 195.43 g of methanol and water, which were by-products, distilled off. The ring-opening rate of the succinic anhydride structure of the obtained polysiloxane (PS-12) solution was 95%, the total weight of the solution was 412.02 g, and the solid content concentration was 52% by weight.

[0101] Synthesis Example 13: Synthesis of Polysiloxane (PS-13) Solution In a 1000 ml three-necked flask, combine 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 × 10⁻¹⁵) of dibutylhydroxytoluene. -3205.95 g of DAA (mol) was charged, and an aqueous phosphoric acid solution (0.336 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-13) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 192.95 g of by-products methanol and water distilled off. The ring-opening rate of the succinic anhydride structure of the obtained polysiloxane (PS-13) solution was 95%, the total weight of the solution was 429.05 g, and the solid content concentration was 52% by weight.

[0102] Synthesis Example 14: Synthesis of Polysiloxane (PS-14) Solution In a 1000 ml three-necked flask, add 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 × 10⁻¹⁵) of dibutylhydroxytoluene. -3 208.34 g of DAA (mol) was charged, and an aqueous phosphoric acid solution (0.340 g of phosphoric acid dissolved in 90.72 g of water) was added over 15 minutes while stirring at room temperature. Then, 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 heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane (PS-14) solution. During heating and stirring, air was flowed at a rate of 0.070 liters / min. During the reaction, a total of 200.95 g of methanol and water, which were by-products, distilled off. The ring-opening rate of the succinic anhydride structure of the obtained polysiloxane (PS-14) solution was 95%, the total weight of the solution was 434.04 g, and the solid content concentration was 52% by weight.

[0103] Synthesis Example 15: Synthesis of naphthoquinone diazide compound (QD-1) Under a stream of dry nitrogen, 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 sulfonylate chloride were dissolved in 66.5 g of acetone and allowed to rise to room temperature. To this, 9.11 g (0.09 mol) of triethylamine mixed with 10 g of acetone was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After 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 added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-1) with the structure shown below.

[0104] [ka]

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

[0106] Synthesis Example 16: Synthesis of Naphthoquinone Diazide Compound (QD-2) Under a stream of dry nitrogen, 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 sulfonylate chloride were dissolved in 69.9 g of acetone and allowed to rise to room temperature. To this, 9.11 g (0.09 mol) of triethylamine mixed with 10 g of acetone was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After 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 added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-2) with the structure shown below.

[0107] [ka]

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

[0109] Synthesis Example 17: Synthesis of naphthoquinone diazide compound (QD-3) Under a stream of dry nitrogen, 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 sulfonylate chloride were dissolved in 67.3 g of acetone and allowed to rise to room temperature. To this, 9.11 g (0.090 mol) of triethylamine mixed with 10 g of acetone was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After 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 added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-3) with the structure shown below.

[0110] [ka]

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

[0112] Synthesis Example 18: Synthesis of naphthoquinone diazide compound (QD-4) Under a stream of dry nitrogen, 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 diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-4) with the structure shown below.

[0113] [ka]

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

[0115] Synthesis Example 19: Synthesis of naphthoquinone diazide compound (QD-5) Under a stream of dry nitrogen, 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 diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (QD-5) with the structure shown below.

[0116] [ka]

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

[0118] Example 1 Under a yellow light, 0.671 g of naphthoquinone diazide compound (QD-1) (10 parts by weight per 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-type photosensitive composition (PP-1). The prepared positive-type photosensitive composition (PP-1) was spin-coated onto a glass substrate (OA-10, manufactured by Nippon Electronic Glass Co., Ltd.) using a spin coater (1H-360S, manufactured by Mikasa Corporation) at an arbitrary rotation speed, 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 thickness of 1.5 μm. The fabricated pre-baked film was subjected to 200, 300, and 400 mJ / cm² testing using a parallel light mask aligner (Canon Inc. PLA-501F, hereinafter referred to as PLA) and a grayscale mask. 2 The film was irradiated (equivalent to the exposure amount at a wavelength of 405 nm). A grayscale mask is a mask that allows for stepwise exposure from 1% to 100% beneath the mask by exposing it from above. Subsequently, the film was shower-developed for 90 seconds with a 2.38 wt% TMAH aqueous solution using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), followed by rinsing with water for 30 seconds. Next, using PLA, the entire film surface was exposed to ultra-high pressure mercury lamps at 200, 300, and 400 mJ / cm². 2 The material was exposed to light at a wavelength of 405 nm (equivalent to the exposure amount). Afterwards, it was cured in air at 230°C for 1 hour using an oven (ESPEC Corporation IHPS-222) to produce a cured product.

[0119] The following measurements were performed on this cured material.

[0120] (1) Film thickness measurement The thickness of the pre-baked film and the cured product was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., with a refractive index of 1.55.

[0121] (2) Percentage of remaining film The residual film percentage is determined by applying the composition to a glass substrate, pre-baking it on a 100°C hot plate for 180 seconds, and then developing it. The film thickness after pre-baking is (i) (μm), and the film thickness in the unexposed area after development is (ii) (μm). Remaining film rate (%)=(ii)×100 / (i) It is calculated as follows.

[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 the patterned film is baked in an oven at 230°C for 1 hour. After baking, the exposure amount that resolves a 20 μm line-and-space pattern with a 1:1 width (hereinafter referred to as the optimal exposure amount) is determined as the sensitivity.

[0123] (4) Storage stability Positive-type photosensitive compositions were prepared, and their initial sensitivity (Eop(0)) was measured. They were then stored for 3 days in a 25°C incubator (Cool Incubator KMH-050 (AS ONE corporation)). The storage stability of the compositions was then evaluated by measuring their sensitivity again (Eop(3)). The sensitivity change x (%) was calculated using the following formula, and the evaluation criteria were defined 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 / cm². 2 The following conditions were met, and the evaluation of the sensitivity change x was B or higher, in which case it was considered a pass.

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

[0126] Examples 2-24, Comparative Examples 1-2 Positive-type photosensitive compositions (PP-2 to PP-26) were obtained by adding polysiloxane (PS-1 to PS-14) solutions and naphthoquinone diazide compounds (QD-1 to QD-5) in the amounts listed in Table 1, except that the procedure was the same as in Example 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] [Table 1-1]

[0128] [Table 1-2]

[0129] The meanings of each term in Table 1 are as follows:

[0130] Explanation 1: (a) Content (mol%) of repeating structural units having aromatic groups relative to 100 mol% of all repeating structural units constituting the component Explanation 2: (a) Content (mol%) of repeating structural units having epoxy groups relative to 100 mol% of all repeating structural units constituting the component Explanation 3: (a) Content (mol%) of repeating structural units having ethylenically unsaturated groups relative to 100 mol% of all repeating structural units constituting the component Explanation 4: (a) Content (mol%) of repeating structural units having a styryl group relative to 100 mol% of all repeating structural units constituting the component Explanation 5: (a) Content (mol%) of repeating structural units having a dicarboxylic acid group relative to 100 mol% of all repeating structural units constituting the component Explanation 6: R for the -OQ group 1 Bonding position Explanation 7: (b) Content of naphthoquinone diazidosulfonyl groups (mol%) when all Q in formula (1) contained in component (b) is assumed to be 100 mol% Explanation 8: (a) Content (parts by weight) per 100 parts by weight of the component

[0131] Table 2

Claims

1. A positive-type photosensitive resin composition comprising (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 repeating structural units having ethylenically unsaturated groups, and the amount of repeating structural units having ethylenically unsaturated groups is 10 mol% or more and 70 mol% or less relative to 100 mol% of the total repeating structural units of component (a), and (a) The component has repeating structural units having aromatic groups, with repeating structural units having aromatic groups as an essential component. (a) Component (a) has an amount of repeating structural units having the aromatic group of 60 mol% or more relative to 100 mol% of the total repeating structural units of component (a), Component (a) has a ratio of 10 to 70 mol% of the repeating structural units having the styryl group relative to 100 mol% of the total repeating structural units of component (a). Furthermore, component (b) is R in formula (1). １ This is a positive-type photosensitive resin composition in which the -OQ group is bonded in an ortho position. 【Chemistry 1】 (In formula (1), R １ ¹ represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazidosulfonyl group or a hydrogen atom represented by the structure shown below. In formula (1), at least one of the Qs is a naphthoquinone diazidosulfonyl group. n is 1 or 2, and m represents an integer from 4 to 8. X represents a 4- to 8 valent organic group having 4 to 30 carbon atoms. 【Chemistry 2】 (In the above structure, * indicates a bonding site.)

2. A positive-type photosensitive resin composition comprising (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 repeating structural units having ethylenically unsaturated groups, and the amount of repeating structural units having ethylenically unsaturated groups is 10 mol% or more and 70 mol% or less relative to 100 mol% of the total repeating structural units of component (a), (a) Component has repeating structural units having a dicarboxylic acid group, Component (a) is such that the amount of repeating structural units having the dicarboxylic acid group is 1 mol% or more relative to 100 mol% of the total repeating structural units of component (a), Furthermore, component (b) is a positive-type photosensitive resin composition in which R 1 is bonded ortho-position to the -OQ group in formula (1). 【Transformation 3】 (In formula (1), R1 represents an alkyl group having 1 to 8 carbon atoms. Q represents a naphthoquinone diazidosulfonyl group or a hydrogen atom represented by the structure shown below. In formula (1), at least one of all Qs is a naphthoquinone diazidosulfonyl group. n is 1 or 2, and m is an integer from 4 to 8. X represents a 4- to 8 valent organic group having 4 to 30 carbon atoms.) 【Chemistry 4】 (In the above structure, * indicates a bonding site.)

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

4. (b) The positive-type photosensitive resin composition according to claim 1 or 2, wherein component (b) comprises an alicyclic skeleton in formula (1).

5. (a) The component has either or both repeating structural units having epoxy groups and repeating structural units having oxetane groups, (a) The positive-type photosensitive resin composition according to claim 1 or 2, wherein the total amount of repeating structural units having epoxy groups and repeating structural units having oxetane groups is 1 to 8 mol% relative to 100 mol% of the total repeating structural units of component.

6. The positive-type photosensitive resin composition according to claim 2, wherein 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 0.2 to 2.

5.

7. A cured product obtained by heat-treating the positive-type photosensitive resin composition according to claim 1 or 2.

8. A display device comprising: 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 unit provided between the partially exposed first electrode and the second electrode described below, which produces an optical change when a voltage is applied; and a second electrode provided opposite the first electrode, A display device comprising the cured product described in claim 7 for the insulating layer.

9. A display device comprising a planarization film provided in such a manner that it covers irregularities on a substrate on which thin-film transistors (TFTs) are formed, wherein the planarization film comprises the cured product described in claim 7.

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