JP6621233B2 - Photosensitive resin composition for forming insulating film in organic EL display element - Google Patents

Description

  The present invention uses a photosensitive resin composition for forming an insulating film in an organic EL display element, an insulating film in an organic EL display element formed using the photosensitive resin composition, and the photosensitive resin composition. And a bank in an organic EL display element formed in the above manner.

  Since the organic EL display element is a self-luminous display element, it does not depend on viewing angle, has low power consumption, has excellent impact resistance, and the like when compared with liquid crystal display elements. Since it has an advantage, the adoption to various display elements is progressing centering on the display element for portable terminals, the display element for vehicle mounting, etc.

  In such an organic EL display element, an insulating film pattern is formed for the purpose of mere insulation or for insulation while separating various functional layers. Such an insulating film pattern is required to have high water resistance, solvent resistance, heat resistance, and the like from the viewpoint of extending the life of the organic EL display element and suppressing image defects.

  Further, when a functional layer is formed between insulating films by a method such as vapor deposition, if the angle (taper angle) formed between the end face of the insulating film and the bottom of the insulating film is too large, cracks are likely to occur in the functional layer. When a crack occurs in the functional layer, a display defect may occur due to penetration of moisture or the like from the crack portion.

  Furthermore, since the pattern of the insulating film in the organic EL display element can easily form a fine insulating film pattern with good dimensional accuracy, it is preferably formed by a photolithography method using a photosensitive resin composition. In this case, the photosensitive resin composition is required to be able to form an insulating film pattern that does not cause excessive film reduction even after a development process or a baking process.

  In order to solve the above problems, for example, a photosensitive resin composition containing a novolak resin and a 1,2-quinonediazide compound has been proposed as a photosensitive resin composition for forming an organic EL display element insulating film. (See Patent Document 1).

JP 2002-169277 A

  When the photosensitive resin composition described in Patent Document 1 is used, an insulating film pattern having high water resistance, solvent resistance, heat resistance, and the like can be formed by a photolithography method. However, when forming an insulating film using the photosensitive resin composition described in Patent Document 1, there is a problem that a long baking process at a high temperature is required to form an insulating film pattern with a low taper angle. There is.

  If the baking process for reducing the taper angle of the insulating film requires a long time, the organic EL display element cannot be produced at a high throughput, and the organic EL display element is made of a material having low heat resistance. There is also a risk of thermal degradation.

  The present invention has been made in view of the above problems, and does not cause excessive film reduction even after a development process or a baking process, and satisfactorily reduces the taper angle of the insulating film by baking in a short time. A photosensitive resin composition capable of forming an insulating film in an organic EL display device having high water resistance, solvent resistance, and heat resistance, and an organic material formed using the photosensitive resin composition An object is to provide an insulating film and a bank in an EL display element.

  The present inventors have (C) a crosslinking agent and (D) for a photosensitive resin composition for forming an insulating film in an organic EL display element, which contains (A) a novolak resin and (B) a photosensitive agent. ) A silane coupling agent having an oxirane ring or an oxetane ring is blended, and the content of the monomer and dimer in (A) novolak resin is 5 to 18% by mass with respect to the mass of (A) novolak resin. Thus, the inventors have found that the above problems can be solved, and have completed the present invention.

The first aspect of the present invention includes (A) a novolak resin, (B) a photosensitizer, (C) a crosslinking agent, and (D) a silane coupling agent having an oxirane ring or an oxetane ring,
(A) The content of monomers and dimers in the novolak resin is 5 to 18% by mass with respect to the mass of the (A) novolak resin, and is a photosensitive resin composition for forming an insulating film in an organic EL display element. .

  The second aspect of the present invention is an insulating film in an organic EL element formed using the photosensitive composition according to the first aspect.

  The third aspect of the present invention is a bank in an organic EL element formed using the photosensitive composition according to the first aspect.

  According to the present invention, excessive film loss does not occur even after a development process and a baking process, the taper angle of the insulating film can be satisfactorily reduced by baking in a short time, and high water resistance is achieved. A photosensitive resin composition capable of forming an insulating film in an organic EL display element having solvent resistance and heat resistance, and an insulating film and a bank in an organic EL display element formed using the photosensitive resin composition Can be provided.

<< Photosensitive resin composition for forming an insulating film in an organic EL display element >>
The photosensitive resin composition for forming an insulating film in the organic EL display device according to the present invention has (A) a novolak resin, (B) a photosensitive agent, (C) a crosslinking agent, and (D) an oxirane ring or an oxetane ring. Contains a silane coupling agent. In the present specification, the “photosensitive resin composition for forming an insulating film in an organic EL display element” is also simply referred to as “photosensitive resin composition”. The (A) novolac resin contains 5 to 18% by mass of monomers and / or dimers with respect to the mass of the (A) novolac resin.

  The type of insulating film using the photosensitive resin composition is not particularly limited. The insulating film formed using the photosensitive resin composition is preferably a bank that is an insulating partition that separates adjacent pixels. As for the bank, it is particularly desirable that the taper angle, which is an angle formed by the end face of the bank and the surface of the substrate in contact with the bank, is low, but by using the photosensitive resin composition according to the present invention, the bank having a low taper angle is used. Can be easily formed by a short heat treatment.

  Hereinafter, essential or optional components contained in the photosensitive resin composition will be described.

<(A) Novolac resin>
As the (A) novolak resin, various novolak resins conventionally blended in the photosensitive resin composition can be used as long as the monomer and dimer contents are predetermined amounts. (A) As the novolak resin, those obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst are preferable.

〔Phenols〕
Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, Xylenols such as 3,4-xylenol and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4- Alkylphenols such as isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phlorogricinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms) And α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

  Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, by adjusting the blending ratio of the two, various characteristics such as sensitivity as the photosensitive resin composition and heat resistance of the insulating film to be formed can be adjusted. The blending ratio of m-cresol and p-cresol is not particularly limited, but the ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less (mass ratio). Sensitivity can be improved by setting the ratio of m-cresol to 3/7 or more, and heat resistance can be improved by setting it to 8/2 or less.

[Aldehydes]
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

[Acid catalyst]
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluenesulfonic acid; and zinc acetate Examples thereof include metal salts. These acid catalysts may be used alone or in combination of two or more.

[Molecular weight]
(A) The polystyrene-reduced mass average molecular weight of the novolak resin is preferably 1000 to 50000 from the viewpoints of developability, resolution, and plating solution resistance of the photosensitive resin composition. In addition, (A) the weight average molecular weight in terms of polystyrene of the novolak resin is obtained by heat-treating the pattern of the insulating film formed using the photosensitive resin composition while suppressing excessive film loss of the pattern after development. Since it is easy to obtain an insulating film having a desired taper angle, it is more preferably 5000 to 7000. Further, the degree of dispersion [mass average molecular weight (Mw) / number average molecular weight (Mn)] of the novolak resin is preferably 50 or less, more preferably 2 or more and 25 or less, and still more preferably 2 or more and 15 or less.

[Adjustment of monomer amount and dimer amount]
(A) As a novolak resin, the total content of monomer and dimer with respect to the mass of (A) novolak resin is 5 to 18% by mass, preferably 5 to 10% by mass, more preferably 7 to 10% by mass. Is used. (A) When the novolak resin contains such an amount of monomer and / or dimer, an insulating film having a desired taper angle can be formed by a short heat treatment. That is, by using the photosensitive resin composition according to the present invention, various substrates including an insulating film having a desirable taper angle can be produced with high throughput.

  When a novolak resin contains a large amount of monomer and dimer, for example, 5% by mass or more, when developing a film of the exposed photosensitive resin composition, for a conventional photosensitive resin composition containing a novolak resin. There is a problem that excessive film loss tends to occur in the formed pattern. That is, such a photosensitive resin composition is inferior in photolithography characteristics and is difficult to form a pattern having a desired shape.

  However, even if the photosensitive resin composition according to the present invention contains (A) a novolac resin containing a large amount of monomers and dimers to some extent, (A) a novolak resin, (C) a crosslinking agent, and (D) Since it contains in combination with a silane coupling agent having an oxirane ring or an oxetane ring, when developing the exposed photosensitive resin composition film, it is difficult to cause excessive film reduction in the exposed area. That is, the photosensitive resin composition according to the present invention has good photolithography characteristics.

  (A) The monomer or dimer contained in the novolak resin is usually a component that has not been polymerized by polymerization reaction among phenols used in the production of the novolak resin. Specifically, the monomer is a phenol that has not undergone a polymerization reaction among (A) the phenols used in the production of the novolak resin and remains in the (A) novolac resin. In addition, the dimer is a phenol that has been subjected only to the dimerization reaction among (A) the novolak resin used in the production of the novolak resin and remains in the (A) novolak resin. For this reason, the monomer or dimer contained in the (A) novolak resin is usually and preferably a phenol or a dimer of the phenol used in the production of the (A) novolak resin.

  However, the monomer or dimer contained in (A) the novolak resin is not limited to the monomer or dimer of the phenol used in the production of (A) the novolak resin, and (A) the phenol used in the production of the novolak resin. Monomers or dimers of phenols other than

  When the (A) novolak resin is a monomer or dimer of a phenol other than the phenols used in the production of the (A) novolak resin, the monomer and dimer include monomers and dimers derived from p-cresol and formaldehyde. preferable. That is, p-cresol and 2,2'-methylenebis (4-methylphenol) are preferred as the monomer and dimer. Since the reaction product of p-cresol and / or 2,2′-methylenebis (4-methylphenol) and (C) a cross-linking agent has a high interaction with (B) the photosensitizer, p- When a photosensitive resin composition containing (A) novolak resin containing cresol and / or 2,2′-methylenebis (4-methylphenol) as a monomer and / or dimer is used, it is easy to form a strong insulating film.

  As a method for preparing the (A) novolak resin containing the monomer and / or dimer in an amount within the above predetermined range, the monomer and / or dimer content is within the predetermined range after the synthesis of the (A) novolak resin. After obtaining a method for purifying a crude novolak resin under conditions adjusted so as to be within, or after obtaining a high-purity novolak resin purified to such an extent that substantially no monomers and dimers are contained, The method of adding the monomer and / or dimer which were prepared beforehand is mentioned.

  (A) As a method of reducing the content of the monomer and / or dimer in the novolak resin, after melting the novolak resin in a depressurizable container, the inside of the container is reduced to, for example, 20 kPa or less, preferably 5 kPa or less. And a method of distilling off the monomer and / or dimer.

  As another method, after dissolving the novolak resin in a hydrophobic organic solvent such as ethyl acetate, the monomer and / or dimer is prepared from the hydrophobic organic solvent solution of the novolak resin using an aqueous solution of the water-soluble organic solvent. The method of extracting is mentioned. After extraction, the hydrophobic organic solvent is distilled off from the hydrophobic organic solvent layer, or a poor solvent such as heptane, hexane, pentane, and cyclohexane is added to the hydrophobic organic solvent layer to contain monomers and / or dimers. A reduced amount of novolac resin is recovered.

  As another method, after dissolving the novolak resin in a water-soluble polar organic solvent, a poor solvent such as water, heptane, hexane, pentane, and cyclohexane is added to the resulting solution to precipitate the novolak resin. A method is mentioned. At this time, since the monomer and / or dimer has relatively high solubility in the poor solvent, it remains dissolved in the poor solvent. For this reason, the novolak resin in which the monomer and / or dimer content is reduced can be obtained by collecting the precipitate.

  Examples of polar solvents for dissolving the novolak resin include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; glycol ether esters such as ethylene glycol monoethyl ether acetate; and cyclic ethers such as tetrahydrofuran. Is mentioned.

  The content of the monomer and / or dimer in the component (A) can be confirmed from the result of GPC measurement. That is, from the GPC chart, the molecular weight distribution of the synthesized phenol novolak resin can be confirmed, and the content can be calculated by measuring the intensity ratio of the peak corresponding to the elution time of the low-nuclear body. . Since the elution time of the low nuclei varies depending on the measurement means, it is important to specify the column, eluent, flow rate, temperature, detector, sample concentration, injection amount, measuring instrument, and the like.

<(B) Photosensitive agent>
Although it does not specifically limit as a photosensitive agent contained in the photosensitive resin composition, A quinonediazide group containing compound is preferable. Examples of the quinonediazide group-containing compound include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,3,6-trihydroxybenzophenone. 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3', 4 4 ′, 6-pentahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,2 ′, 3,4,5-pentahydroxybenzophenone, 2,3 ′, 4,4 ′, Polyhydroxybenzenes such as 5 ′, 6-hexahydroxybenzophenone, 2,3,3 ′, and 4,4 ′, 5′-hexahydroxybenzophenone Nzophenones; bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-tri Hydroxyphenyl) propane, 4,4 ′-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol, and 3,3′-dimethyl- {1- [4- Bis [(poly) hydroxyphenyl] alkanes such as [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol; Tris (4- Droxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4- Hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- Tris (hydroxyphenyl) methanes such as 3,4-dihydroxyphenylmethane and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl-substituted products thereof; bis (3-cyclohexyl) -4-hydroxyphenyl) -3-hydroxyphenylmethane, bi (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl Methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4- Hydroxy-3- Tilphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-) Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as 4-methylphenyl) -4-hydroxyphenylmethane or methyl-substituted products thereof; phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphtho A compound having a hydroxyl group or an amino group, such as alcohol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, and 4,4′-diaminobenzophenone; and novolak , Pyrogallol-acetone resin, and a copolymer of p-hydroxystyrene homopolymer or a monomer copolymerizable therewith, and naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide Examples include a complete ester compound, a partial ester compound, an amidated product, or a partially amidated product with a sulfonic acid containing quinonediazide group such as -4-sulfonic acid and orthoanthraquinonediazidesulfonic acid. These photosensitizers may be used alone or in combination of two or more.

［式（Ｂ−１）及び（Ｂ−２）中、Ｒ^ｂ１〜Ｒ^ｂ７はそれぞれ独立して水素原子、置換基を有していてもよい炭素原子数１〜５のアルキル基、及び置換基を有していてもよい炭素原子数４〜８のシクロアルキル基を示す。］ Among these photosensitizers, quinonediazide sulfonic acid esters of compounds represented by the following formulas (B-1) and (B-2) are preferable.

[In the formulas (B-1) and (B-2), R ^{b1 to} R ^b7 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and a substituent. A cycloalkyl group having 4 to 8 carbon atoms which may have ]

Among the quinonediazide sulfonic acid esters of the compounds represented by the above formulas (B-1) and (B-2), the quinonediazide sulfonic acid ester of the compound represented by the following formula (B-3) is particularly preferable.

Here, in the quinonediazide sulfonic acid ester of the compound represented by the above formulas (B-1) and (B-2) and the formula (B-3), the naphthoquinone-1,2-diazide-sulfonyl group is at the 4-position. Alternatively, those having a sulfonyl group bonded to the 5-position are preferred. These compounds are well dissolved in a solvent usually used when the photosensitive resin composition is used as a solution, and have a good compatibility with the (A) novolak resin. When these compounds are blended in the photosensitive resin composition as a photosensitive agent (B), a highly sensitive photosensitive resin composition is easily obtained.
give.

  The compound represented by the above formula (B-1) is, for example, 1-hydroxy-4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and naphthoquinone-1,2-diazide-sulfonyl chloride. In the presence of an alkali such as triethanolamine, alkali carbonate, and alkali hydrogen carbonate, and complete esterification or partial esterification. The compound represented by the formula (B-2) is, for example, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and naphthoquinone. By condensing -1,2-diazide-sulfonyl chloride in a solvent such as dioxane in the presence of an alkali such as triethanolamine, alkali carbonate, and alkali hydrogen carbonate, and then completely or partially esterified. Can be manufactured.

  As naphthoquinone-1,2-diazide-sulfonyl chloride, it is preferable to use naphthoquinone-1,2-diazide-4-sulfonyl chloride or naphthoquinone-1,2-diazide-5-sulfonyl chloride.

  The content of the photosensitive agent (B) in the photosensitive resin composition is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the (A) novolak resin, from the viewpoint of the sensitivity of the photosensitive resin composition. 50 parts by mass is more preferable.

<(C) Crosslinking agent>
(C) A crosslinking agent will not be specifically limited if it is a compound which bridge | crosslinks (A) novolak resin by operation of insulating film formation. (C) As a preferable thing as a crosslinking agent, a melamine compound and an epoxy compound are mentioned, A melamine compound is more preferable. By mix | blending (C) crosslinking agent with the photosensitive resin composition, the insulating film excellent in water resistance, heat resistance, and solvent resistance can be formed using the photosensitive resin composition.

  The melamine compound is not particularly limited as long as it is a compound having a chemical structure that can be derived from melamine and is a compound that acts as a crosslinking agent for (A) the novolak resin. A suitable melamine compound includes a compound represented by the following formula (C1).

［式（Ｃ１）中、Ｒ^ｃ１〜Ｒ^ｃ６は水素原子又は−ＣＨ_２−Ｏ−Ｒ^ｃ７で表される基であって、Ｒ^ｃ７は水素原子又は炭素原子数１〜６のアルキル基であり、Ｒ^ｃ１〜Ｒ^ｃ６の少なくとも１つは−ＣＨ_２−Ｏ−Ｒ^ｃ７で表される基である。］

[In the formula (C1), R ^{c1 to} R ^c6 are a hydrogen atom or a group represented by —CH ₂ —O—R ^c7 , and R ^c7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , R ^{c1 to} R ^c6 are groups represented by —CH ₂ —O—R ^c7 . ]

  Examples of the melamine compound represented by the above formula (C1) include hexamethylol melamine, hexabutyrol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine, and partially methylolated benzoguanamine and its alkylated compound.

  The epoxy compound is not particularly limited as long as it is a compound having an epoxy group and acts as a crosslinking agent for (A) the novolak resin. As the epoxy compound, a polyfunctional epoxy compound having two or more epoxy groups in one molecule is preferable. In addition, the silane coupling agent which has the (D) oxirane ring or oxetane ring mentioned later is not included in the epoxy compound used as (C) crosslinking agent.

  As the epoxy compound, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyfunctional alicyclic epoxy resin, an aliphatic polyglycidyl ether, and the like are preferable.

  3-30 mass% is preferable in solid content of the photosensitive resin composition, and, as for content of (C) crosslinking agent in the photosensitive resin composition, 3-15 mass% is more preferable. By using the photosensitive resin composition containing the amount of the crosslinking agent (C) in such a range, an insulating film having excellent water resistance, heat resistance, and solvent resistance can be easily formed.

<(D) Silane coupling agent having oxirane ring or oxetane ring>
The photosensitive resin composition includes (D) a silane coupling agent having an oxirane ring or an oxetane ring. (D) The silane coupling agent having an oxirane ring or an oxetane ring includes (A) a phenolic hydroxyl group possessed by a novolac resin, both of the oxirane ring or oxetane ring and a reactive group such as an alkoxy group bonded to a silicon atom. Can react. For this reason, (D) the silane coupling agent having an oxirane ring or an oxetane ring acts as a cross-linking agent and closes the insulating film formed using the photosensitive resin composition. When the insulating film is tight, the water resistance, solvent resistance, heat resistance, and the like of the insulating film are improved.

  In the case where the photosensitive resin composition includes (D) a silane coupling agent having an oxirane ring or an oxetane ring, the organic EL display element is in contact with the insulating film formed using the photosensitive resin composition. Good adhesion to the member.

  (D) The silane coupling agent having an oxirane ring or oxetane ring is not particularly limited as long as it is a silane compound that contains an oxirane ring or oxetane ring in its structure and acts as a silane coupling agent. (D) Among the silane coupling agents having an oxirane ring or an oxetane ring, a silane coupling agent having an oxirane ring is preferred from the viewpoint of reactivity.

(D) As a silane coupling agent which has an oxirane ring or an oxetane ring, the compound represented by a following formula (D1) is preferable.
_{^{R d1 m R d2 (3-}} m) Si-R d3 -Y-X ··· (D1)
(In Formula (D1), R ^d1 is an alkoxy group, R ^d2 is an alkyl group, R ^d3 is an alkylene group, m is an integer of 1 to 3, and Y is —NH— or —O—. Or -S-, and X is an organic group having an oxirane ring or an oxetane ring.

In formula (D1), R ^d1 represents an alkoxy group. Regarding R ^d1 , the number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferable specific examples of R ^d1 include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, and n -A hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

Silanol groups produced by hydrolysis of R ^d1 which is an alkoxy group include hydroxyl groups possessed by novolak resins when forming an insulating film, hydroxyl groups possessed by various components contained in the photosensitive resin composition, carboxyl groups, etc. Reacts with functional groups containing active hydrogen atoms. For this reason, m is preferably 3 from the viewpoint that the silane coupling agent is easily bonded to a component contained in the photosensitive resin composition such as a novolak resin.

In formula (D1), R ^d2 is an alkyl group. About ^Rd2 , the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferred examples of R ^d2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (D1), R ^d3 represents an alkylene group. About ^Rd3 , 1-12 are preferable, as for the carbon atom number of an alkylene group, 1-6 are more preferable, and 2-4 are especially preferable. Preferable specific examples of R ^d3 include a methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1- Diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1,7- And diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. It is done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

  In formula (D1), X represents an organic group having an oxirane ring or an oxetane ring. The organic group having an oxirane ring or an oxetane ring may contain a hetero atom other than an oxygen atom such as a nitrogen atom, a sulfur atom, or a halogen atom. Preferable examples of the group represented by —Y—X in the formula (D1) include groups represented by the following formulas (D1-1) to (D1-8).

Specific examples of the silane coupling agent represented by the formula (D1) include the following.

  The content of the (D) silane coupling agent having an oxirane ring or oxetane ring in the photosensitive resin composition is preferably 3 to 20% by mass, and 3 to 15% by mass in the solid content of the photosensitive resin composition. More preferred. By using the photosensitive resin composition containing the amount of the crosslinking agent (C) in such a range, an insulating film having excellent water resistance, heat resistance, and solvent resistance can be easily formed.

［式（Ｅ−１）において、Ｒ^ｅ１〜Ｒ^ｅ８はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又はシクロアルキル基を表し；Ｒ^ｅ９〜Ｒ^ｅ１１はそれぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を示し；Ｑは水素原子、炭素原子数１〜６のアルキル基、又は下記式（Ｅ−２）で表される基であるか、ＱとＲ^ｅ９とが結合して炭素原子数３〜６のシクロアルキリデン基を形成し；ｗ、ｓは１〜３の整数を示し；ｕは０〜３の整数を示し；ｖは０〜３の整数を示す。］ <(E) Sensitizer>
The photosensitive resin composition may contain the (E) sensitizer as needed. (E) The kind of sensitizer is not specifically limited, It can select suitably from the sensitizer mix | blended with the conventional photosensitive resin composition containing a novolak resin, a photosensitive agent, and a crosslinking agent. Specifically, a phenol compound represented by the following formula (E-1) can be used.

[In the formula (E-1), R ^{e1 to} R ^e8 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group. R ^{e9 to} R ^e11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following formula (E-2) Or Q and R ^e9 are combined to form a cycloalkylidene group having 3 to 6 carbon atoms; w and s are integers of 1 to 3; u is an integer of 0 to 3 V represents an integer of 0 to 3. ]

［式（Ｅ−２）において、Ｒ^ｅ１２及びＲ^ｅ１３はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又はシクロアルキル基を示し；ｔは１〜３の整数を示す。］

[In Formula (E-2), R ^e12 and R ^e13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group. Showing; t shows the integer of 1-3. ]

  Examples of the phenol compound represented by the formula (E-1) include bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4-bis [1- (3,5 -Dimethyl-4-hydroxyphenyl) isopropyl] benzene, 2,4-bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-Hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] ben 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] -4-methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenyl) Methyl) pyrogallol, 4,6-bis (3,5-dimethyl-4-hydroxyphenylmethyl) pyrogallol, 2,6-bis (3-methyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2, 6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol and 1,1-bis (4-hydroxyphenyl) si And the like can be given Rohekisan. In addition, 6-hydroxy-4a- (2,4-dihydroxyphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthene, and 6-hydroxy-5- Methyl-4a- (2,4-dihydroxy-3-methylphenyl) -9-1'-spirocyclohexyl-1,2,3,4,4a, 9a-hexahydroxanthene and the like can also be used. These sensitizers may be used alone or in combination of two or more. Among them, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis ( 4-Hydroxyphenyl) ethyl] benzene and bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane are preferred because the sensitivity of the photosensitive resin composition is good.

［式（Ｅ−３）において、Ｒ^ｅ１４〜Ｒ^ｅ１６は、それぞれ独立に、低級アルキル基、シクロアルキル基、又は低級アルコキシ基を示し；ｑ及びｒは、それぞれ独立に、１〜３、好ましくは１又は２である整数を示し；ｌ、ｏ、及びｐは、それぞれ独立に、０〜３の整数を示す。］ Moreover, as a sensitizer, the phenolic compound represented by a following formula (E-3) can be used.

[In Formula (E-3), R ^{e14 to} R ^e16 each independently represent a lower alkyl group, a cycloalkyl group, or a lower alkoxy group; q and r each independently represent 1 to 3, preferably 1 represents an integer that is 1 or 2; l, o, and p each independently represent an integer of 0 to 3; ]

Here, the lower alkyl group and lower alkoxy group represented by R ^{e14 to} R ^e16 may be linear or branched, and preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. is there. The cycloalkyl group represented by R ^{e14 to} R ^e16 preferably has 5 to 7 carbon atoms.

More specifically, examples of the compound represented by the formula (E-3) include compounds represented by the following formulas (E-4) to (E-8).

［式（Ｅ−９）において、Ｒ^ｅ１７〜Ｒ^ｅ２５は、それぞれ独立に、水素原子、アルキル基、ハロゲン原子、又はヒドロキシル基を示し、Ｒ^ｅ１７〜Ｒ^ｅ２５のうち、少なくとも１つはヒドロキシル基である。Ｒ^ｅ２６〜Ｒ^ｅ３１は、それぞれ独立に、水素原子、アルキル基、アルケニル基、シクロアルキル基、又はアリール基を示す。］ Moreover, as a sensitizer, the phenolic compound represented by a following formula (E-9) can be used.

[In Formula (E-9), R ^{e17 to} R ^e25 each independently represent a hydrogen atom, an alkyl group, a halogen atom, or a hydroxyl group, and at least one of R ^{e17 to} R ^e25 is a hydroxyl group. is there. R ^{e26 to} R ^e31 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group. ]

Here, it is preferable that at least one of R ^{e17 to} R ^e20 and at least one of R ^{e21 to} R ^e25 are hydroxyl groups. The alkyl group represented by R ^{e17 to} R ^e25 may be linear or branched, and preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Furthermore, the alkyl group represented by R ^{e26 to} R ^e31 may be linear or branched, and preferably has 1 to 10 carbon atoms. The alkenyl group represented by R ^{e26 to} R ^e31 preferably has 2 to 4 carbon atoms.

［式（Ｅ−１０）において、Ｒ^ｅ３２及びＲ^ｅ３３は、それぞれ独立にアルキル基を示し、ｆ及びｇは、１〜３、好ましくは１又は２である整数を示し、ｊ及びｚは０〜３の整数を示す。］ More specifically, examples of the phenol compound represented by the formula (E-9) include a compound represented by the following formula (E-10).

[In Formula (E-10), R ^e32 and R ^e33 each independently represent an alkyl group, f and g each represent an integer of 1 to 3, preferably 1 or 2, and j and z are 0 to 0. An integer of 3 is shown. ]

Here, the alkyl group represented by R ^e32 and R ^e33 may be linear or branched, and preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

More specifically, examples of the phenol compound represented by the formula (E-9) include compounds represented by the following formulas (E-11) and (E-12).

  The blending amount of the sensitizer is preferably 1 to 30% by mass and more preferably 3 to 25% by mass or less with respect to the mass of the (A) novolac resin.

<(F) Colorant>
The photosensitive resin composition may contain a colorant (F) as necessary as long as the insulating property of the insulating film formed using the photosensitive resin composition is not impaired.

  The (F) colorant that may be contained in the photosensitive resin composition is not particularly limited. For example, in the color index (CI; issued by The Society of Dyers and Colorists), pigments (Pigment) It is preferable to use the classified compounds, specifically those having the following color index (CI) numbers.

  Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 , And 185.

  Examples of orange pigments that can be suitably used include C.I. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, and 73.

  Examples of purple pigments that can be suitably used include C.I. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50 Can be mentioned.

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7.

  The colorant (F) is also preferably a light shielding agent. For example, when the insulating film is a bank that separates adjacent pixels, the image quality of the organic EL display device can be improved by providing the bank with light shielding properties. (F) When using a colorant as a light-shielding agent, it is preferable to use a black pigment or a purple pigment as the light-shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides In addition, various pigments can be mentioned regardless of organic matter or inorganic matter such as metal sulfate or metal carbonate. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total mass of the carbon black and the mass of the resin.

  A perylene pigment is also preferable as the light-shielding agent. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (f-1), the perylene pigment represented by the following formula (f-2), and the following formula (f-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

式（ｆ−１）中、Ｒ^ｆ１及びＲ^ｆ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｆ３及びＲ^ｆ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (f-1), R ^f1 and R ^f2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^f3 and R ^f4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or Represents an acetyl group.

式（ｆ−２）中、Ｒ^ｆ５及びＲ^ｆ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In formula (f-2), R ^f5 and R ^f6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｆ−３）中、Ｒ^ｆ７及びＲ^ｆ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｆ７及びＲ^ｆ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (f-3), R ^f7 and R ^f8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. Good. When R ^f7 and R ^f8 are alkyl groups, the alkyl group may be linear or branched.

  Examples of the compound represented by the formula (f-1), the compound represented by the formula (f-2), and the compound represented by the formula (f-3) include, for example, JP-A No. 62-1753. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

  In order to satisfactorily disperse the perylene pigment in the photosensitive resin composition, the average particle size of the perylene pigment is preferably 10 to 1000 nm.

  The light-shielding agent may contain a dye having a hue such as red, blue, green, and yellow together with the black pigment and the purple pigment for the purpose of adjusting the color tone. The pigment of other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as the coloring matter of other hues of black pigments and purple pigments. The amount of the dye having a hue other than the black pigment or the purple pigment is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total mass of the light shielding agent.

  In order to uniformly disperse the colorant (F) in the photosensitive resin composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant (F), it is preferable to use an acrylic resin-based dispersant as the dispersant.

  In addition, each of the inorganic pigment and the organic pigment may be used alone or in combination of two or more. It is preferably used in the range, and more preferably in the range of 20 to 40% by mass.

  The amount of the colorant (F) used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention. -70 mass% is preferable, and 25-60 mass% is more preferable.

  (F) It is preferable to add the colorant to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at an appropriate concentration using a dispersant.

<(G) Other ingredients>
The photosensitive resin composition may contain various additives as long as the object of the present invention is not impaired. Examples of the additive that may be contained in the photosensitive resin composition include a surfactant, a plasticizer, and a liquid repellent.

[Surfactant]
The photosensitive resin composition may contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties, and the like. As the surfactant, for example, BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFac F173, MegaFack F183 (Dainippon Ink Chemical Co., Ltd.), Florard FC-135, Fluoraro FC-170C, Fluorado FC-430, Fluorado FC-431 (Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (Asahi Glass Co., Ltd.) , SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone), BYK-310, BYK-330 (manufactured by BYK Japan Japan), etc. Or fluorinated surfactants can be used Wear.

  The content of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the (A) novolak resin.

[Plasticizer]
In order to suppress the occurrence of cracks, the photosensitive resin composition may contain an alkali-soluble acrylic resin as a plasticizer. Generally as an alkali-soluble acrylic resin, what is mix | blended with the positive photoresist composition as a plasticizer can be used.

  More specifically, as the alkali-soluble acrylic resin, a constitutional unit derived from a polymerizable compound having a carboxyl group and a constitutional unit derived from a polymerizable compound having an ether bond is 30% by mass or more and 90% by mass or less. 2 parts by mass or more and 50 parts by mass or less.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meta ), Radically polymerizable compounds such as (meth) acrylic acid derivatives having an ether bond and an ester bond such as methoxypolypropylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Among these, it is preferable to use 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate. These compounds may be used independently and may be used in mixture of 2 or more types.

  Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxyethyl succinic acid, 2- Examples thereof include radical polymerizable compounds such as methacrylic acid derivatives having a carboxyl group and an ester bond such as methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. Among these, it is preferable to use acrylic acid and methacrylic acid. These compounds may be used alone or in combination of two or more.

  30-90 mass% is preferable and, as for content of the polymeric compound which has an ether bond in an alkali-soluble acrylic resin component, 40-80 mass% is more preferable. By blending an amount of the alkali-soluble acrylic resin component in such a range into the photosensitive resin composition as a plasticizer, it is easy to form a homogeneous insulating film while suppressing the occurrence of cracks in the insulating film.

  2-50 mass% is preferable and, as for content of the structural unit derived from the polymeric compound which has a carboxyl group in an alkali-soluble acrylic resin component, 5-40 mass% is more preferable. The developability of the photosensitive resin composition is improved by blending the photosensitive resin composition with an alkali-soluble acrylic resin component containing a structural unit derived from a polymerizable compound having a carboxyl group in such an amount as a plasticizer. Can be.

  The polystyrene-reduced mass average molecular weight of the alkali-soluble acrylic resin component is preferably 10,000 to 800,000, and more preferably 30,000 to 500,000.

  The alkali-soluble acrylic resin component may contain structural units derived from other radical polymerizable compounds for the purpose of appropriately controlling physical and chemical properties. Here, the “other radical polymerizable compound” means a radical polymerizable compound other than the above-described polymerizable compound.

  Such other radically polymerizable compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, And (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate and (meth) acrylic aryl esters such as benzyl (meth) acrylate; diethyl maleate and fumarate Dicarboxylic acid diesters such as dibutyl acid; vinyl group-containing aromatic compounds such as styrene and α-methylstyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; acrylonitrile and methacrylo Nitrile group-containing polymerizable compounds tolyl; can be used as well as amide-bond-containing polymerizable compounds such as acrylamide and methacrylamide; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride. These compounds may be used alone or in combination of two or more. Among these compounds, it is particularly preferable to use n-butyl acrylate, benzyl methacrylate, methyl methacrylate, and the like. The content of structural units derived from other radical polymerizable compounds in the alkali-soluble acrylic resin component is preferably less than 50% by mass, and more preferably less than 40% by mass.

  Examples of the polymerization solvent used for synthesizing the alkali-soluble acrylic resin component include alcohols such as ethanol and diethylene glycol; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol ethyl methyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl isobutyl ketone; and ethyl acetate and butyl acetate Ester etc. can be used. Among these polymerizable solvents, it is particularly preferable to use polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether acetates.

As a polymerization catalyst used when synthesizing the alkali-soluble acrylic resin component, a normal radical polymerization initiator can be used, for example, an azo compound such as 2,2′-azobisisobutyronitrile; and benzoyl peroxide, and An organic peroxide such as di-tert-butyl peroxide can be used.

  30 mass parts or less are preferable with respect to 100 mass parts of (A) novolak resin, and, as for the compounding quantity of the alkali-soluble acrylic resin component in the photosensitive resin composition, 20 mass parts or less are more preferable.

[Liquid repellent]
By mix | blending a liquid repellent with the photosensitive resin composition, liquid repellency is provided to the insulating film formed. For example, in the case where the insulating film is a bank that separates adjacent pixels, a functional layer may be formed by an inkjet printing method in a section partitioned by the bank. In this case, since the bank has liquid repellency, it is possible to effectively prevent unwanted mixing of different types of inks that are driven into adjacent sections. The liquid repellent is not particularly limited, but a fluorine-containing resin is preferable. The kind of fluorine-containing resin is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected from conventionally known fluorine-containing resins.

  0.1-10 mass parts is preferable with respect to 100 mass parts of (A) novolak resin, and, as for the compounding quantity of the liquid repellent in the photosensitive resin composition, 0.2-5 mass parts is more preferable.

<(S) Solvent>
The photosensitive resin composition is preferably used in the form of a solution by dissolving the above-described components in a suitable solvent. Examples of such solvents include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol mono Propylene glycol alkyl ether acetates such as propyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and 2-hydroxy Methyl propionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl- Examples thereof include esters such as 3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These solvents may be used alone or in combination of two or more.

  The content of the (S) solvent in the photosensitive resin composition is appropriately adjusted in consideration of the viscosity and applicability of the photosensitive resin composition. Specifically, the (S) solvent is used so that the solid content concentration of the photosensitive resin composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

≪Method for preparing photosensitive resin composition≫
The photosensitive resin composition can be prepared by blending the above-described components at a predetermined ratio, and then mixing and stirring them by a usual method. Moreover, you may further filter using a mesh, a membrane filter, etc. as needed.

≪Method of forming insulating film≫
The insulating film includes a coating process for forming a coating film of the photosensitive resin composition on the substrate, an exposure process for exposing the coating film to position selective irradiation with active rays, and a development for developing the exposed coating film. And a process including the steps.

[Coating process]
In the coating process, a photosensitive resin composition is coated on a substrate for forming an EL display element having various functional layers as necessary using a spinner or the like to form a coating film. The thickness of the coating film is typically preferably 0.5 to 10 μm. If necessary, the coating film is pre-baked (post-apply bake (PAB)) at a temperature of 80 to 150 ° C. for 40 to 600 seconds, preferably 60 to 360 seconds.

[Exposure process]
For example, a low pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp, which are light sources that emit light in the vicinity of a wavelength of 365 nm (i-line), 405 nm (h-line), and 435 nm (g-line), are used for the coating film. The exposure is selectively performed through the mask pattern. The active rays used for exposure include ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet rays (in addition to G-line, H-line, and I-line from the low-pressure mercury lamp, high-pressure mercury lamp, and ultra-high-pressure mercury lamp. Radiation such as EUV), vacuum ultraviolet (VUV), electron beam (EB), X-ray, and soft X-ray can also be used. After the exposure, post-exposure heating (PEB) may be performed under a temperature condition of 80 to 150 ° C., if necessary, for 40 to 600 seconds, preferably 60 to 360 seconds.

[Development process]
In the development step, the exposed coating film was subjected to development treatment at a temperature of 20 to 30 ° C. using an alkaline developer, for example, an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.1 to 10% by mass. Thereafter, if necessary, water rinsing with pure water and drying are performed.

  After the development, the patterned insulating film is preferably subjected to a baking process (post-bake). By performing post-baking, the taper angle, which is an angle between the end surface of the insulating film and the surface where the insulating film is in contact with the substrate, can be reduced. The baking temperature is preferably from 100 to 400 ° C, more preferably from 150 to 300 ° C. The baking time is preferably 15 to 60 minutes, and more preferably 30 minutes or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In addition, Example 4 shall be read as a reference example.

[Examples 1 to 11 and Comparative Examples 1 to 9]
(Resin component)
In Examples and Comparative Examples, the resins listed in Table 1 below were used as resin components serving as substitute components for (A) novolak resin or (A) novolak resin.

Of the resin components listed in Table 1 below, as the cresol novolac resin, a resin prepared according to the following formulation was used.
<Preparation method of cresol novolac resin>
The reaction vessel was charged with m-cresol and p-cresol in the ratios shown in Table 1, formaldehyde, and a catalytic amount of oxalic acid. The contents of the reaction vessel were reacted under reflux conditions for 4 hours according to a conventional method to prepare a crude cresol novolak resin. Thereafter, the crude cresol novolak resin was heated under reduced pressure to remove low molecular weight components in the resin, thereby obtaining a cresol novolak resin. The monomer and dimer contents in the cresol novolac resin were adjusted by adjusting the heating temperature and the treatment time in the heating step under reduced pressure. The contents of monomer and dimer in the cresol novolak resin were measured from area% of the GPC chart. The measurement conditions for GPC are as follows.
Device name: Shodex SYSTEM21 (manufactured by Shodex)
Column: Shodex KF-G, KF-801
Column oven: 40 ° C
Eluent: THF
Flow rate: 1.0 mL / min
Sample concentration: 0.02 g / 10 ml THF
Injection volume: 20 μl
Detector: Detects UV 280nm absorption

In Comparative Example 9, polyamic acid prepared according to the following method was used as a resin component. A specific method for producing a polyamic acid is as follows.
In a 5 L separable flask equipped with a stirrer, a stirring blade, a reflux condenser, and a nitrogen gas introduction tube, 654.4 parts by mass of pyromellitic dianhydride, 672.8 parts by mass of 4,4′-diaminodiphenyl ether, And 2518 parts by mass of N-methyl-2-pyrrolidone were added. Nitrogen was introduced into the flask through a nitrogen gas introduction tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. Next, while stirring the contents of the flask, tetracarboxylic dianhydride and diamine were reacted at 50 ° C. for 20 hours to obtain a polyamic acid solution. The solvent was distilled off to obtain a polyamic acid.

(Photosensitive agent)
In Examples and Comparative Examples, the following B1 and B2 were used as photosensitive agents.
B1: 1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone B2: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1- 1,2-Naphthoquinonediazide-5-sulfonic acid ester of bis (4-hydroxyphenyl) ethyl] benzene

(Crosslinking agent)
In Examples and Comparative Examples, hexamethylol melamine hexamethyl ether was used as a crosslinking agent.

(Silane coupling agent)
In Examples and Comparative Examples, as (D) a silane coupling agent having an oxirane ring or an oxetane ring, or (D) a silane coupling agent serving as an alternative component of a silane coupling agent having an oxirane ring or an oxetane ring, the following D1 And D1: (3-glycidyloxy-n-propyl) trimethoxysilane D2: vinyltrimethoxysilane

(Sensitizer)
In Examples and Comparative Examples, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene was used as a sensitizer.

(Coloring agent)
In Example 9, perylene black was used as a colorant. In Example 10, C.I. I. Pigment Blue 15: 6 was used. In Example 11, C.I. I. Pigment Red 254 was used.

  After mixing the resin component, the photosensitizer, the crosslinking agent, the silane coupling agent, the sensitizer, the colorant, and the fluororesin of the types and amounts shown in Table 2, the solid content concentration is 28. It diluted with the organic solvent so that it might become mass%, and the photosensitive resin composition of each Example and the comparative example was obtained. In Examples 1-12 and Comparative Examples 1-8, propylene glycol monomethyl ether acetate was used as an organic solvent for dilution. In Comparative Example 9, a mixed solvent composed of 50% by mass of ethyl lactate and 50% by mass of γ-butyrolactone was used as the organic solvent for dilution. About the obtained insulating film formed using the photosensitive resin composition, the remaining film ratio, taper angle, water resistance, heat resistance, and solvent resistance were evaluated according to the following methods. These evaluation results are shown in Table 3.

<Residual film rate evaluation>
(After development)
A photosensitive resin composition was applied on a 6-inch silicon substrate using a spin coater, and prebaked at 110 ° C. for 90 seconds to form a coating film having a thickness of 1.52 μm. After forming the coating film, the coating film was exposed through a photomask with an exposure apparatus (G7E, manufactured by Nikon Corporation) at the minimum exposure amount (Eth) that can be developed. After the exposure, paddle development was performed using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass as a developer. The thickness of the insulating film formed after development was measured, and the residual film ratio after development (ratio of the film thickness after development to the film thickness before exposure (1.52 μm)) was determined. Table 3 shows the residual film ratio after development.

(After post-baking)
Other than changing the exposure apparatus to (MPA-600FA, manufactured by Canon Inc.), an insulating film was formed by performing coating film formation, exposure, and development in the same manner as the evaluation of the remaining film ratio after development. The formed insulating film was post-baked in an oven at 230 ° C. for 30 minutes. The thickness of the post-baked insulating film was measured, and the remaining film ratio after post-baking (the ratio of the film thickness after post-baking to the film thickness before exposure (1.52 μm)) was determined. Table 3 shows the remaining film ratio after post-baking.

<Taper angle evaluation>
The cross section of the insulating film after post-baking formed in the evaluation of the remaining film rate was observed with a microscope, and the taper angle, which is an acute angle, among the angles formed by the substrate surface and the end face of the insulating film was measured. A case where the taper angle was 35 ° or less was determined as a taper angle “◯”, and a case where the taper angle was more than 35 ° was determined as a taper angle “x”. Table 3 shows the taper angle and the evaluation result of the taper angle.

<Water resistance evaluation>
A photosensitive resin composition is applied to the surface of a polyimide film (Kapton (registered trademark) H200, manufactured by Toray DuPont) using a spin coater, and then pre-baked at 100 ° C. for 90 seconds to form a coating film having a thickness of 2 μm. Formed. The formed coating film was post-baked at 230 ° C. for 60 seconds to obtain an insulating film. About the polyimide film and the sample by which the polyimide film and the insulating film were laminated | stacked, the water permeability (g / m < ² > * day) was measured using the water permeability measuring apparatus (L80-5000 type | mold, the product made by Lyssy). The ratio (WVTR (%)) of the water permeability of the sample on which the polyimide film and the insulating film were laminated to the water permeability of the polyimide film was determined as a water resistance index. A case where WVRT was 90% or less was determined as water resistance “◯”, and a case where WVRT was more than 90% was determined as water resistance “x”. Table 3 shows the WVTR and the evaluation results of water resistance.

<Heat resistance evaluation>
Using a sample collected from the insulating film formed in the water resistance evaluation, a differential heat / thermogravimetry apparatus (TG / DTA-6200, manufactured by Seiko Instruments Inc.) was used to raise the temperature rising rate at 10 ° C./min in an air stream. Measurement was performed under the conditions of, and a TG curve was obtained. From the obtained TG curve, the 5% weight reduction temperature of the sample was determined. The case where the 5% weight loss temperature was 310 ° C. or higher was determined as heat resistance “◯”, and the case where it was less than 310 ° C. was determined as heat resistance “x”. Table 3 shows the 5% weight loss temperature and the heat resistance evaluation results.

<Solvent resistance evaluation>
An insulating film having a thickness of 2 μm was formed in the same manner as the evaluation of water resistance except that the polyimide film was changed to a 6-inch silicon substrate. The formed insulating film was immersed for 10 minutes in a mixed solvent consisting of 65 wt% diethylene glycol monobutyl ether and 35 wt% of monoethanolamine was measured insulating film thickness T ₁₀ of the after immersion for 10 minutes. Next, the film thickness increase rate was calculated according to the following formula as an index of solvent resistance. When the rate of film thickness increase is 0.6% / min or less, the solvent resistance is judged as “◯”, and when it exceeds 0.6% / min or a negative value, the solvent resistance is “x”. Judged. Table 3 shows the rate of film thickness increase and the evaluation results of solvent resistance.
Film thickness increase rate (% / min) = (T ₁₀ −2) ÷ 2 × 100 ÷ 10

  Examples 1 to 11 include (A) a novolak resin, (B) a photosensitizer, (C) a crosslinking agent, and (D) a silane coupling agent having an oxirane ring or an oxetane ring, ) If the total content of monomers and dimers in the novolak resin is 5 to 18% by mass, excessive film reduction will not occur even in the development process and baking process, and in a short time It can be seen that the taper angle of the insulating film can be satisfactorily reduced by this baking process, and an insulating film having high water resistance, solvent resistance, and heat resistance can be formed.

  According to Examples 9-11, even if it mix | blends a various coloring agent with the photosensitive resin composition, it turns out that there is no special malfunction in the characteristic of the insulating film formed.

  According to Comparative Examples 1 to 4, when the content of monomer and dimer in the novolak resin contained in the photosensitive resin composition is too small, it is difficult to form an insulating film having a low taper angle, and the formed insulating film is It turns out that it is easy to swell with a solvent.

  According to Comparative Example 5, it can be seen that when the content of the monomer and dimer in the novolak resin contained in the photosensitive resin composition is excessive, excessive film reduction occurs when the insulating film is formed.

  According to Comparative Examples 6 and 7, when the photosensitive resin composition does not contain a silane coupling agent having an oxirane ring or an oxetane ring, it is difficult to form an insulating film having a low taper angle if the amount of the crosslinking agent is increased. Thus, it can be seen that when the amount of the crosslinking agent is lowered, the solvent resistance of the insulating film is impaired.

  According to Comparative Example 8, when the photosensitive resin composition contains vinyltrimethoxysilane instead of a silane coupling agent having an oxirane ring or an oxetane ring, it is difficult to form an insulating film having a low taper angle. It turns out that water resistance and solvent resistance will be impaired.

  According to Comparative Example 9, when the photosensitive resin composition contains a polyamic acid instead of a novolak resin, an excessively thin film is easily formed when an insulating film is formed, and an insulating film having a low taper angle is formed. It can be seen that the insulating film is easily dissolved in the solvent.

Claims (10)

(A) a novolak resin, (B) a photosensitizer, (C) a crosslinking agent, and (D) a silane coupling agent having an oxirane ring or an oxetane ring,
The photosensitive resin composition for forming an insulating film in an organic EL display device, wherein the content of the monomer and dimer in the (A) novolak resin is 7 to 18% by mass with respect to the mass of the (A) novolac resin. The photosensitive resin composition of Claim 1 whose content of the monomer and dimer in said (A) novolak resin is 7.9-10 mass% with respect to the mass of (A) novolak resin. The photosensitive resin composition according to claim 1 or 2 , wherein the (A) novolak resin has a polystyrene-equivalent weight average molecular weight of 5000 to 7000. The photosensitive resin composition of any one of Claims 1-3 whose said (B) photosensitive agent is a compound containing a naphthoquinone diazide group. The photosensitive resin composition of any one of Claims 1-4 whose said (C) crosslinking agent is a compound represented by a following formula (C1).

(In formula (C1), R ^{c1 to} R ^c6 are a hydrogen atom or a group represented by —CH ₂ —O—R ^c7 , and R ^c7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , At least one of R ^{c1 to} R ^c6 is a group represented by —CH ₂ —O—R ^c7 .) The content of the compound represented by the formula (C1) is 3 to 15% by mass in the solid content of the photosensitive resin composition, and (D) the content of the silane coupling agent having an oxirane ring or an oxetane ring. The photosensitive resin composition of Claim 5 whose quantity is 3-20 mass% in solid content of the said photosensitive resin composition. The photosensitive resin composition of any one of Claims 1-6 by which the silane coupling agent which has the said (D) oxirane ring or an oxetane ring is represented by a following formula (D1).
_{^{R d1 m R d2 (3-}} m) Si-R d3 -Y-X ··· (D1)
(In Formula (D1), R ^d1 is an alkoxy group, R ^d2 is an alkyl group, R ^d3 is an alkylene group, m is an integer of 1 to 3, and Y is —NH— or —O—. Or -S-, and X is an organic group having an oxirane ring or an oxetane ring. The monomer is one in which phenols that have not undergone polymerization reaction among the phenols used in the production of the (A) novolak resin remain in the (A) novolak resin,
The dimer is the one that has undergone only dimerization reaction among the phenols used in the production of the (A) novolak resin, and remains in the (A) novolak resin. the photosensitive resin composition according to any one of 7. The insulating film in an organic EL element formed using the photosensitive resin composition of any one of Claims 1-8 . The bank in an organic EL element formed using the photosensitive resin composition of any one of Claims 1-8 .