JPWO2011142391A1 - Photosensitive resin composition and display device - Google Patents

Abstract

A positive type film which can satisfy the basic performance requirements for an electrode protective film, a planarizing film and an insulating film by curing, and can obtain a film having high hardness required for various materials of recent display devices. A photosensitive resin composition is provided. Further, a display device having excellent mechanical strength is provided. A photosensitive resin composition containing an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at a terminal, a quinonediazide compound, a silsesquioxane, and a solvent, and curing the resin composition A display device having a film formed as described above. [Selection figure] None

Description

  The present invention relates to a photosensitive resin composition and a display device.

  An active matrix driving type liquid crystal display device provided with a thin film transistor (TFT), an active matrix driving type organic EL display device provided with an organic EL (Electro-Luminescence) element and a thin film transistor connected thereto, and the like This display device is provided with a patterned electrode protective film, planarization film, insulating film, and the like. A photosensitive resin composition is generally used as a material for forming these films, and among them, a material having a small number of steps for obtaining a predetermined pattern shape and excellent in transparency is widely used.

  Further, the electrode protective film, the planarizing film, and the insulating film are required to have various characteristics necessary for the display device. Specifically, it has excellent process resistance such as heat resistance, solvent resistance, reflow resistance and metal sputtering resistance, good adhesion to the substrate, and various process conditions according to the purpose of use. Examples thereof include a wide process margin capable of forming a pattern, high sensitivity to light, high transparency, and little film thickness unevenness after development. For this reason, the photosensitive resin composition containing a naphthoquinone diazide compound has been used widely conventionally.

  On the other hand, with the spread of touch panels in recent years, the number of display devices in which a touch panel is provided on a liquid crystal display element or an organic EL element is increasing. The touch panel system includes a resistive film system, a capacitive system, an ultrasonic system, an optical system, an electromagnetic induction system, etc., but many manufacturers adopt the capacitive system in terms of performance. In the electrostatic capacity method, a wiring made of a transparent conductive film is formed on a substrate, and an interlayer insulating film is provided to prevent conduction between the wirings. This interlayer insulating film is required to have high hardness. In addition, there is an in-cell touch panel in which a touch panel mechanism is incorporated in the liquid crystal display element, but in this case, higher hardness is required for the electrode protective film.

  In addition, glass substrates are used in conventional display devices, but in recent years, display devices have been required to have high durability in portable devices in addition to lightening, thinning, upsizing, curved display, and the like. It is growing. Therefore, practical application of a resin substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide instead of a glass substrate has been studied. When a flexible display becomes possible by applying a resin substrate, the electrode protective film, the planarizing film, and the insulating film are required to have higher hardness in order to increase mechanical strength.

  By the way, the photosensitive resin composition includes a negative type that is cured by exposure and has low solubility in a developer, and a positive type that has high solubility in a developer by exposure. Many of the negative types have problems in terms of handling and environment because an organic solvent is used as a developer. Further, since the solvent swells the film during development, there is a problem that it is difficult to form fine wiring. On the other hand, the positive type is advantageous over the negative type in terms of the above points, but there is a problem that it is difficult to achieve high hardness as compared with the negative type in which curing proceeds by exposure.

  In Patent Document 1, at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and at least one selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound. A positive radiation sensitive resin composition containing a copolymer of an unsaturated mixture containing a seed, a 1,2-quinonediazide compound and a silsesquioxane having an aryl group having 6 to 15 carbon atoms is described. Has been. According to this composition, it is considered that a patterned thin film suitable for an interlayer insulating film or the like can be formed. However, there is a problem that a crosslinking reaction is slow and it is difficult to obtain reflow resistance.

  Patent Document 2 discloses an acrylic copolymer obtained by copolymerizing at least one of a silsesquioxane polyhedral oligomer-containing unsaturated compound, an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, and an olefinic unsaturated compound. A photosensitive resin composition containing a copolymer and a 1,2-quinonediazide compound is disclosed. This composition is excellent in flatness after development, sensitivity, resolution, heat resistance and transparency, and is considered suitable as an insulating film for a display device. However, in this case, since monofunctional silsesquioxane is used, the silsesquioxane portion is not crosslinked in the polymer after copolymerization, and there is a concern that the hardness of the resulting film is insufficient.

  Patent Document 3 discloses a photosensitive resin composition suitable as an insulating film for a display device. The composition comprises an ethylenically unsaturated group-containing compound and a photopolymerization initiator, a cationic polymerizable compound such as a glycidyl ether compound and a photocationic polymerization initiator, and at least one compound selected from quinonediazide compounds, diazonium compounds and azide compounds. And at least one photosensitive organic component selected from the group consisting of inorganic particles and cage silsesquioxane. However, this configuration has a problem that the resolution is lowered by the added inorganic particles in order to maintain the shape retention during firing. Actually, in the example of Patent Document 3, the via diameter retention ratio after firing a via pattern having a hole diameter of 20 μm is 65%.

JP 2009-229892 A JP 2007-119777 A JP 2007-47247 A

  The present invention has been considered in view of the above problems. That is, an object of the present invention is to provide a film having high hardness required for various display device materials in recent years while satisfying the basic required performance for the electrode protective film, the planarizing film and the insulating film by curing. It is in providing the positive photosensitive resin composition obtained. Another object of the present invention is to provide a display device having excellent mechanical strength.

The photosensitive resin composition of the present invention is
(A): an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal;
(B): a quinonediazide compound,
(C): Silsesquioxane,
(D): Contains a solvent.

  The alkali-soluble acrylic polymer (A) preferably has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.

  In the alkali-soluble acrylic polymer (A), the end of the side chain is preferably an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group.

  The quinonediazide compound (B) is preferably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).

  The silsesquioxane (C) is preferably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).

  The photosensitive resin composition of the present invention further contains (E) a thermal acid generator in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer of (A). Is preferred.

  The photosensitive resin composition of the present invention is 1 to 40 parts by mass of (F) a compound having two or more vinyl groups directly bonded to a benzene ring, based on 100 parts by mass of the alkali-soluble acrylic polymer (A). It is preferable to contain in the quantity used.

  In the photosensitive resin composition of the present invention, 0.5 to 40 parts by mass of (G) an acrylic polymer having an epoxy group in the side chain with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A). It is preferable to contain in the quantity.

  The photosensitive resin composition of the present invention preferably further contains (H) an adhesion promoter in an amount of 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble acrylic polymer (A).

  The photosensitive resin composition of the present invention preferably further contains (I) a surfactant in an amount of 1.0 part by mass or less with respect to 100 parts by mass of the photosensitive resin composition.

  The display device of the present invention has a film formed by curing the photosensitive resin composition of the present invention.

According to the present invention, it is possible to provide a positive-type photosensitive resin composition that, when cured, satisfies basic performance requirements for an electrode protective film, a planarizing film, and an insulating film, and forms a film with high hardness.
Further, by providing a cured film obtained from the photosensitive resin composition, a high-quality display device having excellent mechanical strength is provided.

The positive photosensitive resin composition of the present invention comprises the following component (A), component (B), component (C) and solvent (D).
(A) component: alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal (B) component: quinonediazide compound (C) component: silsesquioxane (D) solvent

In addition, the photosensitive resin composition of the present invention includes, as desired, other components, (E) component: thermal acid generator described later, (F) component: a compound having two or more vinyl groups directly connected to the benzene ring, (G) Component: An acrylic polymer having an epoxy group in the side chain, (H) component; adhesion promoter and (I) component: surfactant, and other components described later can also be contained.
Details of each component will be described below.

<(A) component>
The component (A) is an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal. Preferably, the alkali-soluble acrylic polymer is an acrylic polymer having a polystyrene-equivalent number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 50,000.

  In the present invention, the acrylic polymer refers to a polymer obtained by homopolymerization or copolymerization of monomers having an unsaturated double bond such as acrylic ester, methacrylic ester and styrene. The acrylic polymer as the component (A) may be an acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.

  However, if the number average molecular weight of the acrylic polymer of the component (A) exceeds 50,000, the planarization performance with respect to the step may be lowered. On the other hand, if the number average molecular weight is less than 2,000 and is too small, curing may be insufficient during thermal curing and solvent resistance may be reduced. Accordingly, those having a number average molecular weight in the range of 2,000 to 50,000 are more preferable.

  The (A) component acrylic polymer preferably has 3 to 16 carbon atoms and has a side chain having an unsaturated bond at the terminal (hereinafter referred to as a specific side chain). . In addition, it has terminal unsaturated bonds in such an amount that the acrylic polymer of component (A) is 200 to 1,300 g equivalent per 1 mol equivalent of terminal unsaturated bonds contained in the specific side chain. preferable.

As the specific side chain, one having a structure represented by the following formula (1) is particularly preferable. The specific side chain represented by Formula (1) binds to the ester bond portion of the acrylic polymer as shown in Formula (1-1).

In the formula (1), R ₁ has 1 to 14 carbon atoms and is an organic group selected from the group consisting of an aliphatic group, an aliphatic group having a cyclic structure, and an aromatic group, or from this group An organic group comprising a combination of a plurality of organic groups selected. R ₁ may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.

Specific examples of R ₁ include the following formula (A-1) to formula (A-11).
In the formula, the ** side is bonded to the ester bond portion of the acrylic polymer, and the * side is bonded to the carbon atom having a double bond in the formula (1) (the carbon atom to which R ₂ is bonded).

In the formula (1), R ₂ represents a hydrogen atom or a methyl group, and R ₂ is more preferably a hydrogen atom.
The specific side chain represented by the formula (1) preferably has a terminal that is an acryloyl group, a methacryloyl group, a vinylphenyl group or an isopropenylphenyl group. For example, R ₁ represents the formula (A-1) to the formula (A -3), a specific side chain represented by formula (A-7) to formula (A-11) is preferable.

  The method for obtaining the acrylic polymer having the specific side chain as described above is not particularly limited. For example, an acrylic polymer having a specific functional group described later is generated in advance by a polymerization method such as radical polymerization. Next, by reacting this specific functional group with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to generate a specific side chain, an acrylic polymer as component (A) is obtained. be able to.

Here, the specific functional group refers to a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these functional groups. .
Examples of the specific compound include glycidyl acrylate, glycidyl methacrylate, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, acrylic acid chloride, methacrylic acid chloride, acrylic acid, methacrylic acid, m-tetramethylxylene diisocyanate, chlorostyrene, bromostyrene, Examples include allyl glycidyl ether, vinyl ethylene oxide, vinyl cyclohexene oxide or α, α-dimethyl-m-isopropenyl benzyl isocyanate.

  In the acrylic polymer thus obtained, an example of a preferable structure is an acrylic polymer having a structural unit represented by the formula (2).

In the formula (2), R ₁ has the same meaning as defined in the above formula (1), that is, an aliphatic group having 1 to 14 carbon atoms and containing an aliphatic group or a cyclic structure. And an organic group selected from the group consisting of aromatic groups or a combination of a plurality of organic groups selected from this group. R ₁ may contain a bond such as an ester bond, an ether bond, an amide bond or a urethane bond.
In formula (2), R ₃ represents a hydrogen atom or a methyl group.

  In the reaction for generating the specific side chain described above, the preferred combination of the specific functional group and the functional group of the specific compound that is involved in the reaction is a carboxyl group and a glycidyl group (epoxy group), a hydroxy group and an isocyanate. Group, phenolic hydroxy group and glycidyl group (epoxy group), carboxyl group and isocyanate group, amino group and isocyanate group, or hydroxy group and acid chloride. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

  In the reaction for generating the specific side chain described above, the acrylic polymer having the specific functional group is a monomer having a functional group (specific functional group) for reacting with the specific compound, that is, carboxyl group, glycidyl group, hydroxy group. A copolymer obtained by using a monomer having a group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group as an essential component, and having a number average molecular weight of 2,000 to 25,000 Is mentioned. Here, the monomer having a specific functional group used for the polymerization may be used alone, or a combination of plural types of monomers as long as the specific functional group does not react with each other during the polymerization. Good.

  Specific examples of the monomer suitable for obtaining an acrylic polymer having a specific functional group, that is, a monomer having a specific functional group are shown below, but are not limited thereto.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide and N- (carboxyphenyl) acrylamide.

  Examples of the monomer having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide and the like.

  Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone.

  Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

  Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide.

  As a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

  In the present invention, when an acrylic polymer having a specific functional group is obtained, a monomer having a non-reactive functional group that can be copolymerized with a monomer having a specific functional group can be used in combination.

  Examples of the monomer having a non-reactive functional group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. Hereinafter, although the specific example of the monomer which has a non-reactive functional group is given, it is not limited to these.

  Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, γ-butyrolactone acrylate, dicyclopentani Acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, γ-buty Lactone methacrylate, dicyclopentanyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

  In the present invention, the method for obtaining an acrylic polymer having a specific functional group is not particularly limited. For example, in a solvent in which a monomer having the specific functional group, a monomer having a non-reactive functional group capable of copolymerization, if desired, and a polymerization initiator, if desired, may coexist, It can be obtained by a polymerization reaction at a temperature of 110 ° C. The solvent used at this time is not particularly limited as long as it dissolves the monomer and polymerization initiator involved in the reaction. Specific examples include those described in (D) Solvent below.

  The acrylic polymer having a specific functional group obtained as described above is usually in a solution state dissolved in a solvent.

  By reacting the obtained acrylic polymer having a specific functional group with a specific compound, an acrylic polymer as component (A) (hereinafter referred to as a specific copolymer) is obtained. Normally, after obtaining an acrylic polymer having a specific functional group, the polymer in a solution state is reacted as it is with a specific compound to obtain a specific copolymer.

Specifically, for example, by adding glycidyl methacrylate to a solution of an acrylic polymer having a carboxyl group and reacting at a temperature of 80 ° C. to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride, Coalescence can be obtained. The solvent used at this time is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include those described in (D) Solvent below.
The specific copolymer obtained as described above is usually in a solution state dissolved in a solvent.

In the reaction of an acrylic polymer having a specific functional group with a specific compound, when the combination of the specific functional group and the functional group possessed by the specific compound is a carboxyl group and a glycidyl group, the resulting hydroxy group is reacted with a dicarboxylic acid anhydride. May be. Thereby, since the hydrophilic property of the specific copolymer finally obtained improves, the applicability | paintability and solubility at the time of using for the photosensitive resin composition become favorable.
Examples of such dicarboxylic acid anhydrides include phthalic acid anhydride, trimellitic acid anhydride, naphthalene dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-methyl-1,2-cyclohexanedicarboxylic acid. Anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, bicyclo [2.2 .2. ] Octene-2,3-dicarboxylic acid anhydride and the like.

  The solution of the specific copolymer is added under stirring such as diethyl ether or water to reprecipitate, and after the generated precipitate is filtered and washed, it is dried at normal temperature or reduced pressure at normal temperature or under heat, It can be set as the powder of a specific copolymer. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer is obtained. In addition, when it cannot refine | purify enough by one operation | movement, what is necessary is just to redissolve the obtained powder in a solvent and to repeat said operation. In the present invention, the powder of the specific copolymer may be used as it is, or the powder of the specific copolymer may be redissolved in a solvent (D) described later and used in a solution state. In the present invention, the acrylic polymer of component (A) may be a mixture of a plurality of types of specific copolymers.

<(B) component>
The quinonediazide compound of the component (B) is preferably a quinonediazide compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group. Such a quinonediazide compound is obtained, for example, by reacting a 1,2-quinonediazide compound with a compound having a hydroxy group and / or a compound having an amino group.
The 1,2-quinonediazide compound is preferably 1,2-quinonediazidesulfonic acid such as 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, etc. A compound or the like is preferably used.
More preferably, 10 to 100 mol%, particularly preferably 20 to 95 mol% of a hydroxy group or an amino group (the total amount of both having a hydroxy group and an amino group) is 1, A quinonediazide compound formed by esterification or amidation with a 2-quinonediazidesulfonic acid compound is used.
In this invention, the said quinonediazide compound can be used individually or in combination of 2 or more types.

  Here, as a compound having a hydroxy group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound, for example, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, gallic Acid ethyl, 1,3,3-tris (4-hydroxyphenyl) butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4 ′, 4 ″ -trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4, 4 ′-[1- [4- [1- (4-hydroxyl Nyl) -1-methylethyl] phenyl] ethylidene] bisphenol (α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene), 2,4-dihydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2 Phenol compounds such as, 5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-Butoxyethanol , 2-methoxypropanol, 2-butoxypropanol or aliphatic alcohols such as ethyl lactate and butyl lactate.

  Examples of the compound containing an amino group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminobiphenyl, and o. Examples thereof include anilines such as -phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether, or aminocyclohexane.

  Furthermore, examples of the compound containing both a hydroxy group and an amino group to be reacted with a 1,2-quinonediazide (sulfonic acid) compound include o-aminophenol, m-aminophenol, p-aminophenol, and 4-aminoresorcinol. 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4 -Amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) Propane and 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) Can be exemplified aminophenols or 2-aminoethanol, such as hexafluoropropane, alkanolamines such as 3-aminopropanol and 4-aminocyclohexanol and the like.

  The content of the component (B) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and more preferably 100 parts by mass of the component (A). The amount is preferably 10 to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer is reduced, and patterning by development may be difficult. When the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is reduced, or the component (B) absorbs light and the transparency of the cured film. May be reduced.

<(C) component>
The component (C) is silsesquioxane, specifically, a polysiloxane represented by [(RSiO _3/2 ) _n ] (wherein R represents a monovalent organic group). . The structure of the component (C) may be any of a random structure, a ladder structure, a complete cage structure or an incomplete cage structure, and is not particularly limited. Moreover, the (C) component can use silsesquioxane which consists of single or 2 types or more of combinations.

  Silsesquioxane is usually produced by a sol-gel method in which trialkoxysilane is hydrolyzed. By changing the type of trialkoxysilane used as a raw material, silsesquioxanes having different properties can be obtained. Specific examples of trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2- Aminoethyl) trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 Mercaptopropyl triethoxysilane, phenyl trimethoxysilane, trifluoropropyl trimethoxysilane, isobutyl trimethoxysilane, etc. n- hexyl trimethoxy silane and n- hexyl triethoxy silane. These trialkoxysilanes may be used alone or in combination of two or more. Of these, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3- Silsesquioxane formed by using at least one trialkoxysilane selected from the group consisting of acryloxypropyltrimethoxysilane is preferable from the viewpoint of reacting with the component (A) during thermosetting.

  The content of the component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and more preferably 100 parts by mass of the component (A). The amount is preferably 15 to 60 parts by mass. When the amount is less than 5 parts by mass, the hardness of the cured film formed using the positive photosensitive resin composition may be low, and when it is more than 100 parts by mass, tackiness occurs in the coating film after pre-baking. There is a case.

<(D) Solvent>
(D) The solvent dissolves the component (A), the component (B) and the component (C), and dissolves the components (E) to (I) and other components which are added as required. As long as the solvent has a dissolving ability, its type and structure are not particularly limited.

  As the preferred (D) solvent in the positive photosensitive resin composition of the present invention, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2- Pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxy Ethyl propionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2 -Pyrrolidone etc. are mentioned.

  These solvents may be used alone or in combination of two or more. (D) As a solvent, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate and butyl lactate have good coating properties and safety. It is preferable from the viewpoint of high. These are generally used as solvents for photoresist materials.

<(E) Component to [I] Component>
As described above, the positive photosensitive resin composition of the present invention is constituted by dissolving the component (A), the component (B) and the component (C) in the solvent (D). It is also possible to contain each component of (E) thru | or (I) demonstrated to (1).

<(E) component>
The component (E) is a thermal acid generator, and is a compound that generates an acid by thermal decomposition during post-baking, specifically, a compound that generates an acid by thermal decomposition at 150 ° C. to 250 ° C. It is not limited. Examples of such compounds include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris ( Methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid Butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p- Sylate, N-ethyl-4-toluenesulfonamide, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyl Iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p- tert-butylphenyl) iodonium trifluoromethanesulfonate, bis p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, tri Phenylsulfonium bromide, tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, Triphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) phosphonium tet Examples thereof include lafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, and tri (p-ethoxyphenyl) phosphonium tetrafluoroborate.

  Furthermore, examples of the thermal acid generator of component (E) include compounds represented by the following formulas (3) to (70).

  Of the above thermal acid generators, triphenylsulfonium salt-based thermal acid generators are preferred because of their high transparency.

  The content of the component (E) in the positive photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts per 100 parts by mass of the component (A). Part by mass, more preferably 1 to 10 parts by mass. When the amount is less than 0.1 parts by mass, the thermosetting speed is slow, and the pencil hardness may decrease. On the other hand, if it exceeds 30 parts by mass, partial curing may occur during pre-baking, and a residual film may be generated in the exposed area, or the storage stability of the solution may be reduced.

<(F) component>
The component (F) is a compound having two or more vinyl groups directly connected to the benzene ring, and the compound may be a compound having two or more vinyl groups on the same benzene ring, or 2 In the case of a compound containing two or more benzene rings, any of compounds having a total of two or more vinyl groups bonded to different benzene rings may be used. By adding the compound of the component (F) to the positive photosensitive resin composition of the present invention, the thermosetting property with the component (A) can be improved and the hardness can be improved.
Specific examples of the compound having two or more vinyl groups directly bonded to the benzene ring are o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 4,4′-divinylbiphenyl, Tris- (4-vinylphenyl) methane. And 4,4′-oxybis (vinylbenzene). As the component (F), compounds having two or more vinyl groups directly bonded to a benzene ring can be used alone or in combination of two or more.

  The content of the component (F) in the positive photosensitive resin composition of the present invention is preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, and more preferably 100 parts by weight of the component (A). Preferably it is 5-20 mass parts. When the amount is less than 1 part by mass, the pencil hardness may decrease. Moreover, when it exceeds 40 mass parts, a tack | tuck may generate | occur | produce in the coating film after a prebaking.

<(G) component>
(G) A component is an acrylic polymer which has an epoxy group in a side chain. By adding an acrylic polymer having an epoxy group in the side chain to the photosensitive resin composition of the present invention, it is possible to suppress film loss in unexposed portions during development. In addition, the acrylic copolymer of (G) component can use the mixture of the acrylic copolymer which has multiple types of epoxy groups in a side chain.

  The acrylic polymer as the component (G) can be obtained by the same polymerization method as the component (A) using an epoxy group-containing monomer such as glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and epoxycyclohexylmethyl methacrylate. Its number average molecular weight is 2,000 to 25,000.

  The acrylic polymer as the component (G) can be obtained by using a single monomer or a plurality of monomers having an epoxy group, and a monomer copolymerizable with the monomer having an epoxy group may be used in combination. The copolymerizable monomer is not particularly limited as long as it does not react with the epoxy group during the polymerization, but a monomer having no carboxyl group or amino group is preferable. When copolymerizing with a copolymerizable monomer, the proportion of the monomer having an epoxy group is preferably 20 mol% or more. Examples of such copolymerizable monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

  Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, γ-butyrolactone acrylate, 8-methyl-8- Licyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, 4-hydroxybutyl acrylate, caprolactone 2- ( And acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 3-methacryloyloxypropyltrimethoxysilane, 2- Methyl-2-adamantyl methacrylate, 2 Propyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl Methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6 Examples include lactones.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

  The method for obtaining the acrylic polymer having an epoxy group as the component (G) is not particularly limited. For example, it can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which a monomer having an epoxy group, another copolymerizable monomer if necessary, and a polymerization initiator if necessary coexist. It is done. The solvent used in that case will not be specifically limited if it dissolves the monomer and polymerization initiator which are concerned in reaction. Specific examples include the solvents described in the above (D) solvent. The acrylic polymer having an epoxy group thus obtained is usually in a solution state dissolved in a solvent.

  The solution of the acrylic copolymer of component (G) obtained as described above was added under stirring such as diethyl ether or water for reprecipitation, and the produced precipitate was filtered and washed, and then at atmospheric pressure. Or it can be set as the powder of the acrylic copolymer of (G) component by drying at normal temperature or heat-reducing under pressure reduction. By such an operation, the polymerization initiator and unreacted monomer coexisting with the (G) component acrylic copolymer can be removed. As a result, the purified (G) component acrylic copolymer powder Is obtained. If sufficient purification cannot be achieved by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated. In the present invention, the acrylic copolymer powder of component (G) may be used as it is, or (D) the acrylic copolymer powder of component (G) is re-dissolved in a solvent, You may use it as a state.

  The content of the component (G) in the positive photosensitive resin composition of the present invention is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 3 to 20 parts by mass. When the amount is less than 0.5 parts by mass, the unexposed part may be reduced in film thickness during development. On the other hand, if it exceeds 40 parts by mass, the exposed area may be poorly developed or the sensitivity may be greatly reduced.

<(H) component>
The component (H) is an adhesion promoter. By using the adhesion promoter, the adhesion between the cured film of the positive photosensitive resin composition and the substrate after development can be improved.

  Specific examples of adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, and vinyltrichlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylvinylethoxysilane , Diphenyldimethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (N-piperidinyl) propyltriethoxysilane and γ -Alkoxysilanes such as ureidopropyltriethoxysilane; hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, Silazanes such as dimethyltrimethylsilylamine and trimethylsilylimidazole; such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole and mercaptopyrimidine Heterocyclic compounds; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. One or more of these can be used in combination as component (H).

  Commercially available compounds can be used as the adhesion promoter, and these are easily available from, for example, Shin-Etsu Chemical Co., Ltd., MOMENTIVE, or Toray Dow Corning. For example, what is called a silane coupling agent and marketed may be obtained and used. Specific examples of such products include Z-6011, 6020, 6023, 6026, 6050, 6094, 6610, 6883, 6675, 6676, 6040, 6041, 6042, 6043, 6044, 6920 manufactured by Toray Dow Corning Silicone. , 6940, 6075, 6172, 6300, 6519, 6550, 6825, 6030, 6033, 6530, 6062, 6911 or 6860, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE- 402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-9103, KBM-573, KBM-575, KBM-6123 or KBE-585, MOMENTIVE A-151, A-171, A-172, A-2171, Y-9936, A-174, A-186, A- 187, A-1871, A-189, A-1891, A-1100, A-1110, A-1120, A-2120, Y-9669 or A-1160.

  The addition amount of the component (H) in the positive photosensitive resin composition of the present embodiment is 20 parts by mass or less, preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass of the component (A). Is 0.5 to 10 parts by mass. If it is used in an amount of 20 parts by mass or more, the heat resistance of the coating film may be lowered, and if it is less than 0.1 parts by mass, a sufficient effect of the adhesion promoter may not be obtained.

<(I) component>
The component (I) is a surfactant. By using the surfactant, the coating property of the positive photosensitive resin composition can be improved. (I) A component can be used individually or in combination of 2 or more types.

  The surfactant which is the component (I) of the present embodiment is not particularly limited as long as it does not impair the effects of the present invention. For example, a fluorine-type surfactant, a silicone-type surfactant, a nonionic surfactant, etc. are mentioned. This type of surfactant is readily available from, for example, Sumitomo 3M Co., Ltd., DIC Corporation, Asahi Glass Co., Ltd. or the like. Specific examples thereof include F-top EF301, EF303, EF352 (above, manufactured by Tochem Products Co., Ltd. (currently manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), MegaFac R30, R08, R90, BL20, R61, F171, F173, F471, F475, F479, F474, F477, F480, F482, F483, F484 (manufactured by DIC Corporation), Florard FC430, FC431 (above, Sumitomo 3M Corporation), Asahi Guard AG710, Surflon S -382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

  When a surfactant is used as the component (I) of the positive photosensitive resin composition of the present embodiment, the content thereof is usually 1.0 part by mass in 100 parts by mass of the positive photosensitive resin composition. Or less, preferably 0.5 parts by mass or less. When the amount of the surfactant as component (I) is set to an amount exceeding 1.0 part by mass, the coating property improvement effect expected in response to the increase in the content cannot be obtained. In other words, an inefficient use method will be performed.

<Other ingredients>
As described above, the positive photosensitive resin composition of the present invention can contain the components (E) to (I). However, as long as the effects of the present invention are not impaired, the positive photosensitive resin composition can be used as necessary. Other components can also be contained. Examples of other components include additives such as rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, or dissolution accelerators such as polyphenols and polycarboxylic acids.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention is
(A) an alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the end as a component;
(B) a quinonediazide compound as a component;
(C) Silsesquioxane as a component,
(D) Dissolved in a solvent.
This positive type photosensitive resin composition is further, if desired,
(E) a thermal acid generator as a component,
(F) a compound having two or more vinyl groups directly connected to the benzene ring as a component;
(G) an acrylic polymer having an epoxy group in the side chain as a component,
(H) Adhesion promoter as component,
As the component (I), one or more of the above-mentioned additives can be contained as a surfactant and the other components.

Preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1] Based on 100 parts by mass of component (A), 5 to 100 parts by mass of component (B), 5 to 100 parts by mass of component (C), which are positively dissolved in solvent (D) Type photosensitive resin composition.
[2] The positive photosensitive resin composition further comprising 0.1 to 30 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1].
[3] A positive photosensitive resin composition further comprising 1 to 40 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2].
[4] A positive photosensitive resin further containing 0.5 to 40 parts by mass of component (G) in the composition according to [1], [2] or [3], based on 100 parts by mass of component (A). Composition.
[5] In the composition according to [1], [2], [3] or [4], the composition further comprises (H) component in an amount of 20 parts by mass or less based on 100 parts by mass of component (A). Type photosensitive resin composition.
[6] In the composition of [1], [2], [3], [4] or [5] above, the component (I) is further added in an amount of 1.0 mass relative to 100 mass parts of the positive photosensitive resin composition. A positive photosensitive resin composition contained in an amount of at most parts.

  The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, it is 1 to 80% by mass, and for example 5 to 60% by mass, or 10 to 50% by mass. Here, solid content means what remove | excluded the (D) solvent from all the components of the positive photosensitive resin composition.

  The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited. As an example, (A) component (acrylic polymer) is dissolved in (D) solvent, and (B) component (quinonediazide compound) and (C) component (silsesquioxane) are mixed in this solution at a predetermined ratio. And a uniform solution method. In addition, at an appropriate stage of this preparation method, as necessary, component (E) (thermal acid generator), component (F) (compound having two or more vinyl groups directly connected to the benzene ring), component (G) (Acrylic polymer having epoxy group in side chain), (H) component (adhesion promoter), (I) component (surfactant), and other components are added and mixed.

  In preparing the positive photosensitive resin composition of the present invention, (D) a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is, and in this case, the solution of this component (A) In the same manner as described above, when (B) component, (C) component and the like are added to obtain a uniform solution, (D) a solvent may be further added for the purpose of adjusting the concentration. At this time, the (D) solvent used in the process of forming the specific copolymer and the (D) solvent used for concentration adjustment when preparing the positive photosensitive resin composition may be the same, It may be different.

  Thus, the prepared positive photosensitive resin composition in a solution state is preferably used after being filtered using a filter having a pore diameter of about 0.2 μm.

<Coating film and cured film>
Next, a method for obtaining a cured film by forming a coating film using the positive photosensitive resin composition of the present invention, followed by light irradiation and thermal curing will be described.

  First, a semiconductor substrate such as a silicon substrate or a silicon nitride substrate is prepared. Note that a glass substrate or a quartz substrate may be used instead of the semiconductor substrate. A silicon dioxide film, an ITO (Indium Tin Oxide) film, or a metal film such as aluminum, molybdenum, or chromium may be formed over the substrate.

  On the prepared semiconductor substrate, the positive photosensitive resin composition of the present invention is applied by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, or ink jet coating. Subsequently, a coating film can be formed by predrying with a hot plate or oven. Furthermore, a heat treatment is performed on the coating film. As the heat treatment conditions, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and the heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes, respectively.

  The film obtained above is irradiated with light such as ultraviolet rays through a mask having a predetermined pattern. Subsequently, by developing with an alkaline developer, the exposed portion is washed out, and a relief pattern having a sharp end surface is obtained.

  Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanolamine. And aqueous amine solutions such as propylamine and ethylenediamine. A surfactant or the like may be added to these developers.

  Among the above alkaline developers, a 0.1 to 2.38 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer. Even in a film obtained from the positive photosensitive resin composition of the present invention, this alkaline developer can be used for good development without causing problems such as swelling.

  As a developing method, any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used. The development time is usually 15 to 180 seconds.

  The film after the development processing is washed with running water for 20 to 90 seconds, for example. Subsequently, moisture on the substrate is removed by air drying using compressed air or compressed nitrogen or by spinning to obtain a patterned film.

  Post-baking for thermosetting is performed on the patterned film. Specifically, heating is performed using a hot plate or an oven. The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.

  By post-baking, a cured film having a good relief pattern excellent in heat resistance, transparency, planarization, low water absorption and chemical resistance can be obtained. This cured film is characterized by high hardness, excellent heat resistance and solvent resistance, and high transparency. Therefore, it can be suitably used for various films in liquid crystal displays and organic EL displays, for example, interlayer insulating films, protective films, insulating films and the like. Further, it is also suitably used in applications such as an array flattening film for TFT type liquid crystal elements. The present invention is also directed to a display device having the cured film.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
AA: acrylic acid MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate DCPM: dicyclopentanyl methacrylate THPA: 1,2,3,6-tetrahydrophthalic anhydride PA: phthalic anhydride ACSQ: acryloyl group-modified syl Sesquioxane MACSQ: methacryloyl group-modified silsesquioxane DVB: divinylbenzene (isomer mixture)
AIBN: azobisisobutyronitrile BTEAC: benzyltriethylammonium chloride TAG1: triphenylsulfonium trifluoromethanesulfonate TAG2: diphenyliodonium trifluoromethanesulfonate TAG3: 2-methyl-α- [5-[(propylsulfonyl) oxy] imino]- (5H) -2-Thienylidene] benzeneacetonitrile (compound represented by the formula (6))
PGMEA: Propylene glycol monomethyl ether acetate NMP: n-methyl-2-pyrrolidone QD: 1 mol of α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2 -Compound synthesized by condensation reaction with 2 mol of diazide-5-sulfonyl chloride: MPTS: 3-methacryloyloxypropyltrimethoxysilane UPS: γ-ureidopropyltriethoxysilane R30: Megafac R-30 manufactured by DIC Corporation Name)

[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the specific copolymer and specific cross-linked product obtained according to the following synthesis examples were eluted using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. The measurement was performed under the condition that the solvent tetrahydrofuran was allowed to flow through the column at a flow rate of 1 ml / min (column temperature 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>
GMA (40.0 g) and DCPM (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By making it react, the copolymer solution (copolymer density | concentration: 40 mass%) which is Mn6,300 and Mw10,600 was obtained (P1). The polymerization temperature was adjusted to 60 to 100 ° C.

<Synthesis Example 2>
By adding AA (20.0 g), BTEAC (1.1 g) and PGMEA (31.7 g) to 200 g of the copolymer (P1) and reacting them, the (A) component of Mn7,300 and Mw13,600 A solution (specific copolymer concentration: 40% by mass) of (specific copolymer) was obtained (P2). The reaction temperature was adjusted to 90 to 120 ° C.

<Synthesis Example 3>
By adding THPA (42.8 g) and PGMEA (107 g) to 252.8 g of the specific copolymer solution (P2) and reacting them, the component (A) of Mn7,900 and Mw13,600 (specific copolymer) ) (Specific copolymer concentration: 40% by mass) was obtained (P3). The reaction temperature was adjusted to 80 to 100 ° C.

<Synthesis Example 4>
GMA (20.0 g) and MMA (20.0 g) are used as monomer components constituting the copolymer, AIBN (1 g) is used as a radical polymerization initiator, and these are used in a solvent PGMEA (95.7 g). A copolymer solution (copolymer concentration: 30% by mass) having Mn 4,300 and Mw 8,400 was obtained by performing a polymerization reaction in (P4). The polymerization temperature was adjusted to 60 ° C to 100 ° C.

<Synthesis Example 5>
By adding PA (43.9 g) and PGMEA (110 g) to 252.8 g of the specific copolymer solution (P2) and reacting them, the component (A) of Mn7,800 and Mw13,900 (specific copolymer) ) (Specific copolymer concentration: 40 mass%) was obtained (P5). The reaction temperature was adjusted to 80 to 100 ° C.

<Synthesis Example 6>
MAA (40.0 g) and DCPM (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By making it react, the copolymer solution (copolymer concentration: 40 mass%) which is Mn5,100 and Mw9,800 was obtained (P6). The polymerization temperature was adjusted to 60 ° C to 100 ° C.

<Synthesis Example 7>
By adding GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of the copolymer (P6) and reacting them, the (A) component of Mn6,500 and Mw12,900 A solution (specific copolymer concentration: 40% by mass) of (specific copolymer) was obtained (P7). The reaction temperature was adjusted to 90 to 120 ° C.

<Synthesis Example 8>
GMA (20.0 g) and MPTS (20.0 g) are used as monomer components constituting the copolymer, AIBN (1 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By making it react, the copolymer solution (copolymer density | concentration: 30 mass%) which is Mn3,700 and Mw7,300 was obtained (P8). The polymerization temperature was adjusted to 60 ° C to 100 ° C.

<Examples 1 to 7 and Comparative Examples 1 to 3>
According to the composition shown in the following Table 1, the component (A) is mixed with the component (B) and the component (C), further the solvent (D) and the components (E) to (I) at a predetermined ratio, The mixture was stirred for 3 hours to obtain a uniform solution, thereby preparing positive photosensitive resin compositions of Examples and Comparative Examples.

  For each of the obtained positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, the sensitivity of the coating film, the film reduction (in the unexposed area), the presence or absence of tack after pre-baking, and the cured film, respectively The pencil hardness, transmittance, adhesion to ITO and solvent resistance were measured and evaluated.

[Evaluation of sensitivity]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A 5 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS, including various evaluation tests described later.
This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for a certain period of time by means of an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, development was performed by immersing in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, followed by washing with running ultrapure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was defined as sensitivity.

[Evaluation of film reduction]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A 5 μm coating film was formed.
This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of presence or absence of tack]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A 5 μm coating film was formed.
The surface of this coating film was touched with tweezers.

[Evaluation of pencil hardness]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A 5 μm coating film was formed. This coating film was post-baked by heating at 230 ° C. for 30 minutes to form a cured film having a thickness of 2.2 μm.
The pencil hardness used when the surface of the coating film was not damaged at a load of 500 g was defined as the pencil hardness.

[Evaluation of transmittance]
Each of the positive photosensitive compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2. A 5 μm coating film was formed.
This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for 90 seconds using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.
The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SIMADZU UV-2550 model number, manufactured by Shimadzu Corporation).

[Evaluation of adhesion to ITO]
Each of the positive photosensitive compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2. A 5 μm coating film was formed. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.
This cured film was cut with a cutter knife so as to be 10 × 10 squares at 1 mm vertical and horizontal intervals. A cellophane tape peeling test was performed on this cut using a scotch tape. The one that remained without peeling off 100 squares was marked with ○, and the one that was peeled even with one square was marked with x.

[Evaluation of solvent resistance]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A 5 μm coating film was formed. This coating film was post-baked by heating at 230 ° C. for 30 minutes to form a cured film having a thickness of 2.1 μm.
This coating film was immersed in NMP for 1 minute at room temperature. A film having no change in film thickness before and after immersion was marked with ◯, and a film with a decrease in film thickness was marked with x.

[Evaluation of pattern formability]
Each of the positive photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2. A 5 μm coating film was formed.
The coating film by ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. is the light intensity at 365nm was 200 mJ / cm ² irradiation through a mask of a line and space pattern of 20μm to ultraviolet 5.5 mW / cm ^2. Thereafter, development was performed by immersing in a 0.4% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern.
The produced pattern was baked in an oven at 230 ° C. for 30 minutes. The case where a line pattern of 20 μm ± 2 μm could be formed was marked with ◯, and the case where a pattern was not obtained or the line width was greatly different was marked with x.

[Evaluation results]
Table 2 shows the results of the above evaluation.

  As can be seen from the results shown in Table 2, the positive photosensitive resin compositions of Examples 1 to 7 are all highly sensitive, the film loss in the unexposed area is very small, and no tack after prebaking is observed. It was. Furthermore, the result was that the pencil hardness after curing was as high as 2H or more, excellent in light transmittance, adhesion to ITO, solvent resistance, and excellent pattern formability.

  On the other hand, with respect to Comparative Example 1, the result that the sensitivity, transmittance, adhesion, and solvent resistance were good was obtained, but the pencil hardness was as low as B. As for Comparative Example 2, tack entered after pre-baking, and subsequent evaluation was not achieved. In Comparative Example 3, although the results of good sensitivity, transmittance and adhesion were obtained, the pencil hardness was as low as H and the solvent resistance was insufficient.

  The positive photosensitive resin composition according to the present invention is suitable as a material for forming a protective film, a planarizing film, an insulating film, etc. in a display device including a thin film transistor (TFT) type liquid crystal display element or an organic EL element. It is suitable for a display device provided with a touch panel and a display device using a resin substrate. For example, it is suitable as a material for forming interlayer insulation films for TFT liquid crystal elements, protective films for color filters, array planarization films, interlayer insulation films for capacitive touch panels, insulation films for organic EL elements, and the like. It is also suitable as various electronic materials such as lens materials.

Claims (11)

An alkali-soluble acrylic polymer having a side chain having an unsaturated bond at the terminal;
A quinonediazide compound,
Silsesquioxane,
A photosensitive resin composition comprising a solvent.   The photosensitive resin composition according to claim 1, wherein the alkali-soluble acrylic polymer has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.   3. The photosensitive resin composition according to claim 1, wherein the alkali-soluble acrylic polymer has an acryloyl group, a methacryloyl group, a vinylphenyl group, or an isopropenylphenyl group at the end of the side chain.   4. The photosensitive composition according to claim 1, wherein the quinonediazide compound is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer. 5. Resin composition.   The silsesquioxane is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer. Photosensitive resin composition.   The thermal acid generator is further contained in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer. The photosensitive resin composition as described in 2.   1 to 40 parts by mass of a compound having 2 or more vinyl groups directly bonded to a benzene ring in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer. 6. The photosensitive resin composition according to any one of 6 above.   The acrylic polymer having an epoxy group in the side chain is further contained in an amount of 0.5 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble acrylic polymer. The photosensitive resin composition of any one of these.   The photosensitive resin according to claim 1, further comprising an adhesion promoter in an amount of 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble acrylic polymer. Composition.   The photosensitive material according to claim 1, further comprising a surfactant in an amount of 1.0 part by mass or less based on 100 parts by mass of the photosensitive resin composition. Resin composition.   A display device comprising a film formed by curing the photosensitive resin composition according to claim 1.