JP6540083B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a partition wall, a substrate, a display device, and a substrate evaluation method.

  In recent display devices and the like, a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, and the like are manufactured by an application method such as an inkjet method. In the method of forming an element using such a coating method, the partition formed using the photosensitive resin composition is utilized.

  For example, after forming a thin film made of the photosensitive resin composition on a substrate on which an electrode is formed, an opening is formed in the thin film by photolithography so that the surface of the electrode is exposed, A partition having an opening is provided on the electrode, and then an ink containing a thin film material is dropped into the opening of the partition, and the ink is dried by heating to form a predetermined thin film on the electrode.

  As such a photosensitive resin composition, for example, a photosensitive resin composition containing a polymer obtained by polymerizing an α-substituted acrylate having a fluoroalkyl group having 4 to 6 carbon atoms is known (patented) Literature 1).

JP 2012-73603 A

  As described above, although the photosensitive resin composition is once deposited on the electrode and then removed from the electrode during patterning, the wettability of the electrode surface to the ink is determined by the type of photosensitive resin composition. It changes according to. Therefore, depending on the type of photosensitive resin composition, the ink supplied on the electrode may not spread on the electrode, and in the case of the conventionally proposed photosensitive resin composition, the ink on the electrode in the partition opening is There was a case where the ink spreading of the ink was not always completely satisfactory. Therefore, an object of the present invention is to provide a photosensitive resin composition having a good spread of the inside of the inside of the partition wall opening of the ink applied onto the electrode obtained after the pattern formation.

The present invention provides the following [1] to [12].
[1] A photosensitive resin composition, which is
The photosensitive resin composition is supplied onto a substrate on which an electrode is formed, and the substrate is rotated at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition, and the substrate on which the thin film is formed is After drying under reduced pressure at 66 Pa, prebaking is performed at 110 ° C. for 110 seconds, and then the thin film after the prebaking is exposed at 200 mJ / cm ² so that the surface of the electrode is exposed. The value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film when the opening is formed in the thin film by photolithography using an aqueous hydroxide solution for 80 seconds at 23 ° C. is 15 mN / The photosensitive resin composition which becomes m or more.

［ｉ］
（式［ｉ］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は、それぞれ独立に、−ＯＨ、−ＳＨ、−ＣＯＯＨ、−ＣＨＯ、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、−ＣＯＲ７、−ＣＯＯＲ７、−ＯＣＯＲ７、または-ＯＲ７を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は、少なくとも１つが、−ＯＨ、−ＳＨ、−ＣＯＯＨまたは−ＣＨＯである。Ｒ７は、炭素数１〜８のアルキル基、炭素数２〜５のアルコキシアルキル基、アリール基またはベンジル基を表す。)
（Ｂ）重合性化合物
（Ｃ）重合開始剤 [2] The photosensitive resin composition according to [1], wherein the photosensitive resin composition comprises the following (A), (B) and (C).
(A) Resin having a structural unit containing a group represented by the following formula [i]

[I]
(In formula [i], R 1, R 2, R 3, R 4 and R 5 are each independently -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms,- And R1, R2, R3, R4, and R5 are at least one of -OH, -SH, -COOH or -CHO, and R7 has 1 to 6 carbon atoms. Represents an alkyl group of 8, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group or a benzyl group.)
(B) Polymerizable compound (C) polymerization initiator

（式［ｉｉ］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は、前述と同じ意味を表し、Ｒ６は、水素原子、メチル基またはエチル基を表す。） [3] The photosensitive resin composition according to [2], wherein the structural unit is represented by the following formula [ii].

(In formula [ii], R 1, R 2, R 3, R 4 and R 5 have the same meaning as described above, and R 6 represents a hydrogen atom, a methyl group or an ethyl group.)

[4] The photosensitive resin composition according to [2] or [3], wherein the polymerization initiator is a photopolymerization initiator and the polymerizable compound is polymerized by radical polymerization.

[5] Photosensitivity according to any one of [2] to [4], wherein at least one of R 1, R 2, R 3, R 4 and R 5 is —COOH or —OH, and the others are hydrogen atoms. Resin composition.

[6] The photosensitive resin composition according to any one of [1] to [5], which further contains a liquid repellent.

[7] The photosensitive resin composition according to [6], wherein the liquid repellent agent is a polymer containing a structural unit derived from an unsaturated compound having a C 4 to C 6 perfluoroalkyl group.

[8] The substrate on which the electrode is formed is mounted on a sputtering apparatus with an ITO target, heated to 300 ° C. in a heating chamber, then electric power 1.05 kW, argon gas pressure 0.6 Pa, film forming in a sputtering chamber A transparent conductive film ITO is formed to a thickness of 50 nm on a substrate at a time of 115 seconds, and the substrate after film deposition is a glass substrate with ITO annealed at 230 ° C. for 30 minutes in the atmosphere, [1] to [1] The photosensitive resin composition in any one of 7].

[9] A partition formed of the photosensitive resin composition according to any one of [1] to [8].

[10] A substrate provided with the partition walls and electrodes according to [9].

[11] A display device comprising the substrate according to [10].

[12] A step of supplying a photosensitive resin composition onto a substrate on which an electrode is formed, and rotating the substrate at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition,
Drying the substrate on which the thin film is formed under reduced pressure at 66 Pa and prebaking at 110 ° C. for 110 seconds;
The prebaked thin film is exposed at 200 mJ / cm ² so as to expose the surface of the electrode, and developed for 80 seconds at 23.degree. C. using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Forming an opening in the thin film;
A substrate evaluation method comprising the step of evaluating the wettability of an electrode based on the value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film.

  According to the photosensitive resin composition of the present invention, it is possible to obtain a substrate with a partition which is excellent in coating spread on the entire inner surface of the partition opening of the ink applied on the electrode after pattern formation.

FIG. 2 is a cross-sectional view schematically showing a part of the display device 1 in an enlarged manner. It is a top view which expands a part of display 1 of one embodiment of the present invention, and is shown typically.

In the photosensitive resin composition of the present invention, the photosensitive resin composition is supplied onto a substrate on which an electrode is formed, and the substrate is rotated at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition. The substrate on which the thin film is formed is dried under reduced pressure at 66 Pa and then prebaked at 110 ° C. for 110 seconds, and then the thin film after the prebaking is exposed at 200 mJ / cm ² so that the surface of the electrode is exposed. A surface of the electrode exposed to the opening of the thin film when the opening is formed in the thin film by a photolithography method of developing at 23.degree. C. for 80 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide It is a photosensitive resin composition in which the value of the polar component of energy is 15 mN / m or more.

  When a partition wall is formed on a substrate on which an electrode is formed using such a photosensitive resin composition, when an ink containing a thin film material to be formed on the electrode is applied on the electrode, the ink may become elastic on the electrode Since the ink is spread on the electrode and solidified by drying or the like, a flat thin film can be formed on the entire surface within the opening of the partition.

  The value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film after formation of the opening is preferably 15 mN / m or more, and more preferably 15.5 mN / m or more.

  From the viewpoint of wettability, the value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film after the formation of the opening does not need to set the upper limit in particular, but is usually 50 mN / m or less There is further 40 mN / m or less.

  The resin in the photosensitive resin composition of the present invention is not particularly limited as long as the value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film after opening formation is 15 mN / m or more. And commonly used acrylic resins, polyimide resins, cycloolefin resins, epoxy resins and the like, and among these, acrylic resins and epoxy resins are preferred.

［ｉ］
（Ｂ）重合性化合物
（Ｃ）重合開始剤 The photosensitive resin composition preferably contains the following (A), (B) and (C).
(A) Resin having a structural unit containing a group represented by the following formula [i]

[I]
(B) Polymerizable compound (C) polymerization initiator

  The resin (A) is a resin having a structural unit containing a group represented by the formula [i], and the structural unit is a monomer (a) (hereinafter sometimes referred to as “(a)”) Led.

  (A) is preferably a monomer having a group represented by the formula [i] and an ethylenically unsaturated double bond.

上記式［ｉ］、［ｉｉ］中、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は、それぞれ独立に、−ＯＨ、−ＳＨ、−ＣＯＯＨ、−ＣＨＯ、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、−ＣＯＲ7、−ＣＯＯＲ7、−ＯＣＯＲ7、または−ＯＲ７を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は、少なくとも１つは、−ＯＨ、−ＳＨ、−ＣＯＯＨまたは−ＣＨＯである。Ｒ７は、炭素数１〜８のアルキル基、炭素数２〜５のアルコキシアルキル基、アリール基、またはベンジル基を表す。Ｒ６は、水素原子、メチル基またはエチル基を表す。 Moreover, it is preferable that the structural unit containing group represented by Formula [i] is a structural unit represented by following formula [ii]. That is, the structural unit derived from (a) is preferably a structural unit represented by the following formula [ii].

In the above formulas [i] and [ii], R1, R2, R3, R4 and R5 are each independently -OH, -SH, -COOH, -CHO, a hydrogen atom, a halogen atom, a carbon number of 1 to 3 R 1, R 2, R 3, R 4 and R 5 are alkyl groups, —COR 7, —COOR 7, —OCOR 7 or —OR 7, and at least one of R 1, R 2, R 3, R 4 and R 5 is —OH, —SH, —COOH or —CHO. R7 represents an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group, or a benzyl group. R6 represents a hydrogen atom, a methyl group or an ethyl group.

  Furthermore, from the viewpoint of the wettability on the electrode surface, at least one of R1, R2, R3, R4 and R5 is -COOH or -OH, and -COOH or -OH The different R1, R2, R3, R4 and R5 are preferably hydrogen atoms.

In the formulas [i] and [ii], as long as at least one of R 1, R 2, R 3, R 4 and R 5 is —OH, —SH, —COOH or —CHO, each independently has 1 carbon atom 8 alkoxy _{group, -COOR7, -OCOR7, -COR7, -CN} , -NHR7, -NR7R8, -NO 2, -CONH 2, -CONHR7, -SOR7 or may be _-SO 2 R7. However, R7 represents the same meaning as described above. R8 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an aryl group, or a benzyl group, independently of R7.

  As a halogen atom, Cl, Br or I is mentioned, and Cl or Br is preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propoxy group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, An n-heptyl group and an octyl group are mentioned, A methyl group or an ethyl group is preferable.

  As a C2-C5 alkoxyalkyl group, a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propylmethyl group, a propylethyl group is mentioned, A methoxymethyl group is mentioned. And methoxyethyl are preferred.

  As an aryl group, a phenyl group and a naphthyl group are illustrated. However, it is not limited to this, and may have a substituent.

  As (a), o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-mercaptostyrene, 3-mercaptostyrene, 4-mercaptostyrene, 2-vinyl aniline, 3-vinyl aniline, 4-vinyl aniline 3-Dimethylaminostyrene, 3-diethylaminostyrene, 3-monomethylaminostyrene, 3-monoethylaminostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3-vinylphthalic acid Acid monomethyl ester, 3-vinyl phthalate Ethyl ester, 5-vinyl isophthalic acid, 5-vinyl isophthalic acid monomethyl ester, 5-vinyl isophthalic acid monoethyl ester, 4-vinylsalicylic acid, 5-vinylsalicylic acid, 5-vinylsalicylic aldehyde, 5-vinylacetylsalicylic acid, 4- Ethyl vinylbenzenesulfonate 4-vinylresorcinol, 4-vinylresorcinol monomethoxymethyl ether, 4-vinylresorcinol bismethoxymethyl ether, 4-vinylresorcinol monomethoxyethyl ether, 4-vinylresorcinol bismethoxyethyl ether, 4-vinylbenzo Nitrile, 4-vinylbenzenepropanoic acid, methyl 4-vinylbenzenepropanoate and the like, and preferably o-hydroxystyrene, m-hydroxystyrene, p- Mud alkoxy styrene, o- vinyl benzoate, m- vinylbenzoic acid, p- vinylbenzoic acid. In addition, (a) is not necessarily limited to the said illustration.

  Furthermore, the photosensitive resin composition of the present invention is a resin other than the resin (A) (hereinafter sometimes referred to as “resin (A1)”), solvent (D), polymerization start auxiliary (E), liquid repellent ( F), a surfactant (G), and an adhesion improver (H) may contain at least one selected from the group consisting of

  In the present specification, compounds exemplified as each component can be used alone or in combination unless otherwise noted.

  The resin (A) may further contain a structural unit derived from a monomer (x) other than (a) (hereinafter sometimes referred to as "(x)").

  (X) is not particularly limited as long as it is a monomer other than (a) and does not have a perfluoroalkyl group having 4 to 6 carbon atoms, and for example, a cyclic ether structure having 2 to 4 carbon atoms At least one monomer (e) selected from the group consisting of monomers (b) (hereinafter sometimes referred to as "(b)"), unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as " Other monomers (c) (hereinafter sometimes referred to as "(c)") may be mentioned, and among these, (b) or (c) is preferable.

  (B) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring), preferably having 2 to 4 carbon atoms Or a monomer having a cyclic ether structure and an ethylenically unsaturated double bond, more preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

  As (b), for example, a monomer (b1) having an oxiranyl group (hereinafter sometimes referred to as “(b1)”), a monomer having an oxetanyl group (b2) (hereinafter referred to as “(b2)” And monomers (b3) having a tetrahydrofuryl group (hereinafter sometimes referred to as "(b3)").

  As (b1), a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized may be referred to as “(b1-1)” hereinafter. And a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.

  As (b1), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group Is more preferred. When these monomers are used, the storage stability of the photosensitive resin composition is excellent.

  Specifically as (b1-1), glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxyme (Tyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

［式（Ｉ）及び式（ＩＩ）において、Ｒ^１及びＲ^２は、水素原子、又は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子はヒドロキシ基で置換されていてもよい。Ｘ^１及びＸ^２は、単結合、−Ｒ^３−、＊−Ｒ^３−Ｏ−、＊−Ｒ^３−Ｓ−、＊−Ｒ^３−ＮＨ−を表す。Ｒ^３は、炭素数１〜６のアルカンジイル基を表す。＊は、Ｏとの結合手を表す。］ Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclo Mer A400; Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries, Ltd.), a compound represented by Formula (I), Formula (II) And the like.

[In the formulas (I) and (II), R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group It is also good. X ¹ and ^{X 2} are a single ^{bond, -R 3 -, * - R} 3 -O -, * - R 3 -S -, * - represents the R 3 -NH-. R ³ represents a C 1 to C 6 alkanediyl group. * Represents a bond with O. ]

  Specifically as a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, a sec-butyl group, a tert- butyl group etc. are mentioned.

  As an alkyl group substituted by a hydroxy group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy- Examples thereof include 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

As R < ¹ > and R < ² >, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

  As an alkanediyl group, a methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group etc. are mentioned.

As X ¹ and X ² , preferably, a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- (* represents a bond with O) group, a * -CH ₂ CH ₂ -O- group Among them, more preferably a single _{bond, *} - include CH ₂ CH 2 -O- group.

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) The compound represented by these is preferable, and the compound represented by Formula (I-1), Formula (I-7), Formula (I-9), or Formula (I-15) is more preferable.

  As a compound represented by Formula (II), the compound etc. which are represented by either Formula (II-1)-Formula (II-15) are mentioned. Among them, Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by these is preferable, and the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is more preferable.

式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物は、それぞれ単独で用いても、２種以上を併用してもよい。式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物を併用する場合、これらの含有比率〔式（Ｉ）で表される化合物：式（ＩＩ）で表される化合物〕はモル基準で、好ましくは５：９５〜９５：５、より好ましくは２０：８０〜８０：２０である。

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio of these [compound represented by the formula (I): compound represented by the formula (II)] Preferably, 5:95 to 95: 5, more preferably 20:80 to 80:20, on a molar basis.

  As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl -3- (meth) acryloyl oxyethyl oxetane etc. are mentioned.

  As (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable.

  Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

Examples of (e) include unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
As unsaturated carboxylic acids, acrylic acid, methacrylic acid, crotonic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexenedicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 5 -Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1 Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5 -Carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, succinic acid mono [2- (meth) acryloyloxyethyl], α- (hydroxymethyl) acrylic acid And the like.

  As unsaturated carboxylic acid anhydrides, unsaturated dicarboxylic acids such as maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. Acid anhydride etc. are mentioned.

  Examples of (c) include (meth) acrylic esters, N-substituted maleimides, unsaturated dicarboxylic acid diesters, alicyclic unsaturated compounds, styrenes, and other vinyl compounds. Among them, (meth) acrylic esters and styrenes are preferable.

  As (meth) acrylic acid esters, alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate and the like ;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, a common name for dicyclopenta) It is said to be nil (meth) acrylate.
), Dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, as the common name “dicyclopentenyl (meth) And (iii) cycloalkyl esters such as "acrylate", isobornyl (meth) acrylate and the like;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
And aryl and aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

  Among the (meth) acrylic esters, alkyl esters are preferred.

  As unsaturated dicarboxylic acid diesters, diethyl maleate, diethyl fumarate, diethyl itaconate and the like can be mentioned.

  As N-substituted maleimides, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimido Proate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like can be mentioned.

  As alicyclic unsaturated compounds, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2. 1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxy Ethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 ') -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5 6-Dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2. 1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene 5-tert-Butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2. 1] Hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo 2.2.1] hept-2-ene bicyclo unsaturated compounds such as and the like.

  Styrenes include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene and the like. Among them, styrene is preferred.

  Examples of other vinyl compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

  The resin (A) may be a resin consisting only of a structural unit derived from (a), but a resin consisting of a structural unit derived from (a) and a structural unit derived from (x) is preferred.

When the resin (A) is a resin comprising a structural unit derived from (a) and a structural unit derived from (x), it depends on the acidity of the structural unit used for (a), but each monomer It is preferable that the ratio of the structural unit derived from is in the following range with respect to the total mole number of the structural unit which comprises resin (A).
Structural unit derived from (a); 5 to 70 mol% (more preferably 10 to 60 mol%)
Structural unit derived from (x); 30 to 95 mol% (more preferably 40 to 90 mol%)

  When the ratio of structural units of the resin (A) is within the above range, the storage stability of the photosensitive resin composition, the developability when forming a pattern from the photosensitive resin composition, and the paint obtained can be obtained The solvent resistance, heat resistance and mechanical strength of the film and pattern tend to be good.

In particular, when any one of R 1 to R 5 is —COOH, the ratio of structural units derived from each monomer is as follows relative to the total number of moles of structural units constituting the resin (A): It is preferably in the range.
Structural unit derived from (a); 5 to 50 mol%
Structural unit derived from (x); 50 to 95 mol%

  The resin (A) can be prepared, for example, by the method described in the document "Experimental method of polymer synthesis" (by Takayuki Otsu, Publishing Co., Ltd., Chemical Co., Ltd., First Edition, First Edition, published on March 1, 1972) It can be manufactured with reference to the cited documents described in.

  Specifically, (a) and a predetermined amount of (x) used as needed, a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by substituting oxygen in the air with nitrogen, An example is a method of heating and keeping warm while maintaining a deoxygenated atmosphere and stirring. The polymerization initiator, the solvent and the like used herein are not particularly limited, and any of those commonly used in the relevant field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As the solvent, any solvent can be used as long as it dissolves each monomer, and the solvent described later can be used as the solvent (D) of the photosensitive resin composition. A chain transfer agent may be added during the polymerization reaction to adjust the molecular weight of the resulting resin. As chain transfer agents, n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-sulfanylethanol, thioglycolic acid, ethyl thioglycolate, 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, 3- Thiols such as sulfanyl propionic acid and sulfanyl group-containing silicone (KF-2001: manufactured by Shin-Etsu Chemical Co., Ltd.); and halogenated alkyls such as chloroform, carbon tetrachloride, carbon tetrabromide and the like.

In particular, when (a) has a phenolic hydroxy group, a monomer in which the phenolic hydroxy group possessed by (a) is protected with a protecting group in advance may be used during polymerization. Examples of the protective group include tertiary alkyl groups such as tert-butyl group; and acyl groups such as acetyl group.
After polymerization using such a monomer protected with a protective group in advance, the resin (A) can be obtained by deprotecting the protective group.

  In addition, the obtained polymer may use the solution after reaction as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as reprecipitation. You may use In particular, by using the same solvent as the solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

  The polystyrene equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is in the above range, coating properties tend to be excellent, film reduction in the exposed area is less likely to occur during development, and the unexposed area is more easily removed in development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of the resin (A) is 20 to 200 mg KOH / g, preferably 40 to 180 mg KOH / g, and more preferably 50 to 180 mg KOH / g. By using a resin having an acid value in such a range, the value of the polar component of the surface free energy of the electrode after the opening can be made 15 mN / m or more. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of resin, and can be determined by titration using a potassium hydroxide aqueous solution.

  The content of the resin (A) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, based on the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). And particularly preferably 45 to 80% by mass. When the content of the resin (A) is in the above range, the developability of the photosensitive resin composition, the adhesion of the obtained pattern, the solvent resistance and the mechanical properties tend to be good.

  The photosensitive resin composition of the present invention may contain a liquid repellent (F). The liquid repellent agent (F) is a resin that exhibits liquid repellency, and the substance to be used is not particularly limited as long as the surface of the structure after pattern formation is higher in liquid repellency than the structure itself, but the structure is not limited. It is preferable that the anisole contact angle on the surface of the article be 30 ° or more. Examples of the liquid-repellent resin to be used include structural units having a carbon number of 1 to 8 perfluoroalkyl group (which may have an etheric oxygen atom between carbon atoms), and preferably It is a polymer including a structural unit derived from a monomer (d) having a C 4 to C 6 perfluoroalkyl group (hereinafter sometimes referred to as “(d)”).

［式（ｄ−０）中、Ｒ^ｆは、炭素数４〜６のペルフルオロアルキル基を表す。Ｒ^ｄは、水素原子、ハロゲン原子、シアノ基、フェニル基、ベンジル基又は炭素数１〜２１のアルキル基を表し、該アルキル基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよい。Ｘ^ｄは、単結合、炭素数１〜１０の２価の脂肪族炭化水素基、炭素数３〜１０の２価の脂環式炭化水素基又は炭素数６〜１２の２価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＲ^ｅ−、−Ｓ−又は−ＳＯ_２−で置き換わっていてもよい。］ As (d), the compound represented by Formula (d-0) is mentioned.

[In Formula (d-0), R ^f represents a C 4 to C 6 perfluoroalkyl group. R ^d represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms, and a hydrogen atom contained in the alkyl group is substituted by a halogen atom or a hydroxy group It is also good. X ^d is a single bond, a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon having 6 to 12 carbon atoms And the —CH ₂ — contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group represents a hydrogen group, and is —O—, —CO—, —NR ^e —, —S— or —SO ₂ — It may be replaced. ]

R ^f is a C 4 to C 6 perfluoroalkyl group, preferably a perfluorobutyl group or a perfluorohexyl group.

As a C1-C21 alkyl group in R ^d , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, linear alkyl groups such as n-nonyl group and n-decyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3- Ethylhexyl group, 4-ethylhexyl group, 2-propylpentyl group, 1-butylbutyl group, 1-butyl- -Methylbutyl group, 1-butyl-3-methylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, 2 And-branched alkyl groups such as -ethyl-3-methylbutyl group and the like.

As ^Rd , a hydrogen atom, a halogen atom and a methyl group are preferable.

As a C1-C10 bivalent aliphatic hydrocarbon group in ^Xd , a methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4- Diyl group, butane-1,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane- Alkanediyl groups such as 1,8-diyl group can be mentioned.

As a C3-C10 bivalent alicyclic hydrocarbon group in ^Xd , a cyclopropane diyl group, a cyclobutane diyl group, a cyclopentadiyl group, a cyclohexane diyl group, a cycloheptane diyl group, a cyclodecane diyl group etc. are mentioned. It can be mentioned.

As a C6-C12 bivalent aromatic hydrocarbon group in ^Xd , a phenylene group, naphthalene diyl group, etc. are mentioned.

As X ^d in which -CH ₂ -is replaced by -O-, -CO-, -NR ^e- , -S- or -SO _2- , for example, in formulas (xd-1) to (xd-10) The group etc. which are represented are mentioned.

As ^Xd , a C1-C6 alkanediyl group is preferable, and an ethylene group is more preferable.

（ｙｄ−１）
［式（ｙｄ−１）中、Ｒ^ｈは、炭素数４〜６のペルフルオロアルキル基を表す。Ｒ^ｇは、水素原子、ハロゲン原子又はメチル基を表す。］ As (d), a compound represented by the following formula (yd-1) is preferable.

(Yd-1)
[In Formula (yd-1), R ^h represents a C 4 to C 6 perfluoroalkyl group. R ^g represents a hydrogen atom, a halogen atom or a methyl group. ]

As a compound represented by Formula (d-0), a compound (d-1)-compound (d-94) etc. are mentioned, for example. In the table, the formula number shown in the X ^d column represents the formula number of the group exemplified above. Also, for example, the compound (d-1) is a compound represented by the following formula (d-1).

  The resin (F) is preferably a copolymer containing a structural unit derived from (d) and a structural unit derived from (e), and a structural unit derived from (d) and (e) It is more preferable that it is resin containing the structural unit derived from and the structural unit derived from (b). When the resin (F) contains a structural unit derived from (e), since the developability is excellent, there is a tendency for the unevenness due to the residue and the development to be suppressed. When the resin (F) contains a structural unit derived from (b), it tends to be excellent in solvent resistance, which is preferable. The resin (F) may contain a structural unit derived from (c). Examples of (e), (b) and (c) include the same as described above.

When the resin (F) is a copolymer of (e) and (d), the ratio of structural units derived from each monomer is relative to the total number of moles of structural units constituting the resin (F) Preferably, it is in the following range.
(E) derived structural unit; 5 to 50% by mass (more preferably 10 to 40% by mass)
(D) derived structural unit; 50 to 95% by mass (more preferably 70 to 90% by mass)

When the resin (F) is a copolymer of (e), (b) and (d), the ratio of structural units derived from each monomer is the total mole of structural units constituting the resin (F) It is preferable to be in the following range with respect to the number.
(E) derived structural unit; 5 to 40% by mass (more preferably 10 to 30% by mass)
Structural unit derived from (b); 5 to 80% by mass (more preferably 10 to 70% by mass)
Structural unit derived from (d); 10 to 80% by mass (more preferably 20 to 70% by mass)

When the resin (F) is a copolymer of (e), (b), (c) and (d), the ratio of structural units derived from each monomer constitutes the resin (F) It is preferable to be in the following range with respect to the total number of moles of units.
(E) derived structural unit; 5 to 40% by mass (more preferably 10 to 30% by mass)
Structural unit derived from (b); 5 to 70% by mass (more preferably 10 to 60% by mass)
(C) derived structural unit; 10 to 50% by mass (more preferably 20 to 40% by mass)
Structural unit derived from (d); 10 to 80% by mass (more preferably 20 to 70% by mass)

  When the ratio of each structural unit is in the above range, it tends to be excellent in liquid repellency and developability.

  The polystyrene equivalent weight average molecular weight of the resin (F) is preferably 3,000 to 20,000, more preferably 5,000 to 15,000. When the weight average molecular weight of the resin (F) is in the above range, coating properties tend to be excellent, film reduction in the exposed area is less likely to occur during development, and the unexposed area is more easily removed in development.

  The acid value of the resin (F) is usually 20 to 200 mg KOH / g, preferably 40 to 150 mg KOH / g.

  The content of the resin (F) is preferably 0.001 to 10 parts by mass, more preferably 0. 1 part by mass with respect to 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (B). It is 01-5 mass parts. When the content of the resin (F) is in the above range, the patternability is excellent in developability, and the pattern obtained tends to be excellent in liquid repellency.

The resin (A1) is not particularly limited as long as it is a resin other than the resin (A) and the resin (F). As resin (A1),
Resin (A1-1): copolymer formed by polymerizing (e) and (b),
Resin (A1-2): A copolymer obtained by polymerizing (e), (b) and (c),
Resin (A1-3): copolymer formed by polymerizing (e) and (c),
Resin (A1-4): A resin obtained by reacting (b) with a copolymer obtained by polymerizing (e) and (c),

  Resin (A1-5): A resin obtained by reacting (e) with a copolymer obtained by polymerizing (b) and (c) may, for example, be mentioned.

  Especially, resin (A1-1) and resin (A1-2) are preferable.

In the resin (A1-1), the ratio of structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all structural units constituting the resin (A1-1).
Structural unit derived from (e); 5 to 60 mol% (more preferably 10 to 50 mol%)
(B) derived structural unit; 40 to 95 mol% (more preferably 50 to 90 mol%)

  When the ratio of structural units of the resin (A1-1) is in the above range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the coating obtained The solvent resistance of the film and pattern tends to be good.

In the resin (A1-2), the ratio of structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all structural units constituting the resin (A1-2).
(E) derived structural unit; 2 to 45 mol% (more preferably 5 to 40 mol%)
Structural unit derived from (b); 2 to 95 mol% (more preferably 5 to 80 mol%)
(C) derived structural unit; 1 to 65 mol% (more preferably 5 to 60 mol%)

  When the ratio of structural units of the resin (A1-2) is in the above range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the paint obtained The solvent resistance of the film and pattern tends to be good.

In the resin (A1-3), the ratio of structural units derived from each monomer is preferably in the following range with respect to the total number of moles of all structural units constituting the resin (A1-3).
(E) derived structural unit; 2 to 40 mol% (more preferably 5 to 35 mol%)
(C) derived structural unit; 60 to 98 mol% (more preferably 65 to 95 mol%)

  When the ratio of structural units of the resin (A1-3) is in the above range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the coating obtained The solvent resistance of the film and pattern tends to be good.

  Resin (A1-1)-(A1-3) can be manufactured by the method similar to resin (A).

  Resin (A1-4) is a resin obtained by reacting (b) with the copolymer of (e) and (c).

  The resin (A1-4) can be produced, for example, through a two-step process. Also in this case, the method described in the above-mentioned document "Experimental method of polymer synthesis" (by Takayuki Otsu, Publishing Office, Chemical Co., Ltd., First Edition, First Edition, 1st Edition, published on March 1, 1972), It can manufacture in reference to the method etc. which were described in the 89533 gazette.

  First, as the first step, a copolymer of (e) and (c) is obtained in the same manner as the method for producing the resin (A) described above.

  In this case, in the same manner as described above, the resulting copolymer may use the solution after reaction as it is, or a concentrated or diluted solution may be used, or it may be solid (reprecipitation etc.) What was taken out as powder) may be used. Moreover, it is preferable to set it as the weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of polystyrene conversion similar to the above.

However, the ratio of structural units derived from (e) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the above-mentioned copolymer.
5 to 50 mol% (more preferably 10 to 45 mol%) of a structural unit derived from (e)
50 to 95 mol% (more preferably 55 to 90 mol%) of a structural unit derived from (c)

  Next, in the second step, a portion of the carboxylic acid or carboxylic acid anhydride of (e) derived from the obtained copolymer is reacted with the cyclic ether of (b) described above. (B1) or (b2) is preferable as (b) used for the resin (A1-4) because the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain. (B1-1) Is more preferred.

  Specifically, subsequently to the above, the atmosphere in the flask is replaced with air from nitrogen, and 580 mol% of (b) a reaction catalyst of a carboxy group with a cyclic ether (for example, Tris) with respect to the number of moles of (e) (Dimethylaminomethyl) phenol etc. is 0.001 to 5% by mass with respect to the total amount of (e), (b) and (c), and a polymerization inhibitor (eg hydroquinone etc.) (e), (b) 0.001-5 mass% can be put into a flask with respect to the total amount of (C) and (c), and it can be made to react at 60-130 degreeC for 1 to 10 hours, and resin (A1-4) can be obtained. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the calorific value due to the polymerization.

  In this case, the number of moles of (b) is preferably 10 to 75 mole%, more preferably 15 to 70 mole%, relative to the number of moles of (e). By setting it as this range, the storage stability of the photosensitive resin composition, the developability at the time of forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the obtained coating film and pattern And the balance of sensitivity tends to be good.

  In the resin (A1-5), as a first step, a copolymer of (b) and (c) is obtained in the same manner as the method for producing the resin (A) described above.

  In this case, in the same manner as described above, the resulting copolymer may use the solution after reaction as it is, or a concentrated or diluted solution may be used, or it may be solid (reprecipitation etc.) What was taken out as powder) may be used.

It is preferable that the ratio of the structural unit derived from (b) and (c) is in the following range with respect to the total number of moles of all structural units constituting the above-mentioned copolymer.
Structural unit derived from (b); 5 to 95 mol% (more preferably 10 to 90 mol%)
(C) derived structural unit; 5 to 95 mol% (more preferably 10 to 90 mol%)

  Furthermore, in the same manner as the method for producing the resin (A1-4), the carboxylic acid or carboxylic acid possessed by (e) in the cyclic ether derived from (b) in the copolymer of (b) and (c) It can be obtained by reacting an anhydride. The carboxylic acid anhydride may be further reacted with the hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride.

  It is preferable that the usage-amount of (e) made to react with said copolymer is 5-80 mol% with respect to the number-of-moles of (b). (B1) is preferable as (b), and (b1-1) is more preferable as (b) because the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain.

  The polystyrene equivalent weight average molecular weight of the resin (A1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is in the above range, coating properties tend to be excellent, film reduction in the exposed area is less likely to occur during development, and the non-exposed area is more easily removed in development.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of the resin (A1) is usually 20 to 200 mg KOH / g, preferably 40 to 180 mg KOH / g, and more preferably 50 to 180 mg KOH / g.

  When the resin (A1) is contained, the content thereof is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, with respect to the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is in the above range, the pattern can be formed with high sensitivity, and the developability is excellent.

  When the resin (A1) is contained, the content thereof is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, with respect to the total amount of the resin (A) and the resin (A1). When the content of the resin (A1) is in the above range, the pattern can be formed with high sensitivity, and the developability is excellent.

  The photosensitive resin composition of the present invention preferably contains a polymerizable compound (B).

  The polymerizable compound (B) is a compound which can be polymerized by an active radical generated from the polymerization initiator (C), and is, for example, a compound having an ethylenically unsaturated bond, preferably (meth) acrylic acid ester. It is a compound.

  Examples of the polymerizable compound (B) having one ethylenically unsaturated bond include the same as the compounds listed as the above (a), (b) and (c), and among them, (meth) acrylic esters Is preferred.

  As the polymerizable compound (B) having two ethylenic unsaturated bonds, 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di ) Acrylate, 3-methyl-pentanediol di (meth) acrylate.

  As a polymerizable compound (B) having three or more ethylenically unsaturated bonds, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaery Ritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Reaction product of erythritol (hepta) (meth) acrylate and acid anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meta) ) Acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone Dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol hepta ( Meta) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate with acid anhydride, reaction of caprolactone modified dipentaerythritol penta (meth) acrylate with acid anhydride Products, reaction products of caprolactone modified tripentaerythritol hepta (meth) acrylate and acid anhydride, etc. It can be mentioned. Among them, a polymerizable compound (B) having three or more ethylenic unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate are more preferable.

  The content of the polymerizable compound (B) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, based on the total amount of the resin (A), the resin (A1) and the polymerizable compound (B). It is.

  When the content of the polymerizable compound (B) is in the above range, the sensitivity, the strength of the obtained pattern, the smoothness, and the reliability tend to be good.

  The photosensitive resin composition of the present invention contains a polymerization initiator (C). The polymerization initiator (C) is not particularly limited as long as it is a compound capable of initiating polymerization by the action of light or heat, and a known polymerization initiator can be used.

  As a polymerization initiator (C), an oxime compound, an alkyl phenone compound, a biimidazole compound, a triazine compound, and an acyl phosphine oxide compound are mentioned, for example. Moreover, you may use the light and / or the thermal cationic polymerization initiator (For example, what is comprised from onium cation and the anion derived from Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Among them, at least one selected from the group consisting of biimidazole compounds, alkylphenone compounds and oxime compounds is preferable, and alkylphenone compounds are particularly preferable. A polymerization initiator containing these compounds is particularly preferable because it tends to be highly sensitive.

The oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1-yl 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) And -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. You may use commercial products, such as Irgacure OXE01, OXE02 (above, BASF Corporation make), N-1919 (ADEKA company make), etc.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

  Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4) -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. You may use commercial products, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

  Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2) -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Acetophenone, benzyl dimethyl ketal and the like can be mentioned.

  From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by Formula (d2).

  Examples of the biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A Nos. 6-75372 and 6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Nyl) biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) etc. are mentioned. Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5, 5'- tetraphenyl biimidazole and 2,2'- bis (2, 4- dichlorophenyl)-4, 4 ', 5, 5'- tetraphenyl biimidazole are mentioned.

  As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) ) -1,3,5-Triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-) Methyl phenyl) ether Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and the like.

  Furthermore, as a polymerization initiator (C), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyl diphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, And quinone compounds such as 2-ethyl anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. You may add the below-mentioned polymerization start adjuvant (E) to these.

  In addition, as a polymerization initiator having a group capable of causing chain transfer, a polymerization initiator described in JP-A-2002-544205 may be used.

  The polymerization initiator having a group capable of causing chain transfer can also be used as a monomer (c) to be a structural unit that can be contained in the resin (A).

  In the photosensitive resin composition of this invention, a polymerization start adjuvant (E) can be used with the polymerization initiator (C) mentioned above. The polymerization initiating assistant (E) is a compound or a sensitizer which is used in combination with the polymerization initiator (C) and is used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. . As a polymerization start adjuvant (E), the thioxanthone compound, an amine compound, a carboxylic acid compound, the compound of Unexamined-Japanese-Patent No. 2008-65319, and 2009-139932, etc. are mentioned.

  Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone and the like.

  Examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name; Michler's ketone), 4,4'-bis (diethylamino) benzophenone Such aromatic amine compounds can be mentioned.

  Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  As a combination of a polymerization initiator (C) and a polymerization start adjuvant (E), an acetophenone compound and a thioxanthone compound, an acetophenone compound and an aromatic amine compound are mentioned, and, specifically, 2-morpholino -1- (4) -Methylsulfanylphenyl) -2-methylpropan-1-one and 2,4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one and 2,4-diethyl Thioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2,4-diethylthioxanthone, 2-morpholino-1- (4-methylsulfanylphenyl) -2-Methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxa Ton, 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4- Morpholinophenyl) butan-1-one and 4,4′-bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 4, 4'-bis (diethylamino) benzophenone etc. are mentioned.

  Among them, a combination of an acetophenone compound and a thioxanthone compound is preferable, and 2-morpholino-1- (4-methylsulfanylphenyl) -2-methylpropan-1-one and 2,4-diethylthioxanthone, 2-morpholino-1- ( More preferred are 4-methylsulfanylphenyl) -2-methylpropan-1-one, 2-isopropylthioxanthone and 4-isopropylthioxanthone. With these combinations, a pattern with high sensitivity and high visible light transmittance can be obtained.

  The content of the polymerization initiator (C) is preferably 0.5 to 30 parts by mass, more preferably 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (B). It is 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass. When the content of the polymerization initiator (C) is in the above range, a pattern can be obtained with high sensitivity.

  The amount of the polymerization initiation auxiliary (E) used is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the total amount of the resin (A), resin (A1) and polymerizable compound (B). Is 0.3 to 15 parts by mass. When the amount of the polymerization initiator (E) is in the above range, a pattern can be obtained with high sensitivity, and the obtained pattern has a good shape.

  The photosensitive resin composition of the present invention may contain a solvent (D).

  As a solvent which can be used in the present invention, for example, an ester solvent (a solvent containing -COO- in the molecule but not -O-), an ether solvent (containing -O- in the molecule, -COO-) Solvent, ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule but not -COO-), alcohol solvent, aromatic It can be selected from hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, butyl butyrate, ethyl butyrate, butyl butyrate And methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  As ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

  As ether ester solvents, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and the like diethylene glycol monobutyl ether acetate.

  As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone Etc.

  As the alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like can be mentioned.

  Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.

  As the amide solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can be mentioned.

  These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm is preferable from the viewpoint of coating property and drying property. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and the like are preferable. When the solvent (D) is one of these solvents, it is possible to suppress unevenness during coating and to improve the flatness of the coating.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 90% by mass, with respect to the total amount of the photosensitive resin composition.
In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the content of the solvent (D) is in the above range, the flatness of the film coated with the photosensitive resin composition tends to be high. Here, solid content means the quantity which remove | eliminated the solvent (D) from the photosensitive resin composition.

  The photosensitive resin composition of the present invention may further contain a multifunctional thiol compound (T). The polyfunctional thiol compound (T) refers to a compound having two or more sulfanyl groups (-SH) in the molecule. In particular, when a compound having two or more sulfanyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition of the present invention tends to be high.

  Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate) and butanediol bis (3- (3-sulfanylpropionate). Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydro Shiechirutorisu (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the polymerization initiator (C). When the content of the polyfunctional thiol compound (T) is in the above range, the sensitivity of the photosensitive resin composition tends to be high, and the developability tends to be good, which is preferable.

  The photosensitive resin composition of the present invention may contain a surfactant (G) (but different from the resin (F)). Examples of the surfactant include silicone surfactants, fluorosurfactants, silicone surfactants having a fluorine atom, and the like.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned.
Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH21PA, SH29PA, SH29PA, polyether-modified silicone oil SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP 321, KP 322 , KP 323, KP 324, KP 326, KP 341 (Shin-Etsu Chemical Co., Ltd.), TSF 400, TSF 401, TSF 410, TSF 4300, TSF 4440, TSF 4445, TSF 4446, TSF 4452 (Momentive Performance Materials Japan Ltd. Joint Company And the like.

The fluorine-based surfactant includes a surfactant having a fluorocarbon chain.
Specifically, Florinert (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, R30 (DIC) Ltd., F-top (registered trademark) EF301, the same EF303, the same EF352, the same EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, the same S382, the same SC101, the SC105 (Asahi Glass) Co., Ltd. product, E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

  As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Megafuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be mentioned. Preferably, Megafuck (registered trademark) F475 is mentioned.

  The content of the surfactant (G) is 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass, with respect to the total amount of the photosensitive resin composition. Below, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in this range, the flatness of the coating can be improved.

  The photosensitive resin composition of the present invention may contain, as necessary, various kinds of fillers, other polymer compounds, adhesion improvers (H), antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. Additives of the following.

  The adhesion improver (H) described above is not particularly limited as long as it does not precipitate a solid by reaction with the photosensitive resin composition at the time of addition or storage at normal temperature. Coupling agents are exemplified, for example, KBM-303, KBE-402, KBM-403, KBM-503, KBM-573, KBM-803, KBE-9007 (Shin-Etsu Chemical Co., Ltd.), or Z -6040, Z-6043, Z-6011, Z-6020, Z-6094, Z-6062, Z-6094, Z-6030, Z-6519, Z-6300, Z-6883 (manufactured by Toray Dow Corning Co., Ltd.) Etc.).

  The photosensitive resin composition of the present invention is substantially free of colorants such as pigments and dyes. That is, in the photosensitive resin composition of the present invention, the content of the colorant relative to the whole composition is, for example, preferably less than 1% by mass, more preferably less than 0.5% by mass.

  The photosensitive resin composition of the present invention is preferably packed in a quartz cell having an optical path length of 1 cm, and the average transmittance is preferably measured when the transmittance is measured under the measurement wavelength of 400 to 700 nm using a spectrophotometer. Is 70% or more, more preferably 80% or more.

  When the photosensitive resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. The average transmittance of the coating film having a thickness of 3 μm after heat curing (for example, curing at 100 to 250 ° C. for 5 minutes to 3 hours) is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. It is an average value when measured under conditions. Thereby, the coating film excellent in the transparency in visible region can be provided.

  The photosensitive resin composition of the present invention is coated on a substrate of glass, metal, plastic or the like, or on these substrates on which a color filter, various insulation or conductive films, drive circuits and the like are formed, and a desired shape is obtained. Can be patterned to form a pattern. Furthermore, this pattern may be formed and used as part of a component such as a display device.

  First, the photosensitive resin composition of the present invention is applied onto a substrate, and patterning is performed by the photolithography method described below.

  Coating of the photosensitive resin composition can be carried out using various coating devices such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, a dip coater and the like.

  Then, it is preferable to dry or pre-bake to remove volatile components such as a solvent and to dry. Thereby, a smooth uncured coating film can be obtained.

  The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material to be used, the application and the like, and is, for example, about 1 to 6 μm.

  Further, the obtained uncured coating film is irradiated with light, for example, a mercury lamp, ultraviolet light generated from a light emitting diode, etc., through a photomask for forming a target pattern. The shape of the photomask at this time is not particularly limited, and the shape and size may be selected according to the application of the pattern.

  In recent exposure machines, light having a wavelength of less than 350 nm is cut using a filter that cuts this wavelength range, or light having wavelengths around 436 nm, 408 nm, and 365 nm is extracted using a band pass filter. It is possible to selectively take out and irradiate the substantially parallel light uniformly over the entire exposure surface. At this time, accurate alignment between the mask and the substrate can be performed by using an apparatus such as a mask aligner or a stepper.

  The coated film after exposure is brought into contact with a developer to dissolve a predetermined portion, for example, a non-exposed portion (i.e., a non-pixel portion), and then developed to obtain a target pattern shape.

  The developing method may be any of a liquid deposition method, a dipping method, a spray method and the like. Furthermore, the substrate may be inclined at any angle during development.

  The developer used for development is preferably an aqueous solution of a basic compound.

  The basic compound may be any of inorganic and organic basic compounds.

  Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate and silicic acid Potassium, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia and the like can be mentioned.

  Examples of organic basic compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. Can be mentioned.

  The concentration of these inorganic and organic basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

  The developer may contain a surfactant.

  The surfactant may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.

  As nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned.

  Examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl And alkylaryl sulfonates such as sodium naphthalene sulfonate and the like.

  Examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

  The concentration of the surfactant in the alkaline developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  A pattern can be obtained by washing with water after development. Further, post-baking may be performed as needed. Post-baking preferably has a temperature range of 150 to 240 ° C. for 10 to 180 minutes, for example.

  When exposing an uncured coating film, a coating film having no pattern can be obtained by performing light irradiation on the entire surface and / or omitting development without using a photomask on which a pattern is formed. it can.

  In the present embodiment, the thin film made of the photosensitive resin composition is formed as described above on the substrate on which the electrode is formed, and then, the surface of the electrode is exposed by the photolithography method described above. An opening is formed in the thin film.

  Next, the wettability of the electrode can be evaluated based on the value of the polar component of the surface free energy of the electrode, whereby the substrate can be evaluated.

  If the value of the polar component of the surface free energy of the electrode is, for example, 15 mN / m or more, it is determined that the substrate can be applied to a display device or the like as a substrate with a partition, and conversely, the value of the polar component of surface free energy of the electrode However, if it is 15 mN / m or less, it can be judged as a board | substrate which can not be applied to a display apparatus etc. as a board | substrate with a partition.

  Furthermore, based on this evaluation result, evaluation of the photosensitive resin composition for forming a partition can also be performed.

That is, the thin film made of the photosensitive resin composition is formed as described above on the substrate on which the electrode is formed, and then the thin film is formed by the photolithography method so that the surface of the electrode is exposed. An opening can be formed, and then the wettability of the electrode can be evaluated based on the value of the polar component of the surface free energy of the electrode, whereby the photosensitive resin composition can be evaluated. The preferred embodiment of the substrate evaluation method of the present invention is
Supplying a photosensitive resin composition onto a substrate on which an electrode is formed, and rotating the substrate at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition;
Drying the substrate on which the thin film is formed under reduced pressure at 66 Pa and prebaking at 110 ° C. for 110 seconds;
The prebaked thin film is exposed at 200 mJ / cm ² so as to expose the surface of the electrode, and developed for 80 seconds at 23.degree. C. using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Forming an opening in the thin film;
It is a board | substrate evaluation method including the process of evaluating the wettability of an electrode based on the value of the polar component of the surface free energy of the electrode exposed to the opening part of the said thin film.

  If the value of the polar component of the surface free energy of the electrode is, for example, 15 mN / m or more, it is judged as the photosensitive resin composition applicable as the photosensitive resin composition for forming the partition wall, conversely If the value of the polar component of surface free energy is 15 mN / m or less, it can be determined as a photosensitive resin composition that can not be applied as a photosensitive resin composition for forming partition walls.

  The value of the polar component of the surface energy of the electrode can be calculated, for example, by measuring the contact angle of a predetermined solution on the electrode surface, and using the predetermined calculation formula based on that value.

In the present embodiment, for example, the value of the polar component of the surface energy of the electrode can be calculated using the OwensandWendt method. In the OwensandWendt method, the following equation is applied.
γl (1 + cos θ) = 2 (γsd · γld) ^1/2 + 2 (γsp · γlp) ^1/2
(In the formula, γl is the surface free energy of the liquid, γld is the dispersion force component of the surface free energy of the liquid, γlp is the polar component of the surface free energy of the liquid, γsd is the dispersion force component of the surface energy of solid, and γsp is solid Polar component of surface free energy, θ represents contact angle.)

  Since two unknowns (γsd, γsp) are used here, γsd and γsp can be calculated by using two types of liquids having known dispersion components and polar components.

From the above equations, the following equation is led, is inclined from the linear regression equation of the following formula ^{(γsp) 1/2,} the intercept is (? ^{Sd) 1/2.}
γl (1 + cos θ) / 2 (γld) ^1/2 VS (γlp / γld) ^1/2
In addition, it is possible to calculate the polar component of the surface free energy of the electrode by using two kinds of liquids whose dispersion component and polar component are known, for example, three or more solvents having known polar components (for example, four types The evaluation can also be carried out by measuring the contact angles of a plurality of points (for example, three points) in the substrate surface using the solvent of) and taking an average.

  An organic EL (electroluminescence) display device will be described below as an example of the display device of the present invention.

  FIG. 1 is a cross-sectional view schematically showing an enlarged part of a display device 1 which is an example of the display device of the present invention. FIG. 2 is a plan view schematically showing a part of the display device 1 which is an example of the display device of the present invention in an enlarged manner. The display device 1 mainly includes a support substrate 2, a partition 3 defining a section set in advance on the support substrate 2, and a plurality of organic EL elements 4 provided in the section defined by the partition 3. It comprises.

  For the support substrate 2, for example, a glass substrate, a substrate made of resin, a substrate made of metal, a substrate made of a semiconductor, etc. are used.

  The partition walls 3 are formed, for example, in a grid or stripe on the support substrate 2. In addition, in FIG. 2, the display apparatus 1 in which the grid-shaped partition 3 was provided as one Embodiment is shown. In the figure, the area where the partition 3 is provided is hatched.

  On the support substrate 2, a plurality of recesses 5 (hereinafter sometimes referred to as openings 5) defined by the partition walls 3 and the support substrate 2 are set. The opening 5 corresponds to a section defined by the partition 3.

  The partition walls 3 in the display device 1 are provided in a grid shape. Therefore, when viewed from one side in the thickness direction Z of the support substrate 2 (hereinafter sometimes referred to as “in plan view”), the plurality of openings 5 are arranged in a matrix. That is, the openings 5 are provided at predetermined intervals in the row direction X, and are also aligned in the column direction Y at predetermined intervals. The shape in plan view of each opening 5 is not particularly limited. For example, the opening 5 is formed in a substantially rectangular shape, a substantially elliptical shape, an oval shape, or the like in a plan view. In the present embodiment, the substantially rectangular opening 5 is provided in a plan view. In the present specification, the above row direction X and column direction Y mean directions perpendicular to the thickness direction Z of the support substrate and also perpendicular to each other.

  In the case where stripe-shaped barrier ribs are provided as another embodiment, for example, a plurality of barrier rib members extending in the row direction X are arranged at predetermined intervals in the column direction Y. In this embodiment, the stripe-shaped recessed portion is defined by the stripe-shaped partition wall and the support substrate.

  The partition walls are formed so as to narrow in width as they are separated from the support substrate. For example, the cross-sectional shape when the partition extending in the column direction Y is cut in a plane perpendicular to the extending direction (column direction Y) is formed such that the width becomes narrower as it is separated from the support substrate . FIG. 1 shows a partition having an isosceles trapezoidal shape, and the lower base is wider than the upper base when comparing the upper base and the lower base on the support substrate side. In addition, the cross section of the partition actually formed does not necessarily become a trapezoid shape, and the linear part and trapezoid shape part may be roundish.

  The partition walls can be formed by photolithography as described above. In this embodiment, a thin film made of the photosensitive resin composition is formed on a substrate on which a first electrode of an organic EL element described later is formed, and then a photolithography method is performed so that the surface of the electrode is exposed. By forming an opening in the thin film, the partition wall is formed.

It is preferable that the top surface of the partition 3 exhibits liquid repellency. Here, the top surface means a flat surface of the surfaces of the partition walls 3 which is located at a position most distant from the support substrate 2. As a method of forming the partition 3 in which the top surface shows liquid repellency, the method of using the photosensitive resin composition containing the above-mentioned liquid repellent (F), or the method of carrying out the liquid repellant processing of the surface after partition formation is mentioned. Be For example, liquid repellency can be imparted to the surface of the partition 3 by performing the plasma treatment on the partition 3 in an atmosphere containing fluoride. The fluoride in this treatment is gaseous, and as the fluoride, CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ or the like can be used. By performing such plasma treatment, fluorine atoms are bonded to the surface of the partition 3 and liquid repellency is imparted to the partition 3.

  The top surface of the partition 3 exhibits liquid repellency, so that the ink supplied to the area (opening 5) surrounded by the partition 3 is prevented from flowing along the top surface of the partition 3 and overflowing into the adjacent area. be able to.

The organic EL element 4 is provided in a section (that is, the opening 5) defined by the partition wall 3.
When the grid-like partition walls 3 in the display device 1 are provided, the organic EL elements 4 are provided in the openings 5 respectively. That is, the organic EL elements 4 are arranged in a matrix in the same manner as the openings 5, and on the support substrate 2, they are arranged at predetermined intervals in the row direction X and at predetermined intervals in the column direction Y. Is provided.

  The shape of the partition 3 and the arrangement thereof are appropriately set according to the specification of the display device such as the number of pixels and the resolution and the ease of manufacture. For example, the width in the row direction X or column direction Y of the partition 3 is about 5 μm to 50 μm, the height of the partition 3 is about 0.5 μm to 5 μm, and between the partitions 3 adjacent in the row direction X or column direction Y , Or the width in the row direction X or the column direction Y of the opening 5 is about 10 μm to 200 μm. The width in the row direction X or the column direction Y of the first electrode 6 is about 10 μm to 200 μm, respectively.

  The partition 3 can be formed from the photosensitive resin composition of this invention by the formation method of the above-mentioned pattern.

  In the case where stripe-shaped barrier ribs are provided as another embodiment, the organic EL elements 4 are disposed at predetermined intervals in the row direction X at the respective openings extending in the row direction X.

  The display device 1 is provided with three types of organic EL elements 4. That is, (1) red organic EL element 4R for emitting red light, (2) green organic EL element 4G for emitting green light, and (3) blue organic EL element 4B for emitting blue light are provided.

  The organic EL element 4 is configured by laminating a first electrode, an organic EL layer, and a second electrode in this order from the supporting substrate side. In the present specification, one or more layers provided between the first electrode 6 and the second electrode 10 are each referred to as an organic EL layer. The organic EL element 4 includes at least one light emitting layer as an organic EL layer. In addition to the light emitting layer of one layer, the organic EL element may further include an organic EL layer different from the light emitting layer as necessary. For example, between the first electrode 6 and the second electrode 10, a hole injection layer, a hole transport layer, an electron block layer, an electron transport layer, an electron injection layer, and the like are provided as the organic EL layer. In addition, two or more light emitting layers may be provided between the first electrode 6 and the second electrode 10.

  The organic EL element 4 includes a first electrode 6 and a second electrode 10 as a pair of electrodes consisting of an anode and a cathode. One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode. In the display device 1 of the present embodiment, the first electrode 6 functioning as an anode, the first organic EL layer 7 functioning as a hole injection layer, the second organic EL layer 9 functioning as a light emitting layer, and a cathode The second electrode 10 is stacked on the support substrate 2 in this order.

  A transparent electrode is generally used for the first electrode 6 described above. The type is not limited as long as it is a transparent electrode, for example, tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), titanium oxide transparent electrode, aluminum A doped zinc oxide (AZO), a gallium dope zinc oxide (GZO) are mentioned, A tin dope indium oxide (ITO) and a zinc dope indium oxide (IZO) are preferable.

  The first electrode 6 is provided for each of the organic EL elements 4. That is, the same number of first electrodes 6 as the organic EL elements 4 are provided on the support substrate 2. The first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4 and are arranged in a matrix like the organic EL elements 4. The partition walls 3 are mainly formed in a lattice shape in the region excluding the first electrode 6, and are further formed to cover the peripheral portion of the first electrode 6 (see FIG. 1).

  A layer (a first organic EL layer 7 corresponding to a hole injection layer) provided in contact with the first electrode 6 is provided on the first electrode 6 in the opening 5. The first organic EL layer 7 is provided, as required, with different materials or film thicknesses for different types of organic EL elements. From the viewpoint of simplicity of the process of forming the first organic EL layer 7, all the first organic EL layers 7 may be formed with the same material and the same film thickness.

  The first organic EL layer 7 supplies the ink containing the material to be the first organic EL layer 7 to the region (opening 5) surrounded by the partition wall 3 and dries, heats, and / or irradiates light. It is formed by carrying out to solidify the ink. The method of supplying the ink is not particularly limited, and examples thereof include printing methods such as an inkjet method and an aerosol jet method.

  In the solvent or dispersion medium of the ink used to form the layer (the first organic EL layer 7) provided in contact with the first electrode 6, the material to be the first organic EL layer 7 is dissolved and / or dispersed. It is not particularly limited as long as it is a liquid, but a polar solvent may be included in order to dissolve and / or disperse the material to be the first organic EL layer 7 well.

  As the above polar solvent, a general one is used, and it is not particularly limited. For example, alcohols, ketones, glycol esters, glycol ethers, N, N-dimethylformamide, N, N- Examples include dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethylsulfoxide, N-cyclohexyl-2-pyrrolidinone and the like. In the present specification, the polar solvent means one having a solvent sp (solubility parameter) value of 10 or more.

Thus, when the ink used to form the layer (the first organic EL layer 7) provided in contact with the first electrode 6 particularly contains a polar solvent, when the ink is supplied to the opening of the partition, It is likely to be repelled on the first electrode 6 and difficult to spread evenly on the entire surface within the opening, but as described above, the value of the polar component of the surface free energy of the electrode after the opening is 15 mN / m If it is the above, since the ink supplied on the 1st electrode 6 spreads uniformly on the whole surface in the opening of a partition, it spreads, and the layer (the 1st organic EL layer provided in contact with the 1st electrode 6 flat) 7) can be formed.
As the solvent or dispersion medium other than the polar solvent contained in the ink used for forming the layer (the first organic EL layer 7) provided in contact with the first electrode 6, cyclohexylbenzene, anisole, xylene, toluene, etc. Used.

  The second organic EL layer 9 functioning as a light emitting layer is provided on the first organic EL layer 7 at the opening 5. As described above, the light emitting layer is provided according to the type of the organic EL element. Therefore, the red light emitting layer 9R is provided in the opening 5 where the red organic EL element 4R is provided, the green light emitting layer 9G is provided in the opening 5 where the green organic EL element 4G is provided, and the blue light emitting layer 9B is a blue organic EL element It is provided in the opening 5 in which 4B is provided.

  The second electrode 10 is formed on the entire surface in the display area where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic EL layer 9 but also on the partition walls 3 and continuously formed across a plurality of organic EL elements.

  As described above, the organic EL display device can be manufactured by covering the plurality of organic EL elements 4 formed on the support substrate 2 with the sealing layer and the sealing substrate (not shown).

  Since the pattern obtained from the photosensitive resin composition of the present invention has high wettability, in particular, a color filter, an ITO electrode of a liquid crystal display element, an organic EL display element, a circuit wiring board, etc. It is useful as a partition used to Furthermore, for example, a photo spacer which constitutes a part of a color filter substrate and / or an array substrate, an overcoat capable of patterning, an interlayer insulating film, a projection for liquid crystal alignment control, a micro lens, a coat layer for adjusting film thickness, etc. The coating film which is useful as a member for a touch panel and does not have a pattern obtained as described above is useful as an overcoat which constitutes a part of a color filter substrate and / or an array substrate. The color filter substrate and the array substrate are suitably used for liquid crystal display devices, organic EL display devices, electronic paper and the like.

  Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise indicated, "%" and "parts" in the examples are% by mass and parts by mass.

Synthesis Example 1
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed and nitrogen was replaced, and 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added and heated to 85 ° C. with stirring. Then 233 parts of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate A mixed solution of 115 parts of methoxypropanol was dropped into the flask over 4 hours.
On the other hand, a mixed solution of 32 parts of 2, 2-azobis (2,4-dimethyl valeronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours. After completion of the dropwise addition, the mixture is kept at the same temperature for 3 hours and cooled to room temperature to obtain a B-type viscosity (23 ° C.) 46 mPas, solid content 33.7%, solution acid value 83 mg-KOH / g copolymer (Resin A1a ) Solution was obtained. The weight average molecular weight Mw of the obtained resin A1a was 7.7 × 10 ³ , and the molecular weight distribution was 1.90. Resin A1a has the following structural units.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をジエチレングリコールエチルメチルエーテル２４０部に溶解させた溶液を、別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤溶液の滴下が終了した後、７０℃で４時間保持し、その後室温まで冷却して、固形分４２．３％の共重合体（樹脂Ａ１ｂ）の溶液を得た。得られた樹脂Ａ１ｂの重量平均分子量（Ｍｗ）は８．０×１０^３、分子量分布（Ｍｗ／Ｍｎ）は１．９１、酸価は６０ｍｇ−ＫＯＨ／ｇであった。樹脂Ａ１ｂは、下記の構造単位を有する。

(Composition example 2)
An appropriate amount of nitrogen was flowed in a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and a nitrogen atmosphere was produced, and 140 parts of diethylene glycol ethyl methyl ether was charged and heated to 70 ° C. while stirring. And 40 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1) to monomer (II-1) in the mixture] A solution in which 360 parts of = 50: 50 was dissolved in 190 parts of diethylene glycol ethyl methyl ether was prepared, and this solution was dropped into the flask over 4 hours using a dropping funnel.

On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 240 parts of diethylene glycol ethyl methyl ether was added to the flask over 5 hours using another dropping pump. It dripped. After the dropping of the polymerization initiator solution was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin A1b) having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin A1 b was 8.0 × 10 ³ , the molecular weight distribution (Mw / Mn) was 1.91, and the acid value was 60 mg-KOH / g. Resin A1b has the following structural unit.

(Composition example 3)
In a flask equipped with a condenser, a stirrer and a thermometer, 176 parts of t-butoxystyrene and 5.8 parts of azobisbutyronitrile are added, and 250 parts of propylene glycol monomethyl ether are added and dissolved, and the solution is heated to 75 ° C. It was allowed to polymerize for 4 hours. The obtained poly t-butoxystyrene solution was mixed with 50 parts of a 5% aqueous sulfuric acid solution, and a hydrolysis reaction was performed at 100 ° C. for 3 hours. The reaction product is washed three times with 1000 parts of deionized water, and 500 parts of propylene glycol monomethyl ether acetate is added to carry out solvent substitution, and an alkali-soluble resin (polyhydroxystyrene, resin Ac) having a weight average molecular weight (Mw) of 24,000. Got).

(Composition example 4)
In a flask equipped with a condenser, a stirrer and a thermometer, 145 parts of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Thereto, 20 parts of styrene, 57 parts of glycidyl methacrylate and 82 parts of monoacrylate having a tricyclodecane skeleton (“FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were dropped, and stirring was further continued at 140 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 part of trisdimethylaminomethylphenol and 0.12 part of hydroquinone were added to 27 parts of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts of tetrahydrophthalic anhydride (THPA) and 0.7 parts of triethylamine are added and reacted at 120 ° C. for 3.5 hours, weight average molecular weight (Mw) about 7,000, solid content acid value 84 mg KOH / g alkali-soluble resin (Resin Ad) was obtained.

（式中、ｎは整数を表す。Ｍｅはメチル基を表す。） (Composition example 5)
In a flask equipped with a condenser, a stirrer and a thermometer, 400 parts of an epoxy resin (manufactured by Nippon Kayaku Co., Ltd .: XD-1000) was added to 361 parts of propylene glycol monomethyl ether, and dissolved at 90 ° C for 3 hours. Next, 142 parts of methacrylic acid, 0.27 parts of methoquinone and 10.8 parts of dimethylbenzylamine were added and reacted at 90 ° C. for 15 hours. Thereafter, 201 parts of tetrahydrophthalic anhydride is added, and reaction is carried out at 90 ° C. for 4 hours, and 382 parts of propylene glycol monomethyl ether is added, and the weight average molecular weight (Mw) represented by the following formula is about 2,000, solid content acid value 103 mg An alkali-soluble resin (resin Ae) of KOH / g was obtained.

(In the formula, n represents an integer. Me represents a methyl group.)

Synthesis Example 6
In a flask equipped with a condenser, a stirrer and a thermometer, 450 parts of propylene glycol monomethyl ether, 50 parts of p-vinylbenzoic acid, 12 parts of N-phenylmaleimide, 20 parts of 2-hydroxyethyl methacrylate and 18 parts of 2-ethylhexyl methacrylate The mixture was charged and heated to 92 ° C. while introducing nitrogen gas. Next, a solution of 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and polymerization was performed by maintaining the same temperature for 3 hours. Thereafter, a solution of 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 26.7 parts of propylene glycol monomethyl ether acetate is added, and the temperature of the reaction solution is raised to 100 ° C. The temperature was maintained for 1 hour and polymerization was performed to obtain a solution (solid content concentration = 16% by mass) of the binder resin (resin Af). The weight average molecular weight (Mw) of the resin Af was 9,850, and the number average molecular weight (Mn) was 5,150.

Synthesis Example 7
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer and a stirrer, 78 parts of 3,3,4,4,5,5,6,6,6-nonafluorohexyl α-chloroacrylic acid Add 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, 266 parts of propylene glycol monomethyl ether acetate, heat to 70 ° C, and then under a nitrogen stream for 30 minutes Stir. 1 part of azobisisobutyro nitrile is added to this, and polymerizing for 18 hours, weight average molecular weight (Mw) 7,500, solid content 33 mass%, polymer of solid content acid value 68 mg KOH / g (resin Fa) Solution was obtained. Resin Fa has the following structural units.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained by the synthesis example 1-7 was performed on condition of the following using GPC method.
Device: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
The ratio (Mw / Mn) of the weight average molecular weight in terms of polystyrene and the number average molecular weight obtained above was taken as a molecular weight distribution.

(Examples 1 to 5, Comparative Examples 1 to 3 and Reference Examples 1 to 4)
<Preparation of photosensitive resin compositions 1 to 8>
About Example 1-5, Comparative Example 1 and Reference Examples 1-4, the component of Table 3 is mixed with the solvent (D) mentioned later, respectively so that a solid content (%) may become a ratio of Table 3. Thus, a photosensitive resin composition was obtained.
For Comparative Example 2, Zeocoat CP1010 (manufactured by Nippon Zeon Co., Ltd.) was used.
About comparative example 3, what diluted SU-83000 (made by Nippon Kayaku Co., Ltd.) with propylene glycol monomethyl ether acetate of the same volume as a material was used. Hereinafter, photosensitive resin compositions of Examples 1 to 5 are photosensitive resin compositions 1 to 5 respectively, and photosensitive resin compositions of Comparative Examples 1 to 3 are photosensitive resin compositions 6 to 8 respectively, and Reference Example The photosensitive resin compositions 1 to 4 are described as photosensitive resin compositions 9 to 12, respectively.

  Each component in Table 3 is as follows. The number of parts described in the column of resin represents a part by mass in terms of solid content.

Resin (A); Aa: copolymer of p-hydroxystyrene and butyl acrylate [copolymerization ratio: 50: 50, weight average molecular weight; 12600] (Marcalinker (registered trademark) CBA; Maruzen Petrochemical Co., Ltd.) Made)
Resin (A); Ab: copolymer of p-hydroxystyrene and styrene [copolymerization ratio: 50: 50, weight average molecular weight; 4000] (Marcalinker (registered trademark) CST; manufactured by Maruzen Petrochemical Co., Ltd.)
Resin (A1); A1a: Resin A1a obtained in Synthesis Example 1
Resin (A1); A1b: Resin A1b obtained in Synthesis Example 2
Resin (A); Ac: resin Ac obtained in Synthesis Example 3
Resin (A); Ad; resin Ad obtained in Synthesis Example 4
Resin (A); Ae; Resin Ae obtained in Synthesis Example 5
Resin (A); Af; Resin Af obtained in Synthesis Example 6
Polymerizable compound (B); Ba: trimethylolpropane triacrylate (A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable compound (B); Bb: dipentaerythritol polyacrylate (A-9550; Shin-Nakamura Chemical Co., Ltd. product)
Polymerizable compound (B); Bc: Deconal acrylate DA-314 (manufactured by Nagase ChemteX Corporation)
Polymerizable compound (B); Bd: Ogsol EA-200 (manufactured by Osaka Gas Chemical Co., Ltd.)
Polymerization initiator (C); Ca; 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (IRGACURE (registered trademark) 907; manufactured by BASF)
Polymerization initiator (C); Cb: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (IRGACURE (registered trademark) 309; manufactured by BASF)
Polymerization initiator (C); Cc; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole (Hodogaya chemistry Industrial Co., Ltd.)
Polymerization start auxiliary (E); 4,4'-bis (diethylamino) benzophenone (EAB-F; Hodogaya Chemical Industry Co., Ltd. product)
Liquid-repellent agent (F); Fa; resin Fa obtained in Synthesis Example 7
Liquid repellent (F); Fb; Megafuck (registered trademark) RS 72 (manufactured by DIC Corporation)
Surfactant (G); Ga; polyether modified silicone surfactant "BYK330" (manufactured by BIC Chemical Co., Ltd.)
Surfactant (G); Gb: Polyether modified fluorochemical surfactant "F-550" (manufactured by BIC Chemical Co., Ltd.)
Adhesion improver (H); γ-glycidoxypropyltrimethoxysilane colored dispersion (I); C.I. I. Pigment red 254 / C. I. Pigment red 177 / C. I. Pigment yellow 150 = 50/35/15 (mass ratio) 13 parts by mass, dispersant BYK-LPN 21116 (amine value = 73, acid number = 0, manufactured by Bick Chemie) 10 parts by mass (nonvolatile component = 40 mass%) A mixture of 77 parts by mass of propylene glycol monomethyl ether acetate as a solvent and dispersed by a bead mill for 12 hours The solvent (D) is a mixture of the following solvent components (Da) to (Dd) in the proportions shown in Table 4 is there.
Solvent (D); Da; propylene glycol monomethyl ether acetate solvent (D); Db; ethyl 3-ethoxypropionate solvent (D); Dc; propylene glycol monomethyl ether solvent (D); Dd: 3-methoxybutyl acetate Photosensitivity The components of Table 3 were mixed with the solvent (D) such that the solid content of the resin composition was "solid content (%)" of Table 3.

[Substrate cleaning]
Using a cleaning device (manufactured by Shibaura Mfg. Co., Ltd.), perform 370 seconds by sweeping the surface of a 370 mm × 470 mm × 0.5 mm glass substrate (Econing XG manufactured by Corning Co., Ltd.) with pure water while brushing the surface for 30 seconds. An additional wash for 60 seconds was carried out with a water shower and drying was carried out with air.

[Preparation of a substrate with a transparent conductive film]
An ITO target (manufactured by Tosoh Corp .; 90% In ₂ O ₃ -10% SnO ₂ ) was used as a sputtering apparatus (in-line sputtering apparatus manufactured by ULVAC, model SDP-570VT) using the substrate cleaned as described above. After heating to 300 ° C. in a heating chamber, a transparent conductive film ITO was deposited to a thickness of 50 nm at a power of 1.05 kW, an argon gas pressure of 0.6 Pa, and a deposition time of 115 seconds in the sputtering chamber. Further, the substrate after film formation was annealed at 230 ° C. for 30 minutes in the air to obtain a glass substrate with ITO.

[Preparation of substrate with partition wall]
(Fabrication of a Partitioned Substrate of Example 1)
Implementation used, the integrated light quantity 400 mJ / cm ² down in hydrophilic treatment; - (PL3-200-15 company manufactured by Hitachi High-Technologies) to the transparent substrate with a conductive film produced in the above, _{UV-O 3} cleaning device And washed with pure water and dried with air. To this substrate, 30 g of the prepared photosensitive resin composition 1 was dropped, and rotated at 900 rpm for 7 seconds with a spin coater, to form a thin film of the photosensitive resin composition 1 by coating. Thereafter, drying under reduced pressure was performed to 66 Pa using a vacuum drying apparatus (manufactured by Tokyo Ohka Kogyo Co., Ltd .; TR 28340 CPD-CLT), and contact was made with a hot plate at 110 ° C. for 110 seconds to carry out pre-baking. Next, exposure was carried out using an exposure apparatus (manufactured by Hitachi High-Technologies Corporation; LE4000A). The exposure dose was 200 mJ / cm ² and the gap was 100 μm. The photomask is a pattern (a light shielding part is a rectangle with a shape of 300 μm in the long axis direction and 100 μm in the short axis direction, and a shape (long circle) with its four corners cut into arcs) formed on the same plane Using. Thereafter, a developer prepared by diluting a tetramethyl ammonium hydroxide aqueous solution (Tokuyama Co., Ltd. product, Tokso SD 25) with pure water so as to have a concentration of 2.38% is used, and the coated film is shower-developed After developing for 30 seconds at 23 ° C. (manufactured by Sepha Technology, Inc.), washing with water and air drying, post baking was carried out at 230 ° C. for 20 minutes in an oven (manufactured by Espec: HSC-4) to obtain a pattern .

(Production of Substrates with Partition Walls of Examples 2 to 5 and Comparative Example 1)
In the same manner as in Example 1 except that the photosensitive resin compositions 2 to 6 were used instead of the photosensitive resin composition 1, substrates with partition walls of Examples 2 to 5 and Comparative Example 1 were produced.

(Production of a Partitioned Substrate of Comparative Example 2)
In place of the photosensitive resin composition 1, the photosensitive resin composition 7 was used, and a pattern (the shape of the opening portion was cut in a circular arc shape from a rectangle having a long axis direction of 300 μm and a short axis direction of 100 μm) In the same manner as in Example 1, except that the exposure was carried out using a photomask in which the shapes (long circles) were formed on the same plane, and the post baking was performed at 230.degree. C. for 60 minutes. A substrate with a partition wall was produced.

(Production of a Partitioned Substrate of Comparative Example 3)
Instead of using the photosensitive resin composition 8 instead of the photosensitive resin composition 1, using propylene glycol monomethyl ether acetate as a developing solution, except for immersion while shaking at 23 ° C. for 80 seconds, development is performed. In the same manner as in Example 1, a substrate with a barrier rib of Comparative Example 3 was produced.

  In the same manner as in Example 1 except that the photosensitive resin compositions 9 to 12 were used instead of the photosensitive resin composition 1, substrates with partition walls of Reference Examples 1 to 4 were produced.

[Preparation of solution for evaluation of paintability]
As a solvent for carrying out the evaluation of the paintability of partition walls, N, N-dimethylacetamide (99.5% or more, manufactured by Wako Pure Chemical Industries, Ltd.), 1,3-dimethyl-2-imidazolidinone (Tokyo Chemical Industry Co., Ltd.) Two types of 99.0% or more were selected. Since the selected two types of solvents have low viscosity, cyclohexanol (manufactured by Wako Pure Chemical Industries, Ltd., 98.0% or more) is used as a viscosity adjusting material so that the liquid can be filled in the partition by the ink jet apparatus. It was used as a mixed solvent.

Moreover, since it is difficult to observe the spread after drying with a microscope using a solvent alone, Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., purity: 95% or more) was used as a solute.
Three solutions 1, 2 and 3 shown in Table 5 below were prepared.

[How to check the opening]
When the substrate after patterning is observed using a microscope (MX61L manufactured by OLIMPUS, lens LMPFLN10xBD), an organic film whose existence can be confirmed with the microscope of the magnification described above is a partition, and a partition is present on the substrate, and The organic film is not observed with a microscope of magnification, and the portion where the electrode is exposed is taken as an opening.

[Evaluation of paintability]
In the partition, 200 pL of each of the above solutions 1, 2 and 3 are filled in each partition by using 200 μL of each solution 1, 2 and 3 by using an inkjet device (Litlex 120L manufactured by ULVAC), and after drying, the solute spreads to the partition end About 30 points were observed using a microscope (MX61L manufactured by OLIMPUS, lens LCPFLN 20x LCD), and when all 30 points were spread and spread, the paintability was considered to be good.

  Some of the partitions used this time are evaluated in the absence of liquid repellency, so when the solution is filled, leakage from the partition may occur. The evaluation of the spread was carried out.

[Polarity evaluation]
(Contact angle measurement)
Pure water, glycerol (Sigma Aldrich, purity 99.5% or more), formamide (Sigma Aldrich, purity 99.5% or more), diiodomethane (Diiodomethane) using the part where ITO is exposed in the substrate after the barrier rib formation Three types of in-plane substrate measurements were carried out using four types of solvents manufactured by Sigma Aldrich Inc. (purity 99%), and evaluation was carried out by taking an average.

(Polarity calculation)
The OwensandWendt method described above was applied to the polarity calculation. In this example, contact angles are measured using the above four types of solvents, and based on the values, using the polarity calculation software disclosed in the following URL, the electrodes of the OwensandWendt method are used. The value of the polar component of surface free energy was calculated.
<URL: http: //www007.upp.so-net.ne.jp/y-kondo/surface.htm>

  The results of Examples, Comparative Examples, and Reference Examples are shown in Table 6. In Table 6, "Good" is indicated by "o", and "x" indicates defective.

  From the results of the above examples, when the photosensitive resin composition of the present invention is used, the surface of ITO after forming a pattern that exposes the electrode surface has a high value of the polar component of surface free energy, and the surface of ITO It was confirmed that a pattern having excellent wettability was obtained.

  According to the photosensitive resin composition of the present invention, it is possible to obtain a pattern having excellent wettability on the electrode surface.

Reference Signs List 1 display device 2 support substrate 3 partition wall 4 organic EL element 5 recess (opening)
6 First electrode 7 First organic EL layer (hole injection layer)
9 Second organic EL layer (light emitting layer)
10 Second electrode

Claims (12)

It is a photosensitive resin composition containing the following (A) ,
The photosensitive resin composition is supplied onto a substrate on which an electrode is formed, and the substrate is rotated at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition, and the substrate on which the thin film is formed is After drying under reduced pressure at 66 Pa, it is prebaked at 110 ° C. for 110 seconds, and then the thin film after the prebaking is exposed at 200 mJ / cm ² so that the surface of the electrode is exposed. The value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film when the opening is formed in the thin film by photolithography using an aqueous hydroxide solution for 80 seconds at 23 ° C. is 15 mN / It is a photosensitive resin composition which becomes m or more ,
The substrate on which the electrode is formed is mounted with an ITO target in a sputtering apparatus, heated to 300 ° C. in a heating chamber, and then power 1.05 kW, argon gas pressure 0.6 Pa, film forming time 115 seconds in the sputtering chamber A photosensitive resin composition which is a glass substrate having an ITO film on which a transparent conductive film ITO is formed 50 nm thick on the substrate and the substrate after the film formation is annealed at 230 ° C. for 30 minutes in the atmosphere.

(A) Resin having a structural unit containing a group represented by the following formula [i]

[I]
(In formula [i], R 1, R 2, R 3, R 4 and R 5 each independently represent —OH, —COOH or a hydrogen atom, and at least one of R 1, R 2, R 3, R 4 and R 5 is — OH or -COOH). The photosensitive resin composition of Claim 1 whose resin which has a structural unit containing group shown by said Formula [i] is an acrylic resin or an epoxy resin. The photosensitive resin composition according to claim 1 , wherein the structural unit is a structural unit represented by the following formula [ii].

(In formula [ii], R 1, R 2, R 3, R 4 and R 5 have the same meaning as described above, and R 6 represents a hydrogen atom, a methyl group or an ethyl group.)   The photosensitive resin composition of any one of Claims 1-3 whose acid value of resin which has a structural unit containing group shown by said Formula [i] is 50-180 mgKOH / g. Further comprising a lower SL (B) and (C), the photosensitive resin composition according to any one of claims 1-4.
(B) Polymerizable compound (C) polymerization initiator The photosensitive resin composition according to claim 5, wherein the polymerization initiator is a photopolymerization initiator, and the polymerizable compound is polymerized by radical polymerization.   The photosensitive resin composition according to any one of claims 1 to 6, further comprising a liquid repellent. The photosensitive resin composition according to claim 7 , wherein the liquid repellent agent is a polymer containing a structural unit derived from an unsaturated compound having a C 4 to C 6 perfluoroalkyl group.   The partition formed with the photosensitive resin composition of any one of Claims 1-8.   A substrate comprising the partition wall and the electrode according to claim 9.   A display device comprising the substrate according to claim 10. Supplying a photosensitive resin composition onto a substrate on which an electrode is formed, and rotating the substrate at 900 rpm for 7 seconds to form a thin film of the photosensitive resin composition;
Drying the substrate on which the thin film is formed under reduced pressure at 66 Pa and prebaking at 110 ° C. for 110 seconds;
The prebaked thin film is exposed at 200 mJ / cm ² so as to expose the surface of the electrode, and developed for 80 seconds at 23.degree. C. using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Forming an opening in the thin film;
A substrate evaluation method comprising the step of evaluating the wettability of an electrode based on the value of the polar component of the surface free energy of the electrode exposed to the opening of the thin film.

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