JP6136928B2 - Negative photosensitive resin composition, method for producing partition wall, and method for producing optical element - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition, a partition using the same, and an optical element having the partition.

  As a partition used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element which is an optical element, a method is known in which a photosensitive resin composition is applied to a substrate and is formed by a photolithography technique.

In recent years, a cost reduction process using an inkjet method has been proposed as a method for manufacturing a pixel portion of a color filter or an organic EL element.
For example, in the manufacture of a color filter, after the partition walls are formed by photolithography, R (red), G (green), and B (blue) inks are ejected to the openings (dots) surrounded by the partition walls by an inkjet method. , Apply to form pixels.

  In the ink jet method, it is necessary to prevent color mixing of ink between adjacent pixels. Therefore, the partition wall is required to have a property of repelling ink containing water or an organic solvent which is an inkjet discharge liquid, so-called ink repellency. On the other hand, since the ink layer formed on the pixel by the inkjet method is required to have high film thickness uniformity, the opening (dot) surrounded by the partition wall has good wettability with respect to the discharge liquid. It is required to have so-called ink affinity.

  Therefore, in order to make the surface of the partition walls have ink repellency, a technique for adding an ink repellant to the photosensitive resin composition used for forming the partition walls has been developed. For example, when an ink repellent agent having a small surface free energy is added to the photosensitive resin composition, and the solvent evaporates in the drying process of the coating film, the repellent force acts between the ink repellent agent and other solid components. By utilizing the migration, ink repellency is imparted to the surface of the partition wall obtained. In this case, if the surface transferability of the ink repellent agent is insufficient, the ink repellent agent remains inside the film, resulting in poor ink affinity on the side wall of the partition wall or when the film surface is dissolved in the development process. Since the layer where the ink repellent agent has migrated to the surface is thin, all of the layer is removed, resulting in poor ink repellency on the partition wall surface.

  Further, after development, the photosensitive resin composition may remain on the dots, and ink white spots may occur. In order to prevent this, ultraviolet / ozone irradiation treatment or the like is performed on the dots before ink injection, but there is also a problem that the ink repellency of the partition walls is lowered at that time.

  Patent Document 1 discloses an ink repellent agent comprising a fluorine-containing hydrolyzed condensate that solves such a problem and has a sufficiently small surface free energy and can maintain ink repellency even after being subjected to ultraviolet / ozone irradiation treatment. The technique of the negative photosensitive resin composition used for added partition formation is described.

International Publication No. 2010/013816

  In Patent Document 1, when a photosensitive resin composition containing a fluorine-containing hydrolysis condensate is used, a highly polar solvent is used to stably hold the fluorine-containing hydrolysis condensate in the composition. Yes. According to the knowledge of the present inventor, the solvents (toluene: boiling point 111 ° C., 2-propanol: boiling point 82 ° C., diethylene glycol dimethyl ether: boiling point 162 ° C., propylene glycol monomethyl ether acetate: At a boiling point of 146 ° C., depending on the solvent composition and the amount of the solvent in the resin composition, agglomerated foreign matter of the fluorine-containing hydrolysis condensate may be generated at the time of drying, or the film after coating may be uneven. There was a problem.

  The present invention relates to a negative photosensitive resin composition that has good ink repellency and can produce partition walls that can retain the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment. The present invention provides a negative photosensitive resin composition having a good coating property in which a film is formed and dried using this, the film thickness is uniform, there is no unevenness, and aggregates are not generated on the film surface. For the purpose. Further, the present invention has good ink repellency formed by curing the photosensitive resin composition, can retain the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and has an appearance. It is an object of the present invention to provide a partition wall having a good and uniform film thickness and an optical element having the partition wall.

式（ｃ−１）、（ｃ−２）中の記号は、以下の通りである。
Ｒ^Ｆ：炭素原子数３〜１０のエーテル性酸素原子を含んでいてもよいペルフルオロアルキル基を有する有機基、
Ｒ^Ｈ：ペルフルオロアルキル基を有しない有機基、
Ｘ：加水分解性基、
ｐ：０、１または２である。
ただし、Ｒ^ＨおよびＸが、化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
［２］前記含フッ素オルガノシロキサン化合物におけるフッ素原子の含有割合が１０〜５５質量％である、［１］のネガ型感光性樹脂組成物。
［３］前記溶媒（Ｄ１）が、下式（３）で表される化合物である、［１］または［２］のネガ型感光性樹脂組成物。
Ｒ^１Ｏ（Ｃ_２Ｈ_４Ｏ）_ｙＲ^２ （３）
式（３）中、Ｒ^１は炭素原子数が１〜１０のアルキル基、Ｒ^２は炭素原子数が２〜１０のアルキル基を示し、ｙは１〜１０の整数を示す。
［４］前記溶媒（Ｄ１）が、ジエチレングリコールエチルメチルエーテルである、［１］〜［３］のいずれかのネガ型感光性樹脂組成物。
［５］前記溶媒（Ｄ）が、さらに、水酸基を有し、沸点が１６５℃未満である溶媒（Ｄ２）を、前記溶媒（Ｄ）の全量に対して、１〜５０質量％の割合で含む、［１］〜［４］のいずれかのネガ型感光性樹脂組成物。
［６］前記アルカリ可溶性樹脂（Ａ）が、１分子中に酸性基とエチレン性二重結合とを有する感光性樹脂である、［１］〜［５］のいずれかのネガ型感光性樹脂組成物。
［７］前記光重合開始剤（Ｂ）が、アセトフェノン類またはＯ−アシルオキシム類と、ベンゾフェノン類との組み合わせからなる、［１］〜［６］のいずれかのネガ型感光性樹脂組成物。
［８］さらに、架橋剤（Ｅ）を含み、該架橋剤（Ｅ）が１分子中に２つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、［１］〜［７］いずれかのネガ型感光性樹脂組成物。
［９］基板表面を画素形成用の複数の区画に仕切る形の隔壁を製造する方法であって、［１］〜［８］のいずれかのネガ型感光性樹脂組成物を基板表面に塗布する工程、乾燥工程、露光工程、現像工程を順に有し、その後にポストベーク工程を有することを特徴とする隔壁の製造方法。
［１０］基板表面に［９］の製造方法によって隔壁を形成した後、前記隔壁で仕切られた区画内に、インクジェット法によりインクを注入して画素を形成することを特徴とする光学素子の製造方法。 The present invention provides a negative photosensitive resin composition having the following configurations [1] to [10], a method for producing partition walls , and a method for producing optical elements.
[1] A negative photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C), and a solvent (D), wherein the ink repellent agent (C) is The solvent (D) comprises a fluorine-containing organosiloxane compound, and the solvent (D1) has a boiling point of 165 to 210 ° C. in a proportion of 10 to 100% by mass with respect to the total amount of the solvent (D). The fluorine organosiloxane compound is composed of a partial hydrolysis condensate of a mixture containing a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2). Negative photosensitive resin composition characterized by the above-mentioned.

Symbols in the formulas (c-1) and (c-2) are as follows.
R ^F : an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms,
R ^H : an organic group having no perfluoroalkyl group,
X: hydrolyzable group,
p: 0, 1 or 2.
However, when two or more ^RH and X exist in a compound, these may mutually differ or may be the same.
[2] The negative photosensitive resin composition according to [1], wherein the fluorine-containing organosiloxane compound has a fluorine atom content of 10 to 55% by mass.
[3] The negative photosensitive resin composition of [1] or [2], wherein the solvent (D1) is a compound represented by the following formula (3).
R ¹ O (C ₂ H ₄ O) _y R ² (3)
In formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and y represents an integer of 1 to 10.
[4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the solvent (D1) is diethylene glycol ethyl methyl ether.
[5] The solvent (D) further contains a solvent (D2) having a hydroxyl group and a boiling point of less than 165 ° C. at a ratio of 1 to 50% by mass with respect to the total amount of the solvent (D). Negative photosensitive resin composition in any one of [1]-[4].
[6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. object.
[7] The negative photosensitive resin composition according to any one of [1] to [6], wherein the photopolymerization initiator (B) is a combination of acetophenones or O-acyloximes and benzophenones.
[8] The composition further comprises a crosslinking agent (E), and the crosslinking agent (E) is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. [7] Any negative photosensitive resin composition.
[9] The substrate surface to a method for producing the shape of the septum wall partitioning a plurality of compartments for pixel formation, applied to either of the negative photosensitive resin composition of the substrate surface [1] to [8] The manufacturing method of the partition characterized by having the process to perform, a drying process, an exposure process, and a image development process in order, and having a post-baking process after that.
[10] After forming the barrier ribs by the method of [9] to the substrate surface, producing an optical device characterized in partitioned compartments in the partition wall, forming a pixel by injecting ink by an ink jet method Way .

  According to the present invention, there is provided a negative photosensitive resin composition capable of producing a partition wall having good ink repellency and capable of maintaining the ink repellency even after being subjected to ultraviolet / ozone irradiation treatment. In production, a negative photosensitive resin composition having a good coating property in which a coating film is formed and dried using this, the film thickness is uniform, there is no unevenness, and aggregates are not generated on the film surface. Can be provided. Further, according to the present invention, the ink repellency formed by curing the photosensitive resin composition is good, and the ink repellency can be maintained even after the ultraviolet / ozone irradiation treatment. In addition, a partition wall having a good appearance and a uniform film thickness and an optical element having the partition wall can be provided.

It is sectional drawing which shows typically the manufacture example of the partition for optical elements using the negative photosensitive resin composition of this invention. In an Example, it is a figure which shows the film thickness measurement point in the sample used in order to evaluate the in-plane uniformity of the film thickness of the cured film formed with the negative photosensitive resin composition of this invention.

  In this specification, “(meth) acryloyl...” Is a general term for “methacryloyl...” And “acryloyl. The same applies to (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin.

The group represented by Formula (1) in this specification is called group (1). The same applies to other groups.
The monomer represented by the formula (11) in this specification is referred to as a monomer (11). The same applies to other monomers and compounds.
In the present specification, the “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer in which a repeating unit constitutes the main chain.
The “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue. Specifically, all components other than the volatile component which volatilizes by heating etc. in the partition formation process such as the solvent (D) are shown. The total solid content can also be calculated from the charged amount.
In the present specification, a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”. .

In this specification, the “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
The ink in the present specification is a general term for, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials. Similarly, “pixels” formed by injecting the ink are also used to indicate sections having optical and electrical functions, which are partitioned by partition walls.
In this specification, the ink repellency refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later.
Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Alkali-soluble resin (A)]
The alkali-soluble resin (A) in the present invention is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). The exposed portion thus cured is not removed with an alkaline developer. Moreover, when the alkali-soluble resin (A) has an acidic group in the molecule, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkali developer. As a result, a partition wall can be formed.

Although it does not restrict | limit especially as said acidic group, A carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, These may be used individually by 1 type or may use 2 or more types together.
Although it does not restrict | limit especially as said ethylenic double bond, The double bond which has addition polymerizability, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group, is mentioned, These are 1 You may use a seed | species independently or may use 2 or more types together. In addition, some or all of the hydrogen atoms of the ethylenic double bond group may be substituted with an alkyl group, preferably a methyl group.

  Although it does not specifically limit as alkali-soluble resin (A), Resin (A1-1) which has a side chain which has an acidic group, and a side chain which has an ethylenic double bond, An acidic group and ethylenic double are added to an epoxy resin. Examples thereof include a resin (A1-2) having a bond introduced therein, a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.

Resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).
(I) A monomer having a reactive group other than an acidic group in the side chain, for example, a monomer having a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain are copolymerized and reactive. A copolymer having a side chain having a group and a side chain having an acidic group is obtained. Next, this copolymer is reacted with a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond. Alternatively, after copolymerization of a monomer having an acidic group such as a carboxy group in the side chain, the acidic group remains after the reaction with the functional group capable of bonding to the acidic group and the compound having an ethylenic double bond. Let react.

(Ii) having a monomer having a reactive group other than an acidic group in the side chain as in (i) above, a functional group capable of binding to this reactive group, and a protected ethylenic double bond The compound is reacted. Next, after the monomer and a monomer having an acidic group in the side chain are copolymerized, the protection of the ethylenic double bond is removed. Alternatively, after the monomer having an acidic group in the side chain is copolymerized with the monomer having an ethylenic double bond protected in the side chain, the protection of the ethylenic double bond is removed.
In addition, it is preferable to implement (i) or (ii) in a solvent.
Among these, the method (i) is preferably used in the present invention. Hereinafter, the method (i) will be specifically described.

  Examples of the monomer having a hydroxyl group as a reactive group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl ( Data) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.

  In the above (i), when using a monomer having a hydroxyl group as a reactive group, the monomer having an acidic group to be copolymerized is not particularly limited. In addition to the monomer having a carboxy group described later, examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate. Copolymerization of a monomer having a hydroxyl group as a reactive group and a monomer having an acidic group can be carried out by a conventionally known method.

Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, an isocyanate group and an ethylenic double bond. And a compound having an acyl chloride group and an ethylenic double bond.
Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal An acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc. are mentioned.
Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
As a monomer having an acidic group to be copolymerized with a monomer having an epoxy group as a reactive group, the same monomer as described in the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be performed by a conventionally known method.

  Examples of the compound having a functional group capable of bonding to an epoxy group and an ethylenic double bond to be reacted with the obtained copolymer include a compound having a carboxy group and an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, the hydroxyl group generated here may be reacted with an acid anhydride in which the dehydration condensation part of the carboxylic acid forms a part of the cyclic structure to introduce a carboxy group into the resin (A1-1).

  Examples of the monomer having a carboxy group as a reactive group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. In addition, these monomers are used also as a monomer which has the acidic group mentioned above.

  When using a monomer having a carboxy group as a reactive group, the monomer is polymerized as described above. Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a carboxy group to be reacted with the obtained polymer include compounds having an epoxy group and an ethylenic double bond. Examples of the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate. In this case, the amount of the functional group capable of bonding to the carboxy group and the compound having an ethylenic double bond to be reacted with the polymer having a carboxy group is such that the carboxy group in the polymer becomes an acidic group after the reaction. The amount remaining in the chain.

Resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or its anhydride. Can do.
Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. Next, a carboxyl group can be introduced by reacting a polycarboxylic acid or an anhydride thereof with an epoxy resin into which an ethylenic double bond has been introduced.

  The epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having naphthalene skeleton, Examples include an epoxy resin having a biphenyl skeleton represented by (A1-2a), an epoxy resin represented by the following formula (A1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (A1-2c), and the like. It is done.

（式（Ａ１−２ａ）中、ｖは、１〜５０の整数であり、２〜１０の整数が好ましい。またベンゼン環の水素原子はそれぞれ独立に、炭素原子数１〜１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。）

(In the formula (A1-2a), v is an integer of 1 to 50 and is preferably an integer of 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms or halogen. An atom or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.)

（式（Ａ１−２ｂ）中、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素原子、塩素原子または炭素原子数が１〜５のアルキル基であり、ｗは、０または１〜１０の整数である。）

(In Formula (A1-2b), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 or It is an integer from 1 to 10.)

（式（Ａ１−２ｃ）中、ベンゼン環の水素原子はそれぞれ独立に炭素原子数１〜１２のアルキル基、ハロゲン原子、または、一部の水素原子が置換基で置換されていてもよいフェニル基、で置換されていてもよい。ｚは、０または１〜１０の整数である。）

(In Formula (A1-2c), the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent. And z is an integer of 0 or 1 to 10.

  In the case where the epoxy resin represented by the formulas (A1-2a) to (A1-2c) is reacted with a compound having a carboxy group and an ethylenic double bond, and then reacted with a polyvalent carboxylic acid anhydride. It is preferable to use a mixture of a dicarboxylic acid anhydride and a tetracarboxylic dianhydride as the polyvalent carboxylic acid anhydride. By changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride, the molecular weight can be controlled.

  As the compound having a carboxy group and an ethylenic double bond, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof are preferable, and acrylic acid or Methacrylic acid is particularly preferred.

  A commercial item can be used for resin (A1-2). As a commercial item, all are a brand name, KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2001H, ZAR-2002, ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H ( As described above, Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), Neopole 8430, 8473, 8475, 8478 (manufactured by Nippon Yupica Co., Ltd.) and the like can be mentioned.

  Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1 manufactured by Shin-Nakamura Chemical Co., Ltd.).

As alkali-soluble resin (A), the peeling of the cured film during development is suppressed, a high-resolution pattern can be obtained, the line linearity is good, and the appearance after the post-baking process is maintained. It is preferable to use the resin (A1-2) in that a smooth cured film surface is easily obtained.
As the resin (A1-2), a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acid group and ethylenic double bond introduced into novolac type epoxy resin, resin with acid group and ethylenic double bond introduced into cresol novolac type epoxy resin, acid group and ethylene into trisphenol methane type epoxy resin A resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin represented by the formulas (A1-2a) to (A1-2c) is particularly preferable.

  The number of the ethylenic double bonds that the alkali-soluble resin (A) has in one molecule is preferably 3 or more on average and particularly preferably 6 or more. When the number of ethylenic double bonds is greater than or equal to the lower limit of the above range, the exposed portion is excellent in curability, and a fine pattern can be formed with a smaller exposure amount.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 × 10 ³ to 30 × 10 ³ , and particularly preferably 2 × 10 ^{3 to} 20 × 10 ³ . The number average molecular weight (Mn), preferably from 500 to 20 × 10 ^3, and particularly preferably ^{1 × 10 3 ~10 × 10 3} . When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, the curability at the time of exposure is excellent, and when it is not more than the upper limit of the above range, the developability is good.
The acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is in the above range, the developability of the negative photosensitive resin composition is improved.

The alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
5-80 mass% is preferable and, as for the content rate of alkali-soluble resin (A) in the total solid in a negative photosensitive resin composition, 10-60 mass% is especially preferable. When the content ratio is in the above range, the developability of the negative photosensitive resin composition is good.

[Photoinitiator (B)]
The photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but a compound that generates a radical by light is preferable.

  Examples of the photopolymerization initiator (B) include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. Acylloin ethers: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone- Thioxanthones such as 4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Enone, 2- (4-Toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) Acetophenones such as phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone, 2-ethylanthraquinone, camphorquinone, Quinones such as 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 4-dimethyl Aminobenzoic acid 2-ethylhexyl, etc. Aminobenzoic acids; halogen compounds such as phenacyl chloride, trihalomethylphenylsulfone; acylphosphine oxides; peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1- [4- (phenylthio) )-, 2- (O-benzoyloxime), O-acyloximes such as acetyloxime represented by the following formula (4), triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine Aliphatic amines such as diethylaminoethyl methacrylate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercaptopro Alkanoyloxy-ethyl) isocyanurate, pentaerythritol tetrakis (3-mercapto butyrate) thiol compound such as and the like.

In Formula (4), R ³ represents a hydrogen atom, R ⁶¹ or OR ⁶² , and each of R ⁶¹ and R ⁶² independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring. Is a cycloalkyl group having 3 to 8 carbon atoms which may be substituted with an alkyl group, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group The 6-30 phenyl group or the C7-30 phenylalkyl group which the hydrogen atom in a benzene ring may be substituted by the alkyl group is shown.
R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon atom number 6 to 30 in which a hydrogen atom in the benzene ring may be substituted with an alkyl group. A phenyl group of which the hydrogen atom in the benzene ring may be substituted with an alkyl group, a phenylalkyl group of 7 to 30 carbon atoms, an alkanoyl group of 2 to 20 carbon atoms, a hydrogen atom in the benzene ring is an alkyl group A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a hydrogen atom in the benzene ring which may be substituted with an alkyl group may have 7 to 20 carbon atoms A phenoxycarbonyl group or a cyano group.

R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group. An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R ⁶¹ , OR ⁶² , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring. A benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an amide group having 1 to 20 carbon atoms are shown.
R ⁰ represents R ⁶¹ , OR ⁶² , a cyano group or a halogen atom. a is an integer of 0 or 1-3.

Among the compounds represented by formula (4) (hereinafter referred to as photopolymerization initiator (4)), compounds in which R ^{3 to} R ⁹ and R ⁰ are in the following modes are preferred.
R ³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in the benzene ring substituted with an alkyl group. A phenyl group having 6 to 20 carbon atoms which may be substituted, or a phenoxy group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a hydrogen atom in the benzene ring in which an alkyl group may be substituted with an alkyl group. Phenyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and an alkoxycarbonyl group having 2 to 12 carbon atoms Alternatively, it represents a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.

R ⁵ represents an alkyl group having 1 to 12 carbon atoms.
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group. A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring Is a benzoyl group having 7 to 20 carbon atoms which may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and the number of carbon atoms An alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, and 1 to 20 carbon atoms It shows a bromide group or a nitro group.
“A” indicating the number of R ⁰ is 0.

Specific examples of the photopolymerization initiator (4) include compounds (4-1) to (4) in which R ^{3 to} R ⁹ are each the following groups, and a indicating the number of R ⁰ is 0: (4-10).
Compound (4-1) wherein R ^{3 is a} phenyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group.
Compound (4-2) wherein R ^{3 is a} methyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group.
Compound (4-3) wherein R ^{3 is a} methyl group, R ^{4 is a} butyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group,
Compound (4-4) wherein R ^{3 is a} methyl group, R ^{4 is a} heptyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} benzoyl group,
Compound (4-5) wherein R ^{3 is a} phenyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} 2-methylbenzoyl group.
Compound (4-6) wherein R ^{3 is a} methyl group, R ^{4 is an} octyl group, R ^{5 is an} ethyl group, R ⁶ , R ⁸ , R ^{9 is a} hydrogen atom, and R ^{7 is a} 2-methylbenzoyl group,
Compound (4-7), wherein R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methylbenzoyl group,
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-4-tetrahydropyranylmethoxybenzoyl group (4 -8),
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group (4- 9),
R ³ : methyl group, R ⁴ : methyl group, R ⁵ : ethyl group, R ⁶ , R ⁸ , R ⁹ : hydrogen atom, R ⁷ : 2-methyl-5-tetrahydropyranylmethoxybenzoyl group (4 -10)

A commercial item can be used for a photoinitiator (B). As 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, IRGACURE 907 (trade name, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholino) Examples of phenyl) -butan-1-one include IRGACURE 369 (trade name, manufactured by BASF). Examples of O-acyl oximes include IRGACURE OXE01 (manufactured by BASF, trade name: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)].) , Adekaoptomer N-1919, Adeka Cruz NCI-831, NCI-930 (all manufactured by ADEKA, all trade names), and the like.
Examples of the photopolymerization initiator (4) include IRGACURE OXE02 (trade name: corresponding to the above compound (4-7) manufactured by BASF) as a commercial product. Examples of the photopolymerization initiator (4) include those described in International Publication No. 2008/078678. 1-71 can be used.

Among the photopolymerization initiators (B) exemplified above, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferable because they may exhibit a sensitizing effect when used together with other radical initiators. .
As the photopolymerization initiator (B), 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenones such as butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methyl) O-acyl oximes such as benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (compound corresponding to the above compound (4-7)) and 2,4-diethylthioxanthone are preferable. More preferred are acetophenones and O-acyl oximes. Furthermore, a combination of these with the above benzophenones, for example, 4,4′-bis (diethylamino) benzophenone is particularly preferable.

The photopolymerization initiator (B) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
The proportion of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 5 to 15% by mass. Particularly preferred. Within the above range, the developability of the negative photosensitive resin composition is good.

[Ink repellent (C)]
The ink repellent (C) in the present invention comprises a fluorine-containing organosiloxane compound.
The fluorine-containing organosiloxane compound is preferably a compound having a fluorine atom content ratio (hereinafter also referred to as fluorine atom content) of 10 to 55% by mass. 12-40 mass% is more preferable, and 15-30 mass% is especially preferable. Within the above range, excellent ink repellency and ink repellency UV / ozone resistance can be imparted to the partition obtained from the negative photosensitive resin composition.

  Examples of the fluorine-containing organosiloxane compound include compounds obtained by partial hydrolysis condensation of one or more hydrolyzable silane compounds including a hydrolyzable silane compound having a fluorine-containing organic group. The partially hydrolyzed condensate of the hydrolyzable silane compound is usually a composition that itself has a molecular weight distribution. The fluorine-containing organosiloxane compound as the ink repellent agent (C) in the negative photosensitive resin composition of the present invention is a partially hydrolyzed condensate of a hydrolyzable silane compound having such a fluorine-containing organic group. It is a liquid or solvent-soluble solid.

  As a fluorine-containing organosiloxane compound, the partial hydrolysis-condensation product of the mixture containing a hydrolysable silane compound (c-1) and a hydrolysable silane compound (c-2) as an essential component is preferable. In the production of the partially hydrolyzed condensate, the hydrolyzable silane compound (c-1) and the hydrolyzable silane compound (c-2) are each partially hydrolyzed of the hydrolyzable silane compound (c-1). A condensate or a partially hydrolyzed condensate of a hydrolyzable silane compound (c-2) can also be used.

  The hydrolyzable silane compound (c-1) is a compound represented by the following formula (c-1) (hereinafter also referred to as compound (c-1)).

式（ｃ−１）中の記号は、以下の通りである。
Ｒ^Ｆ：炭素原子数３〜１０のエーテル性酸素原子を含んでいてもよいペルフルオロアルキル基を有する有機基、
Ｘ：加水分解性基。
ただし、化合物内に３個存在するＸは、互いに異なっていても、同一であってもよい。
化合物（ｃ−１）は１種を単独で用いることも２種以上を併用することも可能である。
化合物（ｃ−１）を用いることより、ネガ型感光性樹脂組成物を硬化させた硬化膜は撥水性と撥油性（すなわち撥インク性）を発揮できる。

Symbols in the formula (c-1) are as follows.
R ^F : an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms,
X: Hydrolyzable group.
However, three Xs present in the compound may be different from each other or the same.
As the compound (c-1), one type may be used alone, or two or more types may be used in combination.
By using the compound (c-1), the cured film obtained by curing the negative photosensitive resin composition can exhibit water repellency and oil repellency (that is, ink repellency).

  The hydrolyzable silane compound (c-2) is a compound represented by the following formula (c-2) (hereinafter also referred to as compound (c-2)).

式（ｃ−２）中の記号は、以下の通りである。
Ｒ^Ｈ：ペルフルオロアルキル基を有しない有機基、
Ｘ：加水分解性基、
ｐ：０、１または２である。
ただし、Ｒ^ＨおよびＸが、化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
化合物（ｃ−２）は、ｐが０である４官能性化合物、またはｐが１である３官能性化合物であることが好ましい。化合物（ｃ−２）は１種を単独で用いることも２種以上を併用することも可能である。２種以上を併用する場合、４官能性化合物および／または３官能性化合物とともに２官能性化合物を併用することもできる。
化合物（ｃ−２）を用いることより、撥インク剤（Ｃ）は炭化水素系の溶媒に溶解しやすくなり、基材の表面にネガ型感光性樹脂組成物の塗膜を形成する際に比較的安価な溶媒を選択できる。

Symbols in the formula (c-2) are as follows.
R ^H : an organic group having no perfluoroalkyl group,
X: hydrolyzable group,
p: 0, 1 or 2.
However, when two or more ^RH and X exist in a compound, these may mutually differ or may be the same.
The compound (c-2) is preferably a tetrafunctional compound in which p is 0, or a trifunctional compound in which p is 1. As the compound (c-2), one type may be used alone, or two or more types may be used in combination. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
By using the compound (c-2), the ink repellent agent (C) is easily dissolved in a hydrocarbon-based solvent, which is compared with the case where a negative photosensitive resin composition coating film is formed on the surface of the substrate. Inexpensive solvents can be selected.

The group R ^F and the group R ^H in the ink repellent agent (C) used in the present invention are groups that exhibit water repellency, and oil repellency is mainly expressed by the group R ^F. In order for the cured product of the ink repellent agent (C) to exhibit sufficient oil repellency, the relative ratio of the group R ^F to the total of the groups R ^F and R ^{H in} the ink repellent agent (C). Is preferably high. For p = 0, is improved relative proportion becomes high oil repellency of groups R ^F in the ink repellent (C), also it has the advantage of excellent film forming properties. In the case of p = 1 or 2, the presence of the group ^RH to some extent makes the ink repellent agent (C) easily dissolved in a hydrocarbon solvent, and the negative photosensitive resin composition is coated on the surface of the substrate. There is an advantage that a relatively inexpensive solvent can be selected when forming the film.

As the fluorine-containing organosiloxane compound used in the present invention, in addition to the compound (c-1) and the compound (c-2), a hydrolyzable silane compound other than the compound (c-1) and the compound (c-2) It may be a partially hydrolyzed condensate of a mixture containing
Examples of the hydrolyzable silane compounds other than the compound (c-1) and the compound (c-2) include monofunctional silane compounds, cyclic organopolysiloxanes, and hydrolysates having functional group-containing organic groups called silane coupling agents. And decomposable silane compounds (excluding the above compounds (c-1) and (c-2)). Examples of the monofunctional silane compound include the following hydrolyzable silane compound (c-3) having one hydrolyzable group and the following organodisiloxane (c-4).
Furthermore, a hydrolyzable silane compound having an organic group having a polymerizable functional group can also be used as the hydrolyzable silane compound. The organic group having a polymerizable functional group is preferably an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group. For example, a compound (c-2) in which at least one of ^RH is an organic group having a polymerizable functional group, a monofunctional silane compound having an organic group having a polymerizable functional group, or the like can be used. As the compound (c-2) in which at least one of ^RH is an organic group having a polymerizable functional group, the following hydrolyzable silane compound (c-5) is preferable. In the following description, compound (c-2) in the case of using both compound (c-2) and hydrolyzable silane compound (c-5) is a compound other than hydrolyzable silane compound (c-5). It shall be said.

  The hydrolyzable silane compound (c-3) is a monofunctional hydrolyzable silane compound in which three organic groups and one hydrolyzable group are bonded to a silicon atom. A hydrolyzable silane compound represented by the following formula (c-3) (hereinafter also referred to as compound (c-3)) is preferred.

The symbols X and ^{R H} in the formula (c-3) is the same as X and ^{R H} in the formula (c-1) and (c-2). In formula (c-3), W represents an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group, the above R ^F or the above R ^H. In the formula (c-3), two R ^H (three R ^H when W is R ^H ) may be the same as or different from each other.
By using the compound (c-3), the compatibility of the negative photosensitive resin composition with other components is improved, and the reactivity of the ink repellent agent (C) itself by sealing the silanol group is improved. It is possible to finely adjust the characteristics of the negative photosensitive resin composition such as suppression, adjustment of liquid repellency of the cured film, and improvement of film curability.

  As the fluorine-containing organosiloxane compound used in the present invention, in addition to the hydrolyzable silane compound, the following organodisiloxane (c-4) and octamethylcyclotetrasiloxane which can be a monofunctional siloxane unit such as hexamethyldisiloxane. It may be a partially hydrolyzed condensate of a mixture containing a cyclic organopolysiloxane.

  The organodisiloxane (c-4) is preferably an organodisiloxane represented by the following formula (c-4) (hereinafter also referred to as compound (c-4)). These are silane compounds capable of producing monofunctional siloxane units.

Symbol ^{R H} in the formula (c-4) is the same as ^{R H} in the formula (c-2). In formula (c-4), W represents an organic group having at least one polymerizable functional group selected from an acryloyl group and a methacryloyl group, the above R ^F or the above R ^H. In formula (c-4), W may be the same as or different from each other. In the formula (c-4), four R ^H (5 or 6 R ^H when W is R ^H ) may be the same as or different from each other.
By using the compound (c-4), the compatibility of the negative photosensitive resin composition with other components is improved, and the reactivity of the ink repellent agent (C) itself by sealing the silanol group is improved. It is possible to finely adjust the characteristics of the negative photosensitive resin composition such as suppression, adjustment of liquid repellency of the cured film, and improvement of film curability.

When the compound (c-3) or the compound (c-4) is used, if the W of the compound is R ^F , the relative proportion of the group R ^F of the ink repellent agent (C) is increased and excellent oil repellency is exhibited. This is preferable. W is preferably ^RH because the solubility of the ink repellent agent (C) in a hydrocarbon solvent is improved. It is preferable that W is an organic group having an acryloyl group or a methacryloyl group, since the curability of the ink repellent agent (C) is improved and the solubility in a hydrocarbon solvent is improved.

  The hydrolyzable silane compound (c-5) includes an organic group having at least one polymerizable functional group selected from the group consisting of q (q is 1 or 2) acryloyl group or methacryloyl group on a silicon atom. , A hydrolyzable silane compound in which r (r is 0 or 1) an organic group having no polymerizable functional group and (4-qr) hydrolyzable groups are bonded. However, q + r is 1 or 2.

  As the hydrolyzable silane compound (c-5), a hydrolyzable silane compound represented by the following formula (c-5) (hereinafter also referred to as compound (c-5)) is preferable.

The symbols X and ^{R H} in the formula (c-5) is the same as X and ^{R H} in the formula (c-1) and (c-2). However, ^RH in the compound (c-5) is a group other than Q. In formula (c-5), Q represents an organic group having an acryloyl group or a methacryloyl group. q is 1 or 2, r is 0 or 1, and q + r is 1 or 2. In the formula (c-5), when q = 2, two Qs may be the same or different, and when q + r = 1, the three Xs may be the same. They may be different, and when q + r = 2, the two Xs may be the same or different.

  As the compound (c-5), q is preferably 1 and r is 1, or q is 1 and r is 0. Moreover, when using a compound (c-5), it is also possible to use 1 type individually or to use 2 or more types together.

When the compound (c-5) is used, the obtained ink repellent agent (C) tends to stay on the upper surface of the partition wall after exposure, and has an effect of making the upper surface of the partition wall ink repellent and making the side wall surface of the partition wall ink-philic.
On the other hand, if the compound (c-5) is not used, the ink repellent agent (C) is likely to move to the side walls of the partition after exposure. What is necessary is just to use these suitably according to a use.

  The fluorinated organosiloxane compound is preferably a partially hydrolyzed condensate obtained by using the compound (c-5) as a part of the compound (c-2). Furthermore, it is preferable that it is a partial hydrolysis-condensation product obtained using a compound (c-3) so that the molecular weight of the fluorine-containing organosiloxane compound which is a partial hydrolysis-condensation product may not become high too much.

Hereinafter, the compounds (c-1) to (c-5) will be described more specifically with examples. In addition, instead of the compounds (c-1), (c-2), and (c-5), a partial hydrolysis condensate obtained by partially hydrolyzing and condensing a plurality of each compound in advance as necessary. It may be used. For example, partial hydrolysis condensation of compound (c-1) may be used instead of compound (c-1), and partial hydrolysis condensation of compound (c-2) is used instead of compound (c-2). May be.
Examples of X included in the compounds (c-1) to (c-5) include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which hydrogen of the amino group is substituted with an alkyl group. . X is preferably an alkoxy group having 4 or less carbon atoms or a halogen atom, particularly preferably CH ₃ O—, C ₂ H ₅ O—, or Cl—. When these groups are used, a hydroxyl group (silanol group) is formed by a hydrolysis reaction, and further, a reaction between molecules occurs to facilitate a Si—O—Si bonding reaction.

As R ^{F that the} compound (c-1) has and the compound (c-3) and the compound (c-4) optionally have, a group represented by R ^F1 —Y— is preferable. However, R ^F1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms, and Y represents a divalent linking group containing no fluorine atom.

R ^F1 is preferably a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms, and particularly preferably a perfluoroalkyl group having 6 carbon atoms. When R ^F1 is in the above range, the partition formed using the negative photosensitive resin composition exhibits excellent ink repellency and ink repellency of UV / ozone resistance, and can be applied to a general-purpose solvent. It is preferable because of its excellent solubility.
^Examples of the structure of R ^F1 include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, but a linear structure is preferable.

Specific examples of R ^F1 include the following groups.
_{F (CF 2) 4 -,} F (CF 2) 6 -, F (CF 2) 8 -.
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 _{OCF 2 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 -.
_{CF 3 CF 2 CF 2 OCF 2} -, CF 3 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF (CF 3) -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 -, _{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 OCF (CF 3) -, CF 3 CF 2 CF 2 OCF (CF 3) _{CF 2 OCF (CF 3) CF} 2 -, CF 3 OCF (CF 3) CF 2 OCF (CF 3) -, CF 3 CF 2 OCF (CF 3) CF 2 OCF (CF 3) -.

As the Y is not particularly limited as long as it is a divalent connecting _{group, - (CH 2) g -} , - CH 2 O (CH 2) g -, - SO 2 NR 2 - (CH 2) g -, - ( A group represented by C═O) —NR ² — (CH ₂ ) _g — is preferred. However, g is an integer of 1 to 5, ^{R 2} represents a hydrogen atom, a methyl group or an ethyl group,. Y is particularly preferably — (CH ₂ ) _g — in which g is 2 or 3. The direction of the group Y means that Si is bonded to the right side and R ^F1 is bonded to the left side.
When R ^F1 is a perfluoroalkyl group having 4 to 8 carbon atoms, Y is preferably a group represented by — (CH ₂ ) _g —. g is preferably an integer of 2 to 4, and — (CH ₂ ) ₂ — in which g is 2 is particularly preferable.

In the case where R ^F1 is a perfluoroalkyl group containing an etheric oxygen atom having 4 to 9 carbon atoms, the Y is — (CH ₂ ) _h —, —CH ₂ O (CH ₂ ) _h —, —SO _{2. ^{NR 2 - (CH 2) h}} -, - (C = O) -NR 2 - (CH 2) h - group represented by are preferred. However, h is an integer of 1 to 5, ^{R 2} represents a hydrogen atom, a methyl group or an ethyl group,. Y is particularly preferably — (CH ₂ ) ₂ — in which h is 2. The direction of bonding of the group Y means that Si is bonded to the right side and R ^F1 is bonded to the left side.

^RH of the compound (c-2), the compound (c-3), the compound (c-4) and the compound (c-5) has 1 to 4 carbon atoms except when it is Q. Are preferably alkyl groups, or phenyl groups, more preferably methyl groups or ethyl groups, and particularly preferably methyl groups.
As Q which a compound (c-5) has, group represented by Q < ¹ > -Z- is preferable. However, Q ¹ represents a (meth) acryloyloxy group. Z represents — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, or — (CH ₂ ) ₆ —, and — (CH ₂ ) ₃ — is preferred. Moreover, the same group is preferable as the polymerizable functional group selected from the group consisting of the acryloyl group and the methacryloyl group that the compound (c-3) and the compound (c-4) optionally have.

As specific examples of the compound (c-1), the following examples are preferable.
F (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
F (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 (CF 3) CF 2 CH 2 CH 2 Si (OCH 3) 3, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 CH 2 CH 2 Si ( OCH _{3) 3} -.

As specific examples of the compound (c-2), the following examples are preferable.
Si (OCH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ ,
CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ ,
CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ ,
(CH ₃ ) ₂ Si (OCH ₂ CH ₃ ) ₂ ,
Moreover, the following example is preferable as a specific example of the partial hydrolysis-condensation product of the compound (c-2) which can be used instead of a compound (c-2).
A compound obtained by hydrolytic condensation of Si (OCH ₃ ) ₄ (for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.),
Compounds obtained by hydrolytic condensation of Si (OCH ₂ CH ₃ ) ₄ (for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).

As specific examples of the compound (c-3), the following examples are preferable.
_{F (CF 2) 6 CH 2} CH 2 (CH 3) 2 Si (OCH 3), (CH 3) 3 Si (OCH 3), [CH 2 = C (CH 3) COO (CH 2) 3] (CH ₃ ) ₂ Si (OCH ₃ ).
As specific examples of the compound (c-4), the following examples are preferable.
(CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ .

As specific examples of the compound (c-5), the following examples are preferable.
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 2 CH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (OCH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (OCH 2 CH 3) 3,
_{[CH 2 = C (CH 3} ) COO (CH 2) 3] CH 3 Si (OCH 3) 2,
_{[CH 2 = C (CH 3} ) COO (CH 2) 3] CH 3 Si (OCH 2 CH 3) 2.

The ink repellent agent (C) is a reaction product obtained by reacting a mixture of the above compounds. This reaction is the production | generation of the silanol group by the hydrolysis reaction of a hydrolysable group, and the production | generation of the siloxane bond by the dehydration condensation reaction of silanol groups.
Compound (c-1), Compound (c-2), 2-4 functional (especially trifunctional or tetrafunctional) hydrolyzable silane compound of compound (c-5) or a partial hydrolysis condensate thereof Usually has a silanol group. Furthermore, when a partially hydrolyzed condensate is produced by co-condensing a 2- to 4-functional hydrolyzable silane compound together with a monofunctional silane compound (compound (3) or compound (4)), the silanol group is monofunctional. The silanol group is lost by reacting with the functional silane compound, and the extension reaction of the siloxane chain due to the reaction between the silanol groups is stopped, so that the partial hydrolysis-condensation product having a small number of silanol groups per silicon atom and the molecular weight A low partial hydrolysis condensate is formed.
The ink repellent agent (C) may be a partially hydrolyzed condensate having a small number of silanol groups per silicon atom, or a partially hydrolyzed condensate having a relatively large number of silanol groups per silicon atom. Also good. In the latter case, the average number of silanol groups per silicon atom is preferably 0.2 to 3.5.

When the ink repellent agent (C) is produced using the compound (c-1) and the compound (c-2), the cocondensation ratio of the compound (c-1) and the compound (c-2) is as described above. Although it will not specifically limit if a fluorine atom content rate is obtained, It is preferable to use 0.1-9 mol of compounds (c-2) with respect to 1 mol of compounds (c-1). , 0.5-9 mol is particularly preferable.
In addition, when using the partial hydrolysis condensate instead of the compound (c-1), the compound (c-2) or the compound (c-5), the partial hydrolysis condensate is converted into a compound having one silicon atom. In conversion, the co-condensation ratio is assumed. The same applies to the following cocondensation ratios.

  Ink repellent agent (C) is added to compound (c-1) and compound (c-2) to produce monofunctional siloxane units such as compound (c-3) and / or compound (c-4) In the case of producing using a silane compound that can be used, the co-condensation ratio of the total amount of the compound (c-3) and the compound (c-4) with respect to the total amount of the compound (c-1) and the compound (c-2) is 300 mol% or less is preferable, 200 mol% or less is more preferable, and 100 mol% or less is particularly preferable. However, since one molecule of the compound (c-4) corresponds to two molecules of the compound (c-3), the calculation of the cocondensation ratio is based on the compound (c-3), and the compound (c-4) The molar amount is doubled and regarded as the molar amount of compound (c-3). For example, when only the compound (c-4) is used, the copolymerization ratio calculated from the actual use amount of the compound (c-4) is preferably 150 mol% or less, more preferably 100 mol% or less, and 50 A mol% or less is particularly preferred.

  When the ink repellent agent (C) is produced using the compound (c-5) in addition to the compound (c-1) and the compound (c-2), the compound (c-1) and the compound (c-2) ) Is preferably 500 mol% or less, particularly preferably 400 mol% or less, with respect to the total amount of compound (c-5).

  Further, when the ink repellent agent (C) is produced using the compound (c-3) and the compound (c-5) in addition to the compound (c-1) and the compound (c-2), the compound The cocondensation ratio of the compound (c-3) with respect to the total amount of (c-1) and the compound (c-2) is preferably 300 mol% or less, and the cocondensation ratio of the compound (c-5) is 500 mol% or less. preferable. Particularly preferably, the cocondensation ratio of the compound (c-3) to the total amount of the compound (c-1) and the compound (c-2) is 200 mol% or less, and the cocondensation ratio of the compound (c-5) is It is 400 mol% or less.

  The ink repellent agent (C) in the present invention may be composed of a single compound, but is usually a mixture composed of a plurality of compounds having different degrees of polymerization. That is, the ink repellent agent (C) is produced using the compound (c-3) and / or the compound (c-4) arbitrarily using the compound (c-1) and the compound (c-2) as essential components. In this case, an agent having the structure of the average composition formula represented by the following formula (1) is obtained. However, when the ratio of k to m + n is small, it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, so that it is difficult to express this product by a chemical formula, The average composition formula represented by the formula (1) is a chemical formula when it is assumed that all of the hydrolyzable groups or silanol groups are siloxane bonds in the partially hydrolyzed condensate produced as described above.

式（１）中、Ｒ^Ｆ、Ｒ^Ｈ、Ｗ、およびｐの好ましい範囲は上述と同様である。ｍ、ｎはそれぞれ１以上の整数であり、ｋは０または１以上の整数である。

In formula (1), preferred ranges of R ^F , R ^H , W, and p are the same as described above. m and n are each an integer of 1 or more, and k is 0 or an integer of 1 or more.

  In the partial hydrolysis-condensation product having the structure of the average composition formula represented by the formula (1), the compound (c-1) and the compound (c-2), the compound (c-3) and / or optionally blended Alternatively, it is presumed that the units derived from the compound (c-4) are randomly arranged. However, when the partial hydrolysis-condensation product of compound (c-2) is used instead of compound (c-2), for example, the units derived from compound (c-2) are arranged in blocks. Guessed. The values of m and n are the average values of the entire ink repellent agent (C), and m: n is within the above-described range as the co-condensation ratio of the compound (c-2) to the compound (c-1). Preferably there is. The value of k is preferably (m + n): k as an average value of the entire ink repellent agent (C), and k is preferably 3 or less with respect to 1 in the above range, that is, (m + n). It is particularly preferred that

  When the ink repellent agent (C) is produced using the compound (c-1) and the compound (c-2) as essential components and arbitrarily using the compound (c-5), the following formula (2) It becomes an agent which has the structure of the average composition formula represented. However, since it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product by a chemical formula, and the average composition formula represented by formula (2) Is a chemical formula assuming that all of the hydrolyzable groups or silanol groups are siloxane bonds in the partially hydrolyzed condensate produced as described above.

式（２）中、Ｒ^Ｆ、Ｒ^Ｈ、Ｑ、およびｐ、ｑ、ｒの好ましい範囲は上述と同様である。ｓ、ｔはそれぞれ１以上の整数であり、ｕは０または１以上の整数である。

In Formula (2), R ^F , R ^H , Q, and preferred ranges of p, q, and r are the same as described above. Each of s and t is an integer of 1 or more, and u is 0 or an integer of 1 or more.

  In the partial hydrolysis-condensation product having the structure of the average composition formula represented by the formula (2), the compound (c-1) and the compound (c--) are the same as the partial hydrolysis-condensation product represented by the formula (1). 2) It is estimated that the units derived from the compound (c-5) arbitrarily blended are randomly arranged. However, when the partial hydrolysis-condensation product of compound (c-2) is used instead of compound (c-2), for example, the units derived from compound (c-2) are arranged in blocks. Guessed. The values of s and t are the average values of the entire ink repellent agent (C), and s: t is within the above-described range as the co-condensation ratio of the compound (c-2) to the compound (c-1). Preferably there is. Further, the value of u is preferably (s + t): u as an average value of the entire ink repellent agent (C), and u is preferably 5 or less with respect to 1 in the above range, that is, (s + t). It is particularly preferred that

  When the ink repellent agent (C) is produced using the compound (c-3) and the compound (c-5) using the compound (c-1) and the compound (c-2) as essential components, the formula (1) has a structure of an average composition formula in which units derived from the compound (c5) of the formula (2) are further co-condensed. The above-mentioned range is mentioned as a cocondensation ratio of each compound.

  The number average molecular weight (Mn) of the ink repellent agent (C) in the present invention is preferably 500 or more, preferably less than 1,000,000, more preferably less than 10,000, and particularly preferably less than 5,000. When the number average molecular weight (Mn) is not less than the lower limit, there is an advantage that evaporation from the substrate surface can be prevented when forming the partition using the negative photosensitive resin composition, and the number average molecular weight (Mn) Is less than the upper limit, the solubility in a solvent is improved, and there is an advantage that workability is improved. The number average molecular weight (Mn) of the ink repellent agent (C) can be adjusted by selecting reaction conditions and the like.

(Manufacture of ink repellent agent (C))
The ink repellent agent (C) comprising a fluorine-containing organosiloxane compound can be produced by subjecting a mixture containing the hydrolyzable silane compound to hydrolysis and condensation reactions. The reaction conditions usually used for the reaction for hydrolyzing and condensing the hydrolyzable silane compound can be applied to the reaction without any particular limitation. In this reaction, it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as acetic acid, oxalic acid or maleic acid as a catalyst. As a quantity of the catalyst to be used, 0.01-10 mass% is preferable with respect to the whole quantity of the mixture containing a hydrolysable silane compound, and 0.1-1 mass% is especially preferable.

A solvent may be used for the reaction. Examples of the solvent include water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin, and propylene glycol; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsolves such as 2-methoxyethanol and 2-ethoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2 Carbitols such as butoxyethoxy) ethanol; esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-butyrolactone, butyl acetate, 3-methoxybutyl acetate; Glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, monoalkyl ethers of glycols such as dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dialkyl ethers glycol and dipropylene glycol dimethyl ether. Other examples include benzyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone and the like. A solvent may be used individually by 1 type, or may use 2 or more types together.
The solvent is blended in the negative photosensitive resin composition of the present invention in the form of an ink repellent solution.

  The content ratio of the ink repellent agent (C) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition, 6 mass% is more preferable and 0.5-3 mass% is especially preferable. By setting the content ratio of the ink repellent agent (C) in the above range, the storage stability of the negative photosensitive resin composition is improved, and the partition wall of the optical element obtained from the negative photosensitive resin composition is improved. Ink repellency is improved, and a partition having a smooth surface is obtained.

[Solvent (D)]
The negative photosensitive resin composition of the present invention contains a solvent (D). Moreover, a solvent (D) contains the solvent (D1) whose boiling point is 165-210 degreeC in the ratio of 10-100 mass% with respect to the whole quantity of a solvent (D).
The solvent (D) reacts with the alkali-soluble resin (A) contained in the negative photosensitive resin composition, the photopolymerization initiator (B), the ink repellent agent (C), and optional components contained as necessary. And has a function of uniformly and simply applying the negative photosensitive resin composition to the base material on which the partition walls are formed by uniformly dissolving or dispersing these solid components. In addition, in the process of evaporating the solvent (D) in the drying step of the coating film of the composition, it acts so that a sufficient repulsive force acts between the ink repellent agent (C) and other solid components in the composition. Thus, the ink repellent agent (C) has a function of facilitating transfer to the film surface.

  In addition, as described above, the ink repellent agent (C) has a small surface free energy and high surface migration ability due to the fluorine-containing organosiloxane compound, but the boiling point is different depending on the solvent to be combined. However, by using the solvent (D) containing the solvent (D1) at 165 ° C. or higher, high surface migration is expressed. That is, by adjusting the boiling point of the solvent (D1) to 165 ° C. or higher, the drying speed of the negative photosensitive resin composition is adjusted to be sufficiently slow, and the ink repellent agent (C) moves to the film surface. I was able to secure time. Moreover, the fall of productivity and the fall of the reliability by a residual solvent are prevented by making the boiling point of a solvent (D1) into 210 degrees C or less.

  In the solvent (D1), from the above viewpoint, the boiling point is 165 to 210 ° C, preferably 170 to 200 ° C. When the boiling point of the solvent (D1) is not less than the lower limit of the above range, the ink repellent agent (C) can have sufficient time for surface migration as described above, so that the ink repellent layer in the film of the negative photosensitive resin composition can be secured. The thickness of the agent layer can be increased, and the ink repellency on the partition wall surface is improved. The solvents used in the examples of WO2010 / 013816 (toluene: boiling point 111 ° C., 2-propanol: boiling point 82 ° C., diethylene glycol dimethyl ether: boiling point 162 ° C., propylene glycol monomethyl ether acetate: boiling point 146 ° C.) are sufficient. Therefore, it was difficult to obtain a stable ink repellency because the film thickness of the ink repellent layer could not be obtained.

Moreover, when the drying speed of the coating film is high, the ink repellent agent (C) aggregates and precipitates when the ink repellent agent (C) moves to the surface, and an aggregate is generated. Since the surface transition time of C) can be sufficiently secured, the generation of this aggregate can be prevented. Furthermore, it is possible to prevent the problem of unevenness of the film appearance and non-uniformity of the film thickness that occurs when drying is completed without taking a sufficient leveling period because the drying speed of the coating film is too high.
On the other hand, when the boiling point of the solvent (D1) is less than or equal to the upper limit of the above range, productivity does not decrease due to the occurrence of sticking or an increase in the time required for the drying step. It is possible to prevent influences such as a decrease in reliability due to peeling of a cured film at the time of development that occurs due to the remaining solvent, generation of outgas due to reheating after the formation of partition walls, and the like.

  Content in the solvent (D) of a solvent (D1) is 10-100 mass%, 20-80 mass% is preferable and 30-70 mass% is especially preferable. When the content is in the above range, in the coating and drying process of the negative photosensitive resin composition on the substrate surface, the film thickness is uniform and uniform, and a good film that does not generate aggregates on the film surface is obtained. As a result, it is possible to ensure that the repulsive force is exerted between the ink repellent agent (C) and the other solid components for a long time, so that the surface of the ink repellent agent (C) can be sufficiently transferred. The thickness can be increased, and the ink repellency of the partition obtained is good.

  Specific examples of the solvent (D1) include diethylene glycol ethyl methyl ether (EDM, boiling point 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), propylene glycol diester. Acetate (boiling point: 190 ° C.), propylene glycol n-butyl ether (boiling point: 170 ° C.), 3-methoxybutyl acetate (boiling point: 171 ° C.), 3-methoxy-3-methylbutyl acetate (boiling point: 188 ° C.), dipropylene Examples include glycol dimethyl ether (boiling point: 175 ° C.), ethyl 3-ethoxypropionate (boiling point: 170 ° C.), 4-butyrolactone (boiling point: 204 ° C.), cyclohexanol acetate (boiling point: 173 ° C.), and the like. These may be used alone or in combination of two or more.

As the solvent (D1), a compound represented by the following formula (3) is particularly preferable. Since the compound (3) contains polar etheric oxygen, it has a high ability to dissolve the ink repellent agent (C) and has excellent storage stability.
R ¹ O (C ₂ H ₄ O) _y R ² (3)
In formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and y represents an integer of 1 to 10.

In the compound (3), R ¹ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 carbon atom. R ² is preferably an alkyl group having 2 to 4 carbon atoms, particularly preferably an alkyl group having 2 carbon atoms. Further, y is preferably 1 to 3, and 2 is particularly preferable.

Specific examples of the compound (3) preferably used as the solvent (D1) are shown below together with their abbreviations and boiling points.
Examples include diethylene glycol ethyl methyl ether (EDM, boiling point: 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), and the like. These may be used alone or in combination of two or more. Of these, diethylene glycol ethyl methyl ether is particularly preferable.

  It is preferable that the negative photosensitive resin composition of this invention uses a solvent (D2) together with a solvent (D1) as a solvent (D). The solvent (D2) is a compound having a hydroxyl group in the molecule and having a boiling point of less than 165 ° C., and preferably has a viscosity at 25 ° C. of 2 mPa · s or less.

  Since the ink repellent agent (C) is a partially hydrolyzed condensate, silanol groups remain in the product. Therefore, by including the solvent (D2) having the same hydroxyl structure as the silanol group in the negative photosensitive resin composition, the dispersion state of the ink repellent agent (C) in the composition is further stabilized by solvation. As a result, the storage stability of the negative photosensitive resin composition can be improved. On the other hand, since the solvent (D2) has a hydroxyl group, the viscosity is likely to increase due to hydrogen bonding between molecules as compared with a compound having the same molecular weight without a hydroxyl group. If the boiling point of the solvent (D2) is less than the above upper limit, the viscosity will be generally below the above upper limit, the substrate surface will have good wetting and spreading during coating, a large amount of liquid is required, and in-plane uniformity is There is no deterioration or unevenness.

As the solvent (D2), specifically, propylene glycol monomethyl ether (PGME, boiling point: 120 ° C., viscosity: 1.71 mPa · s (25 ° C.)), water (boiling point: 100 ° C., viscosity: 0.89 mPa · s) (25 ° C.)), 2-propanol (IPA, boiling point: 82 ° C., viscosity: 1.96 mPa · s (25 ° C.)), and the like.
1-50 mass% is preferable and, as for the ratio of the solvent (D2) with respect to the whole quantity of a solvent (D), 5-40 mass% is especially preferable.

  Moreover, the negative photosensitive resin composition of this invention may contain solvent (D3) other than the above-mentioned solvent (D1) and solvent (D2) as needed as a solvent (D). As the solvent (D3), the solvent used in the synthesis of the alkali-soluble resin (A) or the ink repellent agent (C), or the like, together with the alkali-soluble resin (A) or the ink repellent agent (C), the negative photosensitive resin composition. Examples of the solvent used when blended with products.

  In addition, as a solvent used for the synthesis | combination of the said alkali-soluble resin (A) or an ink repellent agent (C), the said solvent (D1) and a solvent (D2) may be used. When the negative photosensitive resin composition contains the solvent (D1) or the solvent (D2) derived from these compounding components, it is calculated by the total amount of the solvent (D1) and the solvent (D2) containing them. What is necessary is just to adjust so that content of the solvent (D1) and the solvent (D2) in a solvent (D) may become said range, respectively.

  Specific examples of the solvent (D3) include diethylene glycol dimethyl ether (MDM, boiling point: 162 ° C.), propylene glycol 1-monomethyl ether 2-acetate (PGMEA, boiling point: 146 ° C.), diethylene glycol monoethyl ether acetate (EDGAC, boiling point: 217). ° C), butyl acetate (boiling point: 126 ° C), cyclohexanone (boiling point: 156 ° C), solvent naphtha (boiling point: 150-200 ° C), and the like. Solvent naphtha is a mixed solvent of petroleum compounds, and as its boiling point indicates, the composition includes a compound classified as solvent (D1). In the present specification, the solvent having a boiling point exceeding the boiling point of the solvent (D1) is classified as the solvent (D3).

  The content of the solvent (D3) in the solvent (D) is an amount obtained by subtracting the amounts of the solvent (D1) and the solvent (D2) from the total amount of the solvent (D), specifically, the total amount of the solvent (D). The amount is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.

  In addition, as a specific aspect of the solvent (D), an aspect composed of only the solvent (D1), the solvent (D1), the solvent (D2), and / or the solvent (D3) can be given. A preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D2) includes solvent (D1): solvent (D2) = 50 to 90:10 to 50. As a preferable blending ratio (mass ratio) when the solvent (D) is composed of the solvent (D1) and the solvent (D3), solvent (D1): solvent (D3) = 50 to 90:10 to 50 can be mentioned. Moreover, as a preferable mixture ratio (mass ratio) when the solvent (D) is composed of the solvent (D1), the solvent (D2), and the solvent (D3), solvent (D1): solvent (D2): solvent (D3) ) = 50-90: 5-45: 5-45.

  Although the content rate of the solvent (D) in a negative photosensitive resin composition changes with compositions, uses, etc. of a negative photosensitive resin composition, it is a ratio of 50-99 mass% in a negative photosensitive resin composition. It is preferable to mix | blend, 60-95 mass% is more preferable, and 65-90 mass% is especially preferable.

[Crosslinking agent (E)]
The negative photosensitive resin composition of the present invention may contain a crosslinking agent (E) as an optional component that promotes radical curing. As the crosslinking agent (E), a compound having two or more ethylenic double bonds in one molecule and having no acidic group is preferable. When the negative photosensitive resin composition contains the crosslinking agent (E), the curability of the negative photosensitive resin composition at the time of exposure is improved, and the partition can be formed even with a low exposure amount.

  As the crosslinking agent (E), diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, bi {4- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide), urethane acrylate and the like. It is preferable to have many ethylenic double bonds from the point of photoreactivity. For example, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, and urethane acrylate are preferable. In addition, these may be used individually by 1 type, or may use 2 or more types together.

  A commercial item can be used as a crosslinking agent (E). Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd., bis {4- (allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyl (Mid) phenyl} methane), BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd., N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide)) and the like. Examples of the urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20. Etc.

  Among these, KAYARAD DPHA and NK ester A-9530 are preferable because they improve the sensitivity of the cured film obtained from the negative photosensitive resin composition. NK ester A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the cured film and suppressing thermal sagging. NK ester A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured film. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.

  The content of the crosslinking agent (E) in the total solid content in the negative photosensitive resin composition is preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass. When it is in the above range, the storage stability of the negative photosensitive resin composition becomes good, and when the patterned substrate obtained using the negative photosensitive resin composition is formed, the ink-jet ink in the pixel becomes wet. Property is improved.

  The negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C), and a solvent (D). Furthermore, a crosslinking agent (E) is contained as needed. Further, the following thermal crosslinking agent (F), colorant (G), polymer dispersant (H), dispersion aid (I), silane coupling agent (J), fine particles (K), phosphoric acid compound (L ) And other additives.

[Thermal crosslinking agent (F)]
The thermal crosslinking agent (F) in the present invention is a compound having two or more groups capable of reacting with a carboxy group and / or a hydroxyl group. When the alkali-soluble resin (A) has a carboxy group and / or a hydroxyl group, the thermal crosslinking agent (F) reacts with the alkali-soluble resin (A) to increase the crosslinking density of the cured film and improve the heat resistance. Have

  Preferred examples of the thermal crosslinking agent (F) include at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.

  1-50 mass% is preferable and, as for the content rate of the thermal crosslinking agent (F) in the total solid in the negative photosensitive resin composition of this invention, 5-30 mass% is especially preferable. The developability of the negative photosensitive resin composition obtained when it is in the above range becomes good.

[Colorant (G)]
When the negative photosensitive resin composition of the present invention is used for forming a black matrix that is a grid-like black portion surrounding the three color pixels R, G, and B of a color filter of a liquid crystal display element, a colorant (G ) Is preferably included. Examples of the colorant (G) include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically, C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned. As the colorant (G), a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments can also be used.

  When the negative photosensitive resin composition of the present invention contains a colorant (G) and is used for forming a black matrix or the like, the content of the colorant (G) in the total solid content in the negative photosensitive resin composition is 15-65 mass% is preferable, and 20-50 mass% is especially preferable. The negative photosensitive resin composition obtained when it is in the above range has good sensitivity, and the formed partition has excellent light shielding properties.

[Polymer dispersant (H)]
When the negative photosensitive resin composition of the present invention contains a dispersible material such as the colorant (G), it preferably contains a polymer dispersant (H) in order to improve the dispersibility. . The polymer dispersant (H) is not particularly limited, and is urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride acetic acid. A vinyl copolymer system, a polyamide system, a polycarbonate system, and the like can be mentioned, and a urethane system or a polyester system is preferable. The polymer dispersant (H) may have a structural unit derived from ethylene oxide and / or propylene oxide.

When the polymer dispersant (H) is used for dispersing the colorant (G), the polymer dispersant (H) having a basic group should be used in consideration of the affinity for the colorant (G). Is preferred. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
A commercially available product may be used as the polymer dispersant (H). As commercial products, Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all trade names, manufactured by BYK-Chemie), Solspurs 5000, Solspers 17000 (all trade names, Zeneca).
The amount of the polymer dispersant (H) used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the colorant (G). When the amount used is not less than the lower limit of the above range, the dispersibility of the colorant (G) is improved, and when it is not more than the upper limit of the above range, the developability of the negative photosensitive resin composition becomes good.

[Dispersion aid (I)]
The negative photosensitive resin composition of the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as the dispersion aid (I). It is considered that the dispersion aid (I) has a function of improving the dispersion stability by being adsorbed on the dispersible material such as the colorant (G) and the polymer dispersant (H).

  The amount of the dispersion aid (I) used is preferably 1 to 10% by mass, particularly preferably 2 to 8% by mass, based on the colorant (G). When the amount used is not less than the lower limit of the above range, the dispersion stability of the colorant (G) is improved, and when it is not more than the upper limit of the above range, the developability of the negative photosensitive resin composition becomes good. .

[Silane coupling agent (J)]
When the negative photosensitive resin composition of the present invention uses a silane coupling agent (J), the substrate adhesion of the formed cured film is improved.
Specific examples of the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl. Examples include trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.

  0.1-20 mass% is preferable, and, as for the content rate of the silane coupling agent (J) in the total solid in the negative photosensitive resin composition of this invention, 1-10 mass% is especially preferable. When it is at least the lower limit of the above range, the substrate adhesion of the cured film formed from the negative photosensitive resin composition is improved, and when it is at most the upper limit of the above range, the ink repellency is good.

[Fine particles (K)]
The negative photosensitive resin composition of the present invention may contain fine particles (K) as necessary. By mix | blending microparticles | fine-particles (K), it becomes possible to prevent the heat dripping of the partition obtained from a negative photosensitive resin composition.

  The fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); organic materials such as polyethylene and polymethyl methacrylate (PMMA) In view of heat resistance, inorganic fine particles are preferable, and in view of availability and dispersion stability, silica or zirconia is particularly preferable. In addition, when the negative photosensitive resin composition contains the colorant (G) and the polymer dispersant (H), the fine particles (K ) Is preferably negatively charged. Furthermore, considering the exposure sensitivity of the negative photosensitive resin composition, it is preferable that the fine particles (K) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultrahigh pressure mercury lamp, It is particularly preferable not to absorb h-line (405 nm) and g-line (436 nm).

The particle diameter of the fine particles (K) is preferably 1 μm or less, particularly preferably 200 nm or less, because the surface smoothness of the partition walls is good.
5-35 mass% is preferable and, as for the content rate of microparticles | fine-particles (K) in the total solid in a negative photosensitive resin composition, 10-30 mass% is especially preferable. When the content ratio is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency due to post-baking, and when it is not more than the upper limit of the above range, the storage stability of the negative photosensitive resin composition is good. Become.

[Phosphate compound (L)]
The negative photosensitive resin composition of the present invention may contain a phosphoric acid compound (L) as necessary. Adhesiveness with a board | substrate can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (L). Examples of the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.

  0.1-10 mass% is preferable and, as for the content rate of the phosphoric acid compound (L) in the total solid in a negative photosensitive resin composition, 0.1-1 mass% is especially preferable. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.

[Other additives]
The negative photosensitive resin composition of the present invention may further contain a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber and the like as necessary. .

[Preferred combination of negative photosensitive resin composition]
In the negative photosensitive resin composition of the present invention, it is preferable to appropriately select the composition and the mixing ratio in accordance with the application and required characteristics.
The preferable composition of the various compounding components in the negative photosensitive resin composition of the present invention is shown below.

<Combination 1-1>
Alkali-soluble resin (A): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resin with an acidic group and ethylenic double bond introduced into an epoxy resin, a resin with an acidic group and ethylenic double bond introduced into a cresol novolac type epoxy resin, an acidic group and an ethylenic double group into a trisphenolmethane type epoxy resin A resin having a double bond introduced therein, or at least one resin selected from resins having an acidic group and an ethylenic double bond introduced into the epoxy resins represented by the above formulas (A1-2a) to (A1-2c). And 5 to 80% by mass in the total solid content in the negative photosensitive resin composition,

Photopolymerization initiator (B): 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- A photopolymerization initiator in which at least one selected from 1-one and 4,4′-bis (diethylamino) benzophenone are combined, and 0.1 to 50 in the total solid content in the negative photosensitive resin composition mass%,
Ink repellent agent (C): partially hydrolyzed condensate of mixture of compounds (c-1), (c-2) and (c-3), compounds (c-1), (c-2) and (c- 5) a partial hydrolysis condensate of the mixture of compounds (c-1), (c-2), (c-3) and (c-5). An ink agent, 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition,

  Solvent (D): The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- A solvent (D) containing 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate and 10 to 50% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, respectively. In the negative photosensitive resin composition in an amount of 50 to 99% by mass.

<Combination 1-2>
The alkali-soluble resin (A), the photopolymerization initiator (B), and the ink repellent agent (C) are the same as in the combination 1-1, and the solvent (D) is as follows.
Solvent (D): The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate, 5 to 45% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2 -A solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, solvent naphtha, 5 to 45 mass%, Respectively containing 50 to 99 wt% solvent (D) to the negative photosensitive resin composition.

<Combination 2>
Alkali-soluble resin (A): a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol A type epoxy resin, a resin in which acidic groups and ethylenic double bonds are introduced into bisphenol F type epoxy resin, phenol novolac type Resin with an acidic group and ethylenic double bond introduced into an epoxy resin, a resin with an acidic group and ethylenic double bond introduced into a cresol novolac type epoxy resin, an acidic group and an ethylenic double group into a trisphenolmethane type epoxy resin A resin having a double bond introduced therein, or at least one resin selected from resins having an acidic group and an ethylenic double bond introduced into the epoxy resins represented by the above formulas (A1-2a) to (A1-2c). And 5 to 80% by mass in the total solid content in the negative photosensitive resin composition,

Photopolymerization initiator (B): 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- A photopolymerization initiator in which at least one selected from 1-one and 4,4′-bis (diethylamino) benzophenone are combined, and 0.1 to 50 in the total solid content in the negative photosensitive resin composition mass%,
Ink repellent agent (C): partially hydrolyzed condensate of mixture of compounds (c-1), (c-2) and (c-3), compounds (c-1), (c-2) and (c- 5) a partial hydrolysis condensate of the mixture of compounds (c-1), (c-2), (c-3) and (c-5). An ink agent, 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition,

  Solvent (D): The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate, 5 to 45% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2 -A solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, solvent naphtha, 5 to 45 mass%, Respectively containing 50 to 99 wt% solvent (D) to the negative photosensitive resin composition.

  Cross-linking agent (E): pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, urethane acrylate At least one cross-linking agent selected from 10 to 60% by mass in the total solid content in the negative photosensitive resin composition,

<Combination 3>
Alkali-soluble resin (A): an epoxy resin having a biphenyl skeleton represented by the above formula (A1-2a), an epoxy resin represented by the above formula (A1-2b), and the above formula (A1-2c) A resin in which an acidic group and an ethylenic double bond are introduced into at least one resin selected from epoxy resins having a biphenyl skeleton, and 5 to 80% by mass in the total solid content in the negative photosensitive resin composition,

Photopolymerization initiator (B): 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), which is at least one photopolymerization initiator, 0.1 to 50 in the total solid content in the negative photosensitive resin composition mass%,
Ink repellent agent (C): partially hydrolyzed condensate of mixture of compounds (c-1), (c-2) and (c-3), compounds (c-1), (c-2) and (c- 5) a partial hydrolysis condensate of the mixture of compounds (c-1), (c-2), (c-3) and (c-5). An ink agent, 0.01 to 10% by mass in the total solid content in the negative photosensitive resin composition,

  Solvent (D): The total amount of the solvent (D) is diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 3-methoxybutyl acetate, dipropylene glycol dimethyl ether, ethyl 3-ethoxypropionate, 4- 50 to 90% by mass of a solvent (D1) selected from butyrolactone and cyclohexanol acetate, 5 to 45% by mass of a solvent (D2) selected from water, 2-propanol and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2 -A solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, solvent naphtha, 5 to 45 mass%, Respectively containing 50 to 99 wt% solvent (D) to the negative photosensitive resin composition.

Cross-linking agent (E): pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, urethane acrylate At least one cross-linking agent selected from 10 to 60% by mass in the total solid content in the negative photosensitive resin composition,
Colorant (G): at least one colorant selected from a mixture of organic pigments such as carbon black, red pigment, blue pigment, and green pigment, and 15 to 15 in the total solid content in the negative photosensitive resin composition 65% by weight.

[Method for producing negative photosensitive resin composition]
As a method for producing a negative photosensitive resin composition, an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C), a solvent (D), if necessary, a crosslinking agent (E), heat Crosslinking agent (F), colorant (G), polymer dispersant (H), dispersion aid (I), silane coupling agent (J), fine particles (K), phosphate compound (L) and other additions A method of mixing with an agent is preferred.

  The negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film is an ordinary negative photosensitive resin composition. It can be used as a member of an optical element in which a cured film is used. In particular, when the negative photosensitive resin composition of the present invention is used for forming a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate, such as ultraviolet / ozone cleaning treatment A partition wall having sufficient ink repellency can be obtained even after the lyophilic treatment, which is preferable. Further, in the negative photosensitive resin composition of the present invention, in the production of the partition wall, in the film formed using this and dried, the film thickness is uniform and there is no unevenness, and aggregates are formed on the film surface. Good coatability that does not occur.

[Partition and manufacturing method thereof]
The partition of this invention is a partition formed in order to provide a division on a board | substrate, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention. The partition of this invention is used suitably for the use of an optical element, and when the said negative photosensitive resin composition contains a coloring agent (G), the partition obtained can be applied as a black matrix. . The partition of the present invention is applied to a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on a substrate, for example.

  Examples of the method for producing the partition for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.

  The negative photosensitive resin composition of the present invention is applied on the substrate to form a coating film (coating film forming process), and then the coating film is dried to form a film (drying process). Only the part to be the partition wall is exposed and photocured (exposure process), and then the coating film other than the photocured part is removed to form the partition wall comprising the photocured part of the coating film (development process) Then, the partition walls for the optical element of the present invention can be manufactured by further thermally curing the formed partition walls and the like as necessary (post-baking step). Moreover, you may put further the photocuring (post exposure process) of the said formed partition etc. between a image development process and a post-baking process.

The material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc. Thermoplastic plastic sheet; Cured sheet of thermosetting resin such as epoxy resin and unsaturated polyester can be used. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance. Moreover, since a post exposure may be performed from the back surface (board | substrate side) in which the partition is not formed, it is preferable that it is a transparent substrate.
It is preferable to clean the application surface of the negative photosensitive resin composition on the substrate by alcohol cleaning, ultraviolet / ozone cleaning or the like before application.

FIG. 1 is a cross-sectional view schematically showing a production example of an optical element partition using the negative photosensitive resin composition of the present invention. FIG. 1 (I) is a view showing a cross section in a state where a coating film 2 made of the negative photosensitive resin composition of the present invention is formed on a substrate 1. (II) is a figure which shows an exposure process typically. (III) is sectional drawing which shows the board | substrate 1 after the image development process, and the partition 6 formed on the board | substrate.
Hereinafter, the manufacturing method of the partition for optical elements using the negative photosensitive resin composition of this invention is demonstrated concretely using FIG.

(Coating film formation process)
As shown in a cross section in FIG. 1 (I), the negative photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition. In addition, before forming the coating film 2 of the negative photosensitive resin composition on the board | substrate 1, the application surface of the negative photosensitive resin composition of the board | substrate 1 is wash | cleaned by alcohol washing | cleaning, ultraviolet rays / ozone washing | cleaning, etc. preferable.

The coating method of the negative photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed. Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned. In particular, a slit coating method that can be applied to a large area at once is preferable. As described above, the negative photosensitive resin composition of the present invention is a surface of the ink repellent agent (C) in the coating of the negative photosensitive resin composition on the substrate and the drying step such as the following prebaking step. Since a sufficient transition time can be secured, generation of aggregates on the film surface can be prevented, and a sufficient leveling period can be taken, so that a good film having a uniform film thickness and no unevenness can be obtained. From such a viewpoint, the negative photosensitive resin composition of the present invention can be advantageously used particularly in the slit coating method.
The film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably 100 to 200%, particularly preferably 100 to 130%, of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably from 0.3 to 325 μm, particularly preferably from 1.3 to 65 μm.

(Pre-baking process)
The coating film 2 formed on the substrate 1 in the coating film forming step is heated to obtain the film 2. By heating, the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained. Further, the ink repellent agent (A) moves to the vicinity of the coating film surface. Examples of the heating method include a method in which the coating film 2 is heat-treated at 50 to 120 ° C. for about 10 to 2,000 seconds with a heating apparatus such as a hot plate and an oven together with the substrate 1.

  In addition, although it is possible to remove volatile components such as a solvent by heating in the pre-baking step as described above, a drying step such as vacuum drying other than heating (drying) is performed in order to remove volatile components such as a solvent. You may provide separately before a prebaking process. Further, in order to efficiently dry the film without causing unevenness of the film appearance, it is more preferable to use heating and vacuum drying in combination with the drying by the pre-baking process. The vacuum drying conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably performed at 500 to 10 Pa in a wide range of about 10 to 300 seconds.

(Exposure process)
As shown in FIG. 1 (II), the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern. Only the predetermined pattern portion cut by the mask 4 is transmitted through the light 5, reaches the film on the substrate 1, and only the portion is photocured. Therefore, when forming a partition, the said predetermined pattern is provided in the form suitable for the shape of a partition.
For example, the average partition wall width after the post-baking step is preferably 100 μm or less, and particularly preferably 20 μm or less. Further, the average distance between adjacent partition walls is preferably 300 μm or less, and particularly preferably 100 μm or less. It is preferable to use a mask in which a pattern is formed so as to be in this range.

  In FIG. 1 (II), the exposed portion 3 of the film irradiated with light is composed of a cured film of a negative photosensitive resin composition, while the unexposed portion is a film 2 of an uncured negative photosensitive resin composition. It is a state in which it remains.

The irradiation light 5 is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-ray; Examples include lines. The irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm) and g-line (436 nm). preferable.

As the irradiation device (not shown), a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used. Exposure is preferably ^{5~1,000mJ / cm 2, 50~400mJ / cm} 2 is particularly preferred. When the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as a partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate 1. A high resolution is obtained when it is not more than the upper limit of the above range. The exposure time depends on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.

(Development process)
Development is performed using a developer, and the unexposed portion 2 on the substrate 1 shown in FIG. 1 (II) is removed. Thereby, the structure of the partition 6 formed with the cured film of the negative photosensitive resin composition on the board | substrate 1 and the said board | substrate as FIG. 1 (III) shows sectional drawing is obtained. Further, a portion surrounded by the partition wall 6 and the substrate 1 is a portion called a dot 7 where a pixel is formed by ink injection or the like. The obtained substrate 10 becomes a substrate that can be used for manufacturing an optical element by an inkjet method through a post-bake process described later.

  As the developer, an aqueous alkali solution containing alkalis such as inorganic alkalis, amines, alkanolamines, and quaternary ammonium salts can be used. Further, an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.

  The development time (time for contacting with the developer) is preferably 5 to 180 seconds. Examples of the developing method include a liquid piling method, a dipping method, and a shower method. After the development, water on the substrate 1 and the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.

(Post bake process)
The partition 6 on the substrate 1 is heated. Examples of the heating method include a method in which the partition wall 6 together with the substrate 1 is heated at 150 to 250 ° C. for 5 to 90 minutes using a heating device such as a hot plate or an oven. By the heat treatment, the partition walls 6 made of a cured film of the negative photosensitive resin composition on the substrate 1 are further cured, and the shape of the dots 7 surrounded by the partition walls 6 and the substrate 1 is further fixed. The heating temperature is particularly preferably 180 ° C. or higher. If the heating temperature is too low, curing of the partition wall 6 is insufficient, so that sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, the solvent contained in the ink As a result, the partition wall 6 may swell or ink may ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.

  In the negative photosensitive resin composition of the present invention, the average width of the partition walls is preferably 100 μm or less, and particularly preferably 20 μm or less. In addition, the average distance between adjacent partition walls (dot width) is preferably 300 μm or less, and particularly preferably 100 μm or less. Moreover, 0.05-50 micrometers is preferable and, as for the average of the height of a partition, 0.2-10 micrometers is especially preferable.

[Method for Manufacturing Optical Element]
After the partition wall is formed on the substrate by the above manufacturing method, for example, the substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to an ink affinity treatment (ink affinity treatment process), and then the region An optical element can be obtained by injecting ink into the ink jet method to form the pixel (ink injection step).

(Ink affinity process)
Examples of the lyophilic process include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
The cleaning process with an alkaline aqueous solution is a wet process in which the substrate surface is cleaned with an alkaline aqueous solution (potassium hydroxide, tetramethyl ammonium hydroxide aqueous solution, or the like).
The ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.
The ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light of 185 nm and 254 nm.
The excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp that emits light at 172 nm.
The corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
The oxygen plasma treatment is a dry treatment in which oxygen is excited in a vacuum mainly using a high frequency power source as a trigger to clean the substrate surface using a highly reactive “plasma state”.

  As a method for the ink-philic treatment, a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple. UV / ozone can be generated using commercially available equipment. An ink-repellent treatment can be performed by placing a substrate on which a partition wall is formed inside an ultraviolet / ozone device and performing the treatment in air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition wall. it can. In addition, about processing time, what is necessary is just to adjust to the time used as the range which does not impair the oil repellency of a partition according to each ultraviolet-ray / ozone apparatus.

  By this ink repellency treatment, the removal of impurities remaining on the dots after the formation of the partition walls can be sufficiently performed to sufficiently measure the dot ink fondness, such as a color display device using an optical element obtained. It is possible to prevent white spots. In addition, when the partition obtained from the negative photosensitive resin composition of the present invention is used, it is possible to make the ink affinity by the ultraviolet cleaning treatment or the like without reducing the ink repellency of the partition.

  Here, the ink repellency (water / oil repellency) of the cured film formed from the negative photosensitive resin composition is water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent often used as a solvent for the ink. ) And the contact angle can be estimated. When an optical element is produced using a substrate having a partition formed using the negative photosensitive resin composition of the present invention, the partition is required to have sufficient ink repellency even after the ink-philic treatment. It is done. Therefore, the water contact angle of the partition walls is preferably 90 ° or more, and particularly preferably 95 ° or more. Similarly, the contact angle of PGMEA of the partition wall is preferably 30 degrees or more, particularly preferably 35 degrees or more. On the other hand, when an optical element is produced using a substrate having a partition wall formed using the negative photosensitive resin composition of the present invention, the dots are required to be ink-philic, and the water The contact angle is preferably 20 degrees or less, and particularly preferably 10 degrees or less.

(Ink injection process)
This is a step of forming pixels by injecting ink into the dots after the ink affinity treatment step by an ink jet method. This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. The ink jet device used for forming such pixels is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element. An ink jet apparatus using various methods such as a method, a method of heating ink, and intermittently ejecting the ink using the foaming can be used.

  Examples of the optical element produced using the negative photosensitive resin composition of the present invention include a color filter, an organic EL element, and an organic TFT array.

[Manufacture of color filters]
The formation of partition walls, the process of making dots ink-philic, and ink injection by the inkjet method are as described above. In the color filter, the shape of the pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.

The ink used for forming the pixel mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like. As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.
Moreover, after injecting ink by the inkjet method, it is preferable to perform drying, heat curing, and ultraviolet curing as necessary.

After the pixel formation, a protective film layer is formed as necessary. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. If the ink repellency is not removed, the overcoat coating solution is repelled, and a uniform film thickness cannot be obtained. Examples of the method for removing the ink repellency of the partition include plasma ashing and optical ashing.
Further, if necessary, it is preferable to form a photo spacer on a black matrix composed of partition walls in order to improve the quality of a liquid crystal panel manufactured using a color filter.

[Manufacture of organic EL elements]
Before forming the partition walls, a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary. Next, a barrier rib is formed using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-inking treatment, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an ink jet method and dried. Thus, a hole transport layer and a light emitting layer are formed. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like, thereby obtaining a pixel of the organic EL element.

[Manufacture of organic TFT array]
An organic TFT array can be manufactured through the following steps (1) to (3).
(1) A partition wall is formed on a transparent substrate such as glass using the negative photosensitive resin composition of the present invention. After the dot is made into an ink-philic process, a gate electrode material solution is applied to the dots using an inkjet method to form a gate electrode.
(2) After forming the gate electrode, a gate insulating film is formed thereon. A barrier rib is formed on the gate insulating film using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-philic process, a solution of a source / drain electrode material is applied to the dot using an ink jet method. A drain electrode is formed.
(3) After forming the source / drain electrodes, a partition is formed using the negative photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes, and the ink is made to be an ink-insensitive dot. Thereafter, an organic semiconductor solution is applied to the dots using an ink jet method to form an organic semiconductor layer between the source and drain electrodes.
In (1) to (3), the partition using the negative photosensitive resin composition of the present invention may be used in only one step, or the negative photosensitive resin of the present invention in two or more steps. You may utilize the partition using a conductive resin composition.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1 to 5 and 8 to 10 are Examples, and Examples 6, 7, and 11 are comparative examples.

Each measurement was performed by the following method.
[Number average molecular weight (Mn)]
Gel permeation chromatography (GPC) of several types of monodisperse polystyrene polymers with different degrees of polymerization, which are commercially available as standard samples for molecular weight measurement, were prepared using a commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). ) And a calibration curve was created based on the relationship between the molecular weight of polystyrene and the retention time (retention time).
The sample was diluted to 1.0% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then the GPC of the sample was measured using the GPC measurement apparatus.
The number average molecular weight (Mn) of the sample was determined by computer analysis of the GPC spectrum of the sample using the calibration curve.

[Water contact angle]
In accordance with JIS R3257 “Testing method for wettability of substrate glass surface”, water droplets were placed on three measurement surfaces on the substrate by the sessile drop method, and each water droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

[PGMEA contact angle]
In accordance with JIS R3257 “Testing method for wettability of substrate glass surface”, PGMEA droplets were placed at three locations on the measurement surface of the substrate by the sessile drop method, and each PGMEA droplet was measured. The droplet was 2 μL / droplet, and the measurement was performed at 20 ° C. The contact angle is indicated by an average value of three measured values (n = 3).

Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.
(Alkali-soluble resin (A))
CCR1235: trade name: KAYARAD CCR-1235, manufactured by Nippon Kayaku Co., Ltd., a resin obtained by introducing a carboxy group and an ethylenic double bond into a cresol novolac type epoxy resin, an acid value of 60 mgKOH / g, a solid content of 60% by mass, a solvent, EDGAC: 27% by mass, solvent naphtha: 13% by mass ).
ZAR2002: Trade name; KAYARAD ZAR-2002H, manufactured by Nippon Kayaku Co., Ltd., a resin in which a carboxy group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, an acid value of 60 mgKOH / g, a solid content of 70% by mass, PGMEA: 30% by mass).
(Photopolymerization initiator (B))
IR907: Trade name: IRGACURE 907, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone.
EAB: 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
OXE02: Trade name; IRGACURE OXE02, manufactured by BASF, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime).

(Solvent (D))
(I) Solvent (D1)
EDM: Diethylene glycol ethyl methyl ether.
Metoace: 3-methoxybutyl acetate.
EEP: ethyl 3-ethoxypropionate.
(ii) Solvent (D2)
PGME: Propylene glycol monomethyl ether.
(iii) Solvent (D3)
MDM: Diethylene glycol dimethyl ether.
PGMEA: Propylene glycol monomethyl ether acetate.
EDGAC: Diethylene glycol monoethyl ether acetate.
Solvent naphtha: A mixed solvent of petroleum compounds. Although the boiling point is in the range of 150 to 200 ° C. and contains a compound classified as the solvent (D1), since the composition is unknown, in Table 1, the total content is described as (D3).
(Crosslinking agent (E))
A9530: trade name; NK ester A-9530, manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.

[Synthesis Example 1: Synthesis of ink repellent agent (C1) and adjustment of (C1-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.5 g of the above compound (c-1) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (Asahi Glass Co., Ltd.), the above compound 1.11 g of Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.) which is (c-2), CH ₂ ═CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (which is the above compound (c-5)) 0.63 g of Tokyo Chemical Industry Co., Ltd. and 0.28 g of (CH ₃ ) ₃ SiOCH ₃ (Tokyo Chemical Industry Co., Ltd.), which is the above compound (c-3), were added. Next, 10.26 g of PGME was added to obtain a mixture.
While stirring the mixture at room temperature, 1.27 g of a 1.0% aqueous nitric acid solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent (C1) at 10% by mass is referred to as a (C1-1) liquid. The fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the obtained (C1-1) liquid is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the (C1-1) solution was 740.

[Synthesis Example 2: Synthesis of ink repellent agent (C2) and preparation of (C2-1) liquid]
A synthesis example except that 0.76 g of ethyl silicate 48 (manufactured by Colcoat: partial hydrolysis-condensation product of Si (OC ₂ H ₅ ) ₄ ) and 10.26 g of PGME are used instead of the compound (c-2). A mixture was prepared as in 1.
While stirring the mixture at room temperature, 0.93 g of a 1.0% nitric acid aqueous solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent (C2) at 10% by mass is referred to as a (C2-1) liquid. The fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the obtained (C2-1) liquid is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the (C2-1) solution was 866.

[Synthesis Example 3: Synthesis of ink repellent agent (C3) and preparation of (C3-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.5 g of the above compound (c-1) CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (Asahi Glass Co., Ltd.), the above compound 0.83 g of Si (OC ₂ H ₅ ) ₄ (manufactured by Colcoat Co.) which is (c-2), CH ₂ ═CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ( 0.94 g of Tokyo Chemical Industry Co., Ltd. was added. Next, 9.89 g of PGME was added to obtain a mixture.
While stirring the above mixture at room temperature, 1.12 g of a 1.0% nitric acid aqueous solution was added dropwise. After completion of dropping, the mixture was further stirred for 5 hours. A PGME solution containing the ink repellent agent (C3) at 10% by mass is referred to as a (C3-1) liquid. The fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the obtained (C3-1) liquid is 18.8 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the (C3-1) solution was 768.

[Example 1]
(Preparation of negative photosensitive resin composition)
(C1-1) 10 g of liquid (solid content is 1.0 g, the rest is PGME of the solvent), 75 g of CCR-1235 (solid content is 45 g, the rest is EDGAC of the solvent: 20 g, solvent naphtha: 10 g), IR907 6 g, 3 g of EAB, 45 g of A9530, 180 g of EDM, and 81 g of PGME were placed in a stirring vessel of 1,000 cm ³ and stirred for 30 minutes to prepare a negative photosensitive resin composition 1. Table 1 shows the composition in the solid content of the negative photosensitive resin composition, the composition in the solvent component, and the content of the solvent (D) component in the composition.

(Manufacture of cured film 1)
A 10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to ultraviolet / ozone cleaning for 5 minutes. For UV / ozone cleaning, PL7-200 (manufactured by Sen Engineering) was used as an UV / ozone generator. In addition, this apparatus was used as an ultraviolet / ozone generator for all the following ultraviolet / ozone treatments.

The negative photosensitive resin composition 1 was applied to the cleaned glass substrate surface using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1.3 μm. A gap of 50 μm is formed on the surface of the obtained film from the film side through a photomask having a hole pattern (2.5 cm × 5 cm) (a photomask in which light is irradiated to a region other than the pattern portion). The cured film was obtained by irradiating ultraviolet rays from a high pressure mercury lamp at 25 mW / cm ² for 10 seconds.

  Next, the exposed glass substrate was developed by immersing it in a 0.4% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the coating film of the unexposed part was washed away with water and dried. Next, this was heated on a hot plate at 230 ° C. for 20 minutes to obtain a glass substrate (1) in which a cured film of the negative photosensitive resin composition 1 was formed in a region excluding the hole pattern portion. .

(Manufacture of cured film 2)
The glass substrate was washed in the same manner as in the production of the cured film 1, and the negative photosensitive resin composition 1 was applied to the glass substrate surface using a spinner, and then dried on a hot plate at 100 ° C. for 2 minutes. A film having a thickness of 1.3 μm was formed. A glass substrate (2) in which the surface of the obtained film is irradiated with ultraviolet light from a high-pressure mercury lamp from the film side at 25 mW / cm ² for 10 seconds to form a cured film of the negative photosensitive resin composition 1 on the entire surface of the substrate. Got.
(Manufacture of cured film 3)
The same operation was performed except that the glass substrate was changed to a chromium metal vapor deposition substrate in the production of the cured film 2 to obtain a chromium metal vapor deposition substrate (3) on which the cured film of the negative photosensitive resin composition 1 was formed. .

(Evaluation)
<Ink repellency (partition wall) / ink affinity (dot)>
The contact angle with respect to PGMEA of the cured film of the obtained glass substrate (1), that is, the partition wall surface (exposed part), and the contact angle with water of the part where the coating film was removed by development, that is, the dot part (glass substrate surface) were measured. . Thereafter, the entire surface of the glass substrate (1) on which the cured film was formed was irradiated with ultraviolet rays / ozone for 2 minutes. The contact angle with respect to PGMEA on the surface of the cured film after irradiation for 2 minutes and the contact angle with water on the surface of the glass substrate were measured. The measuring method is as described above. The evaluation results are shown in Table 1.

<Presence of aggregates>
Next, the appearance of the cured film in the glass substrate (2) produced in Production 2 of the cured film was visually confirmed to check for the presence of aggregates. The evaluation criteria at this time are as follows. The evaluation results are shown in Table 1.
○ (excellent): There are 5 or less aggregates confirmed in the sample.
Δ (good): 6 to 20 aggregates were confirmed in the sample.
X (defect): 21 or more aggregates were confirmed in the sample.

<Variation in ink repellency of cured film>
Next, in-plane variation of ink repellency was evaluated. In the measurement of the PGMEA contact angle, the variation from the measured value was evaluated according to the following criteria.
○ (Good): (Maximum contact angle)-(Minimum contact angle) is within 2 ° x (Bad): (Maximum contact angle)-(Minimum contact angle) exceeds 2 °.

<Average thickness and in-plane uniformity of cured film>
Next, the in-plane uniformity of the film thickness was evaluated. Using the glass substrate (2) produced in production 2 of the cured film described above, film thicknesses at 10 points of measurement points P1 to P10 shown in FIG. 2 were measured. That is, six points (P1 to P1) from one apex 21 of the glass substrate (2) 20 to the central part C of the substrate and from the position P1 of 20 mm toward the central part C to the central part C (P6) at intervals of 10 mm. The film thickness was measured in P6). Furthermore, it is inclined at an angle of 45 ° with respect to the line connecting the aforementioned measurement points from the central part C, and 10 mm from the side toward the central part C at intervals of 10 mm on a line drawn perpendicularly to one side of the glass substrate (2) 20. The film thickness was measured at four points (P7 to P10) up to position P10. In-plane uniformity was determined by the following formula using the measured values of film thickness at 10 points.
(In-plane uniformity) = (maximum film thickness-minimum film thickness) / (2 × average film thickness) × 100
The results were evaluated as follows. In addition, the film thickness of Table 1 is an average value of the film thickness measured at this time. The evaluation results are shown in Table 1.
○ (Good): 5% or less.
X (defect): It exceeds 5%.

<Appearance of cured film (unevenness)>
The appearance of the cured film in the chromium metal vapor deposition substrate (3) produced in Production 3 of the cured film was visually observed under a sodium lamp, and unevenness was evaluated as follows.
○ (Good): Circular unevenness and unevenness such as chuck marks are not visible.
X (defect): Circular irregularities and irregularities such as chuck marks are visible.

<Storage stability>
The negative photosensitive composition was stored in a glass screw bottle at 23 ° C. (room temperature) for 2 weeks. After storage for 2 weeks, the negative photosensitive composition was applied to the surface of a 10 cm × 10 cm glass substrate washed in the same manner as in the production 1 of the cured film using a spinner to form a coating film. Furthermore, it was dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1 μm. The appearance of the film was visually observed and evaluated as follows.
(Excellent): There are 5 or less foreign matters on the film.
○ (good): There are 6 to 20 foreign substances on the film.
X (defect): There were 21 or more foreign substances on the film, and radial streaks were observed from the center of the glass substrate.

[Examples 2 to 11]
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the negative photosensitive resin composition film and cured film were formed as a glass substrate (1), glass A substrate (2) and a chromium metal vapor deposition film substrate (3) were obtained. These were evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As can be seen from Table 1, Examples 1-5 and Examples 8-10 using diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate having a boiling point of the solvent (D1) of 165 to 210 ° C. The negative photosensitive resin composition had good appearance with no unevenness or aggregates in the film. Furthermore, the in-plane uniformity was also good. Further, the cured film obtained from the negative photosensitive resin composition exhibits good ink repellency, maintains high ink repellency even after irradiation with ultraviolet rays / ozone, and the glass substrate surface has good hydrophilicity. I understand that. On the other hand, in Examples 6 and 7, sufficient ink repellency was obtained, but unevenness in appearance and aggregates were generated, and in-plane uniformity was low. In Example 11, although sufficient ink repellency was obtained, the appearance was uneven and the in-plane uniformity was low.

The negative photosensitive resin composition of the present invention is a negative photosensitive resin composition capable of producing a partition having good ink repellency and capable of retaining ink repellency even when irradiated with ultraviolet rays / ozone. Thus, in the production of the partition walls, a film obtained by using this to form a coating film and dried has a uniform film thickness, no unevenness, and good coating properties in which no aggregate is generated on the film surface. Therefore, the obtained partition walls also have good appearance and uniform film thickness. For example, the partition walls are formed for color filter manufacturing, organic EL element manufacturing, and organic TFT array manufacturing using the inkjet recording technology method. In particular, it is preferably used for forming a partition wall of a large-area substrate.
It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2011-187864 filed on August 30, 2011 are cited herein as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Coating film of negative photosensitive resin composition, 3 ... Coating film exposure part, 4 ... Mask, 5 ... Light, 6 ... Partition, 7 ... Dot, 10 ... Substrate for optical elements used for inkjet system 20 ... glass substrate (2), 21 ... apex, C ... center, P1-P10 ... film thickness measurement point

Claims (10)

A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent (C) and a solvent (D), wherein the ink repellent agent (C) is a fluorine-containing organo consists siloxane compound, the solvent (D) is seen containing a solvent (D1) having a boiling point of 165-210 ° C. at a rate of 10 to 100% by weight relative to the total amount of the solvent (D), the fluorine-containing organo The siloxane compound is composed of a hydrolyzable silane compound represented by the following formula (c-1) and a partial hydrolysis condensate of a mixture containing the hydrolyzable silane compound represented by the following formula (c-2). Negative photosensitive resin composition characterized by the above.

Symbols in the formulas (c-1) and (c-2) are as follows.
R ^F : an organic group having a perfluoroalkyl group which may contain an etheric oxygen atom having 3 to 10 carbon atoms,
R ^H : an organic group having no perfluoroalkyl group,
X: hydrolyzable group,
p: 0, 1 or 2.
However, when two or more ^RH and X exist in a compound, these may mutually differ or may be the same.   The negative photosensitive resin composition of Claim 1 whose content rate of the fluorine atom in the said fluorine-containing organosiloxane compound is 10-55 mass%. The negative photosensitive resin composition of Claim 1 or 2 whose said solvent (D1) is a compound represented by the following Formula (3).
R ¹ O (C ₂ H ₄ O) _y R ² (3)
In formula (3), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an alkyl group having 2 to 10 carbon atoms, and y represents an integer of 1 to 10. The negative photosensitive resin composition according to any one of claims 1 to 3 , wherein the solvent (D1) is diethylene glycol ethyl methyl ether. The solvent (D) further contains a solvent (D2) having a hydroxyl group and a boiling point of less than 165 ° C in a proportion of 1 to 50% by mass with respect to the total amount of the solvent (D). The negative photosensitive resin composition as described in any one of 1-4 . The negative photosensitive resin composition according to any one of claims 1 to 5 , wherein the alkali-soluble resin (A) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. . The negative photosensitive resin composition according to any one of Claims 1 to 6 , wherein the photopolymerization initiator (B) is a combination of acetophenones or O-acyloximes and benzophenones. Furthermore, the crosslinking agent comprises a (E), has two or more ethylenic double bonds crosslinker (E) is in one molecule, a compound having no acidic group, any one of claims 1-7 The negative photosensitive resin composition according to one item. The substrate surface to a method for producing the shape of the septum wall partitioning a plurality of compartments for pixel formation, a negative type photosensitive resin composition according to any one of claims 1 to 8 is applied to the substrate surface The manufacturing method of the partition which has a process, a drying process, an exposure process, and a image development process in order, and has a post-baking process after that. After forming the barrier ribs by the method described in 請 Motomeko 9 on the substrate surface, producing an optical device characterized in partitioned compartments in the partition wall, forming a pixel by injecting ink by an ink jet method Way .

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