WO2015163379A1

WO2015163379A1 - Negative photosensitive resin composition, partition, and optical element

Info

Publication number: WO2015163379A1
Application number: PCT/JP2015/062288
Authority: WO
Inventors: 川島　正行; 古川　豊
Original assignee: 旭硝子株式会社
Priority date: 2014-04-25
Filing date: 2015-04-22
Publication date: 2015-10-29
Also published as: TWI655501B; JP6565904B2; CN106462069A; CN106462069B; KR20160146719A; KR102378162B1; JPWO2015163379A1; TW201546546A

Abstract

　Provided are: a negative photosensitive resin composition that can be used in the manufacture of a partition which can have formed on the upper surface thereof an ink-repelling layer having sufficient ink repellence at low amounts of light exposure, and which can sustain exceptional ink repellence even through an ink-attracting treatment; a partition of an optical element having an ink-repelling layer on the top surface, the partition being able to undergo fine high-precision pattern forming, and able to sustain exceptional ink repellence even through an ink-attracting treatment; and an optical element in which an opening divided by the partition is uniformly coated with ink, the optical element having precisely formed dots. A negative photosensitive resin composition contains an ink-repelling agent containing an alkali-soluble resin, a crosslinking agent, a photo-acid generator, and a hydrolyzable silane compound having a fluoroalkylene group and/or a fluoroalkyl group and a hydrolyzable group; a curing film and a partition are formed using the negative photosensitive resin composition; and an optical element has a plurality of dots on a substrate surface, and the partition positioned between adjacent dots.

Description

Negative photosensitive resin composition, partition and optical element

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

In the production of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays, thin film solar cells, etc., an organic layer such as a light emitting layer is used as a dot by an inkjet (IJ) method. A pattern printing method may be used. In such a method, a partition is provided along the outline of the dot to be formed, and an ink containing the material of the organic layer is injected into a partition (hereinafter also referred to as “opening”) surrounded by the partition. This is dried and / or heated to form dots having a desired pattern.

In the above method, the upper surface of the partition wall has ink repellency to prevent mixing of ink between adjacent dots and the uniform application of ink in the formation of dots, while for dot formation surrounded by the partition wall including the partition wall side surface. The opening needs to have ink affinity.

Therefore, in order to obtain a partition having ink repellency on the upper surface, a method of forming a partition corresponding to a dot pattern by a photolithography method using a photosensitive resin composition containing an ink repellent agent is known. ing. The photosensitive resin is roughly classified into radical polymerization type photosensitive resins and cationic polymerization type photosensitive resins. However, in the radical polymerization type photosensitive resin composition, it is known that curing of the outermost surface is inhibited by oxygen. Therefore, in order to develop sufficient ink repellency on the outermost surface using a photosensitive resin composition containing an ink repellent agent, a large amount of exposure is required. As a result, sensitivity, patterning shape The residue may be affected.

On the other hand, when a cationic polymerization type photosensitive resin is used, it is difficult to be affected by oxygen inhibition related to surface curing as described above, and it is possible to impart ink repellency to the surface with a small exposure amount. . As a composition combining such a cationic polymerization type photosensitive resin and an ink repellent, Patent Document 1 includes a structural unit derived from an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms. A composition is described in which a liquid repellent composed of an addition polymer and a cationic polymerization type photosensitive resin are combined.

International Publication No. 2012/057058

The liquid repellent described in Patent Document 1 is fixed to the surface of the partition wall with a small exposure amount at the time of forming the partition wall, but is performed for the purpose of removing impurities remaining on the dots after the partition wall formation, for example, a cleaning process using an alkaline aqueous solution Insufficient resistance to ink-philic treatment such as ultraviolet cleaning treatment, ultraviolet / ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment and oxygen plasma treatment.
The present invention has been made from the above viewpoint, and it is possible to form an ink-repellent layer having sufficient ink repellency at a low exposure amount on the upper surface of the partition wall, and the ink-repellent layer has undergone an ink affinity treatment. Another object of the present invention is to provide a negative photosensitive resin composition that can be used for the production of a partition wall that can maintain excellent ink repellency.
The present invention is a partition wall having an ink repellent layer having sufficient ink repellency on the upper surface and capable of forming a fine and highly accurate pattern, and maintains excellent ink repellency even after being subjected to a lyophilic process. An object of the present invention is to provide a partition wall for an optical element.
In addition, the present invention provides an optical element having dots formed by applying ink uniformly to the openings partitioned by the partition walls, specifically, an organic EL element, a quantum dot display, a TFT array, or a thin film solar. The purpose is to provide batteries.

The present invention provides a negative photosensitive resin composition, partition walls, and optical elements having the following configurations [1] to [15].
[1] Alkali-soluble resin (A), cross-linking agent (B), photoacid generator (C), hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group ( A negative photosensitive resin composition comprising an ink repellent agent (D) containing s1) as a monomer and / or a partially hydrolyzed (co) condensate.
[2] The negative photosensitive resin composition according to the above [1], wherein the fluorine atom content in the ink repellent agent (D) is 1 to 40% by mass.
[3] The ink repellent agent (D) contains a hydrolyzable silane compound (s2) in which four hydrolyzable groups are bonded to a silicon atom as a monomer and / or a partially hydrolyzed (co) condensate. The negative photosensitive resin composition as described in [1] or [2] above.
[4] The ink repellent agent (D) contains a hydrolyzable silane compound (s3) having only a hydrocarbon group and a hydrolyzable group as a monomer and / or a partially hydrolyzed (co) condensate. The negative photosensitive resin composition according to any one of [1] to [3].
[5] The ink repellent agent (D) comprises a hydrolyzable silane compound (s4) having a cationic polymerizable group and a hydrolyzable group and containing no fluorine atom as a monomer and / or partially hydrolyzed (co-polymerized). ) The negative photosensitive resin composition according to any one of the above [1] to [4], which is contained as a condensate.
[6] In any one of the above [1] to [5], the content of the alkali-soluble resin (A) is 10 to 90% by mass in the total solid content in the negative photosensitive resin composition. The negative photosensitive resin composition as described.
[7] The content of the crosslinking agent (B) and the photoacid generator is 2 to 50 parts by mass and 0.1 to 20 parts by mass, respectively, with respect to 100 parts by mass of the alkali-soluble resin (A). The negative photosensitive resin composition according to any one of the above [1] to [6].
[8] Any one of the above [1] to [7], wherein the content of the ink repellent agent (D) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Negative photosensitive resin composition as described in the item.
[9] The above [1], further comprising at least one solvent (E) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate and 2-propanol ] The negative photosensitive resin composition according to any one of [8] to [8].

[10] The negative type according to any one of the above [1] to [9], wherein the content of the solvent (E) is 50 to 99% by mass with respect to the total amount of the negative photosensitive resin composition. Photosensitive resin composition.
[11] A partition formed so as to partition the substrate surface into a plurality of sections for forming dots, and from the cured film of the negative photosensitive resin composition according to any one of [1] to [10] Partition wall.
[12] The partition wall described in [11] above, wherein the width is 100 μm or less, the distance between the partition walls (pattern width) is 300 μm or less, and the height is 0.05 to 50 μm.
[13] An optical element having a plurality of dots on a substrate surface and a partition located between adjacent dots, wherein the partition is formed by the partition described in [11] or [12]. A featured optical element.
[14] The optical element according to [13], wherein the dots are formed by an inkjet method.
[15] The optical element according to [13] or [14], wherein the optical element is an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.

By using the negative photosensitive resin composition of the present invention, it is possible to form an ink repellent layer having sufficient ink repellency at a low exposure amount on the upper surface of the partition wall, and the ink repellent layer is subjected to an ink affinity treatment. Even after passing, it is possible to produce partition walls that can maintain excellent ink repellency.
In addition, the partition wall of the present invention has an ink repellent layer having sufficient ink repellency on the upper surface, can form a fine and highly accurate pattern, and the ink is evenly distributed in the openings partitioned by the partition wall. An organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell using an optical element having dots that are coated on and accurately formed can be provided.

It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the partition of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the optical element of embodiment of this invention. It is process drawing which shows typically the manufacturing method of the optical element of embodiment of this invention.

Definitions of terms in the present specification will be explained together below.
“(Meth) acryloyl group” is a general term for “methacryloyl group” and “acryloyl group”. The (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin also conform to this.

The group represented by the formula (x) may be simply referred to as a group (x).
The compound represented by the formula (y) may be simply referred to as the compound (y).
Here, the expressions (x) and (y) indicate arbitrary expressions.

The “side chain” is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which a repeating unit composed of carbon atoms constitutes the main chain. “Unit” such as a fluorine atom-containing unit indicates a polymerized unit.

The “total solid content of the photosensitive resin composition” refers to a component that forms a cured film, which will be described later, among the components contained in the photosensitive resin composition. The photosensitive resin composition is heated at 140 ° C. for 24 hours. Determine from the residue after removing the solvent. The total solid content can also be calculated from the charged amount.

A film made of a cured product of a composition containing resin as a main component is referred to as a “resin cured film”.
A film coated with the photosensitive resin composition is referred to as a “coating film”, and a film obtained by drying the film is referred to as a “dry film”. A film obtained by curing the “dry film” is a “resin cured film”. Further, the “resin cured film” may be simply referred to as “cured film”.

The “partition wall” is a form of a cured resin film formed in a shape that partitions a predetermined region into a plurality of sections. For example, the following “ink” is injected into the partitions partitioned by the partition walls, that is, the openings surrounded by the partition walls to form “dots”.

“Ink” is a generic term for liquids that have optical and / or electrical functions after drying, curing, and the like.
In an optical element such as an organic EL element, a color filter of a liquid crystal element, and a TFT (Thin Film Transistor) array, dots as various components are pattern-printed by using an ink for forming the dots by an inkjet (IJ) method. Sometimes. “Ink” includes ink used in such applications.

“Ink repellency” is a property of repelling the above ink and has both water repellency and oil repellency. The ink repellency can be evaluated by, for example, a contact angle when ink is dropped. “Ink affinity” is a property opposite to ink repellency, and can be evaluated by the contact angle when ink is dropped as in the case of ink repellency. Alternatively, the ink affinity can be evaluated by evaluating the degree of ink wetting and spreading (ink wetting and spreading property) when ink is dropped on a predetermined standard.

“Dot” indicates the minimum area where optical modulation is possible in the optical element. In the organic EL element, the color filter of the liquid crystal element, and the optical element of the organic TFT array, 1 dot = 1 pixel in the case of monochrome display, and 3 dots (R (red), G (green), B (blue), etc.) = 1 pixel.

Hereinafter, embodiments of the present invention will be described. In addition, unless otherwise indicated in this specification,% represents the mass%.

[Negative photosensitive resin composition]
The negative photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a crosslinking agent (B), a photoacid generator (C), a fluoroalkylene group and / or a fluoroalkyl group, and a hydrolyzable group. And an ink repellent agent (D) containing a hydrolyzable silane compound (s1) having a monomer and / or a partially hydrolyzed (co) condensate.
The negative photosensitive resin composition of the present invention further contains a solvent (E) and other optional components as necessary.

(Alkali-soluble resin (A))
As alkali-soluble resin (A) in the negative photosensitive resin composition of this invention, it couple | bonds with crosslinking agent (B) by the effect | action of the acid which a photo-acid generator (C) generate | occur | produces by irradiation (exposure) of actinic light. Any cationic polymerization type alkali-soluble resin (A) that is crosslinked and insoluble in alkali can be used without particular limitation.

Examples of the alkali-soluble resin (A) include phenols and aldehydes, and if necessary, unmodified or modified novolak-type phenol resins and vinylphenol resins (hereinafter referred to as “polyphenols”) produced by polycondensation with various modifiers. , “Polyvinylphenol”), N- (4-hydroxyphenyl) methacrylamide copolymers, hydroquinone monomethacrylate copolymers, and the like. In addition, various alkali-soluble polymer compounds such as sulfonylimide polymers, carboxyl group-containing polymers, acrylic resins containing phenolic hydroxyl groups, acrylic resins having sulfonamide groups, and urethane resins may be used. it can.

As the alkali-soluble resin (A), a novolac type phenol resin or a vinyl phenol resin is preferable.

Examples of the phenols and aldehydes used for producing the novolak-type phenol resin include those described in International Publication No. 2013/133392, for example, in paragraphs [0021] and [0022].

Among the novolak type phenol resins, novolak type phenol resins using cresols, xylenols and the like are preferable as phenols from the viewpoints of easy availability and few metal impurities, and novolak type using cresols. Phenol resin (hereinafter also referred to as “cresol novolac resin”) is particularly preferable.

Examples of the polyvinylphenol include vinylphenol homopolymers, copolymers of vinylphenol and monomers copolymerizable therewith.
Polyvinylphenol is a vinylphenol such as 4-vinylphenol, 3-vinylphenol, 2-vinylphenol, 2-methyl-4-vinylphenol, 2,6-dimethyl-4-vinylphenol, or a combination of two or more. Then, it can be obtained by radical polymerization using a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide.

Examples of the monomer copolymerizable with vinylphenol include isopropenylphenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic imide, and vinyl acetate. Among these, a vinylphenol homopolymer is preferable, and a 4-vinylphenol homopolymer is particularly preferable.

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 500 to 20,000, particularly preferably 2,000 to 15,000. If the mass average molecular weight (Mw) of the alkali-soluble resin (A) is too low, the molecular weight does not increase sufficiently even if a cross-linking reaction occurs in the exposed region, so that it is easily dissolved in an alkali developer. If the mass average molecular weight (Mw) of the alkali-soluble resin (A) is too large, the difference in solubility in the alkali developer between the exposed area and the unexposed area becomes small, and it becomes difficult to obtain a good resist pattern.

In addition, a mass average molecular weight (Mw) means the mass average molecular weight converted on the basis of standard polystyrene, which is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. The number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

Commercially available products may be used as the alkali-soluble resin (A). For example, commercially available products of cresol novolak resin include EP4020G (Mw: 9,000 to 14,000), EPR5010G (Mw: 7,000 to 12,000). 500) (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), and commercial products of polyvinylphenol include Marcalinker M (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) and the like.

Alkali-soluble resin (A) may be used individually by 1 type, or may use 2 or more types together.
The content of the alkali-soluble resin (A) in the total solid content in the negative photosensitive resin composition is preferably 10 to 90% by mass, more preferably 30 to 85% by mass, and particularly preferably 40 to 80% by mass. When the content is in the above range, the developability of the negative photosensitive resin composition is improved.

(Crosslinking agent (B))
The crosslinking agent (B) binds to the alkali-soluble resin (A) by the action of the acid generated by the photoacid generator (C) upon irradiation (exposure) with actinic rays, thereby converting the alkali-soluble resin (A). It is a compound (acid-sensitive substance) that can be rendered insoluble in alkali by crosslinking.

Examples of the crosslinking agent (B) include low molecular crosslinking agents such as melamine-based, benzoguanamine-based, urea-based and isocyanate-based compounds, polyfunctional epoxide group-containing compounds, oxetane-based compounds, alkoxyalkylated melamine resins or alkoxyalkylated ureas. Polymer crosslinking agents such as alkoxyalkylated amino resins such as resins are preferred.

Examples of the melamine compounds include melamine, methoxymethylated melamine, ethoxymethylated melamine, propoxymethylated melamine, butoxymethylated melamine, hexamethylol melamine and the like.
Examples of the benzoguanamine compound include benzoguanamine and methylated benzoguanamine.
Examples of the urea compound include urea, monomethylol urea, dimethylol urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea, ethylene urea carboxylic acid, tetrakis (methoxymethyl) glycoluril and the like. Examples of the isocyanate compound include hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, toluene diisocyanate, bisisocyanate methylcyclohexane, bisisocyanate methylbenzene, and ethylene diisocyanate.

As the polyfunctional epoxide group-containing compound, one containing one or more benzene rings or heterocyclic rings and two or more epoxy groups in one molecule is preferable. For example, bisphenolacetone diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane , Triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 4,4′-bis (2,3-epoxypropoxy) -octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl meta-xylenediamine, etc. be able to.

As the oxetane compound, one containing two or more oxetanyl groups in one molecule is preferable. For example, xylylenebisoxetane, 3-ethyl-3 {[3-ethyloxetane-3-yl) methoxy] methyl} And oxetane.

Examples of the alkoxyalkylated melamine resin or alkoxyalkylated urea resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, Examples thereof include propoxymethylated urea resins and butoxymethylated urea resins.

As the cross-linking agent (B), a commercially available product may be used. For example, as a commercially available product of alkoxymethylated amino resin, PL-1170, PL-1174, UFR65, CYMEL300, CYMEL303 (manufactured by Mitsui Cytec) BX-4000, Nicalac MW-30, MX290, MW-100LM (manufactured by Sanwa Chemical Co., Ltd.) and the like.

The crosslinking agent (B) can be used alone or in combination of two or more. The blending amount is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass, and further preferably 10 to 25 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). If the amount of the crosslinking agent (B) used is too small, it is difficult for the crosslinking reaction to proceed sufficiently, and the residual film ratio of the resist pattern after development using an alkali developer decreases, Deformation such as meandering is likely to occur. When there is too much usage-amount of a crosslinking agent (B), there exists a possibility that the resolution may fall.

(Photoacid generator (C))
The photoacid generator (C) is not particularly limited as long as it is a compound that decomposes to generate an acid upon irradiation with an actinic ray. In the photosensitive resin composition using the cationic polymerization type alkali-soluble resin (A), an arbitrary compound can be selected from compounds generally used as a photoacid generator.

In the negative photosensitive resin composition of the present invention, the acid generated from the photoacid generator (C) is related to the bond between the alkali-soluble resin (A) and the crosslinking agent (B), and the ink repellent. It functions as a catalyst for the hydrolysis reaction of the fluorine-containing hydrolyzable silane compound (s1) contained in the agent (D). Usually, an acid catalyst is blended together with a composition containing a hydrolyzable silane compound. As a result, the reaction proceeds gradually and storage stability may become a problem. However, in the negative photosensitive resin composition of the present invention, it is necessary to add an acid separately from the photoacid generator (C). Storage stability is good.

The photoacid generator (C) is decomposed by irradiation with actinic rays to generate an acid. Specific examples of the actinic rays include high energy rays such as ultraviolet light, X-rays, and electron beams. When manufacturing the partition for optical elements using a negative photosensitive resin composition, i line (365 nm), h line (405 nm), and g line (436 nm) are used preferably for exposure. As the photoacid generator (C), it is preferable to select a photoacid generator having a large absorbance at the wavelength of light used for exposure.

Specific examples of the photoacid generator include onium salt photoacid generators and nonionic photoacid generators. Examples of the onium salt photoacid generator include onium salts and iodonium salt compounds of a compound having a triphenylsulfonium skeleton represented by the following formula (C1) or (C2). In the compounds (C1) and (C2), compounds in which the hydrogen atom of the phenyl group of the triphenylsulfonium skeleton is substituted can also be used as the photoacid generator.

In the formulas (C1) and (C2), Xa ^- and Xb ^- represent anions. Specific examples include phosphorus anions such as PF ₆ ⁻ , (R ^f1 ) _n PF _6-n ⁻ (R ^f1 is a fluoroalkyl group, n is 1 to 3), and the like. Anions such as R ^a SO ₃ ^— (R ^a is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 18 carbon atoms, part or all of which may be substituted with a fluorine atom). It is done. R ^a SO ₃ ^- The a ^{R a,} for _{_{_{_{example, -CF 3, -C 4 F 9}}}} , perfluoroalkyl groups such as _{_{_{-C 8 F 17, -C 6 F}}} 5 , etc. perfluoroalkyl aryl group, -Ph-CH ₃ (However, Ph represents a phenyl group.) And the like.
In these onium salts, the cation moiety absorbs the irradiated light, and the anion moiety becomes a source of acid generation.

In the compounds (C1) and (C2), for example, as a compound used when exposure is performed with i-line (365 nm), triphenylsulfonium / nonafluorobutanesulfonate represented by the following formula (C1-1), or The triarylsulfonium / PF ₆ salt and triarylsulfonium / special phosphorus salt represented by the following formulas (C2-1) and (C2-2) have large absorbance at a wavelength of 365 nm and are easily available. This is preferable.

In the formula (C2-2), R ^f1 is a fluoroalkyl group, and n is 1 to 3.

Examples of the iodonium salt-based compounds include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonate diphenyliodonium, p-toluenesulfonate (p-tert-butoxyphenyl). Examples thereof include phenyliodonium.

Commercially available onium salt photoacid generators can also be used. For example, TPSP-PFBS (compound (C1-1), trade name, manufactured by Toyo Gosei Co., Ltd.), CPI-100P (compound (C2-1), trade name, manufactured by San Apro), CPI-210S (compound (C2- 2), trade name, manufactured by San Apro Co., Ltd.).

Examples of the nonionic photoacid generator include a naphthalimide skeleton, a nitrobenzene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, a thiochitosan skeleton, a triazine skeleton, and a structure in which a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid, or the like is bonded. The compound which has is mentioned.

Specifically, as such a compound, a naphthalimide skeleton represented by the following formula (C3), the following formula (C4), the following formula (C5), the following formula (C6), and the following formula (C7), respectively. , A compound having a nitrobenzene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, or a thiochitosan skeleton, and a structure in which alkanesulfonic acid, arylsulfonic acid, or the like is bonded. In addition, a compound having a triazine skeleton and a chlorine atom represented by the following formula (C8) can be given. Furthermore, a sulfonyl compound of dialkylglyoxime represented by the following formula (C9), a sulfonyloxyiminoacetonitrile represented by the following formula (C10), and the like can be mentioned.
In the compounds (C3), (C4), (C6), and (C7), a compound in which a hydrogen atom of a benzene ring forming the skeleton of each compound is substituted also has a function as a photoacid generator.

R ^b1 to R ^b5 , R ^b7 and R ^b9 in formulas (C3) to (C7), (C9), and (C10) each independently may be partially or entirely substituted with a fluorine atom. It is a linear, branched or cyclic (including those having a partial cyclic structure) alkyl group having 1 to 12 carbon atoms or aryl group having 6 to 18 carbon atoms. Specific examples include perfluoroalkyl groups such as —CF ₃ , —C ₄ F ₉ , —C ₈ F ₁₇ , perfluoroaryl groups such as —C ₆ F ₅ , aryl groups such as —Ph—CH _{3, and the} like. . R ^b6 , R ^b8 and R ^b10 in the formulas (C8), (C9) and (C10) are each independently an organic group having 1 to 18 carbon atoms which may have a substituent.
In these nonionic photoacid generators, a portion where a chlorine atom, alkane sulfonic acid, aryl sulfonic acid, or the like is bonded serves as an acid generation source.

Examples of the nonionic photoacid generator include N-trifluoromethanesulfonic acid-1,8 represented by the following formula (C3-1) as a compound used for performing exposure with i-line (365 nm). -Naphthalimide, 2-Phenyl-2- (p-toluenesulfoxy) acetophenone represented by the following formula (C6-1), and 2- (4-Methoxystyryl) -4, represented by the following formula (C8-1) 6-bis (trichloromethyl) -1,3,5-triazine is preferred because of its high absorbance at a wavelength of 365 nm and easy availability.

Commercially available products can be used as the nonionic photoacid generator. For example, NHNI-TF (compound (C3-1), trade name, manufactured by Toyo Gosei Co., Ltd.) can be mentioned.

Acids generated by the action of light from these onium salt photoacid generators and nonionic photoacid generators are hydrochloric acid, alkane sulfonic acids, aryl sulfonic acids, and partially or fully fluorinated aryls. Examples thereof include sulfonic acid and alkane sulfonic acid.

As the photoacid generator (C), one type of the above compounds may be used alone, or two or more types may be used in combination.
The content of the photoacid generator (C) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Part is particularly preferred. By setting the content of the photoacid generator (C) within the above range, a partition wall having sufficient ink repellency and capable of forming a fine and accurate pattern can be obtained.

(Ink repellent agent (D))
The ink repellent agent (D) in the present invention contains a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group. The ink repellent agent (D) may be a hydrolyzable silane compound (s1) or a hydrolyzable silane compound (s1) and any other hydrolyzable silane compound (s1) as an optional component to be described later. It is good also as a mixture with a silane compound. The ink repellent agent (D) is preferably composed only of a hydrolyzable silane compound containing the hydrolyzable silane compound (s1).

The ink repellent agent (D) contains the hydrolyzable silane compound (s1) as a monomer and / or a partially hydrolyzed (co) condensate. That is, the ink repellent agent (D) may contain the hydrolyzable silane compound (s1) as a monomer or a partially hydrolyzed condensate thereof. Further, when the ink repellent agent (D) contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s1), a portion of the hydrolyzable silane compound (s1) and the other hydrolyzable silane compound. You may contain as a hydrolysis (co) condensate. Further, the hydrolyzable silane compound (s1) is a mixture of two or more selected from monomers, partially hydrolyzed condensates thereof, and partially hydrolyzed (co) condensates with other hydrolyzable silane compounds. It may be contained in the ink repellent agent (D).

Hereinafter, the ink repellent agent (D) containing a specific hydrolyzable silane compound means containing the hydrolyzable silane compound as a monomer and / or a partially hydrolyzed (co) condensate. . Here, the “monomer and / or partially hydrolyzed (co) condensate” is the same as the range defined above.

Since the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group, the ink repellent agent (D) forms a cured film using a negative photosensitive resin composition containing this. It has a property of shifting to the upper surface in the process (upper surface shifting property) and ink repellency. By using the ink repellent agent (D), the upper layer portion including the upper surface of the obtained partition wall is a layer in which the ink repellent agent (D) is present densely (hereinafter also referred to as “ink repellent layer”). Ink repellency is imparted to the upper surface of the partition wall. Such an ink repellent layer is mainly formed from a cured product of a hydrolyzable silane compound containing a hydrolyzable silane compound (s1), and therefore, even after an ink-philic treatment such as an ultraviolet ray / ozone cleaning treatment. It is advantageous in that excellent ink repellency can be maintained.

The content of fluorine atoms in the ink repellent agent (D) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass, from the viewpoints of upper surface migration and ink repellency. preferable. When the fluorine atom content of the ink repellent agent (D) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and when it is not more than the upper limit, the negative photosensitive resin composition Good compatibility with other components in the product.

The ink repellent agent (D) is preferably a mixture (hereinafter also referred to as “mixture (M)”) consisting essentially of a hydrolyzable silane compound containing the hydrolyzable silane compound (s1). Or a partially hydrolyzed (co) condensate of the mixture (M). The mixture (M) contains a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group as an essential component, and optionally other than the hydrolyzable silane compound (s1). Contains hydrolyzable silane compounds.

Note that the fact that the hydrolyzable silane compound is substantially a monomer does not mean that the entire amount of the hydrolyzable silane compound is a monomer, but a low level of about 2 to 10 mer. It means that even if it contains a partial hydrolysis condensate having a molecular weight, it may consist only of the partial hydrolysis condensate.

Examples of the hydrolyzable silane compound optionally contained in the mixture (M) include the following hydrolyzable silane compounds (s2) to (s4). Furthermore, other hydrolyzable silane compounds may be included. As the hydrolyzable silane compound optionally contained in the mixture (M), a hydrolyzable silane compound (s2) is particularly preferable. In addition, when ink repellent agent (D) contains a hydrolysable silane compound (s4), it is preferable that ink repellent agent (D) consists of a mixture (M). When the hydrolyzable silane compound (s4) is not included, the ink repellent agent (D) may consist of the mixture (M) or a partially hydrolyzed (co) condensate thereof.

Hydrolyzable silane compound (s2): a hydrolyzable silane compound in which four hydrolyzable groups are bonded to a silicon atom.
Hydrolyzable silane compound (s3); a hydrolyzable silane compound having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom.
Hydrolyzable silane compound (s4); a hydrolyzable silane compound having a cationically polymerizable group and a hydrolyzable group and containing no fluorine atom.
The hydrolyzable silane compounds (s1) to (s4) and other hydrolyzable silane compounds will be described below.

<1> Hydrolyzable silane compound (s1)
By using the hydrolyzable silane compound (s1), the ink repellent agent (D) has a fluorine atom in the form of a fluoroalkylene group and / or a fluoroalkyl group, and has excellent top surface migration and ink repellency. In order to make these properties of the hydrolyzable silane compound (s1) higher, the hydrolyzable silane compound (s1) is selected from the group consisting of a fluoroalkyl group, a perfluoroalkylene group and a perfluoroalkyl group. It is more preferable to have at least one, and it is particularly preferable to have a perfluoroalkyl group. A perfluoroalkyl group containing an etheric oxygen atom is also preferred. That is, the most preferable compound as the hydrolyzable silane compound (s1) is a compound having a perfluoroalkyl group and / or a perfluoroalkyl group containing an etheric oxygen atom.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, a group in which at least one hydrogen of the amino group is substituted with an alkyl group, and the like. An alkoxy group having 1 to 4 carbon atoms or a halogen atom is easily converted into a hydroxyl group (silanol group) by a hydrolysis reaction, and further a condensation reaction between molecules to form a Si—O—Si bond. Are preferred, a methoxy group, an ethoxy group or a chlorine atom is more preferred, and a methoxy group or an ethoxy group is particularly preferred.
A hydrolysable silane compound (s1) may be used individually by 1 type, or may use 2 or more types together.

As the hydrolyzable silane compound (s1), a compound represented by the following formula (dx-1) is preferable.
(A-R ^F11 ) _a -Si (R ^H11 ) _b X ¹¹ _(4-ab) (dx-1)
In formula (dx-1), R ^F11 is a divalent organic group having 1 to 16 carbon atoms, which may contain an etheric oxygen atom, including at least one fluoroalkylene group.
R ^H11 is a hydrocarbon group having 1 to 6 carbon atoms.
a is 1 or 2, b is 0 or 1, and a + b is 1 or 2.
A is a fluorine atom or a group represented by the following formula (Ia).
—Si (R ^H12 ) _c X ¹² _(3-c) (Ia)
R ^H12 is a hydrocarbon group having 1 to 6 carbon atoms.
c is 0 or 1;
X ¹¹ and X ¹² are each independently a hydrolyzable group.
If X ¹¹ there are a plurality, they may be the same or different from each other.
If X ¹² there are a plurality, they may be the same or different from each other.
When a plurality of ^{AR F11} are present, these may be different from each other or the same.

The compound (dx-1) is a fluorine-containing hydrolyzable silane compound having one or two bi- or trifunctional hydrolyzable silyl groups.

R ^H11 and R ^H12 are each independently preferably a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
In formula (dx-1), it is particularly preferred that a is 1 and b is 0 or 1.
Specific examples and preferred embodiments of X ¹¹ and X ¹² are as described above.

As the hydrolyzable silane compound (s1), a compound represented by the following formula (dx-1a) is particularly preferable.
TR ^F12 -Q ¹¹ -SiX ¹¹ ₃ (dx-1a)
In the formula (dx-1a), R ^F12 is a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms.
T is a fluorine atom or a group represented by the following formula (Ib).
-Q ¹² -SiX ¹² ₃ (Ib)
X ¹¹ and X ¹² are each independently a hydrolyzable group.
The three X ¹¹ may be different from each other or the same.
The three X ¹² may be different from each other or the same.
Q ¹¹ and Q ¹² each independently represent a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms.

In the formula (dx-1a), when T is a fluorine atom, R ^F12 is preferably a perfluoroalkylene group having 4 to 8 carbon atoms or a perfluoroalkylene group containing an etheric oxygen atom having 4 to 10 carbon atoms. A perfluoroalkylene group having 4 to 8 carbon atoms is more preferred, and a perfluoroalkylene group having 6 carbon atoms is particularly preferred.
In the formula (dx-1a), when T is a group (Ib), R ^F12 represents a perfluoroalkylene group having 3 to 15 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 3 to 15 carbon atoms. An alkylene group is preferred, and a perfluoroalkylene group having 4 to 6 carbon atoms is particularly preferred.

When R ^F12 is the above group, the ink repellent agent (D) has good ink repellency, and the compound (dx-1a) is excellent in solubility in a solvent.

^Examples of the structure of R ^F12 include a linear structure, a branched structure, a ring structure, a structure having a partial ring, and the like, and a linear structure is preferable.

Specific examples of R ^F12 include those described in paragraph [0043] of International Publication No. 2014/046209.

In the case where Q ¹¹ and Q ¹² indicate that Si is bonded to the right bond and R ^F12 is bonded to the left bond, specifically, — (CH ₂ ) _i1 — (i1 is 1 to 5) Integer)), —CH ₂ O (CH ₂ ) _i2 — (i2 is an integer of 1 to 4), —SO ₂ NR ¹ — (CH ₂ ) _i3 — (R ¹ is a hydrogen atom, a methyl group, or an ethyl group) I3 is an integer of 1 to 4, and the total number of carbon atoms of R ¹ and (CH ₂ ) _i3 is an integer of 4 or less), or — (C═O) —NR ¹ — ( CH ₂ ) _i4 — (R ¹ is the same as above, i4 is an integer of 1 to 4, and the total number of carbon atoms of R ¹ and (CH ₂ ) _i4 is an integer of 4 or less). The group represented is preferred. As Q ¹¹ and Q ¹² , — (CH ₂ ) _i1 — in which _i1 is an integer of 2 to 4 is more preferable, and — (CH ₂ ) ₂ — is particularly preferable.

When R ^F12 is a perfluoroalkylene group not containing an etheric oxygen atom, Q ¹¹ and Q ¹² are preferably groups represented by — (CH ₂ ) _i1 —. i1 is more preferably an integer of 2 to 4, and 2 is particularly preferable.
When R ^F12 is a perfluoroalkyl group containing an etheric oxygen atom, Q ¹¹ and Q ¹² include — (CH ₂ ) _i1 —, —CH ₂ O (CH ₂ ) _i2 —, —SO ₂ NR ¹ — ( A group represented by CH ₂ ) _i3 — or — (C═O) —NR ¹ — (CH ₂ ) _i4 — is preferred. Also in this case, as Q ¹¹ and Q ¹² , — (CH ₂ ) _i1 — is more preferable. i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.

When T is a fluorine atom, specific examples of the compound (dx-1a) include those described in paragraph [0046] of International Publication No. 2014/046209.

When T is a group (Ib), specific examples of the compound (dx-1a) include those described in paragraph [0047] of International Publication No. 2014/046209.

In the present invention, the compound (dx-1a) includes, among others, F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ or F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ O (CF ₂ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ is particularly preferred.

The content of the hydrolyzable silane compound (s1) in the mixture (M) is such that the fluorine atom content in the mixture or a partially hydrolyzed (co) condensate obtained from the mixture is 1 to 40% by mass. Preferably there is. The content of the fluorine atom is more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. When the content ratio of the hydrolyzable silane compound (s1) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. Compatibility with other components in the decomposable silane compound and the negative photosensitive resin composition is improved.

<2> Hydrolyzable silane compound (s2)
By including the hydrolyzable silane compound (s2) in which four hydrolyzable groups are bonded to silicon atoms in the mixture (M), the negative photosensitive resin composition containing the ink repellent (D) is cured. In the cured film, the film-forming property after the ink repellent agent (D) moves to the upper surface can be improved. That is, since the number of hydrolyzable groups in the hydrolyzable silane compound (s2) is large, the ink-repellent agent (D) is well condensed after the upper surface transition, and a thin film is formed on the entire upper surface. It is considered to be an ink repellent layer.
Further, when the hydrolyzable silane compound (s2) is included in the mixture (M), the ink repellent agent (D) is easily dissolved in a hydrocarbon-based solvent when a partially hydrolyzed condensate is obtained.
A hydrolysable silane compound (s2) may be used individually by 1 type, or may use 2 or more types together.

As the hydrolyzable group, those similar to the hydrolyzable group of the hydrolyzable silane compound (s1) can be used.

The hydrolyzable silane compound (s2) can be represented by the following formula (dx-2).
SiX ² ₄ (dx-2)
In formula (dx-2), X ² represents a hydrolyzable group, and four X ² may be different from each other or the same. As X ² , the same groups as those for X ¹¹ and X ¹² are used.

Specific examples of the compound (dx-2) include the following compounds. As the compound (dx-2), a partial hydrolysis condensate obtained by partial hydrolysis condensation of a plurality of, for example, 2 to 10 compounds in advance may be used as necessary.
Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OCH ₃ ) ₄ partial hydrolysis condensate, or Si (OC ₂ H ₅ ) ₄ partial hydrolysis condensate.

The content of the hydrolyzable silane compound (s2) in the mixture (M) is preferably 1 to 20 mol, particularly preferably 3 to 18 mol, relative to 1 mol of the hydrolyzable silane compound (s1). When the content ratio is at least the lower limit of the above range, the film forming property of the ink repellent agent (D) is good, and when it is at most the upper limit value, the ink repellent property of the ink repellent agent (D) is good.

<3> Hydrolyzable silane compound (s3)
When the hydrolyzable silane compound (s2) is used in the mixture (M), for example, in the partition formed by curing the photosensitive resin composition, a bulge may be formed at the end of the upper surface. This bulge is a minute level observed with a scanning electron microscope (SEM) or the like, but it was confirmed that the content of F and / or Si was larger than that of other portions.

The above bulge does not particularly hinder the partition walls or the like. However, the present inventor used a part of the hydrolyzable silane compound (s2) as a hydrolyzable silane compound (s3) having a small number of hydrolyzable groups. It has been found that the occurrence of the above swell can be suppressed by replacing with.
The film-forming property of the ink repellent agent (D) is increased by the reaction between silanol groups generated by the hydrolyzable silane compound (s2) having a large number of hydrolyzable groups, but due to its high reactivity, It is thought that the above climax occurs. Therefore, by replacing a part of the hydrolyzable silane compound (s2) with the hydrolyzable silane compound (s3) having a small number of hydrolyzable groups, the reaction between the silanol groups is suppressed, and the occurrence of the swell is generated. It is thought that it can be suppressed.
A hydrolysable silane compound (s3) may be used individually by 1 type, or may use 2 or more types together.
As the hydrolyzable group, those similar to the hydrolyzable group of the hydrolyzable silane compound (s1) can be used.

As the hydrolyzable silane compound (s3), a compound represented by the following formula (dx-3) is preferable.
(R ^H5 ) _j -SiX ⁵ _(4-j) (dx-3)
In the formula (dx-3), R ^H5 is a hydrocarbon group having 1 to 20 carbon atoms.
X ⁵ is a hydrolyzable group.
j is an integer of 1 to 3, preferably 2 or 3.
When a plurality of ^RH5 are present, these may be different from each other or the same.
If X ⁵ is present a plurality, they may be the same or different from each other.

Examples of R ^H5 include an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms when j is 1, and an alkyl group having 1 to 10 carbon atoms. Group, phenyl group and the like are preferable. When j is 2 or 3, R ^H5 is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms.
As X ⁵ , the same groups as those described above for X ¹¹ and X ¹² are used.

Specific examples of the compound (dx-3) include those described in paragraph [0063] of International Publication No. 2014/046209.

The content of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 1 to 10 mol, particularly preferably 3 to 8 mol, relative to 1 mol of the hydrolyzable silane compound (s1). When the content ratio is equal to or higher than the lower limit of the above range, it is possible to suppress the bulge of the end of the partition upper surface. When the amount is not more than the upper limit, the ink repellency of the ink repellent agent (D) is good.

<4> Hydrolyzable silane compound (s4)
The mixture (M) optionally contains a hydrolyzable silane compound (s4) which has a cationically polymerizable group and a hydrolyzable group and does not contain a fluorine atom. By including the hydrolyzable silane compound (s4) in the mixture (M), the ink repellent layer reacts with, for example, the crosslinking agent (B) contained in the photosensitive resin composition via the cationic polymerizable group. The effect of improving the fixability of the ink repellent agent (D) is obtained.

As the hydrolyzable silane compound (s4), a compound represented by the following formula (dx-4) is preferable.
(EQ ⁶ ) _s -Si (R ^H6 ) _t X ⁶ _(4- ^st ) (dx-4)
In the formula (dx-4), E is a cationically polymerizable group such as an oxetanyl group, an epoxy group, a glycidoxy group, or a 3,4-epoxycyclohexyl group.
Q ⁶ is a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms.
R ^H6 is a hydrocarbon group having 1 to 6 carbon atoms.
X ⁶ is a hydrolyzable group.
s is 1 or 2, t is 0 or 1, and s + t is 1 or 2.
When a plurality of EQ ⁶ are present, these may be different from each other or the same.
If X ⁶ is present a plurality, they may be the same or different from each other.

As X ⁶ , the same group as X ¹¹ and X ¹² is used.
Q ⁶ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms.
As R ^H6 , the same groups as those described above for R ^H11 and R ^H12 are used.

Specific examples of the compound (dx-4) include E— (CH ₂ ) ₂ —Si (OCH ₃ ) ₃ , E— (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ , E— (CH ₂ ) ₃ —. _{_{_{_{Si (OCH 2 CH 3) 3}}}} , E- (CH 2) 3 -Si (CH 3) (OCH 2 CH 3) 2 and the like. Among these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Etc. are preferred.

The content of the hydrolyzable silane compound (s4) in the mixture (M) is preferably 0 to 99 mol%, more preferably 15 to 80 mol%, and more preferably 15 to 50 mol% with respect to the total amount of the mixture (M). Particularly preferred. A hydrolysable silane compound (s4) may be used individually by 1 type, or may use 2 or more types together.

<5> Other hydrolyzable silane compounds The mixture (M) further comprises one or more hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s4), and the effect of the present invention. It can be included as long as it is not impaired. The total content of other hydrolyzable silane compounds in the mixture (M) is preferably 40 mol% or less, more preferably 10 mol% or less, based on the total amount of the mixture (M).

Other hydrolyzable silane compounds include a group having an ethylenic double bond and a hydrolyzable group, a hydrolyzable silane compound not containing a fluorine atom, a mercapto group and a hydrolyzable group. , A hydrolyzable silane compound containing no fluorine atom, an oxyalkylene group and a hydrolyzable group, a hydrolyzable silane compound containing no fluorine atom, an amino group or an isocyanate group and a hydrolyzable group, Examples include hydrolyzable silane compounds that do not contain fluorine atoms.

Specific examples of the hydrolyzable silane compound having a group having an ethylenic double bond and a hydrolyzable group and not containing a fluorine atom are described in, for example, paragraph [0057] of International Publication No. 2014/046209. And the like.

Specific examples of hydrolyzable silane compounds having a mercapto group and a hydrolyzable group and not containing a fluorine atom include HS- (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ , HS— (CH ₂ ) ₃ -Si (CH ₃ ) (OCH ₃ ) _{2 and the} like.

Specific examples of hydrolyzable silane compounds having an oxyalkylene group and a hydrolyzable group and not containing a fluorine atom include CH ₃ O (C ₂ H ₄ O) _k Si (OCH ₃ ) ₃ (polyoxyethylene group) Containing trimethoxysilane) (for example, k is about 10).

Examples of the hydrolyzable silane compound having an amino group and a hydrolyzable group and not containing a fluorine atom include C ₆ H ₅ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (phenylaminopropyltrimethoxysilane). ) And the like.
Examples of the hydrolyzable silane compound having an isocyanate group and a hydrolyzable group and not containing a fluorine atom include NCO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (isocyanatopropyltriethoxysilane). Can be mentioned.

<6> Ink repellent agent (D)
The ink repellent agent (D) is a mixture (M) or a partially hydrolyzed (co) condensate thereof.
As an example of the ink repellent agent (D), the compound (dx-1a) is contained as an essential component, the compound (dx-2) and the compound (dx-4) are contained as optional components, and a group in the compound (dx-1a) The mixture (M) whose T is a fluorine atom is mentioned. The content of each compound is preferably as described above.

When the ink repellent agent (D) is contained in the negative photosensitive resin composition in the form of the mixture (M) as described above, the step of partially hydrolyzing and condensing the ink repellent agent (D) in advance can be omitted. It is advantageous in terms of sex. Furthermore, it is preferable in terms of storage stability of the negative photosensitive resin composition.

As another example of the ink repellent agent (D), the compound (dx-1a) is contained as an essential component, the compound (dx-2) and the compound (dx-3) are contained as optional components, and the compound (dx-1a) The average composition formula of the ink repellent agent (D1), which is a partial hydrolysis-condensation product of the mixture (M) in which the group T is a fluorine atom, is shown in the following formula (II). Use of a partially hydrolyzed condensate as the ink repellent agent (D) is advantageous in that the residue in the development removal portion (opening portion) of the negative photosensitive resin composition can be reduced.

[T-R ^F12 -Q ¹¹ -SiO _3/2 ] _n1 · [SiO ₂ ] _n2 · [(R ^H5 ) _j —SiO _{(4-j) / 2} ] _n3 (II)
In the formula (II), n1 to n3 represent mole fractions of the respective structural units with respect to the total molar amount of the structural units. n1> 0, n2 ≧ 0, n3 ≧ 0, and n1 + n2 + n3 = 1. Other symbols are as described above. However, T is a fluorine atom.

The ink repellent agent (D1) 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 (II) is a chemical formula assuming that all of the hydrolyzable groups or silanol groups are siloxane bonds in the ink repellent agent (D1).
In the formula (II), the units derived from the compounds (dx-1a), (dx-2), and (dx-3) are assumed to be randomly arranged.

In the average composition formula represented by the formula (II), n1: n2: n3 is the same as the charged composition of the compounds (dx-1a), (dx-2), and (dx-3) in the mixture (M) To do.
The molar ratio of each component is preferably designed from the balance of the effects of each component.
n1 is preferably 0.02 to 0.4, particularly preferably 0.02 to 0.3, in such an amount that the fluorine atom content in the ink repellent agent (D1) is within the above-mentioned preferable range.
n2 is preferably 0 to 0.98 when n3 = 0, and preferably 0.05 to 0.6 when n3> 0.
n3 is preferably 0 to 0.5.
The preferred molar ratio of each component is the same when T in the compound (dx-1a) is a group (Ib).

Moreover, as for the preferable molar ratio of said each component, a mixture (M) contains a hydrolysable silane compound (s1), and optionally contains a hydrolysable silane compound (s2) and a hydrolysable silane compound (s3). In this case, the same applies. That is, the preferable amounts of the hydrolyzable silane compounds (s1) to (s3) in the mixture (M) for obtaining the ink repellent agent (D) correspond to the preferable ranges of n1 to n3, respectively.

The number average molecular weight (Mn) when the ink repellent agent (D) is a partially hydrolyzed condensate of the mixture (M) is preferably 500 or more, preferably less than 1,000,000, particularly preferably less than 10,000. .
When the number average molecular weight (Mn) is not less than the above lower limit, the ink repellent agent (D) is likely to shift to the upper surface when forming the partition using the photosensitive resin composition. If it is less than the above upper limit, the solubility of the ink repellent agent (D) in the solvent will be good.
The number average molecular weight (Mn) of the ink repellent agent (D) can be adjusted by the production conditions.

The ink repellent agent (D) can be produced by subjecting the mixture (M) described above to hydrolysis and condensation reaction by a known method.
In the above reaction, it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or an organic acid such as acetic acid, oxalic acid and maleic acid as a catalyst. Moreover, you may use alkali catalysts, such as sodium hydroxide and tetramethylammonium hydroxide (TMAH), as needed.
A known solvent can be used for the above reaction.
You may mix | blend the ink repellent agent (D) obtained by the said reaction with the photosensitive resin composition with the property of a solution with a solvent.
The content of the ink repellent agent (D) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Part by mass is particularly preferred. By setting the content of the ink repellent agent (D) in the above range, a partition having sufficient ink repellency on the upper surface can be obtained.

(Solvent (E))
When the negative photosensitive resin composition of the present invention contains the solvent (E), the viscosity is reduced, and the negative photosensitive resin composition can be easily applied to the substrate surface. As a result, a coating film of a negative photosensitive resin composition having a uniform film thickness can be formed.
A known solvent is used as the solvent (E). A solvent (E) may be used individually by 1 type, or may use 2 or more types together.

Examples of the solvent (E) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, and solvent naphtha. Among these, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable. Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol More preferred is at least one solvent selected from the group consisting of monoethyl ether acetate and 2-propanol.

The content ratio of the solvent (E) in the negative photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass with respect to the total amount of the composition.

(Other ingredients)
The negative photosensitive resin composition in the present invention may further include a colorant, a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, if necessary. You may contain 1 type (s) or 2 or more types of other additives, such as a plasticizer, an antifoamer, a leveling agent, and a repellency inhibitor.

The negative photosensitive resin composition of the present invention is obtained by mixing a predetermined amount of each of the above components. The negative photosensitive resin composition of the present invention has good storage stability.
Moreover, when the negative photosensitive resin composition of the present invention is used, it is possible to produce a partition wall having an ink repellent layer having a good ink repellency on the upper surface with a low exposure amount. Furthermore, even if the ink repellent layer is subjected to an ink affinity treatment such as an ultraviolet / ozone cleaning treatment, it is possible to produce a partition that can maintain excellent ink repellency.
The partition wall manufactured according to the present invention has an ink repellent layer having sufficient ink repellency on the upper surface, and can form a fine and highly accurate pattern.
According to the present invention, an optical element having dots that are uniformly formed by applying ink uniformly to an opening partitioned by a partition, specifically, an organic EL element, a quantum dot display, a TFT array, and a thin film solar A battery or the like can be provided.

[Partition wall]
The partition of this invention consists of hardened | cured material of said negative photosensitive resin composition formed in the form which partitions off the board | substrate surface into several division for dot formation. For example, the partition wall is formed by applying the negative photosensitive resin composition of the present invention on the surface of a base material such as a substrate, and if necessary, drying to remove the solvent and the like. This portion can be obtained by masking and exposing, and then heating and developing as necessary.

Hereinafter, an example of the manufacturing method of the partition wall according to the embodiment of the present invention will be described with reference to FIGS. 1A to 1D, but the manufacturing method of the partition wall is not limited to the following. In addition, the following manufacturing methods are demonstrated as a negative photosensitive resin composition containing a solvent (E).

As shown in FIG. 1A, a negative photosensitive resin composition is applied to one entire main surface of the substrate 1 to form a coating film 21. At this time, the ink repellent agent (D) is totally dissolved and uniformly dispersed in the coating film 21. The ink repellent agent (D) may be a hydrolyzable silane compound mixture (M) containing the hydrolyzable silane compound (s1) or a partially hydrolyzed (co) condensate thereof. In FIG. 1A, the ink repellent agent (D) is schematically shown, and does not actually exist in such a particle shape.

Next, as shown in FIG. 1B, the coating film 21 is dried to form a dry film 22. Examples of the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying. Although depending on the type of the solvent (E), in the case of heat drying, the heating temperature is preferably 50 to 120 ° C, more preferably 90 to 115 ° C.
In this drying process, the ink repellent agent (D) moves to the upper layer of the dry film. In addition, even if a negative photosensitive resin composition does not contain a solvent (E), the upper surface transfer of an ink repellent agent (D) is similarly achieved within a coating film.

Next, as shown in FIG. 1C, the dry film 22 is irradiated with actinic rays and exposed through a photomask 30 having a masking portion 31 having a shape corresponding to the opening surrounded by the partition walls. The film after the dry film 22 is exposed is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23 </ b> A is photocured, and the non-exposed portion 23 </ b> B is in the same state as the dry film 22. The exposure is performed when the dry film 22 absorbs actinic rays and the photoacid generator (C) is decomposed to generate an acid. Due to the generated acid, a reaction in which the alkali-soluble resin (A) and the crosslinking agent (B) are combined proceeds, and a curing reaction by hydrolysis condensation of the ink repellent agent (D) proceeds.

As the light to be irradiated, excimer laser such as visible light; ultraviolet light; far ultraviolet light; KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Kr ₂ excimer laser light, KrAr excimer laser light, and Ar ₂ excimer laser light. Examples include light; X-ray; electron beam.
The light to be irradiated is preferably light having a wavelength of 100 to 600 nm, more preferably light having a wavelength of 300 to 500 nm, and particularly preferably light containing i-line (365 nm), h-line (405 nm), or g-line (436 nm). Moreover, you may cut light below 330 nm as needed.

The exposure method includes full-surface batch exposure, scan exposure, and the like. You may expose in multiple times with respect to the same location. At this time, the multiple exposure conditions may or may not be the same.

Exposure amount, In any of the above exposure method, for example, preferably 5 ~ 1,000mJ / cm ^2, more preferably 5 ~ 500mJ / cm ^2, more preferably ^{5 ~ 300mJ / cm 2, 5} ~ 200mJ / cm ² is particularly preferable, and 5 to 50 mJ / cm ² is most preferable. The exposure amount is appropriately optimized depending on the wavelength of light to be irradiated, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the like. The negative photosensitive resin composition of the present invention can be sufficiently cured with such a low exposure amount.

The exposure time per unit area is not particularly limited, and is designed from the exposure power of the exposure apparatus to be used, the required exposure amount, and the like. In the case of scan exposure, the exposure time is determined from the light scanning speed.
The exposure time per unit area is usually about 1 to 60 seconds, preferably 1 to 30 seconds.

After the exposure, heating may be performed for the purpose of diffusing the acid generated by the decomposition of the photoacid generator (C) into the dry film 22 and performing the reaction uniformly in the film. The heating conditions are 70 to 120 ° C., preferably 90 to 115 ° C., about 1 to 5 minutes, preferably 1 to 3 minutes.

Next, as shown in FIG. 1D, development using an alkali developer is performed to form the partition wall 4 composed only of a portion corresponding to the exposed portion 23A of the exposed film 23. The opening 5 surrounded by the partition wall 4 is a portion where the non-exposed portion 23 </ b> B exists in the exposed film 23. FIG. 1D shows a state after the non-exposed portion 23B is removed by development. As described above, the non-exposed portion 23B is dissolved by an alkali developer in a state where the ink repellent agent (D) moves to the upper layer portion and the ink repellent agent (D) is hardly present in the lower layer. Therefore, the ink repellent agent (D) hardly remains in the opening 5.

In the partition 4 shown in FIG. 1D, the uppermost layer including the upper surface is the ink repellent layer 4A. At the time of exposure, the ink repellent agent (D) present at a high concentration in the uppermost layer is cured using the acid generated by the photoacid generator (C) as a catalyst to form an ink repellent layer. Further, at the time of exposure, the alkali-soluble resin (A) and the crosslinking agent (B) present around the ink repellent agent (D) and other photo-curing components are also strongly photocured, and the ink repellent agent (D ) And the ink repellent layer.

Further, when the ink repellent agent (D) contains the hydrolyzable silane compound (s4), the ink repellent agent (D) is bonded to each other, and at the same time, the alkali-soluble resin (A) and the crosslinking agent (B), and the others The ink repellent layer 4A in which the ink repellent agent (D) is firmly bonded is formed by photocuring with the photocuring component.

In any of the above cases, the alkali-soluble resin (A), the crosslinking agent (B), and other photo-curing components are photocured mainly on the lower side of the ink-repellent layer 4A. A layer 4B containing almost no is formed.
Thus, the ink repellent agent (D) is sufficiently fixed to the partition including the ink repellent layer 4A and the lower layer 4B, and therefore hardly migrates to the opening during development.

After the development, the partition 4 may be further heated. The heating temperature is preferably 130 to 250 ° C., more preferably 150 to 230 ° C., and the heating time is about 20 to 60 minutes, preferably 30 to 60 minutes.
By heating, the partition 4 is hardened and the ink repellent agent (D) is more firmly fixed in the ink repellent layer 4A.

The thus obtained cured resin film and partition 4 of the present invention have good ink repellency on the upper surface even when exposure is performed at a low exposure amount. In the partition 4, the ink repellent (D) hardly exists in the opening 5 after development, and the uniform coating property of the ink in the opening 5 can be sufficiently ensured.

In order to more reliably obtain the ink affinity of the opening 5, the partition wall is used to remove a development residue or the like of the negative photosensitive resin composition that may be present in the opening 5 after heating. The substrate 1 with 4 may be subjected to ultraviolet / ozone treatment. In this case, the ink repellent layer above the partition obtained using the negative photosensitive resin composition of the present invention has sufficient resistance to ultraviolet / ozone treatment.

The partition formed from the negative photosensitive resin composition of the present invention (hereinafter also referred to as the partition of the present invention) preferably has a width of, for example, 100 μm or less, and particularly preferably 20 μm or less. Usually, the width is preferably 5 μm or more. The distance between adjacent partition walls (pattern width) is preferably 300 μm or less, and particularly preferably 100 μm or less. Usually, the distance between adjacent barrier ribs (pattern width) is preferably 10 μm or more.
The height of the partition wall is preferably 0.05 to 50 μm, particularly preferably 0.2 to 10 μm.

The barrier ribs of the present invention are particularly excellent as barrier ribs for organic EL elements because the edge portions when formed in the above width have few irregularities and are excellent in linearity, and such highly accurate pattern formation is possible. Useful.

The partition of the present invention can be used as a partition having the opening as an ink injection region when pattern printing is performed by the IJ method (inkjet method). When pattern printing is performed by the IJ method, if the partition wall of the present invention is formed and used so that the opening thereof coincides with a desired ink injection region, the partition top surface has good ink repellency. It is possible to suppress ink from being injected into an undesired opening, that is, an ink injection region, beyond the partition wall. In addition, since the opening surrounded by the partition wall has good ink wetting and spreading properties, it is possible to print the ink uniformly in a desired region without causing white spots or the like.

If the partition wall of the present invention is used, pattern printing by the IJ method can be performed with precision as described above. Therefore, the partition wall of the present invention has an optical element, particularly an organic EL element, a quantum dot display, a TFT array, etc., having a partition wall positioned between dots adjacent to a plurality of dots on the substrate surface on which dots are formed by the IJ method. It is useful as a partition wall.

[Optical element]
As an optical element of the embodiment of the present invention, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell having a plurality of dots and a partition wall of the present invention located between adjacent dots on the substrate surface can be mentioned. . In the organic EL element, quantum dot display, TFT array, or thin film solar cell, the dots are preferably formed by the IJ method.

The organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode, and the partition of the present invention is used for a partition that separates the organic light emitting layer, a partition that separates the organic TFT layer, and a coating type oxide semiconductor. It can be used for separating partition applications.

In addition, the organic TFT array element is a semiconductor layer including a plurality of dots arranged in a matrix in plan view, each pixel having a pixel electrode and a TFT as a switching element for driving it, and including a TFT channel layer. An element in which an organic semiconductor layer is used. The organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.

For example, an organic EL element which is an optical element according to an embodiment of the present invention will be described below by using an IJ method to form dots in the opening using the partition obtained above.
In addition, the formation method of the dot in the organic EL element etc. which are the optical elements of embodiment of this invention is not limited to the following.
2A and 2B schematically show a method for manufacturing an organic EL element using the partition walls 4 formed on the substrate 1 shown in FIG. 1D. Here, the partition 4 on the substrate 1 is formed such that the opening 5 matches the dot pattern of the organic EL element to be manufactured.

As shown in FIG. 2A, ink 10 is dropped from the inkjet head 9 into the opening 5 surrounded by the partition wall 4 and a predetermined amount of ink 10 is injected into the opening 5. As the ink, known inks for organic EL elements are appropriately selected and used in accordance with the function of dots.

Next, depending on the type of the ink 10 used, for example, a process such as drying and / or heating is performed to remove or cure the solvent, and as shown in FIG. The organic EL element 12 in which 11 is formed is obtained.

In particular, an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, which is an optical element according to an embodiment of the present invention, is formed in the opening partitioned by the partition in the manufacturing process by using the partition of the present invention. Ink can be spread evenly and uniformly without unevenness, which makes it possible to have dots formed accurately.

The organic EL element can be manufactured, for example, as follows, but is not limited thereto.
A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The translucent electrode is patterned as necessary.
Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in plan view along the outline of each dot by photolithography including coating, exposure and development.
Next, the materials of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are respectively applied and dried in the dots by the IJ method, and these layers are sequentially stacked. To do. The kind and number of organic layers formed in the dots are appropriately designed.
Finally, a reflective electrode such as aluminum is formed by vapor deposition or the like.

Further, for example, in the manufacture of the organic EL element, the quantum dot display can be manufactured in the same manner except that the light emitting layer is a quantum dot layer, but is not limited thereto.

Furthermore, the optical element of the embodiment of the present invention can be applied to, for example, a blue light conversion type quantum dot display manufactured as follows.
A negative photosensitive resin composition of the present invention is used for a light-transmitting substrate such as glass, and partition walls are formed in a lattice shape in plan view along the outline of each dot.

Next, a nanoparticle solution that converts blue light into green light by the IJ method, a nanoparticle solution that converts blue light into red light, and a blue color ink as necessary are applied to the dots and dried. Make a module. A liquid crystal display having excellent color reproducibility can be obtained by using a light source that emits blue as a backlight and using the module as a color filter alternative.

The TFT array can be manufactured, for example, as follows, but is not limited thereto.
A gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This gate electrode is patterned as necessary.

Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like. A source electrode and a drain electrode may be formed over the gate insulating film. The source electrode and the drain electrode can be manufactured by forming a metal thin film such as aluminum, gold, silver, copper, or an alloy thereof by, for example, vacuum deposition or sputtering. As a method of patterning the source electrode and the drain electrode, after forming a metal thin film, a resist is applied, exposed and developed, and the resist is left in a portion where the electrode is to be formed, and then phosphoric acid or aqua regia is used. There is a technique of removing the exposed metal and finally removing the resist. In addition, when a metal thin film such as gold is formed, a resist is applied in advance, exposed and developed, and the resist is left in a portion where the electrode is not desired to be formed. There is also a technique for removing the photoresist. Alternatively, the source electrode and the drain electrode may be formed using a metal nanocolloid such as silver or copper by a method such as an inkjet method.

Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice pattern in plan view along the outline of each dot by photolithography including coating, exposure and development.
Next, a semiconductor solution is applied in the dots by the IJ method, and the solution is dried to form a semiconductor layer. As this semiconductor solution, an organic semiconductor solution, an inorganic coating type oxide semiconductor solution, or the like can also be used. The source electrode and the drain electrode may be formed using a method such as an ink jet method after the semiconductor layer is formed.
Finally, a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1, 2, and 3 are examples, and example 4 is a comparative example.

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 measurement device (manufactured by Tosoh Corporation, device name: HLC- 8320 GPC), 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]
According to JIS R3257 “Test method for wettability of substrate glass surface”, PGMEA droplets were placed at three locations on the measurement surface on 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))
EP4020G (trade name, manufactured by Asahi Organic Materials Co., Ltd., cresol novolak resin, (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (angstrom / second)).
(Crosslinking agent (B))
MW-100LM; Nicalak MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd., methylated melamine resin based on hexamethoxymethylmelamine)
(Photoacid generator (C)
CPI-210S; trade name, manufactured by San Apro, a compound represented by the above formula (C2-2).

(Hydrolyzable silane compound as a raw material for the ink repellent agent (D))
Compound (d-11) corresponding to the hydrolyzable silane compound (dx-1a): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
Compound (d-21) corresponding to the hydrolyzable silane compound (dx-2): Si (OC ₂ H ₅ ) ₄ .
Compound (d-31) corresponding to the hydrolyzable silane compound (dx-3): CH ₃ Si (OCH ₃ ) ₃ .
Compound (d-32) corresponding to the hydrolyzable silane compound (dx-3): C ₆ H ₅ Si (OCH ₃ ) ₃ .

(Compound used for production of ink repellent agent (Dcf) used in Comparative Example (addition polymer containing structural unit derived from unsaturated compound having fluoroalkyl group having 4 to 6 carbon atoms))
_{_{C6FMA: CH 2 = C (CH}} 3) COOCH 2 CH 2 (CF 2) 6 F
MAA: methacrylic acid GMA: glycidyl methacrylate MMA: methyl methacrylate MEK: methyl ethyl ketone (solvent)
V-65: (trade name, manufactured by Wako Chemical Industries, Ltd. (2,2′-azobis (2.4dimethylvaleronitrile) (polymerization initiator))

(Solvent (E))
PGMEA: Propylene glycol monomethyl ether acetate.
PGME: Propylene glycol monomethyl ether.

[Synthesis Example 1: Synthesis of ink repellent agent (D1) and preparation of (D1-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.38 g of the compound (d-11) and 2.35 g of the compound (d-21) were placed, and a raw material mixture of the ink repellent agent (D1) was added. Obtained. Next, 5.56 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).

1.71 g of 1.0 mass% nitric acid aqueous solution was dropped into the obtained raw material solution while stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to obtain a (D1-1) solution that was a PGME solution containing 10% by mass of (D1). The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (D1-1) is 20.0 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (D1-1) was 773.

[Synthesis Example 2: Synthesis of ink repellent agent (D2) and preparation of (D2-1) liquid]
A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of the compound (d-11), 1.11 g of the compound (d-21), and 0.72 g of the compound (d-31). Thus, a raw material mixture of the ink repellent agent (D2) was obtained. Next, 6.36 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).

1.43g of 1.0 mass% nitric acid aqueous solution was dripped at the obtained raw material solution, stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to obtain a (D2-1) solution that was a PGME solution containing 10% by mass of (D2). The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (D2-1) is 20.0 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (D2-1) was 810.

[Synthesis Example 3: Synthesis of ink repellent agent (D3) and preparation of (D3-1) liquid]
In a 50 cm ³ three-necked flask equipped with a stirrer, 0.38 g of the compound (d-11), 0.74 g of the compound (d-21), and 0.71 g of the compound (d-32) were placed. Thus, a raw material mixture of the ink repellent agent (D1) was obtained. Next, 7.18 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).

0.99 g of 1.0 mass% nitric acid aqueous solution was dropped into the obtained raw material solution while stirring at room temperature. After completion of the dropwise addition, the mixture was further stirred for 5 hours to obtain a liquid (D3-1) which was a PGME solution containing 10% by mass of (D3). The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the liquid (D3-1) is 20.0 mass%. The number average molecular weight (Mn) of the composition excluding the solvent of the solution (D3-1) was 880.

[Synthesis Example 4: Synthesis of ink repellent agent (Dcf) and preparation of (Dcf-1) solution]
An autoclave with an internal volume of 1 L equipped with a stirrer was charged with 420.0 g of MEK, 86.4 g of C6FMA, 18.0 g of MAA, 21.6 g of GMA, 54.0 g of MMA and 0.8 g of V-65. The mixture was charged and polymerized at 50 ° C. for 24 hours with stirring in a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the resulting crude copolymer solution for reprecipitation purification, followed by vacuum drying. To the obtained solid, 14643 g of PGMEA was added and stirred to obtain a liquid (Dcf-1) which is a PGMEA solution containing 10% by mass of an ink repellent agent (Dcf). The obtained fluorine-containing content (mass% of fluorine atoms) of the composition excluding the solvent of the (Dcf-1) solution is 27.4 mass%. The composition excluding the solvent in the (Dcf-1) solution had a number average molecular weight (Mn) of 49,325.

In the ink repellent agent solutions obtained in Synthesis Examples 1 to 4, the fluorine atom content and the number average molecular weight (Mn) of the ink repellent agent (D) are the same as the charged amount composition (mol%) of the ink repellent agent (D). In addition, it is shown in Table 1 together.

[Example 1]
(Preparation of negative photosensitive resin composition)
0.967 g of liquid (D1-1) (solid content is 0.097 g, the rest is PGME (solvent)), 19.34 g of EP4020G, 4.84 g of MW-100LM, 0.73 g of CPI-210S, and PGMEA Was put in a stirring vessel of 500 cm ³ and stirred for 30 minutes to prepare a negative photosensitive resin composition 1.

(Manufacture of cured film (partition))
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.

After applying the negative photosensitive resin composition 1 to the cleaned glass substrate surface using a spinner, a drying treatment is performed on a hot plate at a temperature of 100 ° C. for 2 minutes to obtain a film thickness of 2.5 μm. A dry film was formed. A gap of 50 μm is formed on the surface of the obtained dry film from the film side through a photomask having a hole pattern (2.5 cm × 5 cm) (a photomask that is irradiated with light other than the pattern area). Open and irradiated with ultraviolet light from a high pressure mercury lamp at 25 mW / cm ² for 1 second, 2 seconds, 5 seconds or 10 seconds.

Next, the exposed glass substrate was developed by immersing it in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds, and the dry film of the unexposed part was washed away with water and dried. Next, by heating this on a hot plate at 230 ° C. for 50 minutes, four types of glass in which a cured film (partition) of the negative photosensitive resin composition 1 was formed in a region excluding the hole pattern portion. A substrate (1) was obtained.

(Evaluation)
The following evaluation was performed about the glass substrate (1) in which the negative photosensitive resin composition 1 obtained above and the cured film (partition) were formed. The evaluation results are shown in Table 2 together with the composition of the negative photosensitive resin composition.
<Ink repellency (partition wall), ink affinity (dot), development residue>
The cured film of the obtained glass substrate (1), that is, the contact angle with respect to PGMEA of the partition wall surface (exposed part) and the part where the dry film (unexposed part) was removed by development, that is, the dot part (glass substrate surface) The contact angle with water was measured. At this time, the development residue was also evaluated based on the contact angle of the dot portion with water. Evaluation was performed according to the following criteria.

(Standard)
○ (Good): Water contact angle is less than 30 degrees
X (Bad): Water contact angle of 30 degrees or more

After that, for the glass substrate (1) in which the cured film was produced with an exposure time of 10 seconds, the entire surface on which the cured film was formed was irradiated with ultraviolet rays / ozone for 1 minute. The contact angle to PGMEA on the surface of the cured film (partition) after irradiation for 1 minute and the contact angle to water on the glass substrate surface were measured. The measurement method is the same as described above.

<Storage stability>
The negative photosensitive resin composition was stored in a glass screw bottle at 23 ° C. (room temperature) for one month. After storage for one month, a negative photosensitive resin composition is applied to the surface of a 10 cm × 10 cm glass substrate that has been cleaned in the same manner as in the production of the above cured film (partition wall) using a spinner to form a coating film did. Furthermore, it was dried on a hot plate at 100 ° C. for 2 minutes to form a dry film having a thickness of 2 μm. The appearance of the dried film was visually observed and evaluated according to the following criteria.

(Standard)
○ (Good): There are 5 or less foreign matters on the dry film.
X (defect): There were 6 or more foreign matters on the dry film, and radial streaks were observed from the center of the glass substrate.

[Example 2]
Negative photosensitive resin composition 2 and a cured film of negative photosensitive resin composition 2 were formed in the same manner as in Example 1 except that (D2-1) liquid was used instead of (D1-1) liquid. A glass substrate (2) was prepared and evaluated in the same manner as in Example 1.

[Example 3]
The negative photosensitive resin composition 3 and a cured film of the negative photosensitive resin composition 3 were formed in the same manner as in Example 1 except that the (D3-1) liquid was used instead of the (D1-1) liquid. A glass substrate (3) was prepared and evaluated in the same manner as in Example 1.

[Example 4]
The negative photosensitive resin composition 4 and the cured film of the negative photosensitive resin composition 4 were formed in the same manner as in Example 1 except that the (Dcf-1) liquid was used instead of the (D1-1) liquid. A glass substrate (4) was prepared and evaluated in the same manner as in Example 1.
The evaluation results of Examples 2 to 4 are shown in Table 2 together with the composition of the negative photosensitive resin composition.

From Table 2, the cured films obtained in Examples 1, 2 and 3 used the ink repellent agent of the present invention, and therefore showed good ink repellency even after low exposure, and after UV / ozone irradiation. It can be seen that high ink repellency is maintained and the glass substrate surface has good hydrophilicity. Moreover, it turns out that storage stability is also high. On the other hand, in Example 4, since the ink repellent agent not according to the present invention was used, it was found that high ink repellency could not be maintained after ultraviolet / ozone irradiation.

The partition formed using the negative photosensitive resin composition of the present invention has good ink repellency and can retain ink repellency even after ultraviolet / ozone irradiation, and the openings partitioned by the partition It is useful for optical elements having dots that are uniformly coated with ink and formed with high precision. Further, the negative photosensitive resin composition of the present invention can be used for various optical elements, particularly organic layers such as a light emitting layer of organic EL elements, quantum dot layers and hole transport layers of quantum dot displays, and conductors of TFT arrays Composition for forming barrier ribs for pattern printing by the IJ method in patterns, semiconductor patterns, organic semiconductor layers forming TFT channel layers, gate electrodes, source electrodes, drain electrodes, gate wirings and source wirings, thin film solar cells, etc. It can be suitably used as a product.

It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2014-092092 filed on April 25, 2014 is cited here as the disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 21 ... Coating film, 22 ... Dry film, 23 ... Exposure film | membrane, 23A ... Exposure part, 23B ... Non-exposure part, 4 ... Partition, 4A ... Ink-repellent layer, 5 ... Opening part, 31 ... Masking part, 30: Photomask, 9 ... inkjet head, 10 ... ink, 11 ... dot, 12 ... organic EL element.

Claims

An alkali-soluble resin (A), a crosslinking agent (B), a photoacid generator (C), a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group A negative photosensitive resin composition comprising: an ink repellent agent (D) contained as a monomer and / or a partially hydrolyzed (co) condensate.
The negative photosensitive resin composition according to claim 1, wherein the content of fluorine atoms in the ink repellent agent (D) is 1 to 40% by mass.
The ink repellent agent (D) contains a hydrolyzable silane compound (s2) in which four hydrolyzable groups are bonded to a silicon atom as a monomer and / or a partially hydrolyzed (co) condensate. The negative photosensitive resin composition according to 1 or 2.
The ink repellent agent (D) contains a hydrolyzable silane compound (s3) having only a hydrocarbon group and a hydrolyzable group as a monomer and / or a partially hydrolyzed (co) condensate. The negative photosensitive resin composition of any one of 3.
The ink repellent agent (D) has a cationically polymerizable group and a hydrolyzable group, and a monomer and / or partially hydrolyzed (co) condensation of a hydrolyzable silane compound (s4) containing no fluorine atom. The negative photosensitive resin composition according to any one of claims 1 to 4, which is contained as a product.
The negative photosensitive resin according to any one of claims 1 to 5, wherein the content of the alkali-soluble resin (A) is 10 to 90% by mass in the total solid content in the negative photosensitive resin composition. Resin composition.
Content of the crosslinking agent (B) and the photoacid generator is 2 to 50 parts by mass and 0.1 to 20 parts by mass, respectively, with respect to 100 parts by mass of the alkali-soluble resin (A). Item 7. The negative photosensitive resin composition according to any one of Items 1 to 6.
The negative type according to any one of claims 1 to 7, wherein the content of the ink repellent agent (D) is 0.01 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Photosensitive resin composition.
Further, it comprises at least one solvent (E) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate and 2-propanol. The negative photosensitive resin composition of any one.
The negative photosensitive resin composition according to any one of claims 1 to 9, wherein the content of the solvent (E) is 50 to 99 mass% with respect to the total amount of the negative photosensitive resin composition.
A partition formed of a cured film of the negative photosensitive resin composition according to any one of claims 1 to 10, wherein the partition is formed so as to partition the substrate surface into a plurality of sections for dot formation.
The partition wall according to claim 11, wherein the width is 100 μm or less, the distance between the partition walls (pattern width) is 300 μm or less, and the height is 0.05 to 50 μm.
An optical element having a plurality of dots on a substrate surface and a partition located between adjacent dots, wherein the partition is formed by the partition according to claim 11 or 12.
The optical element according to claim 13, wherein the dots are formed by an inkjet method.
The optical element according to claim 13 or 14, wherein the optical element is an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.