TWI655501B - Negative photosensitive resin composition, partition and optical component - Google Patents

Abstract

Provided is a negative-type photosensitive resin composition that can be used for manufacturing a partition wall. The partition wall can form an ink repellent layer having sufficient ink repellency on an upper surface at a low exposure amount, and can maintain an excellent Ink repellency; and a partition wall of an optical element, which has an ink repellent layer on the upper surface, can form a fine and high-precision pattern, and can maintain excellent ink repellency even after being ink-friendly; and, The optical element has dots, and the dots are precisely formed by uniformly applying printing ink to the opening portion divided by the partition wall.

A negative photosensitive resin composition containing an alkali-soluble resin, a cross-linking agent, a photoacid generator, and an ink repellent containing a hydrolyzable silane compound, the hydrolyzable silane compound having a fluoroalkylene group and / or a fluoroalkyl group And a hydrolyzable group; a hardened film and a partition wall formed using the negative photosensitive resin composition; and an optical element having the plurality of points on the surface of the substrate and the aforementioned partition wall located between adjacent points.

Description

Negative photosensitive resin composition, partition wall and optical element Field of invention

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

Background of the invention

In the production of organic EL (Electro-Luminescence) elements, quantum dot displays, thin film transistors (TFTs) arrays, and thin-film solar cells, optical elements such as light-emitting layers A method of pattern printing by an inkjet (IJ) method. In this method, a partition wall is provided along the outline of the point to be formed, and a printing ink containing an organic layer material is injected into a partition area (hereinafter also referred to as an "opening portion") surrounded by the partition wall to dry and / Or heating to form a desired pattern.

In the above method, in order to prevent the ink mixing between adjacent dots and the ink to be evenly applied during dot formation, the upper surface of the partition must have ink repellency, and the dot formation surrounded by the partition including the side of the partition is used for the formation of dots. The opening must be ink-friendly.

Therefore, in order to obtain a partition wall having an ink repellent property on the upper surface, it is known to use a photosensitive resin composition containing an ink repellent agent to shape it by photolithography. A method of forming a wall next to a dot pattern. The photosensitive resin is roughly classified into a radical polymerization type photosensitive resin and a cation polymerization type photosensitive resin. However, it is known that in the radical polymerization type photosensitive resin composition, the hardening of the outermost surface is hindered by oxygen. Therefore, in order to use the photosensitive resin composition containing an ink repellent agent to make sufficient ink repellency on the outermost surface, a large amount of exposure is required, and as a result, sensitivity, patterned shape, and residues are affected.

On the other hand, when a cationically polymerizable photosensitive resin is used, it is less susceptible to the influence of oxygen on surface hardening as described above, and can impart ink repellency to the surface with a small amount of exposure. In this way, a composition obtained by combining a cationically polymerizable photosensitive resin and an ink repellent is described in Patent Document 1, which is a composition obtained by combining a liquid repellent with a cationically polymerizable photosensitive resin. It is composed of an addition polymer having a fluoroalkyl group having 4 to 6 carbon atoms and containing a structural unit derived from an unsaturated compound.

Prior art literature Patent literature

Patent Document 1: International Publication No. 2012/057058

Summary of invention

The liquid-repellent agent described in Patent Document 1 can be fixed to the surface of the partition wall with a small amount of exposure when the partition wall is formed. However, after the partition wall is formed to remove impurities remaining in the spots, for example, washing with an alkaline aqueous solution Treatment, UV cleaning treatment, UV / ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment, oxygen plasma treatment, etc. Patience is not enough.

The present invention has been made from the foregoing viewpoint, and an object thereof is to provide a negative photosensitive resin composition which can be used for manufacturing a partition wall, and the negative photosensitive resin composition can be formed on the upper surface of the partition wall with a low exposure amount and has sufficient Ink-repellent ink-repellent layer, and the ink-repellent layer can maintain excellent ink-repellency even after ink-repellent treatment.

The problem of the present invention is also to provide a partition wall of an optical element. The partition wall has an ink repellent layer with sufficient ink repellency on the upper surface, which can form a fine and high-precision pattern, and can maintain excellent repellency even after being ink-friendly. Ink.

Another object of the present invention is to provide an optical element having dots, which are accurately formed by uniformly coating printing ink in an opening portion divided by a partition wall. Specifically, the optical element is an organic EL element, a quantum dot display, TFT array or thin film solar cell.

The present invention provides a negative-type photosensitive resin composition having the following structures [1] to [15], a partition wall, and an optical element.

[1] A negative photosensitive resin composition containing an alkali-soluble resin (A), a crosslinking agent (B), a photoacid generator (C), and an ink repellent (D), the ink repellent (D) containing The hydrolyzable silane compound (s1) is a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group.

[2] The negative photosensitive resin composition according to the above [1], wherein the fluorine atom content rate in the ink repellent (D) is 1 to 40% by mass.

[3] The negative photosensitive resin composition according to the above [1] or [2], wherein The ink repellent (D) contains a hydrolyzable silane compound (s2) as a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane compound (s2) has four hydrolyzable groups bonded to a silicon atom.

[4] The negative photosensitive resin composition according to any one of the above [1] to [3], wherein the ink repellent (D) contains a hydrolyzable silane compound (s3) as a monomer and / or is partially hydrolyzed (Co) condensate, and the hydrolyzable silane compound (s3) has only a hydrocarbon group and a hydrolyzable group.

[5] The negative photosensitive resin composition according to any one of the above [1] to [4], wherein the ink repellent (D) contains a hydrolyzable silane compound (s4) as a monomer and / or is partially hydrolyzed (Co) condensate, the hydrolyzable silane compound (s4) has a cationically polymerizable group and a hydrolyzable group and does not contain a fluorine atom.

[6] The negative photosensitive resin composition according to any one of the above [1] to [5], wherein the content of the alkali-soluble resin (A) accounts for the total solid content of the negative photosensitive resin composition 10 to 90% by mass.

[7] The negative photosensitive resin composition according to any one of the above [1] to [6], wherein the crosslinking agent (B) and the photoacid are relative to 100 parts by mass of the alkali-soluble resin (A) The content of the generator is 2 to 50 parts by mass and 0.1 to 20 parts by mass.

[8] The negative photosensitive resin composition according to any one of the above [1] to [7], wherein the content of the ink repellent (D) is 100 parts by mass of the alkali-soluble resin (A) 0.01 to 20 parts by mass.

[9] The negative photosensitive resin composition according to any one of the above [1] to [8], further comprising a solvent (E) selected from propylene glycol monomethyl ether ethyl Acid esters, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol At least one of the group consisting of ethylene glycol monoethyl ether acetate and 2-propanol.

[10] The negative photosensitive resin composition according to any one of the above [1] to [9], wherein the content of the solvent (E) is 50 to 99 relative to the total amount of the negative photosensitive resin composition. quality%.

[11] A partition wall formed into a shape that divides the substrate surface into a plurality of dot-forming partitions, and the partition wall is made of the negative photosensitive resin composition as described in any one of [1] to [10] above. Made of hardened film.

[12] The partition wall according to the above [11], which has a width of 100 μm or less, a distance (pattern width) between the partitions of 300 μm or less, and a height of 0.05 to 50 μm.

[13] An optical element having a plurality of points on a surface of a substrate and a partition wall between adjacent points, wherein the partition wall is formed by the partition wall as described in [11] or [12] above.

[14] The optical element according to the above [13], wherein the dots are formed by an inkjet method.

[15] The optical element according to the above [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, a partition having the following characteristics can be produced: an ink repellent layer having sufficient ink repellency can be formed on the upper surface of the partition at a low exposure amount, and After ink-repellent treatment, excellent ink repellency can be maintained.

In addition, the partition wall of the present invention has an ink repellent layer with sufficient ink repellency on the upper surface, which can form a fine and highly accurate pattern, so it can provide a use An organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell composed of optical elements. The optical element has dots, and the dots are accurately formed by uniformly coating ink on the opening portion divided by the partition wall.

1‧‧‧ substrate

4‧‧‧ next door

4A‧‧‧Ink layer

4B‧‧‧ Lower floor

5‧‧‧ opening

9‧‧‧ inkjet head

10‧‧‧Ink

11 o'clock

12‧‧‧Organic EL element

21‧‧‧coating film

22‧‧‧ dry film

23‧‧‧ exposure film

23A‧‧‧Exposure Department

23B‧‧‧Unexposed

30‧‧‧Mask

31‧‧‧Mask

(D) ‧‧‧ Ink Repellent

FIG. 1A is a step diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.

FIG. 1B is a schematic view showing a step of the method for manufacturing a partition wall according to the embodiment of the present invention.

FIG. 1C is a step diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.

FIG. 1D is a step diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.

FIG. 2A is a step diagram schematically showing a method of manufacturing an optical element according to an embodiment of the present invention.

FIG. 2B is a flowchart schematically showing a method of manufacturing an optical element according to an embodiment of the present invention.

Forms used to implement the invention

The definitions of terms used in this manual are summarized as follows.

"(Meth) acrylfluorenyl" is a general term for "methacrylfluorenyl" and "acrylfluorenyl". (Meth) acrylic acid, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin are also explained accordingly.

The base represented by the formula (x) may be described only as the base (x).

The compound represented by the formula (y) may be described only as the compound (y).

Here, expressions (x) and (y) represent arbitrary expressions.

A "side chain" refers to a group other than a hydrogen atom or a halogen atom of a carbon atom constituting a main chain in a polymer constituting a main chain of repeating units composed of carbon atoms. "Unit" such as a fluorine atom-containing unit means a polymerized unit.

"Total solid content of the photosensitive resin composition" refers to a component that forms a cured film described later among the components contained in the photosensitive resin composition, and can be left after the photosensitive resin composition is heated at 140 ° C for 24 hours and the solvent is removed. Find things. In addition, the total solid content can also be calculated from the feed amount.

A film made of a hardened material of a resin-based composition is called a "resin hardened film".

A film obtained by applying a photosensitive resin composition is referred to as a "coating film", and a film obtained by drying is referred to as a "dry film". The film obtained by hardening this "dry film" is a "resin cured film". The "resin cured film" is sometimes referred to simply as a "cured film".

The "partition wall" is a form of a resin hardened film having a shape in which a predetermined region is divided into a plurality of sections. The "dot" can be formed by injecting the "printing ink" described below into the partition divided by the next wall, that is, the opening surrounded by the next wall.

The term "printing ink" refers to a liquid that has optical and / or electrical functions after being dried and hardened.

In optical elements such as organic EL elements, color filters for liquid crystal elements, and TFT (Thin Film Transistor) arrays, dots used as dots for forming various elements may be used to form inkjet inks (IJ). Method for pattern printing. "Ink" includes printing inks used for such purposes.

"Ink repellency" refers to the properties of non-sticking the above-mentioned printing ink, and has both water repellency and oil repellency. The ink repellency can be evaluated by, for example, the contact angle when the ink is dropped. "Ink affinity" is the opposite of ink repellency, and can be evaluated by the contact angle when the ink is dripped as well as ink repellency. Alternatively, the wet spreading degree of the printing ink (wetting diffusivity of the printing ink) when the printing ink is dropped can be evaluated with a predetermined reference to evaluate the ink affinity.

"Dots" refer to the smallest area of light modulation in an optical element. Among organic EL elements, color filters for liquid crystal elements, and optical elements for organic TFT arrays, black and white display is 1 point = 1 pixel, and color display is, for example, 3 points (R (red), G (green), B (blue) Etc.) = 1 pixel.

Embodiments of the present invention will be described below. In addition, unless otherwise specified in this specification, the symbol% means mass%.

[Negative photosensitive resin composition]

The negative photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a cross-linking agent (B), a photoacid generator (C), and an ink repellent (D), and the ink repellent (D) contains a hydrolyzability The silane compound (s1) is a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group.

The negative photosensitive resin composition of the present invention may further contain a solvent (E) and other optional components as required.

(Alkali soluble resin (A))

The alkali-soluble resin (A) in the negative photosensitive resin composition of the present invention can be used without particular limitation as long as it is a cation-polymerizable alkali-soluble resin (A). The cation-polymerizable alkali-soluble resin ( A) can be borrowed The action of the acid generated by the photoacid generator (C) by irradiation (exposure) with active light is bonded and crosslinked with the crosslinking agent (B) to become alkali-insoluble.

Examples of the alkali-soluble resin (A) include phenols and aldehydes, and unmodified or modified phenol-formaldehyde phenol resins and ethylene phenol resins (hereinafter also referred to as " Polyvinylphenol "), a copolymer of N- (4-hydroxyphenyl) methacrylamide, and a hydroquinone monomethacrylate copolymer. In addition, various alkali-soluble polymers such as a sulfonylimide-based polymer, a carboxyl group-containing polymer, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin having a sulfonamide group, and a urethane-based resin can be used. Compound.

The alkali-soluble resin (A) is preferably a phenol-type phenol resin or an ethylene phenol resin.

Examples of the phenols and aldehydes used to produce the phenolic phenol resin include those described in paragraphs [0021] and [0022] of International Publication No. 2013/133392.

From the viewpoints of easy availability and low metal impurities, the above-mentioned phenol-type phenol resins are preferably phenol-type phenol-type phenol resins such as cresols and xylenols. Novolac phenol resin (hereinafter also referred to as "cresol novolac resin") is particularly preferred.

Examples of polyvinylphenol include homopolymers of vinylphenol and copolymers of vinylphenol and a monomer copolymerizable therewith.

Polyvinylphenol can use 4-vinylphenol, 3-vinylphenol, 2-vinylphenol, 2-methyl-4-vinylphenol, 2, and other polymerization initiators such as azobisisobutyronitrile and benzamidine peroxide. Ethylene phenol such as 6-dimethyl-4-vinylphenol alone Or it can be obtained by performing a radical polymerization in combination of 2 or more types.

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

The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 500 to 20,000, and more preferably 2,000 to 15,000. If the mass average molecular weight (Mw) of the alkali-soluble resin (A) is too low, even if a cross-linking reaction occurs in the exposed area, the molecular weight cannot be sufficiently increased, and therefore it is easy to dissolve in the alkali developer. When the mass-average molecular weight (Mw) of the alkali-soluble resin (A) is too large, the difference in solubility between the exposed region and the unexposed region with respect to the alkali developer solution becomes small, so it is difficult to obtain a good resist pattern.

In addition, the mass average molecular weight (Mw) means a mass average molecular weight measured by gel permeation chromatography (GPC) with tetrahydrofuran as a mobile phase and conversion based on standard polystyrene. The number average molecular weight (Mn) means a number average molecular weight measured by the same GPC.

Alkali-soluble resin (A) can also be a commercially available product. For example, for a commercially available product of cresol novolac resin, EP4020G (Mw: 9,000 to 14,000), EPR5010G (Mw: 7,000 to 12,500) (the above are all products) (Name, manufactured by Asahi Organic Materials Industry Co., Ltd.), and for commercially available products of polyvinyl phenol, MARUKA LYNCUR M (trade name, manufactured by Maruzan Petrochemical Co., Ltd.) and the like can be mentioned.

Alkali soluble resin (A) can be used alone or in combination of two or more. And use.

The content of the alkali-soluble resin (A) in the total solid content of the negative photosensitive resin composition is preferably 10 to 90% by mass, more preferably 30 to 85% by mass, and even more preferably 40 to 80% by mass. If the content is within the above range, the developability of the negative photosensitive resin composition is good.

(Crosslinking agent (B))

The cross-linking agent (B) is formed by the photoacid generator (C) being irradiated (exposed) with active light and bonded to the alkali-soluble resin (A) to crosslink the alkali-soluble resin (A). It becomes an alkali-insoluble compound (acid-sensitive substance).

The crosslinking agent (B) is preferably a melamine-based, benzoguanidine System, urea-based and isocyanate-based compounds, polyfunctional epoxy-containing compounds, low-molecular-weight compounds such as oxyfluorene-based compounds, and alkoxyalkylated melamine resins or alkoxyalkylated urea resins Polymer crosslinking agents such as oxyalkylated amine resins.

Examples of the melamine-based compound include melamine, methoxymethylated melamine, ethoxymethylated melamine, propoxymethylated melamine, butoxymethylated melamine, and hexamethylol melamine.

Benzoguanidine For compounds such as benzoguanidine Methylated benzoguanidine Wait.

Examples of the urea-based compound include urea, monomethylurea, dimethylolurea, alkoxymethyleneurea, N-alkoxymethyleneurea, diethylurea, diethylureacarboxylic acid, and Methoxymethyl) acetylene urea and the like. Examples of the isocyanate-based compound include Hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, toluene diisocyanate, diisocyanate methylcyclohexane, diisocyanate methylbenzene, diisocyanate, and the like.

The compound containing a polyfunctional epoxy group is preferably one containing more than one benzene ring or heterocyclic ring and containing two or more epoxy groups in one molecule. Examples include bisphenol acetone diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanate, tetraglycidyl-interstitial diamine, tetracyclic Oxypropyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenylglycidyl ether ethane, bisphenol hexafluoroacetone dipropylene oxide Ether, 4,4'-bis (2,3-glycidoxy) -octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl diamine and the like.

As for the oxygen-based compound, it is preferable to include two or more oxetanyl groups in one molecule, and examples thereof include stilbene-based dioxin and 3-ethyl-3 {[3-ethyloxin -3-yl) methoxy] methyl} oxamidine and the like.

Examples of the alkoxyalkylated melamine resin or alkoxyalkylated urea resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, and butoxymethyl Mesylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like.

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

The cross-linking agent (B) can be used alone or in combination of two or more. With respect to 100 parts by mass of the alkali-soluble resin (A), the blending amount is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 25 parts by mass. If the amount of the cross-linking agent (B) is too small, the cross-linking reaction will be difficult to proceed sufficiently. The residual film rate of the resist pattern after development using an alkali developing solution will be reduced, or deformation of the resist pattern such as swelling or serpentine will easily occur. If the amount of the cross-linking agent (B) used is too much, the resolution may decrease.

(Photoacid generator (C))

The photoacid generator (C) is not particularly limited as long as it is a compound that is decomposed by irradiation with active light to generate an acid. In the photosensitive resin composition using a cationically polymerizable alkali-soluble resin (A), an arbitrary compound can be selected from compounds generally used as a photoacid generator.

In addition, 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 cross-linking agent (B), and the ink repellent agent is simultaneously formed. The hydrolysis reaction of the fluorine-containing hydrolyzable silane compound (s1) contained in (D) functions as a catalyst. Usually, an acid catalyst is added to a composition containing a hydrolyzable silane compound. Therefore, the reaction proceeds slowly and storage stability is a problem. However, the negative photosensitive resin composition of the present invention does not need to be mixed with an acid in addition to the photoacid generator (C), and therefore has good storage stability.

The photoacid generator (C) is decomposed by irradiation with active light to generate an acid. Specific examples of the active light include high-energy rays such as ultraviolet light, X-rays, and electron rays. When a negative photosensitive resin composition is used to manufacture a partition for an optical element, i-line (365 nm) and h-line should be used for exposure (405nm) and g-line (436nm). As for 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 an onium salt-based photoacid generator or a nonionic photoacid generator. Examples of the onium salt-based photoacid generator include an onium salt and a sulfonium salt-based compound of a compound having a triphenylsulfonium skeleton represented by the following formula (C1) or (C2). In addition, among the compounds (C1) and (C2), a compound in which a hydrogen atom of a phenyl group of a triphenylsulfonium skeleton is substituted may be used as a photoacid generator.

In the formulae (C1) and (C2), Xa ^- and Xb ^- represent anions. Specifically, for example phosphorus-based anion such as _{^{PF 6 -, (R f1)}} n PF 6-n - (R f1 is a fluoroalkyl group, n is 1 to 3) or the like, for example may be sulfonate anion such as R ^a SO ₃ ^- (R ^a may be partially or entirely substituted with the fluorine atom or an alkyl group having a carbon number of 1 to 12 carbon atoms of the aryl group having 6 to 18) and the like. To R ^a SO ₃ ^- of R ^a, for example, include _{-CF 3, -C 4 F 9,} -C 8 F 17 like a perfluoroalkyl group, -C ₆ F ₅ perfluorinated aryl group and the like -Ph- An aryl group such as CH ₃ (however, Ph represents a phenyl group).

In these onium salts, the cationic part absorbs the light of irradiation, and the anionic part is the origin of the acid.

Among the compounds (C1) and (C2), for example, in the case of a compound used for exposure under i-line (365 nm), from the viewpoint of a large absorbance at a wavelength of 365 nm and a viewpoint of easy availability, the following formula ( C1-1) triphenyl hydrazone. The nonafluorobutane sulfonate is a triarylsulfonium represented by each of the following formulae (C2-1) and (C2-2). PF ₆ salt and triaryl hydrazone. Special phosphorus salts are preferred.

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

Examples of the phosphonium salt compound include diphenylsulfonium triflate, p-trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenylsulfonium, diphenylsulfonium p-toluenesulfonate, and p-toluene Sulfonic acid (p-tert-butoxyphenyl) phenylhydrazone and the like.

A commercially available onium salt-based photoacid generator can also be used. Examples include TPSP-PFBS (compound (C1-1), trade name, manufactured by Toyo Kogyo Co., Ltd.), CPI-100P (compound (C2-1), trade name, manufactured by San-Apro Ltd.), CPI-210S (Compound (C2-2), trade name, manufactured by San-Apro Ltd.).

Examples of the non-ionic photoacid generator include compounds having the following structure: a naphthalene dimethyl imine skeleton, a nifediene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, and 9-oxysulfur Skeleton, three The backbone is bonded to a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid, and the like.

Specific examples of such compounds include compounds having a naphthalenedimethylimide skeleton represented by the following formula (C3), (C4), (C5), (C6), and (C7): Nifediene skeleton, diazomethane skeleton, phenylacetophenone skeleton, or 9-oxysulfur A skeletal compound having a structure such as alkanesulfonic acid or arylsulfonic acid. In addition, the following formula (C8) has three Skeleton and chlorine atom compounds. In addition, a sulfofluorenyl compound of a dialkylglyoxaldioxime represented by the following formula (C9), and a sulfofluorenoxyiminoacetonitrile represented by the following formula (C10) can also be cited.

In addition, among the compounds (C3), (C4), (C6), and (C7), compounds in which the hydrogen atom of the benzene ring forming the skeleton of each compound is substituted also have a function as a photoacid generator.

[Chemical 3]

R ^b1 to R ^b5 , R ^b7 and R ^{b9 in the} formulae (C3) to (C7), (C9) and (C10) are each independently a linear, branched or Cyclic (but also including those having a cyclic structure) alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 18 carbon atoms. Specific examples include perfluoroalkyl groups such as -CF ₃ , -C ₄ F ₉ , and -C ₈ F _17; perfluoroaryl groups such as -C ₆ F _{5 ;} and aryl groups such as -Ph-CH ₃ . R ^b6 , R ^b8 and R ^b10 in the formulae (C8), (C9) and (C10) are each independently an organic group having 1 to 18 carbon atoms which may have a substituent.

In addition, among these non-ionic photoacid generators, a portion where a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid, or the like has been bonded becomes a source of generation of an acid.

For a nonionic photoacid generator, for example, in the case of a compound used when exposure is performed at i-line (365nm), from the viewpoint of a large absorbance at a wavelength of 365nm or a viewpoint of easy availability, the following formula ( C3-1) N-trifluoromethanesulfonic acid-1,8-naphthalenedimethylimide, 2-phenyl-2- (p-toluenesulfonyloxy) group represented by the following formula (C6-1) ) Acetophenone and 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-tris represented by the following formula (C8-1) And so on.

As the non-ionic photoacid generator, a commercially available product may be used. For example, NHNI-TF (compound (C3-1), trade name, manufactured by Toyo Kogyo Co., Ltd.).

In addition, acidic hydrochloric acid, alkanesulfonic acid, arylsulfonic acid, and partially or fully fluorinated arylsulfonic acid generated from the onium salt-based photoacid generator and nonionic photoacid generator under the action of light. , Alkane sulfonic acid, etc.

The photoacid generator (C) may be used singly or in combination of two or more kinds.

Photoacid generator (C) based on 100 parts by mass of alkali-soluble resin (A) The content is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, and even more preferably from 1 to 8 parts by mass. When the content of the photoacid generator (C) is in the above range, a partition wall having sufficient ink repellency on the upper surface and capable of forming a fine and highly accurate pattern can be obtained.

(Ink Repellent (D))

The ink repellent (D) in the present invention contains a hydrolyzable silane compound (s1), which has a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group. The ink repellent (D) may be a hydrolyzable silane compound (s1) alone, or a mixture of a hydrolyzable silane compound (s1) and a hydrolyzable silane compound other than the hydrolyzable silane compound (s1) as an optional component described later. The ink repellent (D) is preferably composed of only a hydrolyzable silane compound containing a hydrolyzable silane compound (s1).

The ink repellent (D) contains a hydrolyzable silane compound (s1) as a monomer and / or a partially hydrolyzed (co) condensate. That is, the ink repellent (D) may contain a hydrolyzable silane compound (s1) as a monomer, and may also contain a hydrolyzable silane compound (s1) as a partially hydrolyzed condensate thereof. When the ink repellent (D) contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s1), it may be contained as a partially hydrolyzed (co) condensate of the hydrolyzable silane compound (s1) and other hydrolyzable silane compounds. In addition, the hydrolyzable silane compound (s1) may be contained in the ink repellent agent as a mixture of two or more kinds selected from monomers, partial hydrolyzed condensates thereof, and partially hydrolyzed (co) condensates with other hydrolyzable silane compounds. D).

In the following, the ink repellent (D) contains a specific hydrolyzable silane compound means that it contains the hydrolyzable silane compound as a monomer and / or a partially hydrolyzed (co) condensate. Here, "monomer and / or partial hydrolysis (co) condensation "Material" has the same definition as above.

Considering that the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group, the ink repellent agent (D) has a process of forming a cured film using the negative photosensitive resin composition containing the ink repellent agent (D). Properties of migration to the upper surface (top surface migration) and ink repellency. By using the ink-repellent agent (D), the upper layer portion including the upper surface of the obtained partition wall becomes a layer where the ink-repellent agent (D) exists densely (hereinafter sometimes referred to as "ink-repellent layer"), and the upper surface of the partition wall can be imparted. Repellency. This ink repellent layer is mainly formed of a hardened product of a hydrolyzable silane compound containing a hydrolyzable silane compound (s1). From this point of view, it can maintain excellent ink-repellent treatment even after ultraviolet / ozone cleaning treatment. It is quite advantageous from the viewpoint of ink repellency.

From the viewpoint of the upper surface migration and ink repellency, the fluorine atom content in the ink repellent (D) is preferably from 1 to 40% by mass, more preferably from 5 to 35% by mass, and even more preferably from 10 to 30% by mass. . If the fluorine atom content of the ink repellent (D) is above the lower limit of the above range, a good ink repellency can be imparted to the upper surface of the cured film; if it is below the upper limit, it is compatible with a negative photosensitive resin composition The compatibility of other ingredients in the compound is better.

The ink repellent (D) is preferably a mixture (hereinafter also referred to as a "mixture (M)") composed of a substantial monomer of a hydrolyzable silane compound containing a hydrolyzable silane compound (s1), or a mixture of the same (M). Partially hydrolyzed (co) condensate. This 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 contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s1).

In addition, the so-called hydrolyzable silane compound is substantially a monomer and It does not only mean that all of the hydrolyzable silane compounds are monomers, but also means that it may contain a partially hydrolyzed condensate with a low molecular weight of about 2 to 10 polymers, and even means that the partially hydrolyzed condensate may be composed only of the partially hydrolyzed condensate.

Examples of the hydrolyzable silane compound contained in the mixture (M) include the following hydrolyzable silane compounds (s2) to (s4). It may also contain other hydrolyzable silane compounds. The hydrolyzable silane compound optionally contained in the mixture (M) is particularly preferably a hydrolyzable silane compound (s2). When the ink repellent (D) contains a hydrolyzable silane compound (s4), the ink repellent (D) is preferably composed of a mixture (M). When the hydrolyzable silane compound (s4) is not contained, the ink repellent (D) may be composed of the mixture (M), or may be a partially hydrolyzed (co) condensate thereof.

Hydrolyzable silane compound (s2); a hydrolyzable silane compound having 4 hydrolyzable groups 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); Hydrolyzable silane compound having a cationic polymerizable group and a hydrolyzable group and containing no fluorine atom.

The hydrolyzable silane compounds (s1) to (s4) and other hydrolyzable silane compounds are described below.

<1> Hydrolyzable Silane Compound (s1)

By using a hydrolyzable silane compound (s1), the ink repellent (D) has a fluorine atom in the form of a fluoroalkylene group and / or a fluoroalkyl group, and has excellent upper surface migration and ink repellency. In order to raise these properties of the hydrolyzable silane compound (s1) to a higher level, the hydrolyzable silane compound (s1) has a group selected from the group consisting of a fluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkyl group. Up to One less is preferred, and a perfluoroalkyl group is particularly preferred. A perfluoroalkyl group containing an etheric oxygen atom is also preferred. That is, the most suitable compound as the hydrolyzable silane compound (s1) is a compound having a perfluoroalkyl group and / or an etheric oxygen atom-containing perfluoroalkyl group.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a fluorenyl group, an isocyanate group, an amine group, and a group in which at least one hydrogen of the amine group has been replaced with an alkyl group. From the viewpoint of facilitating the smooth reaction of forming a Si-O-Si bond by a hydrolysis reaction to form a hydroxyl group (silanol group) and then performing a condensation reaction between the molecules, an alkoxy group or a halogen having 1 to 4 carbon atoms Atoms are preferred, methoxy, ethoxy, or chlorine atoms are preferred, and methoxy or ethoxy is particularly preferred.

The hydrolyzable silane compound (s1) may be used alone or in combination of two or more.

The hydrolyzable silane compound (s1) is preferably a compound represented by the following formula (dx-1).

(AR ^F11 ) _a -Si (R ^H11 ) _b X ¹¹ _(4-ab) … (dx-1)

In the formula (dx-1), R ^F11 is a divalent organic group having 1 to 16 carbon atoms containing at least one fluoroalkylene group and may contain etheric oxygen atoms.

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.

When there is a plurality of X ¹¹ , these may be different or the same.

When there is a plurality of X ¹² , these may be different or the same.

When there are multiple AR ^F11 , these can be different or the same.

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

R ^H11 and R ^H12 are each independently a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

In formula (dx-1), it is particularly preferable that a is 1 and b is 0 or 1.

Specific examples and ideal aspects of X ¹¹ and X ¹² are as described above.

The hydrolyzable silane compound (s1) is particularly preferably a compound represented by the following formula (dx-1a).

TR ^F12 -Q ¹¹ -SiX ¹¹ ₃ … (dx-1a)

In the formula (dx-1a), R ^F12 is a perfluoroalkylene group having 2 to 15 carbon atoms and which may contain an ethereal oxygen atom.

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 can be different or the same.

The three X ¹² can be different or the same.

Q ¹¹ and Q ¹² each independently represent a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom.

When T in the formula (dx-1a) is a fluorine atom, R ^{F12 is} a perfluoroalkylene group having 4 to 8 carbon atoms or a perfluoroalkylene group having 4 to 10 carbon atoms and containing an etheric oxygen atom as Preferably, a perfluoroalkylene group having 4 to 8 carbon atoms is preferred, and a perfluoroalkylene group having 6 carbon atoms is particularly preferred.

When T is a group (Ib) in formula (dx-1a), R ^{F12 is} a perfluoroalkylene group having 3 to 15 carbon atoms or a perfluoro group having 3 to 15 carbon atoms and containing an etheric oxygen atom. Alkylene is preferred, and perfluoroalkylene having 4 to 6 carbon atoms is particularly preferred.

In the case where R ^F12 is the above-mentioned group, the ink repellent (D) has good ink repellency, and the compound (dx-1a) has good solubility in a solvent.

As for the structure of R ^F12 , straight chain structure, branched chain structure, ring structure, and some structures having a ring can be listed, and a straight chain structure is preferred.

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

When Si is bonded to the right bonding position and R ^F12 is bonded to the left bonding position, specifically, Q ¹¹ and Q ¹² should _be- (CH ₂ ) _i1- (i1 is an integer from 1 to 5) -CH ₂ O (CH ₂ ) _i2- (i2 is an integer of 1 ~ 4), -SO ₂ NR ^1- (CH ₂ ) _i3- (R ¹ is a hydrogen atom, methyl or ethyl, i3 is 1 ~ An integer of 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 A base represented by 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). In terms of Q ¹¹ and Q ¹² ,-(CH ₂ ) _i1 with i1 being an integer of 2 to 4 is preferred, _and- (CH ₂ ) ₂ -is particularly preferred.

When R ^F12 is a perfluoroalkylene group having no etheric oxygen atom, Q ¹¹ and Q ^{12 are} preferably a group represented _by- (CH ₂ ) _i1- . It is preferable that i1 is an integer of 2 to 4, and 2 is more preferable.

When R ^F12 is a perfluoroalkyl group containing an etheric oxygen atom, Q ¹¹ and Q ^{12 are} preferably-(CH ₂ ) _i1- , -CH ₂ O (CH ₂ ) _i2- , -SO ₂ NR ^1- (CH ₂ ) _i3 - _or- (C = O) -NR ^1- (CH ₂ ) _i4- . In this case, Q ¹¹ and Q ^{12 are} also preferably-(CH ₂ ) _i1- . It is more preferable that i1 is an integer of 2 to 4, and it is more preferable that i1 is 2.

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

In the present invention, as far as the compound (dx-1a) is concerned, 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 ratio of the hydrolyzable silane compound (s1) in the mixture (M) is such that the fluorine atom content in the mixture or the partially hydrolyzed (co) condensate obtained from the mixture is 1 to 40% by mass. good. The fluorine atom content is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass. If the content ratio of the hydrolyzable silane compound (s1) is above the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film; if it is below the upper limit, it is compatible with other hydrolyzable silanes in the mixture. The compatibility of the compound or other components in the negative photosensitive resin composition is good.

<2> Hydrolyzable Silane Compound (s2)

The mixture (M) contains a hydrolyzable silane compound (s2) having four hydrolyzable groups bonded to a silicon atom, thereby curing the negative photosensitive resin composition containing the ink repellent (D). In the cured film, the film forming property after the ink repellent (D) migrates to the upper surface is improved. That is, we think it is because of hydrolyzable silylation The compound (s2) has a large number of hydrolyzable groups, so the ink repellent agents (D) can condense well with each other after moving to the upper surface, and a film is formed on the entire upper surface to become an ink repellent layer.

When the partially hydrolyzed condensate is prepared by containing the hydrolyzable silane compound (s2) in the mixture (M), the ink repellent (D) can be easily dissolved in a hydrocarbon-based solvent.

The hydrolyzable silane compound (s2) may be used alone or in combination of two or more.

As the hydrolyzable group, the same thing as 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 the formula (dx-2), X ² represents a hydrolyzable group, and four X ² may be different from each other or may be the same. As for X ² , the same bases as X ¹¹ and X ¹² described above can be used.

Specific examples of the compound (dx-2) include the following compounds. In addition, the compound (dx-2) may be a partially hydrolyzed condensate prepared by subjecting a plurality of the compounds (dx-2), for example, 2 to 10, to partial partial hydrolysis and condensation in advance.

Partially hydrolyzed condensates of Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OCH ₃ ) ₄ or partially hydrolyzed condensates of Si (OC ₂ H ₅ ) ₄ .

The content ratio of the hydrolyzable silane compound (s2) in the mixture (M) is preferably 1 to 20 mol, and more preferably 3 to 18 mol relative to 1 mol of the hydrolyzable silane compound (s1). If the content ratio is above the lower limit of the above range, the film-forming property of the ink repellent (D) is better; if it is below the upper limit, the ink repellency of the ink repellent (D) is better.

<3> Hydrolyzable Silane Compound (s3)

When a hydrolyzable silane compound (s2) is used for the said mixture (M), a protrusion may be formed in the upper surface edge part in the partition wall which hardened the photosensitive resin composition, for example. The protrusions are minute objects that can be observed with a scanning electron microscope (SEM) or the like, and it is confirmed that the content of F and / or Si is larger than that of other parts.

Although the protrusion is not particularly obstructive as a partition wall or the like, the inventors have found that the protrusion can be suppressed by substituting a part of the hydrolyzable silane compound (s2) with a small number of hydrolyzable silane compounds (s3). To produce.

The reaction of the silanol groups formed by the hydrolyzable silane compound (s2) with a large number of hydrolyzable groups can increase the film-forming property of the ink repellent (D), which we believe is caused by its high reactivity. The above protrusions. Therefore, we believe that by partially substituting a part of the hydrolyzable silane compound (s2) with a small number of hydrolyzable groups, the hydrolyzable silane compound (s3) can suppress the reaction of the silanol groups with each other, thereby suppressing the aforementioned protrusions. produce.

The hydrolyzable silane compound (s3) may be used alone or in combination of two or more.

As the hydrolyzable group, the same thing as the hydrolyzable group of the hydrolyzable silane compound (s1) can be used.

The hydrolyzable silane compound (s3) is preferably a compound represented by the following formula (dx-3).

(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 from 1 to 3, and ideally is 2 or 3.

When there is a plurality of R ^H5 , these may be different or the same.

When there are multiple X5s, these may be different or the same.

In the case of R ^H5 , when j is 1, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, Phenyl and the like are preferred. When j is 2 or 3, R ^H5 is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.

X ⁵ may use the same base as X ¹¹ and X ¹² described above.

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

The content ratio of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 1 to 10 mol, and more preferably 3 to 8 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, it is possible to suppress the protrusion at the end portion of the upper surface of the partition wall. If it is below the upper limit, the ink repellency of the ink repellent (D) is better.

<4> Hydrolyzable Silane Compound (s4)

The mixture (M) preferably contains a hydrolyzable silane compound (s4), which has a cationic polymerizable group and a hydrolyzable group and does not contain a fluorine atom. When the mixture (M) contains a hydrolyzable silane compound (s4), a cationic polymerizable group can be reacted with a crosslinking agent (B) contained in, for example, a photosensitive resin composition to obtain an ink repellent agent for improving the ink repellent layer. (D) Effect of fixing property.

The hydrolyzable silane compound (s4) is represented by the following formula (dx-4) The compounds shown are preferred.

(EQ ⁶ ) _s -Si (R ^H6 ) _t X ⁶ _(4-st) … (dx-4)

In formula (dx-4), E is a cationic polymerizable group, for example, an oxetanyl group, an epoxy group, an propylene oxide group, or a 3,4-epoxycyclohexyl group.

Q ⁶ is a divalent organic group having 1 to 10 carbon atoms and not containing a fluorine atom.

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 there are multiple EQ ⁶ , these can be different or the same.

When there is a plurality of X ⁶ , these may be different or the same.

X ⁶ may use the same base as X ¹¹ and X ¹² described above.

Q ⁶ is preferably an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is particularly preferred.

As for R ^H6 , the same groups as those of the aforementioned R ^H11 and R ^H12 can be 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 , and 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. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane and 3-glycidoxypropylmethyldiethoxysilane 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 15 to 50 mol% relative to the total amount of the mixture (M). It's better. The hydrolyzable silane compound (s4) may be used alone or in combination of two or more.

<5> Other hydrolyzable silane compounds

As long as the effect of the present invention is not impaired, the mixture (M) may further contain one or two or more kinds of hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s4). Relative to the total amount of the mixture (M), the total content of other hydrolyzable silane compounds in the mixture (M) is preferably 40 mol% or less, and more preferably 10 mol% or less.

Examples of other hydrolyzable silane compounds include hydrolyzable silane compounds having a vinyl double bond and a hydrolyzable group and containing no fluorine atom, and hydrolyzable silane compounds having a mercapto group and a hydrolyzable group and containing no fluorine atom. A hydrolyzable silane compound having an oxyalkylene group and a hydrolyzable group and containing no fluorine atom, a hydrolyzable silane compound having an amine group or an isocyanate group and a hydrolyzable group and containing no fluorine atom, and the like.

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 include, for example, those described in paragraph [0057] of International Publication No. 2014/046209.

Specific examples of the hydrolyzable silane compound having a mercapto group and a hydrolyzable group and not containing a fluorine atom include HS- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ and HS- (CH ₂ ) ₃ -Si (CH ₃ ) (OCH ₃ ) ₂ and so on.

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

Examples of the hydrolyzable silane compound having an amine 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). .

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 (isocyanatepropyltriethoxysilane).

<6> Ink Repellent (D)

The ink repellent (D) is a mixture (M) or a partially hydrolyzed (co) condensate thereof.

As an example of the ink repellent (D), for example, the compound (dx-1a) is contained as an essential component, the compound (dx-2) and the compound (dx-4) are contained as an optional component, and the compound (dx-1a) The group T is a mixture (M) of fluorine atoms. 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, which is equivalent in productivity. advantageous. Moreover, it is also excellent in the storage stability of a negative photosensitive resin composition.

The average composition formula of the ink repellent (D1) is shown in the following formula (II). As another example of the ink repellent (D), the ink repellent (D1) is a partially hydrolyzed condensate of the mixture (M), and the mixture (M) 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 group T in the compound (dx-1a) is a fluorine atom. If a partially hydrolyzed condensate is used as the ink repellent (D), it is very advantageous in terms of reducing residues in the development removal section (opening section) of the negative photosensitive resin composition.

[TR ^F12 -Q ¹¹ -SiO _3/2 ] _n1 . [SiO ₂ ] _n2 . [(R ^H5 ) _j -SiO _{(4-j) / 2} ] _n3 … (II)

In Formula (II), n1 to n3 represent the mole fractions of each constituent unit with respect to the total mole amount of the constituent units. n1> 0, n2 ≧ 0, n3 ≧ 0, and n1 + n2 + n3 = 1. The other symbols are as described above. However, T is a fluorine atom.

In addition, since the ink repellent (D1) is actually a product (partially hydrolyzed condensate) remaining from a hydrolyzable group or a silanol group, it is difficult to express the product by a chemical formula.

The average composition formula represented by the formula (II) is a chemical formula when all the hydrolyzable groups or silanol groups in the ink repellent (D1) become siloxane bonds.

In addition, we speculate that the units derived from compounds (dx-1a), (dx-2), and (dx-3) in formula (II) are randomly arranged.

In the average composition formula represented by formula (II), n1: n2: n3 is consistent with the feed composition of the compounds (dx-1a), (dx-2), and (dx-3) in the mixture (M).

The molar ratio of each component should be designed from the balance of the effects of each component.

In terms of n1, the amount of fluorine atom content in the ink repellent (D1) can reach the above-mentioned ideal range, preferably 0.02 to 0.4, and particularly preferably 0.02 to 0.3.

In the case of n3 = 0, 0 ~ 0.98 is preferable, and in the case of n3> 0, 0.05 ~ 0.6 is preferable.

n3 is preferably 0 ~ 0.5.

Moreover, in the case where T in the compound (dx-1a) is a group (Ib), the ideal mole ratios of the aforementioned components are also the same.

The ideal molar ratio of each of the components described above is also applicable when the mixture (M) contains a hydrolyzable silane compound (s1) and optionally contains a hydrolyzable silane compound (s2) and a hydrolyzable silane compound (s3). That is, the ideal feeding amounts for obtaining the hydrolyzable silane compounds (s1) to (s3) in the mixture (M) of the ink repellent (D) correspond to the above-mentioned ideal ranges of n1 to n3, respectively.

When the ink repellent (D) is a partially hydrolyzed condensate of the mixture (M) The number average molecular weight (Mn) is preferably 500 or more, more preferably less than 1,000,000, and most preferably less than 10,000.

When the number average molecular weight (Mn) is at least the above-mentioned lower limit value, when the photosensitive resin composition is used to form the partition wall, the ink repellent (D) will easily migrate to the upper surface. If it is lower than the above upper limit, the solubility of the ink repellent (D) in the solvent is better.

The number average molecular weight (Mn) of the ink repellent (D) can be adjusted according to manufacturing conditions.

The ink repellent (D) can be produced by subjecting the mixture (M) to a hydrolysis and condensation reaction by a known method.

In the above reaction, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids such as acetic acid, oxalic acid, and maleic acid are preferably used as catalysts. In addition, alkali catalysts such as sodium hydroxide and tetramethylammonium hydroxide (TMAH) can be used according to demand.

A well-known solvent can be used for the said reaction.

The ink repellent (D) obtained by the above reaction may be blended with the solvent in the form of a solution together with the photosensitive resin composition.

The content of the ink repellent (D) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A), more preferably 0.1 to 10 parts by mass, and even more preferably 0.2 to 3 parts by mass. When the content of the ink repellent (D) is in the above range, a partition wall having sufficient ink repellency on the upper surface can be obtained.

(Solvent (E))

Since the negative photosensitive resin composition of the present invention contains a solvent (E), the viscosity is reduced, so the negative photosensitive resin composition can be easily applied to a substrate. surface. As a result, a coating film of a negative photosensitive resin composition having a uniform film thickness can be formed.

As the solvent (E), a known solvent can be used. The solvent (E) may be used alone or in combination of two or more.

Examples of the solvent (E) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, and solvent oils. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferred, and at least one solvent is selected from At least one of 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 Solvents are better.

The content 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 even more 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 contain one or more coloring agents, thermal cross-linking agents, polymer dispersants, dispersing aids, silane coupling agents, fine particles, hardening accelerators, Thickener, plasticizer, defoamer, leveling agent, anti-shrinking agent and other additives.

The negative-type photosensitive resin composition of the present invention is prepared by mixing predetermined amounts of the aforementioned components. The negative photosensitive resin composition of the present invention has good storage stability.

Moreover, by using the negative photosensitive resin composition of the present invention, a partition wall having an ink repellent layer having a good ink repellent property on the upper surface can be manufactured at a low exposure. In addition, it is possible to manufacture a partition wall that can maintain excellent ink repellency even if the ink repellent layer is subjected to an ink-receptive treatment such as ultraviolet / ozone cleaning treatment.

The partition wall which can be manufactured by the present invention has an ink repellent layer with sufficient ink repellency on the upper surface, and can form a fine and highly accurate pattern.

According to the present invention, there can be provided an optical element having dots, which are accurately formed by uniformly coating ink on an opening portion divided by a partition wall, and the optical element is specifically an organic EL element, a quantum dot display, a TFT Arrays, thin-film solar cells, etc.

[next door]

The partition wall of the present invention is formed in a shape that divides the surface of the substrate into a plurality of dot-forming sections, and is composed of a hardened body of the negative photosensitive resin composition. This partition can be, for example, coated with the negative photosensitive resin composition of the present invention on the surface of a substrate such as a substrate, dried and removed the solvent, etc. as needed, and then masked and exposed to the portion that becomes the zone for dot formation. It can be made by heating and developing according to demand.

Hereinafter, an example of a method for manufacturing a partition wall according to an embodiment of the present invention will be described with reference to FIGS. 1A to 1D. However, the method for manufacturing a partition wall is not limited to the following. The following production method will be described with reference to a case where the negative photosensitive resin composition contains a solvent (E).

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

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 it also varies depending on the type of the solvent (E), in the case of heating and drying, the heating temperature is preferably 50 to 120 ° C, and more preferably 90 to 115 ° C.

During this drying process, the ink repellent (D) will migrate to the upper part of the drying film. In addition, even if the negative photosensitive resin composition does not contain the solvent (E), the upper surface of the ink repellent (D) can still be shifted in the coating film.

Next, as shown in FIG. 1C, the dry film 22 is irradiated with active light through a photomask 30, and the photomask 30 has a mask portion 31 corresponding to the shape of an opening portion surrounded by the partition wall. The film after exposing the dry film 22 is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23A is subjected to light curing, and the non-exposed portion 23B is in the same state as the dry film 22. The exposure is performed by causing the dry film 22 to absorb active light and decomposing the photoacid generator (C) to generate an acid. With the generated acid, the reaction between the alkali-soluble resin (A) and the cross-linking agent (B) is bonded, and at the same time, the hardening reaction caused by the hydrolysis and condensation of the ink repellent (D) is performed.

As for the irradiated light, 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 and other excimer laser light; X-rays; electron rays and so on.

The light to be irradiated is preferably light having a wavelength of 100 to 600 nm, light of 300 to 500 nm is more preferable, and light containing i-line (365 nm), h-line (405 nm) or g-line (436 nm) is particularly preferable. It is also possible to cut off light below 330 nm according to requirements.

As for the exposure method, the whole surface can be uniformly exposed and scanned. Exposure, etc. You can also expose the same spot several times. At this time, the exposure conditions for several times may be the same or different.

The exposure amount in any of the above exposure methods is preferably 5 to 1,000 mJ / cm ^{2, more} preferably 5 to 500 mJ / cm ^{2, more} preferably 5 to 300 mJ / cm ^{2, and most} preferably 5 to 200 mJ / cm ² , and The best is 5 ~ 50mJ / cm ² . The exposure amount can be appropriately optimized in accordance with the wavelength of light emitted, the composition of the negative photosensitive resin composition, and the thickness of the coating film. In the negative photosensitive resin composition of the present invention, sufficient curing can be performed at such a low exposure amount.

There is no particular limitation on the exposure time per unit area, and it can be designed from the exposure power and required exposure amount of the exposure device used. In the case of scanning exposure, the exposure time can be obtained from the scanning speed of light.

The exposure time per unit area is usually about 1 to 60 seconds, ideally 1 to 30 seconds.

After the exposure, the acid generated by decomposing the photoacid generator (C) is diffused in the dry film 22, and heating may be performed in order to make the reaction uniform in the film. The heating conditions are 70 to 120 ° C, preferably 90 to 115 ° C, and the heating is performed for about 1 to 5 minutes, and preferably 1 to 3 minutes.

Next, as shown in FIG. 1D, development is performed using an alkali developing solution to form a partition wall 4 composed of only a portion corresponding to the exposure portion 23A of the exposure film 23. The opening portion 5 surrounded by the partition wall 4 is a portion of the exposure film 23 where the non-exposure portion 23B originally exists. 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 and removed by the alkali developing solution in a state where the ink repellent (D) moves to the upper layer portion and there is almost no ink repellent (D) in the layer below it. 5 almost never Residual ink repellent (D).

In addition, in the partition wall 4 shown in FIG. 1D, the uppermost layer including the upper surface thereof is an ink repellent layer 4A. During exposure, the ink repellent (D) present in the upper layer at a high concentration is hardened by the acid generated by the photoacid generator (C) as a catalyst to become the ink repellent layer. In addition, during exposure, the alkali-soluble resin (A) and the cross-linking agent (B) and other light-hardening components existing around the ink-repellent agent (D) are also strongly light-hardened together with the ink-repellent agent (D). Fixed to the ink repellent layer.

In addition, when the ink repellent (D) contains a hydrolyzable silane compound (s4), the ink repellent (D) is bonded to each other, and the alkali-soluble resin (A) and the cross-linking agent (B) and others The light-hardening component will be light-hardened together to form the ink-repellent layer 4A formed by the strong bonding of the ink-repellent agent (D).

In any of the above cases, a layer 4B will be formed on the lower side of the ink repellent layer 4A. The layer 4B is mainly an alkali-soluble resin (A), a crosslinking agent (B) and other light-hardening components. Does not contain ink repellent (D).

In this way, since the ink repellent (D) is sufficiently fixed to the partition wall including the ink repellent layer 4A and the lower layer 4B, it is hardly transferred to the opening portion during development.

After the development, the partition wall 4 may be further heated. The heating temperature is preferably 130 to 250 ° C, and more preferably 150 to 230 ° C. The heating time is about 20 to 60 minutes, and ideally 30 to 60 minutes.

The hardening of the partition wall 4 can be made stronger by heating, and the ink repellent agent (D) can be more firmly fixed in the ink repellent layer 4A.

The resin hardened film and partition wall of the present invention obtained in the above manner 4. Even at low exposure, the upper surface still has good ink repellency. In addition, in the partition wall 4, the ink repellent (D) is hardly stored in the opening portion 5 after development, and the uniform coating property of the ink in the opening portion 5 can be sufficiently ensured.

In addition, in order to more surely obtain the ink affinity of the opening 5, ultraviolet rays may be applied to the substrate 1 with the partition wall 4 to remove the development residues of the negative photosensitive resin composition that may exist in the opening 5 after heating. / Ozone treatment. At this time, the ink-repellent layer on the upper part of the partition wall prepared by using the negative photosensitive resin composition of the present invention is one having sufficient resistance to ultraviolet / ozone treatment.

The partition wall made of the negative photosensitive resin composition of the present invention (hereinafter also referred to as the partition wall of the present invention) is preferably, for example, 100 μm or less in width, and more preferably 20 μm or less. Generally, the width is preferably 5 μm or more. The distance (pattern width) between adjacent partition walls is preferably 300 μm or less, and more preferably 100 μm or less. Generally, the distance (pattern width) between adjacent partition walls is preferably 10 μm or more.

The height of the partition wall is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 10 μm.

When the partition wall of the present invention is formed to have the above-mentioned width, the edge portion has few irregularities, and the linearity is good. Such a highly accurate pattern can be formed. From this viewpoint, it is particularly useful as a partition wall for an organic EL element.

When pattern printing is performed by the IJ method (inkjet method), the partition wall of the present invention can be used as a partition wall in which the opening portion is used as a printing ink injection area. When pattern printing is performed by the IJ method, if the partition wall of the present invention is formed so that its opening is consistent with the desired ink injection area for use, The surface has good ink repellency. From this point of view, it is possible to prevent the ink from being injected into the undesired opening, that is, the ink injection area, beyond the partition wall. In addition, since the opening portion surrounded by the partition wall has good wet diffusion properties of the printing ink, the printing ink can be uniformly printed in a desired area without generation of a blank or the like.

As described above, the use of the partition wall of the present invention allows delicate pattern printing using the IJ method. Therefore, the partition wall of the present invention can be effectively used as a partition wall for optical elements, especially organic EL elements, quantum dot displays, TFT arrays, etc. The optical element has a plurality of dots on the surface of a substrate that can be formed by the IJ method and is located adjacent to each other. Next to it.

[Optical element]

The optical element according to the embodiment of the present invention includes an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell having a plurality of dots on a substrate surface and a partition wall of the present invention located between adjacent dots. In the above-mentioned 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 an anode and a cathode sandwich an organic thin-film light-emitting layer. The barrier ribs of the present invention can be used for barrier ribs that separate organic light-emitting layers, barrier ribs that separate organic TFT layers, and barrier ribs that coat oxide semiconductors Use, etc.

In addition, an organic TFT array element is a device in which a plurality of dots are arranged in a dot-planar shape, and TFTs are provided as pixel electrodes and switching elements for driving the pixel electrodes at each point, and an organic semiconductor layer is used as an element including a TFT channel layer as a semiconductor layer . The organic TFT array element is, for example, an organic EL element or a liquid crystal element and is arranged on a TFT array substrate.

An optical element such as an organic EL element according to an embodiment of the present invention will be described below with an example in which dots are formed in the openings by the IJ method using the barrier ribs prepared as described above.

However, the dot formation method in the organic EL element and the like of the optical element according to the embodiment of the present invention is not limited to the following.

2A and 2B are schematic views showing a method for manufacturing an organic EL element using the partition wall 4 formed on the substrate 1 shown in FIG. 1D. Here, the partition wall 4 on the substrate 1 is formed so that the opening portion 5 and the dot pattern of the organic EL element to be manufactured coincide with each other.

As shown in FIG. 2A, the printing ink 10 is dropped from the inkjet head 9 in the opening portion 5 surrounded by the partition wall 4, and a predetermined amount of the printing ink 10 is injected into the opening portion 5. As for the printing ink, a well-known printing ink used as an organic EL element can be appropriately selected in accordance with the function of the dot.

Next, depending on the type of the printing ink 10 used, for example, drying and / or heating is performed to remove or harden the solvent, so as to obtain a desired point 11 formed adjacent to the partition wall 4 as shown in FIG. 2B. Organic EL element 12.

The optical element of the embodiment of the present invention, especially an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, can use the partition wall of the present invention to uniformly wet and spread the printing ink without gaps during the manufacturing process. In the opening portion divided by the partition wall, there can be precisely formed points.

The organic EL element can be produced, for example, by the following method, 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 can be patterned as required.

Next, using the negative-type photosensitive resin composition of the present invention, the partition wall is formed into a plan lattice shape along the outline of each dot by a photolithography method 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 were coated by the IJ method in the spots, and the layers were sequentially laminated in this order. The type and number of organic layers formed in the dots can be appropriately designed.

Finally, a reflective electrode such as aluminum is formed by a vapor deposition method or the like.

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

The optical element according to the embodiment of the present invention can also be applied to, for example, a blue light conversion type quantum dot display that can be manufactured in the following manner.

On a light-transmitting substrate such as glass, the partition wall is formed in a plan view lattice shape along the outline of each point using the negative photosensitive resin composition of the present invention.

Next, apply the nano-particle solution that can convert blue light to green light, the nano-particle solution that can convert blue light to red light, and the blue color printing ink according to demand by IJ method in the spot, and Allow these to dry to make modules. A blue light source is used as a backlight and the aforementioned module is used instead of a color filter, whereby a liquid crystal display having excellent color reproducibility can be obtained.

The TFT array can be manufactured, for example, in the following manner, 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. The gate electrode can be patterned as required.

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 can also be formed on the gate insulating film. The source electrode and the drain electrode can be formed by, for example, forming a metal thin film of aluminum, gold, silver, copper, or an alloy thereof by vacuum evaporation or sputtering. The method of patterning the source electrode and the drain electrode may include the following methods: After forming a metal thin film, apply a resist and expose and develop it, leaving a resist on the portion where the electrode is to be formed, and then phosphoric acid Or aqua regia to remove the exposed metal, and finally remove the resist. In the case where a metal thin film such as gold is formed, the following methods are also applied: a resist is applied in advance, exposed and developed, and a resist is left on the portion where the electrode is not to be formed, and then a metal thin film is formed, The photoresist is removed together with the metal film. Further, the source electrode and the drain electrode may be formed by a method such as an inkjet method and using metal nano colloids such as silver and copper.

Next, using the negative-type photosensitive resin composition of the present invention, the partition wall is formed into a plan view lattice shape along the outline of each point by a photolithography method including coating, exposure, and development.

Then, a semiconductor solution is applied into the spots by the IJ method and the solution is dried to form a semiconductor layer. As the semiconductor solution, an organic semiconductor solution, an inorganic coated oxide semiconductor solution, or the like can also be used. The source electrode and the drain electrode can also be formed by using a method such as an inkjet method after forming the semiconductor layer.

Finally, a light-transmitting electrode such as ITO can be formed by sputtering, and then formed into a protective film such as silicon nitride.

Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited by 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)]

A commercially available GPC measuring device (manufactured by Tosoh Corporation, device name: HLC-8320GPC) was used to measure the gel permeation layer of several monodisperse polystyrene polymers with different degrees of polymerization that are commercially available as standard samples for molecular weight measurement. Analysis (GPC), and based on the relationship between the molecular weight of polystyrene and the retention time (residence time) as the basis for the calibration curve.

The sample was diluted with tetrahydrofuran to 1.0% by mass and passed through a 0.5 μm filter, and then the GPC for the sample was measured using the GPC measurement device.

The GPC spectrum of the sample was computer-analyzed using the aforementioned calibration curve to obtain the number average molecular weight (Mn) of the sample.

[Water contact angle]

According to JIS R3257 "Test method for wettability of the surface of a substrate glass" by a non-drip liquid droplet method, water droplets were dripped on three measurement surfaces on a substrate, and the measurement was performed for each water droplet. The droplet was 2 μL / drop, and the measurement was performed at 20 ° C. The contact angle is represented by an average value of 3 measured values (n = 3).

[PGMEA contact angle]

According to JIS R3257 "Test method for wettability of substrate glass surface" by using the non-drip liquid droplet method, PGMEA droplets were dripped on three measurement surfaces on the substrate, and each PGMEA droplet was measured. The droplet was 2 μL / drop, and the measurement was performed at 20 ° C. The contact angle is represented by an average value of 3 measured values (n = 3).

The 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 novolac resin, (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (Å / sec)).

(Crosslinking agent (B))

MW-100LM; NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co. Ltd .; methylated melamine resin with hexamethoxymethyl melamine as the basic skeleton)

(Photo acid generator (C)

CPI-210S; trade name, manufactured by San-Apro Ltd .; compound represented by the above formula (C2-2).

(Hydrolyzable Silane Compound as Raw Material of Ink Repellent (D))

Compound (d-11) equivalent to hydrolyzable silane compound (dx-1a): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Compound (d-21) equivalent to hydrolyzable silane compound (dx-2): Si (OC ₂ H ₅ ) ₄ .

Compound (d-31) equivalent to hydrolyzable silane compound (dx-3): CH ₃ S i (OCH ₃ ) ₃ .

Compound (d-32) equivalent to hydrolyzable silane compound (dx-3): C ₆ H ₅ Si (OCH ₃ ) ₃ .

(Compound used to produce the ink repellent (Dcf) (addition polymer having a fluoroalkyl group having 4 to 6 carbon atoms and containing a structural unit derived from an unsaturated compound) used in the comparative example)

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, (2,2'-azobis (2.4 dimethylvaleronitrile) (polymerization initiator) manufactured by Wako Chemical Industry Co., Ltd.)

(Solvent (E))

PGMEA: propylene glycol monomethyl ether acetate.

PGME: propylene glycol monomethyl ether.

[Synthesis Example 1: Synthesis of Ink Repellent (D1) and Preparation of (D1-1) Liquid]

A 50 cm ³ three-necked flask equipped with a stirrer was charged with 0.38 g of the above-mentioned compound (d-11) and 2.35 g of the above-mentioned compound (d-21) to obtain a raw material mixture of an ink repellent (D1). Then, 5.56 g of PGME was put into this raw material mixture to prepare a solution (raw material solution).

To the prepared raw material solution, 1.71 g of a 1.0% by mass nitric acid aqueous solution was dropped while stirring at room temperature. After completion of the dropping, the solution was further stirred for 5 hours to obtain a PGME solution (D1-1) solution containing 10% by mass of (D1). be made of The fluorine-containing content (fluorine atomic mass%) of the composition after the solvent was removed from the (D1-1) liquid was 20.0 mass%. The number-average molecular weight (Mn) of the composition after the solvent was removed from the (D1-1) liquid was 773.

[Synthesis Example 2: Synthesis of Ink Repellent (D2) and Preparation of (D2-1) Liquid]

In a 50 cm ³ three-necked flask equipped with a stirrer, 0.38 g of the above-mentioned compound (d-11), 1.11 g of the above-mentioned compound (d-21), and 0.72 g of the above-mentioned compound (d-31) were placed to obtain a raw material for the ink repellent (D2) mixture. Next, 6.36 g of PGME was put into this raw material mixture to prepare a solution (raw material solution).

To the prepared raw material solution, 1.43 g of a 1.0% by mass nitric acid aqueous solution was dropped while stirring at room temperature. After completion of the dropping, the solution was further stirred for 5 hours to obtain a PGME solution (D2-1) solution containing 10% by mass of (D2). The solvent-removed composition of the obtained (D2-1) liquid had a fluorine content (fluorine atomic mass%) of 20.0% by mass. The number-average molecular weight (Mn) of the composition after the solvent was removed from the (D2-1) liquid was 810.

[Synthesis Example 3: Synthesis of Ink Repellent (D3) and Preparation of (D3-1) Liquid]

In a 50 cm ³ three-necked flask equipped with a stirrer, 0.38 g of the above-mentioned compound (d-11), 0.74 g of the above-mentioned compound (d-21), and 0.71 g of the above-mentioned compound (d-32) were placed to obtain a raw material for the ink repellent (D1) mixture. Then, 7.18 g of PGME was put into this raw material mixture to prepare a solution (raw material solution).

A 0.99 g 1.0% by mass nitric acid aqueous solution was dropped on the prepared raw material solution while stirring at room temperature. After completion of the dropping, the solution was further stirred for 5 hours to prepare a PGME solution (D3-1) solution containing 10% by mass of (D3). be made of The fluorine-containing content (fluorine atomic mass%) of the composition after the solvent was removed from the (D3-1) liquid was 20.0 mass%. The number-average molecular weight (Mn) of the composition after the solvent was removed from the (D3-1) liquid was 880.

[Synthesis Example 4: Synthesis of Ink Repellent (Dcf) and Preparation of (Dcf-1) Liquid]

In a 1L autoclave equipped with a mixer, feed MEK 420.0g, C6FMA 86.4g, MAA 18.0g, GMA 21.6g, MMA 54.0g, and V-65 0.8g, and stir at 50 ° C while stirring in a nitrogen environment These polymers were polymerized for 24 hours to synthesize a crude copolymer. Hexane was added to the obtained crude copolymer solution for reprecipitation and purification, and then vacuum drying was performed. 14643 g of PGMEA was added to the obtained solid content and stirred to obtain a PGMEA solution (Dcf-1) liquid containing 10% by mass of an ink repellent (Dcf). The solvent-removed composition of the obtained (Dcf-1) solution had a fluorine content rate (fluorine atomic mass%) of 27.4% by mass. The number-average molecular weight (Mn) of the composition after the solvent was removed from the (Dcf-1) solution was 49,325.

The fluorine atom content ratio and number average molecular weight (Mn) of the ink repellent (D) in the ink repellent solutions obtained in Synthesis Examples 1 to 4 are combined with the feed composition (mole%) of the ink repellent (D). Shown in Table 1.

[Table 1]

[example 1]

(Preparation of negative photosensitive resin composition)

Put 0.967g of (D1-1) liquid (0.097g in solid content and PGME (solvent) in the rest), EP4020G 19.34g, MW-100LM 4.84g, CPI-210S 0.73g and PGMEA 74.1g into 500cm ³ for stirring The container was stirred for 30 minutes to prepare a negative photosensitive resin composition 1.

(Manufacture of hardened film (partition))

A 10 cm square glass substrate was ultrasonically washed with ethanol for 30 seconds, followed by ultraviolet / ozone cleaning for 5 minutes. For UV / ozone cleaning, PL7-200 (manufactured by Senengineering Co., Ltd.) was used as the UV / ozone generator. In addition, this apparatus is used as an ultraviolet / ozone generating apparatus with respect to all the ultraviolet / ozone processes described below.

After the negative photosensitive resin composition 1 was coated on the surface of the cleaned glass substrate using a spinner, a drying process was performed on a hot plate at a temperature of 100 ° C. for 2 minutes to form a film thickness of 2.5 μm. membrane. With respect to the surface of the prepared dry film, a 50 μm gap was formed from the film side with a mask (2.5 cm × 5 cm) with an opening pattern (a mask capable of irradiating light outside the area of the pattern portion) at a 25 mW / cm ² for 1 second irradiation, UV high pressure mercury lamp of 2 seconds, 5 seconds or 10 seconds.

Next, the glass substrate subjected to the exposure treatment was immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds for development, and then the dry film of the unexposed portion was washed with water and dried. Next, it was heated on a hot plate at 230 ° C. for 50 minutes, thereby obtaining 4 types of glass substrates having a cured film (partition wall) of the negative photosensitive resin composition 1 formed in a region other than the opening pattern portion. (1).

(Evaluation)

The following evaluations were performed on the negative photosensitive resin composition 1 prepared by the above method and the glass substrate (1) on which a cured film (partition wall) was formed. The evaluation results are shown in Table 2 together with the composition of the negative photosensitive resin composition.

<Ink repellency (next door). Intimacy (dot). Development residue>

The contact angle of the hardened film of the prepared glass substrate (1), that is, the surface of the partition wall (exposed portion) with respect to PGMEA, and the point portion (glass substrate surface) where the dried film (unexposed portion) was removed by development were measured. Contact angle with respect to water. At this time, the evaluation of the development residue was also performed with the contact angle with respect to water at the point portion. The evaluation was performed on the following basis.

(Benchmark)

○ (Good): Water contact angle is less than 30 degrees

× (bad): water contact angle is 30 degrees or more

Then, for a person who produces a cured film with an exposure time of 10 seconds on the glass substrate (1), the entire surface of the side where the cured film is formed is irradiated with UV / ozone for 1 minute, and the cured film is measured after 1 minute of irradiation ( The contact angle of the surface of the (partition wall) with respect to PGMEA and the contact angle of the surface of the glass substrate with respect to water. The measurement method is the same as described above.

<Storage stability>

The negative-type photosensitive resin composition was stored in a glass screw bottle at 23 ° C. (room temperature) for one month. After one month of storage, a negative-type photosensitive resin composition was applied to a surface of a 10 cm × 10 cm glass substrate which was washed in the same manner as in the production of the cured film (partition wall) using a spinner to form a coating film. Then, it was dried on a hot plate at 100 ° C. for 2 minutes to form a dry film having a film thickness of 2 μm. The appearance of the dried film was visually observed and evaluated based on the following criteria.

(Benchmark)

○ (Good): The number of foreign matters on the dried film was 5 or less.

× (defective): There are 6 or more foreign matters on the dried film, and a radial wrinkle pattern is observed from the center portion of the glass substrate.

[Example 2]

A negative photosensitive resin composition 2 and a glass having a cured film of the negative photosensitive resin composition 2 formed in the same manner as in Example 1 except that the (D2-1) solution was used instead of the (D1-1) solution. The substrate (2) was evaluated in the same manner as in Example 1.

[Example 3]

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

[Example 4]

A negative photosensitive resin composition 4 and a glass on which a cured film of the negative photosensitive resin composition 4 was formed were produced in the same manner as in Example 1 except that the (Dcf-1) solution was used instead of the (D1-1) solution. The substrate (4) was 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.

[Table 2]

As can be seen from Table 2, since the hardened films obtained in Examples 1, 2, and 3 use the ink repellent of the present invention, even if the exposure amount is very low, good ink repellency can still be displayed, and it can be maintained after ultraviolet / ozone irradiation. High ink repellency, and the glass substrate surface has good hydrophilicity. It is also known that the storage stability is also high. On the other hand, it can be known that, since the ink repellent agent according to the present invention is used in Example 4, it is impossible to maintain high ink repellency after ultraviolet / ozone irradiation.

Industrial availability

The partition wall formed by using the negative photosensitive resin composition of the present invention has good ink repellency, and can maintain the ink repellency after ultraviolet / ozone irradiation, and can be effectively used as a uniform coating printing on the opening portion divided by the partition wall. The optical element forming the dots accurately is used next to the wall. In addition, the negative photosensitive resin composition of the present invention is used in organic layers such as light emitting layers of various optical elements, especially organic EL elements, quantum dot layers and hole transport layers in quantum dot displays, conductor patterns and semiconductor patterns in TFT arrays, Among the organic semiconductor layer, gate electrode, source electrode, drain electrode, gate wiring and source wiring, thin-film solar cell, etc. constituting the TFT channel layer, it can be suitably used as a barrier wall for pattern printing using the IJ method. Composition is used.

However, the entire contents of the specification, patent application scope, drawings, and abstract of Japanese Patent Application No. 2014-092092, which was filed on April 25, 2014, are incorporated herein as a disclosure of the specification of the present invention.

Claims (15)

A negative photosensitive resin composition containing an alkali-soluble resin (A), a crosslinking agent (B), a photoacid generator (C), and an ink repellent (D), the ink repellent (D) containing a hydrolyzable silane Compound (s1) is a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group; The content of the alkali-soluble resin (A), the ink repellent (D) is 0.2 to 3 parts by mass. The negative photosensitive resin composition according to claim 1, wherein the fluorine atom content in the ink repellent (D) is 1 to 40% by mass. For example, the negative photosensitive resin composition of claim 1 or 2, wherein the ink repellent (D) contains a hydrolyzable silane compound (s2) as a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane The compound (s2) has four hydrolyzable groups bonded to a silicon atom. For example, the negative photosensitive resin composition of claim 1 or 2, wherein the ink repellent (D) contains a hydrolyzable silane compound (s3) as a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane The compound (s3) has only a hydrocarbon group and a hydrolyzable group. For example, the negative photosensitive resin composition of claim 1 or 2, wherein the ink repellent (D) contains a hydrolyzable silane compound (s4) as a monomer and / or a partially hydrolyzed (co) condensate, and the hydrolyzable silane compound (s4) It has a cationically polymerizable group and a hydrolyzable group and does not contain a fluorine atom. According to the negative photosensitive resin composition of claim 1 or 2, wherein the content of the alkali-soluble resin (A) mentioned above accounts for 10 to 90% by mass of the total solid content of the negative photosensitive resin composition. For example, the negative photosensitive resin composition of claim 1 or 2, wherein the content of the crosslinking agent (B) and the photoacid generator is 2 to 50 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). And 0.1 to 20 parts by mass. For example, the negative photosensitive resin composition of claim 1 or 2, wherein the content of the ink repellent (D) is 0.01 to 20 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). For example, the negative photosensitive resin composition of claim 1 or 2 further contains a solvent (E) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and diethyl ether. At least one of the group consisting of glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, and 2-propanol. For example, the negative photosensitive resin composition of claim 9, wherein the content of the solvent (E) is 50 to 99% by mass based on the total amount of the negative photosensitive resin composition. A partition wall is formed in a shape that divides a substrate surface into a plurality of dot-forming partitions, and the partition wall is made of a cured film of a negative photosensitive resin composition according to any one of claims 1 to 10. For example, the partition wall of claim 11 has a width of 100 μm or less, a distance (pattern width) between the partitions of 300 μm or less, and a height of 0.05 to 50 μm. An optical element has a plurality of points on a substrate surface and a partition wall between adjacent points. The optical element is characterized in that the partition wall is formed by a partition wall according to claim 11 or 12. The optical element according to claim 13, wherein the aforementioned dots are formed by an inkjet method. The optical element according to claim 13 or 14, wherein the aforementioned optical element is an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell.