KR20160146719A - Negative photosensitive resin composition, partition, and optical element - Google Patents

Abstract

A negative photosensitive resin composition which is capable of forming a repellent ink layer having a sufficient ink repellency at a low exposure amount on an upper surface thereof and which can be used for the production of barrier ribs capable of maintaining excellent ink repellency even after an ink- A partition wall of an optical element having an ink layer and capable of forming a fine and highly precise pattern and capable of maintaining good ink repellency even after an ink fusing treatment and an opening uniformly coated with an opening divided by the partition wall, Provided is an optical element having dots formed with good precision. A negative-working photosensitive resin composition comprising an alkali-soluble resin, a crosslinking agent, a photoacid generator, and a repellent agent containing a fluoroalkyl group and / or a hydrolyzable silyl compound having a fluoroalkyl group and a hydrolyzable group, An optical element having a cured film and barrier ribs formed using the composition, and barrier ribs located between the plurality of dots and adjacent dots on the substrate surface.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative photosensitive resin composition, a barrier rib and an optical element,

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

In the production of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays and thin film solar cells, organic layers such as light emitting layers are used as dots, There is a case to use the method. In this method, a partition wall is formed along the contour of a dot to be formed, and ink containing a material for the organic layer is injected into a partition surrounded by the partition (hereinafter also referred to as " opening " Heating or the like to form dots of a desired pattern.

In this method, in order to prevent mixing of the ink between adjacent dots and to uniformly apply the ink in the dot formation, the upper surface of the partition has ink-repellency and the dot formation The opening of the mask needs to have an inkphilic property.

In order to obtain barrier ribs having ink repellency on the upper surface, there is known a method of forming barrier ribs corresponding to dot patterns by photolithography using a photosensitive resin composition containing a repellent agent. As the photosensitive resin, radical polymerization type photosensitive resin and cationic polymerization type photosensitive resin are widely used. However, in a radical polymerization type photosensitive resin composition, it is known that curing of the outermost surface is inhibited by oxygen. Therefore, in order to develop sufficient ink repellency on the outermost surface by using a photosensitive resin composition containing a repellent agent, a sufficient amount of exposure is required, and as a result, when the sensitivity, patterning shape, .

On the other hand, when a cationic polymerization type photosensitive resin is used, it is possible to impart the ink repellency to the surface with a small exposure dose without being affected by the oxygen inhibition associated with the above surface hardening. As a composition comprising such a cationic polymerization type photosensitive resin and a repelling ink agent, Patent Document 1 discloses a composition comprising a copolymer comprising a structural unit derived from an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms, A composition comprising a liquid agent and a cationic polymerization type photosensitive resin is described.

International Publication No. 2012/057058

The liquid repellent agent described in Patent Document 1 is fixed to the surface of the partition wall with a small exposure dose at the time of forming the partition wall, but the liquid repellent agent is not cleaned by, for example, cleaning with an aqueous alkaline solution Resistance to the ink-affinity treatment such as treatment, ultraviolet cleaning treatment, ultraviolet / ozone cleaning treatment, excimer cleaning treatment, corona discharge treatment and oxygen plasma treatment is not sufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the above point, and it is an object of the present invention to provide an ink repellent ink composition which can form a repellent ink layer having sufficient ink repellency at a low exposure dose on the upper surface of a partition wall, Which can be used for the production of barrier ribs that can be used for a negative photosensitive resin composition.

An object of the present invention is to provide an optical element which has a repellent ink layer having a sufficient ink repellency on the upper surface and which is capable of forming a fine and highly precise pattern, And to provide a barrier rib of the electrode.

It is another object of the present invention to provide an optical element having dots uniformly coated with openings divided into barrier ribs and formed with good precision, specifically, an organic EL element, a quantum dot display, a TFT array or a thin film solar cell The purpose.

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

[1] A method for producing a fluorine-containing polymer, which comprises reacting an alkali-soluble resin (A), a crosslinking agent (B), a photo acid generator (C), a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable silane compound (s1) And / or a partially hydrolyzable (co) condensate. The negative-working photosensitive resin composition according to claim 1,

[2] The negative-type photosensitive resin composition according to [1], wherein the content of fluorine atoms in the repellent agent (D) is 1 to 40 mass%.

[3] The ink-repellent agent (D) as described in [1] or [2], wherein the ink-repellent agent (D) contains a hydrolyzable silane compound (s2) having four hydrolyzable groups bonded to a silicon atom as monomers and / 2]. ≪ / RTI >

[4] The ink-repellent agent (D) as described in any one of [1] to [3] above, wherein the repellent silane compound (s3) having only a hydrocarbon group and a hydrolyzable group as a monomer and / The negative-type photosensitive resin composition described in any one of < 1 >

[5] The ink-repellent agent (D) is a composition comprising a cationically polymerizable group and a hydrolyzable silane compound (s4) having a hydrolyzable group and containing no fluorine atom as a monomer and / or a partially hydrolyzed (co) The negative-working photosensitive resin composition according to any one of [1] to [4] above.

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

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the crosslinking agent (B) and the photoacid generator is 2 to 50 parts by mass and 0.1 to 20 parts by mass relative to 100 parts by mass of the alkali- (2) The negative-type photosensitive resin composition according to any one of (1) to (3) above.

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

[9] The ink composition according to any one of [1] to [8], further comprising at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate and 2- ) As described in any one of [1] to [8] above.

[10] The negative-working photosensitive resin composition according to any one of the above-mentioned [1] to [9], wherein the content of the solvent (E) is 50 to 99% by mass with respect to the total amount of the negative-working photosensitive resin composition.

[11] A partition made of a cured film of the negative photosensitive resin composition according to any one of [1] to [10], wherein the partition is formed by dividing the substrate surface into a plurality of sections for dot formation.

[12] A partition according to the above [11], wherein the width is 100 μm or less, the distance between the partition walls (width of the pattern) is 300 μm or less, and the height is 0.05 to 50 μm.

[13] An optical element having a plurality of dots on a surface of a substrate and barrier ribs positioned between adjacent dots, wherein the barrier ribs are formed of barrier ribs as described in [11] or [12] above.

[14] The optical element according to [13], wherein the dot is formed by an ink-jet method.

[15] The optical element described in [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-working photosensitive resin composition of the present invention, it is possible to form a repellent ink layer having sufficient ink repellency at a low exposure amount on the upper surface of the partition wall, and even when the repellent ink layer is subjected to the ink- It is possible to manufacture a barrier wall capable of sustaining the characteristics.

The partition wall of the present invention is a partition wall having an ink repellent layer having sufficient ink repellency on the upper surface and capable of forming a fine and highly precise pattern and uniformly applying ink to the opening divided by the partition wall, An organic EL device, a quantum dot display, a TFT array, or a thin film solar cell using an optical element having dots formed thereon.

1A is a process diagram schematically showing a manufacturing method of a partition wall according to an embodiment of the present invention.
Fig. 1B is a process diagram schematically showing a manufacturing method of a partition wall according to an embodiment of the present invention.
Fig. 1C is a process diagram schematically showing a manufacturing method of a partition wall according to an embodiment of the present invention.
FIG. 1D is a process diagram schematically showing a manufacturing method of a barrier rib in the embodiment of the present invention.
2A is a process diagram schematically showing a manufacturing method of an optical element according to an embodiment of the present invention.
Fig. 2B is a process diagram schematically showing a manufacturing method of an optical element according to an embodiment of the present invention.

The definitions of terms in this specification are summarized below.

The "(meth) acryloyl group" is a general term for "methacryloyl group" and "acryloyl group". (Meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide and (meth) acrylic resins.

The group represented by the formula (x) may be simply referred to as group (x).

The compound represented by the formula (y) may be simply referred to as the compound (y).

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

The "side chain" is a polymer other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which the repeating unit composed of carbon atoms constitutes the main chain. The "unit" of the fluorine atom-containing unit and the like represents a polymerization unit.

Refers to a component that forms a cured film to be described later among the components contained in the photosensitive resin composition. The photosensitive resin composition is heated at 140 占 폚 for 24 hours to obtain a residue from which the solvent has been removed. In addition, the total solid content can also be calculated from the amount of injection.

The film comprising the cured product of the composition containing the resin as the main component is referred to as " resin cured film ".

The film coated with the photosensitive resin composition is referred to as a " coating film ", and the film obtained by drying it is referred to as a " dried film ". The film obtained by curing the "dry film" is a "resin cured film". Also, the " resin cured film " may be simply referred to as a " cured film ".

The " barrier rib " is a form of a resin cured film formed by dividing a predetermined region into a plurality of sections. For example, the following " ink " is injected into an opening surrounded by the partition, that is, the partition surrounded by the partition, to form a " dot ".

The term " ink " is a generic term for a liquid having optical and / or electrical functions after drying, curing and the like.

In an optical element such as an organic EL element, a color filter of a liquid crystal element, and a TFT (Thin Film Transistor) array, a dot as various constituent elements is pattern printed by an inkjet (IJ) method using the ink for forming the dot There is a case. The " ink " includes an ink used for such use.

The term " ink repellency " means a property of repelling the ink, and has both water repellency and oil repellency. The ink repellency can be evaluated, for example, by the contact angle when the ink is dripped. The " inkphilic property " is a property that is inferior to that of the ink on ink, and can be evaluated by the contact angle when the ink is dripped in the same manner as the ink performance. Alternatively, the inkphilicity can be evaluated by evaluating the degree of wetting diffusion of the ink when the ink is dripped (wettability of the ink) on a predetermined basis.

The " dot " refers to the minimum light-modulating area in the optical element. In the case of the organic EL element, the color filter of the liquid crystal element, and the optical element of the organic TFT array, one dot = one pixel in the case of monochrome display and three dots (R (red) G (green), B (blue), etc.) = 1 pixel.

Hereinafter, embodiments of the present invention will be described. In the present specification, unless otherwise specified,% represents mass%.

[Negative photosensitive resin composition]

The negative-working photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a crosslinking agent (B), a photo acid generator (C), a hydrolyzable silane having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group (D) containing a compound (s1) as a monomer and / or a partially hydrolyzed (co) condensate.

The negative-working photosensitive resin composition of the present invention further contains, if necessary, a solvent (E) and other optional components.

(Alkali-soluble resin (A))

As the alkali-soluble resin (A) in the negative-working photosensitive resin composition of the present invention, it is preferable that the alkali-soluble resin (A) is combined with the crosslinking agent (B) by the action of an acid generated by the photoacid generator (C) , And a cationically polymerizable alkali-soluble resin (A) which is cross-linked and becomes alkali-insoluble, can be used without particular limitation.

Examples of the alkali-soluble resin (A) include non-modified or modified novolac phenolic resins and vinylphenol resins (hereinafter referred to as " polyvinylphenol resins ") prepared by polycondensation of phenols and aldehydes, ), A copolymer of N- (4-hydroxyphenyl) methacrylamide, a hydroquinone monomethacrylate copolymer, and the like. A variety of alkali-soluble polymer compounds such as a sulfonylimide polymer, a carboxyl group-containing polymer, an acrylic resin containing a phenolic hydroxyl group, an acryl resin having a sulfonamide group, and a urethane resin can also be used.

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

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

Of the novolak type phenolic resins, novolak type phenolic resins using cresols, xylenols, and the like are preferably used as the phenols from the viewpoints of availability and less metal impurities, and novolak type phenol resins (Hereinafter also referred to as " cresol novolak resin ") is particularly preferable.

Examples of the polyvinyl phenol include a homopolymer of vinylphenol, a copolymer of vinylphenol and a monomer copolymerizable therewith, and the like.

The polyvinyl phenol may be a vinylphenol such as 4-vinylphenol, 3-vinylphenol, 2-vinylphenol, 2-methyl-4-vinylphenol and 2,6-dimethyl- , And radical polymerization using a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide.

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

The weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 500 to 20,000, particularly preferably 2,000 to 15,000. If the mass average molecular weight (Mw) of the alkali-soluble resin (A) is too low, the molecular weight can not be sufficiently increased even if a crosslinking reaction occurs in the exposed area, so that the resin tends to be dissolved in an alkali developing solution. 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 developing solution becomes small, so that it becomes difficult to obtain a good resist pattern.

The mass-average molecular weight (Mw) means a mass-average molecular weight of a polystyrene standard based on standard polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. The number average molecular weight (Mn) means the number average molecular weight measured by the same GPC.

As the commercially available products of cresol novolak resins, for example, EP4020G (Mw: 9,000 to 14,000) and EPR5010G (Mw: 7,000 to 12,500) (trade names, Ltd.) and commercially available products of polyvinyl phenol include Marukarinka M (trade name, manufactured by Maruzen Petrochemical Co., Ltd.).

The alkali-soluble resin (A) may be used alone or in combination of two or more.

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

(Crosslinking agent (B))

The crosslinking agent (B) binds to the alkali-soluble resin (A) by the action of an acid generated by the photoacid generator (C) by irradiation of an actinic ray (exposure) A compound capable of becoming insoluble in alkali (a reducing substance).

Examples of the crosslinking agent (B) include low-molecular crosslinking agents such as melamine-based, benzoguanamine-based, urea-based and isocyanate-based compounds, polyfunctional epoxide group-containing compounds and oxetane-based compounds, alkoxyalkylated melamine resins or alkoxyalkylated urea resins A polymer crosslinking agent such as alkylated amino resin and the like are preferable.

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

Examples of the benzoguanamine compound include benzoguanamine, methylated benzoguanamine, and the like.

Examples of the urea compound include urea, monomethylol urea, dimethylol urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea, ethylene urea carboxylic acid, tetrakis (methoxymethyl) glycoluril . Examples of the isocyanate compound include hexamethylene diisocyanate, 1,4-cyclohexyldiisocyanate, toluene diisocyanate, bisisocyanate methylcyclohexane, bisisocyanate methylbenzene, and ethylene diisocyanate.

The polyfunctional epoxide group-containing compound preferably contains at least one benzene ring or heterocyclic ring in one molecule and further contains two or more epoxy groups. For example, there may be mentioned bisphenol acetone diglycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl-m-xylenediamine, tetraglycidyl- 3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetated diglycidyl ether, 4,4'-bis Phenoxy) -oxafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metha xylene diamine, and the like.

The oxetane-based compound preferably contains two or more oxetanyl groups in one molecule, and examples thereof include xylylene bisoxetane, 3-ethyl-3 {[3-ethyloxetan-3-yl] Methoxy] methyl} oxetane, and the like.

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

PL-1170, PL-1174, UFR65, CYMEL300, CYMEL303 (manufactured by Mitsui Cytec), BX-4000 (trade name) , NIKARAK MW-30, MX290, MW-100LM (manufactured by Sanwa Chemical Co., Ltd.), and the like.

The crosslinking agent (B) may be used alone or in combination of two or more. The blending amount thereof is preferably 2 to 50 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). When the amount of the cross-linking agent (B) is too small, it is difficult for the cross-linking reaction to proceed sufficiently, and the residual film ratio of the resist pattern after development using an alkali developing solution is lowered and the resist pattern is more likely to be deformed . If the amount of the cross-linking agent (B) used is too large, the resolution may be lowered.

(Photoacid generator (C))

The photoacid generator (C) is not particularly limited as long as it is a compound capable of decomposing to generate an acid upon irradiation with an actinic ray. In the photosensitive resin composition using the cationically polymerizable alkali-soluble resin (A), any of the compounds generally used as the photoacid generator may be selected and used.

In the negative-working photosensitive resin composition of the present invention, the acid generated from the photoacid generator (C) is related to the bond between the alkali-soluble resin (A) and the crosslinking agent (B) And functions as a catalyst for the hydrolysis reaction of the fluorine-containing hydrolyzable silane compound (s1) contained therein. Usually, an acid catalyst is added to a composition containing a hydrolyzable silane compound. As a result, the reaction progresses slowly and storage stability becomes a problem. However, in the negative photosensitive resin composition of the present invention, since it is not necessary to form an acid separately from the photoacid generator (C), the storage stability Good.

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

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

[Chemical Formula 1]

In the formulas (C1) and (C2), Xa ^- and Xb ^- represent an anion. Specifically, the anion of phosphorus, for example, PF ₆ ^- , (R ^f1 ) _n PF _{6 -n} ^- (R ^f1 is a fluoroalkyl group, n is 1 to 3) An anion such as R ^a SO ₃ ^- (R ^a is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 18 carbon atoms which may be partially or wholly substituted with a fluorine atom). Examples of R ^{a in} R ^a SO ₃ ^- include perfluoroalkyl groups such as -CF ₃ , -C ₄ F ₉ and -C ₈ F ₁₇ , perfluoroaryl groups such as -C ₆ F ₅ , Ph-CH ₃ (wherein Ph represents a phenyl group), and the like.

Further, in these onium salts, the cationic portion absorbs the irradiated light and becomes the source of the anionic addition acid.

In the compounds (C1) and (C2), for example, the compound used when the exposure is carried out with i-line (365 nm) includes triphenylsulfonium nonafluoro Or a triarylsulfonium · PF ₆ salt and a triarylsulfonium · special phosphorus salt represented by the following formulas (C2-1) and (C2-2), respectively, have a large absorbance at a wavelength of 365 nm And is preferable in terms of easiness to obtain.

(2)

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

Examples of the iodonium salt compound include diphenyliodonium trifluoromethanesulfonate, phenyl iodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyl iodonium p-toluenesulfonate, p-toluenesulfonic acid (p -tert-butoxyphenyl) phenyliodonium, and the like.

Commercially available onium salt photoacid generators may be used. CPI-210S (compound (C2-1), trade name, manufactured by SANA PRO), TPSP-PFBS (compound (C1-1), trade name, manufactured by Toyobo Co., 2), trade name, manufactured by SANA PRO.

Examples of the nonionic system photoacid generator include a naphthalimide skeleton, a nitrobenzene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, a thiokitosan skeleton, and a triazine skeleton, and a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid And the like.

Specific examples of such a compound include naphthalimide skeleton represented by the following formula (C3), the following formula (C4), the following formula (C5), the following formula (C6) , A diazomethane skeleton, a phenylacetophenone skeleton, or a thiochitosan skeleton, and having a structure in which alkanesulfonic acid, arylsulfonic acid, etc. are bonded. Further, a compound having a triazine skeleton and a chlorine atom shown by the following formula (C8) can be mentioned. A sulfonyl compound of a dialkylglyoxime represented by the following formula (C9), sulfonyloxyiminoacetonitrile represented by the following formula (C10), and the like.

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

(3)

R ^b1 to R ^b5 , R ^b7 and R ^b9 in the formulas (C3) to (C7), (C9) and (C10) each independently represents a linear, branched or cyclic alkyl group which may be partially or wholly substituted with a fluorine atom, An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 18 carbon atoms in a branched or cyclic form (including partially cyclic structures). 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 formulas (C8), (C9) and (C10) each independently represent an organic group having 1 to 18 carbon atoms which may have a substituent.

In these non-ionic photoacid generators, a portion in which a chlorine atom, an alkane sulfonic acid, an aryl sulfonic acid, or the like is bonded becomes a source of an acid.

Examples of the nonionic system photoacid generator include N-trifluoromethanesulfonic acid-1 represented by the following formula (C3-1) as a compound used for carrying out exposure with i-line (365 nm) 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone represented by the following formula (C6-1) and 2- (4-methoxy Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine are preferred because of their high absorbance at a wavelength of 365 nm or because they are easy to obtain.

[Chemical Formula 4]

Commercially available products may be used for the nonionic system photoacid generators. For example, NHNI-TF (compound (C3-1), trade name, manufactured by Toyobo Co., Ltd.) can be mentioned.

Examples of the acid generated by the action of light from the onium salt-based photoacid generator and the nonionic system photoacid generator include hydrochloric acid, alkanesulfonic acid, arylsulfonic acid, partially or fully fluorinated arylsulfonic acid, alkanesulfonic acid, and the like.

As the photoacid generator (C), one of the above compounds may be used alone, or two or more of them may be used in combination.

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

(The ink-repellent agent (D))

The repelling ink (D) in the present invention contains a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group. The repellent silane compound (s1) may be used singly or as a mixture of a hydrolyzable silane compound (s1) and a hydrolyzable silane compound other than the hydrolyzable silane compound (s1) You can. The repellent ink (D) is preferably composed of only the hydrolyzable silane compound containing the hydrolyzable silane compound (s1).

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

In the following, it is meant that the repellent agent (D) contains a specific hydrolyzable silane compound and contains the hydrolyzable silane compound as a monomer and / or partial hydrolyzed (co) condensate. Here, the " monomer and / or partially hydrolyzed (co) condensation product " is the same as that defined above.

Since the hydrolyzable silane compound (s1) has a fluoroalkylene group and / or a fluoroalkyl group, the negative tone photosensitive resin composition containing the hydrolyzable silane compound (s1) (Top surface transition property) and ink repellency. By using the repellent agent (D), the upper layer portion including the upper surface of the resulting partition wall becomes a layer in which the repellent ink (D) is densely present (hereinafter also referred to as a " repellent ink layer " Ink repellency is imparted to the upper surface. Since such a ink layer is mainly formed of a cured product of a hydrolyzable silane compound containing a hydrolyzable silane compound (s1), excellent ink repellency can be obtained even when it is subjected to an inking treatment such as an ultraviolet / ozone cleaning treatment It is advantageous in terms of sustainability.

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

The ink-repellent agent (D) is preferably a mixture (hereinafter sometimes referred to as a "mixture (M)") of a substantially monomer of a hydrolyzable silane compound containing a hydrolyzable silane compound (s1) M). ≪ / RTI > The mixture (M) contains, as an essential component, a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolysable group, and optionally a hydrolyzable silane compound (s1) other than the hydrolyzable silane compound Lt; / RTI >

The fact that the hydrolyzable silane compound is substantially a monomer does not mean that the total amount of the hydrolyzable silane compound is a monomer but may include a partial hydrolysis and condensation product of a low molecular weight of about 2 to 10 , And further, it may consist of only the partially hydrolyzed condensate.

Examples of the hydrolyzable silane compound optionally contained in the mixture (M) include the following hydrolyzable silane compounds (s2) to (s4). In addition, other hydrolyzable silane compounds may be contained. As the hydrolyzable silane compound optionally contained in the mixture (M), the hydrolyzable silane compound (s2) is particularly preferable. When the repellent silane compound (s4) is contained in the repellent agent (D), the repellent agent (D) is preferably composed of the mixture (M). When the hydrolyzable silane compound (s4) is not contained, the repellent agent (D) may be composed of the mixture (M) or may be a partially hydrolyzed (co) condensation product thereof.

A hydrolyzable silane compound (s2); Hydrolyzable silane compounds having four hydrolyzable groups bonded to silicon atoms.

A 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.

A hydrolyzable silane compound (s4); A hydrolyzable silane compound having a cationically polymerizable group and a hydrolyzable group and containing no fluorine atom.

Hereinafter, the hydrolyzable silane compounds (s1) to (s4) and other hydrolyzable silane compounds will be described.

≪ 1 > The hydrolyzable silane compound (s1)

By using the hydrolyzable silane compound (s1), the repellent agent (D) has a fluorine atom in the form of a fluoroalkylene group and / or a fluoroalkyl group, and has excellent surface migration and ink repellency. The hydrolyzable silane compound (s1) is preferably at least one selected from the group consisting of a fluoroalkyl group, a perfluoroalkylene group and a perfluoroalkyl group, in order to increase the properties of the hydrolyzable silane compound (s1) And more preferably one having a perfluoroalkyl group. A perfluoroalkyl group containing an etheric oxygen atom is also preferable. That is, the most preferred compound as the hydrolyzable silane compound (s1) is a compound having a perfluoroalkyl group and / or a perfluoroalkyl group containing an etheric oxygen atom.

Examples of the hydrolyzable group include groups in which at least one hydrogen of an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group or an amino group is substituted with an alkyl group. An alkoxy group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferable since it is a hydroxyl group (silanol group) by a hydrolysis reaction, and a reaction for condensation reaction between molecules to form a Si- A halogen atom is preferable, a methoxy group, an ethoxy group or a chlorine atom is more preferable, and a methoxy group or an ethoxy group is particularly preferable.

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

As the hydrolyzable silane compound (s1), a compound represented by the following formula (dx-1) is preferable.

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

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

R ^H11 is a hydrocarbon group having 1 to 6 carbon atoms.

a is 1 or 2, b is 0 or 1, and a + b is 1 or 2.

A is a fluorine atom or a group represented by the following formula (Ia).

-Si (R ^H12 ) _c ^X12 _(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 a plurality of X < ¹¹ > exist, they may be different from each other or may be the same.

When a plurality of X < ¹² > exist, they may be different from each other or may be the same.

When a plurality of AR ^F11 exist, they may be the same or different.

The compound (dx-1) is a fluorinated hydrolyzable silane compound having one or two hydrolyzable silyl groups having two or three functionalities.

Each of R ^H11 and R ^H12 is independently a hydrocarbon group having 1 to 3 carbon atoms, and a methyl group is particularly preferable.

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

Specific examples and preferred embodiments of X < ¹¹ > and X < ¹² > are as described above.

As the hydrolyzable silane compound (s1), a compound represented by the following formula (dx-1a) is particularly preferable.

TR ^F12 -Q ¹¹ -SiX ¹¹ ₃ ... (dx-1a)

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

T is a fluorine atom or a group represented by the following formula (Ib).

-Q ¹² -SiX ¹² ₃ ... (Ib)

X ¹¹ and X ¹² are each independently a hydrolyzable group.

The three X < ¹¹ > may be the same or different.

The three X ¹² may be the same or different.

Q ¹¹ and Q ¹² each independently represent a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms.

In the formula (dx-1a), when T is a fluorine atom, R ^F12 is a perfluoroalkylene group having 4 to 8 carbon atoms or a perfluoroalkylene group containing an etheric oxygen atom having 4 to 10 carbon atoms A perfluoroalkylene group having 4 to 8 carbon atoms is more preferable, and a perfluoroalkylene group having 6 carbon atoms is particularly preferable.

In the formula (dx-1a), when T is the group (Ib), R ^F12 represents a perfluoroalkylene group having 3 to 15 carbon atoms or an etheric oxygen atom having 3 to 15 carbon atoms Is preferable, and a perfluoroalkylene group having 4 to 6 carbon atoms is particularly preferable.

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

^Examples of the structure of R ^{F12 include} a linear chain structure, a branched chain structure, a cyclic structure, and a structure having a partially cyclic structure, and a linear chain structure is preferable.

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

Q ¹¹ and Q ¹² are represented by - (CH ₂ ) _i 1 - (i 1 is an integer of 1 to 5, when Si is bonded to the right hand and R ^F12 is bonded to the left hand, _{), -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, a methyl group, or ethyl group, i3 is 1 is an integer of 1-4, R ¹ and (CH _{2) i3} sum of the carbon atoms is an integer of less than 4), or ^{- (C = O) -NR 1} - (CH 2) i4 - (R 1 is the identical to, i4 is preferably a group represented by an integer from ¹ ~ 4, R 1 and (CH ₂₎ the sum of the number of carbon atoms in the _i4 is an integer of less than 4). As Q ¹¹ and Q ¹² , - (CH ₂ ) _{i 1} -, in which i 1 is an integer of 2 to 4, is more preferable, and - (CH ₂ ) ₂ - is particularly preferable.

When R ^F12 is a perfluoroalkylene group containing no etheric oxygen atom, groups represented by - (CH ₂ ) _i1 - are preferable as Q ¹¹ and Q ¹² . i1 is more preferably an integer of 2 to 4, and particularly preferably 2.

When R ^F12 is a perfluoroalkyl group containing an etheric oxygen atom, roneun Q ¹¹ and _{^{Q 12, - (CH 2)}} i1 -, -CH 2 O (CH 2) i2 -, -SO 2 NR 1 - ( CH _{2) i3} -, or ^{- (C = O) -NR 1} - (CH 2) i4 - groups are preferred as shown. In this case also, - (CH ₂ ) _{i 1} - is more preferable as Q ¹¹ and Q ¹² . i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.

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

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

Roneun In the present invention, the compound (dx-1a), among _{them, 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 ratio of the fluorine atom content in the partially hydrolyzed (co) condensate obtained from the mixture or the mixture thereof to 1 to 40 mass% . The fluorine atom content is more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. If the content of the hydrolyzable silane compound (s1) is not lower than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. If the content is lower than the upper limit value, the other hydrolyzable silane compound or the negative photosensitive resin composition The compatibility with other components in the composition is improved.

≪ 2 > The hydrolyzable silane compound (s2)

In a cured film obtained by curing a negative photosensitive resin composition containing a repellent agent (D) by containing a hydrolyzable silane compound (s2) having silicon atoms bonded to four hydrolyzable groups in a mixture (M) It is possible to increase the film-forming property after the upper surface of the layer (D) has shifted. That is, since the number of hydrolyzable groups in the hydrolyzable silane compound (s2) is large, it is thought that the ink D is well condensed after the top surface is transferred, and a thin film is formed on the entire upper surface, do.

When the hydrolyzable silane compound (s2) is contained in the mixture (M), when the partially hydrolyzed condensate is used, the ink D is easily dissolved in the hydrocarbon solvent.

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

As the hydrolyzable group, the same hydrolyzable group 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 the same or different. As X ² , the same groups as X ¹¹ and X ¹² are used.

Specific examples of the compound (dx-2) include the following compounds. As the compound (dx-2), a partial hydrolysis-condensation product obtained by partially hydrolyzing and condensing a plurality of such compounds, for example, 2 to 10, may be used, if necessary.

_{Si (OCH 3) 4, Si} (OC 2 H 5) 4, Si (OCH 3) ₄ parts of the product of hydrolysis and condensation, or Si (OC ₂ H _{5) 4} partially hydrolyzed condensate of.

The content of the hydrolyzable silane compound (s2) in the mixture (M) is preferably 1 to 20 moles, more preferably 3 to 18 moles, per 1 mole of the hydrolyzable silane compound (s1). If the content of the ink D is less than the lower limit of the above range, the film forming property of the ink D is good, and if it is not more than the upper limit value, the ink repellency of the ink D is good.

≪ 3 > The hydrolyzable silane compound (s3)

In the case of using the hydrolyzable silane compound (s2) in the mixture (M), for example, a bulge may be formed at the end of the upper surface of the partition wall formed by curing the photosensitive resin composition. This ridge was microscopic at a level observed by a scanning electron microscope (SEM) or the like, but it was confirmed that the content of F and / or Si was larger than other portions.

However, the present inventors have found that, by replacing a part of the hydrolyzable silane compound (s2) with the hydrolyzable silane compound (s3) having a small number of hydrolyzable groups, The occurrence of which is suppressed.

The film forming property of the ink repellent agent (D) is increased by the reaction between the silanol groups formed by the hydrolyzable silane compound (s2) having a large number of hydrolyzable groups, but the ridges are thought to occur due to the high reactivity thereof. Thus, it is considered that the substitution of a part of the hydrolyzable silane compound (s2) with the hydrolyzable silane compound (s3) having a small number of hydrolyzable groups suppresses the reaction between the silane groups and suppresses the occurrence of the ridges.

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

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

As the hydrolyzable silane compound (s3), a compound represented by the following formula (dx-3) is preferable.

^{_{(R H5) j -SiX 5 (}} 4-j) ... (dx-3)

In the formula (dx-3), R ^H5 is a hydrocarbon group having 1 to 20 carbon atoms.

X ⁵ is a hydrolyzable group.

j is an integer of 1 to 3, preferably 2 or 3.

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

When a plurality of X < ⁵ > exist, they may be the same or different.

As 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 can be exemplified, and an alkyl group having 1 to 10 carbon atoms, a phenyl group and the like are preferable . When j is 2 or 3, R ^H5 is preferably a hydrocarbon group of 1 to 6 carbon atoms, more preferably a hydrocarbon group of 1 to 3 carbon atoms.

As X ⁵ , the same groups as X ¹¹ and X ¹² are used.

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

The content of the hydrolyzable silane compound (s3) in the mixture (M) is preferably 1 to 10 moles, more preferably 3 to 8 moles, per 1 mole of the hydrolyzable silane compound (s1). If the content ratio is not less than the lower limit of the above range, the rise of the end portion of the upper surface of the partition can be suppressed. If it is not more than the upper limit value, the ink repellency of the repellent agent (D) is good.

≪ 4 > The hydrolyzable silane compound (s4)

It is preferable that the mixture (M) optionally contains a hydrolyzable silane compound (s4) having a cationically polymerizable group and a hydrolyzable group and not containing a fluorine atom. The hydrolyzable silane compound (s4) is contained in the mixture (M), for example, by reacting with the cross-linking agent (B) contained in the photosensitive resin composition via the cationic polymerizable group, An effect of enhancing the fixability of the toner (D) can be obtained.

As the hydrolyzable silane compound (s4), a compound represented by the following formula (dx-4) is preferable.

_{^{(EQ 6) s -Si (R}} H6) t X 6 (4-st) ... (dx-4)

In the formula (dx-4), E is a cationic polymerizable group, for example, an oxetanyl group, an epoxy group, a glycidoxy 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 a plurality of EQ ⁶ exist, they may be the same or different.

When a plurality of X < ⁶ > exist, they may be the same or different.

As X ⁶ , the same groups as X ¹¹ and X ¹² are used.

As Q ⁶ , an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.

As R ^H6 , the same groups as R ^H11 and R ^H12 are used.

Concrete examples of the compound (dx-4) _{is, E- (CH 2) 2 -Si} (OCH 3) 3, E- (CH 2) 3 -Si (OCH 3) 3, E- (CH 2) 3 - Si (OCH ₂ CH ₃ ) ₃ , E (CH ₂ ) ₃ -Si (CH ₃ ) (OCH ₂ CH ₃ ) ₂ and the like. Among them, preferred are 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl di Ethoxy silane and the like.

The content of the hydrolyzable silane compound (s4) in the mixture (M) is preferably 0 to 99 mol%, more preferably 15 to 80 mol%, and more preferably 15 to 50 mol% based on the total amount of the mixture (M) % Is particularly preferable. The hydrolyzable silane compound (s4) may be used alone or in combination of two or more.

≪ 5 > Another hydrolyzable silane compound

The mixture (M) may further contain one or more kinds of hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s4) within a range that does not impair the effect of the present invention. The content of other hydrolyzable silane compounds in the mixture (M) is preferably not more than 40 mol%, more preferably not more than 10 mol%, based on the total amount of the mixture (M).

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

Examples of the hydrolyzable silane compound having a group having an ethylenic double bond and a hydrolyzable group and containing no fluorine atom include those described in paragraph [0057] of International Publication No. 2014/046209 have.

Specific examples of the hydrolyzable silane compound having a mercapto group and a hydrolyzable group and containing no fluorine atom include HS- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , HS- (CH ₂ ) ₃ -Si CH ₃ ) (OCH ₃ ) ₂ , and the like.

Specific examples of the hydrolyzable silane compound having an oxyalkylene group and a hydrolyzable group and containing no fluorine atom include CH ₃ O (C ₂ H ₄ O) _k Si (OCH ₃ ) ₃ (polyoxyethylene group-containing trimethylene (For example, k is about 10), and the like.

Examples of the hydrolyzable silane compound having an amino group and a hydrolyzable group and containing no fluorine atom include C ₆ H ₅ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (phenylaminopropyltrimethoxysilane) and the like .

Examples of the hydrolyzable silane compound having an isocyanate group and a hydrolyzable group and containing no fluorine atom include NCO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ (isocyanate propyltriethoxysilane) have.

≪ 6 >

The ink-repellent agent (D) is a mixture (M) or a partially hydrolyzed (co) condensation product thereof.

As an example of the ink-repellent agent (D), the compound (dx-1a) is contained as an essential component and the compound (dx-2) and the compound (dx- And a mixture (M) in which the group T is a fluorine atom. The content of each compound is preferably as described above.

In the case where the negative type photosensitive resin composition contains the repellent agent (D) in the form of the mixture (M) as described above, the step of partially hydrolyzing and condensing the repellent agent (D) can be omitted, . In addition, from the viewpoint of storage stability of the negative-working photosensitive resin composition, it is preferable.

As another example of the ink-repellent agent (D), the compound (dx-1a) is contained as an essential component, the compound (dx-2) and the compound (dx- (II) shows the average composition formula of the repellent ink (D1) which is a partially hydrolyzed condensation product of the mixture (M) in which the group T is a fluorine atom. Use of a partial hydrolysis-condensation product as the ink-repellent agent (D) is advantageous in that residues in developer rejection (openings) of the negative-type photosensitive resin composition can be reduced.

_{^{[TR F12 -Q 11 -SiO 3/2]}} n1 · [SiO 2] n2 · [(R H5) j -SiO (4-j) / 2] n3 ... (II)

In the formula (II), n1 to n3 represent the molar fraction of each constituent unit with respect to the total molar amount of the constituent units. n1 > 0, n2 > 0, n3 > 0, n1 + n2 + n3 = The other symbols are as described above. Provided that T is a fluorine atom.

Further, since the repellent agent D1 is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or silanol group remains, it is difficult to express this product in the formula.

The average composition formula represented by the formula (II) is a formula when it is assumed that both the hydrolyzable group and the silanol group in the repellent agent (D1) are siloxane bonds.

It is presumed that the units derived from the compounds (dx-1a), (dx-2) and (dx-3) in the formula (II) are randomly arranged.

N1: n2: n3 in the average composition formula represented by the formula (II) corresponds to the injection composition of the compounds (dx-1a), (dx-2) and (dx-3) in the mixture (M).

The molar ratio of each component is preferably designed from the balance of effects of each component.

n1 is preferably from 0.02 to 0.4, more preferably from 0.02 to 0.3, in an amount such that the content of fluorine atoms in the repellent agent (D1) falls within the above preferable range.

n2 is preferably 0 to 0.98 when n3 = 0, and is preferably 0.05 to 0.6 when n3 > 0.

n3 is preferably 0 to 0.5.

The preferable molar ratio of the respective components is the same when T in the compound (dx-1a) is the group (Ib).

The preferable molar ratio of the above components is such that even when the mixture (M) contains the hydrolyzable silane compound (s1), optionally the hydrolyzable silane compound (s2) and the hydrolyzable silane compound (s3) The same can be applied. That is, the preferable amount of the hydrolyzable silane compounds (s1) to (s3) in the mixture (M) for obtaining the ink for ink D repre- sents a preferable range of n1 to n3.

The number average molecular weight (Mn) when the repellent agent (D) is a partial hydrolyzed condensate of the mixture (M) is preferably 500 or more, more preferably 1,000,000 or less, and particularly preferably 10,000 or less.

When the number average molecular weight (Mn) is not lower than the lower limit value, when the partition wall is formed using the photosensitive resin composition, the ink D is liable to migrate to the upper surface. If it is less than the upper limit, the solubility of the solvent of the repellent agent (D) becomes better.

The number average molecular weight (Mn) of the releasing agent (D) can be controlled by the production conditions.

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

As the reaction, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or an organic acid such as acetic acid, oxalic acid or maleic acid is preferably used as a catalyst. If necessary, an alkali catalyst such as sodium hydroxide or tetramethylammonium hydroxide (TMAH) may be used.

A known solvent may be used for the reaction.

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

The content of the repellent agent (D) is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, and particularly preferably from 0.2 to 3 parts by mass, per 100 parts by mass of the alkali-soluble resin (A). By setting the content of the repelling agent (D) within the above range, a partition wall having sufficient ink repellency on the upper surface is obtained.

(Solvent (E))

The negative photosensitive resin composition of the present invention contains the solvent (E), whereby the viscosity is reduced, and the negative type photosensitive resin composition can be easily applied onto the substrate surface. As a result, a coating film of a negative-type photosensitive resin composition having a uniform film thickness can be formed.

As the solvent (E), a known solvent is used. As the solvent (E), one type may be used alone, or two or more types may be used in combination.

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

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

(Other components)

The negative-working photosensitive resin composition of the present invention may further contain a colorant, a thermal crosslinking agent, a polymer dispersant, a dispersion auxiliary, a silane coupling agent, a fine particle, a hardening accelerator, a thickener, a plasticizer, a defoaming agent, And the like may be contained.

The negative-working photosensitive resin composition of the present invention is obtained by mixing predetermined amounts of the respective components. The negative-working photosensitive resin composition of the present invention has good storage stability.

In addition, when the negative photosensitive resin composition of the present invention is used, it is possible to manufacture a barrier rib having a ink repellent layer having good ink repellency on the top surface at a low exposure dose. Further, even if the ink layer of the ink is subjected to an ink-lubrication treatment such as an ultraviolet / ozone cleaning treatment, it is possible to manufacture a partition wall capable of sustaining excellent ink-repellency.

The partition wall that can be produced by the present invention has a depression ink layer having sufficient ink repellency on the upper surface, and it is possible to form a fine and highly precise pattern.

According to the present invention, it is possible to provide an optical element having dots uniformly coated with ink and formed with good precision, specifically, an organic EL element, a quantum dot display, a TFT array, a thin film solar cell and the like .

[septum]

The barrier rib of the present invention comprises a cured product of the negative photosensitive resin composition formed in such a manner that the surface of the substrate is divided into a plurality of sections for dot formation. The barrier rib can be formed by applying the negative photosensitive resin composition of the present invention to the surface of a base material such as a substrate and removing the solvent or the like as necessary after drying to form a masking portion Followed by exposure, if necessary, heating and development.

Hereinafter, an example of a method of manufacturing a barrier rib in the embodiment of the present invention will be described with reference to Figs. 1A to 1D, but the method of manufacturing the barrier rib is not limited to the following. In addition, the following production method is explained as the case where the negative photosensitive resin composition contains the solvent (E).

1A, a negative photosensitive resin composition is applied to the entire one main surface of the substrate 1 to form a coating film 21. As shown in Fig. At this time, the ink D is entirely dissolved in the coating film 21 and is uniformly dispersed. 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) condensation product thereof. Note that, in Fig. 1A, the repellent agent (D) is shown schematically and does not actually exist in such a particle shape.

Next, as shown in Fig. 1B, the coating film 21 is dried to form a dried film 22. As shown in Fig. Examples of the drying method include heat drying, vacuum drying, and drying under reduced pressure. Depending on the type of the solvent (E), the heating temperature is preferably 50 to 120 ° C, more preferably 90 to 115 ° C in the case of heat drying.

In this drying process, the ink D is transferred to the upper layer of the dried film. Also, even when the negative photosensitive resin composition does not contain the solvent (E), the top surface migration of the repelling agent (D) in the coating film is achieved in the same manner.

Next, as shown in Fig. 1C, the dry film 22 is exposed to an actinic ray through a photomask 30 having a masking portion 31 having a shape corresponding to the opening surrounded by the partition wall . The film after the dry film 22 is exposed is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23A is photo-cured and the unexposed portion 23B is in the same state as the dried film 22. The exposure is carried out by the dry film 22 absorbing the active ray and decomposing the photoacid generator (C) to generate an acid. The reaction between the alkali-soluble resin (A) and the crosslinking agent (B) proceeds by the generated acid, and the curing reaction by the hydrolysis and condensation of the repelling agent (D) proceeds.

As the light to be irradiated, visible light; UV-rays ; Deep ultraviolet light; Excimer laser lights such as 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; X-rays; Electron beam and the like.

As the light to be irradiated, light having a wavelength of 100 to 600 nm is preferable, light having a wavelength of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm) Is particularly preferable. If necessary, light of 330 nm or less may be cut.

Examples of the exposure method include whole-surface batch exposure and scan exposure. It may be exposed by dividing a plurality of circuits at the same point. At this time, a plurality of exposure conditions may or may not be the same.

The exposure dose is preferably 5 to 1,000 mJ / cm 2, more preferably 5 to 500 mJ / cm 2, still more preferably 5 to 300 mJ / cm 2, and more preferably 5 to 200 mJ / / Cm < 2 > is particularly preferable, and 5 to 50 mJ / cm < 2 > The exposure amount is appropriately customized according to the wavelength of the light to be irradiated, the composition of the negative-type photosensitive resin composition, the thickness of the coating film, and the like. In the negative-working photosensitive resin composition of the present invention, sufficient curing at such a low exposure dose is possible.

The exposure time per unit area is not particularly limited, and is designed from the exposure power of the exposure apparatus to be used, the necessary exposure amount, and the like. Further, in the case of the scan exposure, the exposure time is obtained from the scanning speed of light.

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

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

Next, as shown in Fig. 1D, development using an alkaline developer is performed to form a partition 4 composed of only the portion corresponding to the exposed portion 23A of the exposure film 23. The opening portion 5 surrounded by the partition wall 4 is a portion where the non-visible portion 23B was present in the exposure film 23. FIG. 1D shows a state after the non-visible portion 23B is removed by development. As described above, the unexposed portion 23B is dissolved by the alkali developing solution in a state in which the ink D is transferred to the upper layer and the ink D is substantially absent from the lower layer So that the ink D is hardly left in the opening portion 5.

In addition, in the partition 4 shown in Fig. 1D, the uppermost layer including the upper surface is the ink repellent layer 4A. At the time of exposure, the repellent ink (D) present in the highest concentration on the uppermost layer is cured with the acid generated by the photoacid generator (C) as a catalyst to form a repellent layer. In addition, at the time of exposure, the alkali-soluble resin (A), the crosslinking agent (B), and other photo-curing components present in the periphery of the ink D are strongly cured by light, And is fixed to the ink layer.

When the repellent silane compound (s4) is contained in the repellent silane compound (s4), the repellent agent (D) binds to each other, and the alkali soluble resin (A) and the crosslinking agent (B) And is photo-cured together with the curing component to form a repellent ink layer 4A in which the repelling ink D is firmly bonded.

In any of the cases described above, the alkali-soluble resin (A), the crosslinking agent (B), and other photo-curing components are photo-cured mainly on the lower side of the ink repellent layer (4A) Layer 4B is formed.

In this manner, since the ink D is sufficiently fixed on the partition walls including the ink repellent layer 4A and the lower layer 4B, the repellent ink D is hardly migrated to the openings at the time of development.

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

By heating, the hardening of the partition wall 4 becomes stronger, and the ink D is more firmly fixed in the ink repellent layer 4A.

The resin cured film and the partition wall 4 of the present invention thus obtained have good ink repellency on the upper surface even when exposure is performed at a low exposure dose. In the barrier ribs 4, there is almost no presence of the repellent agent D in the openings 5 after development, and the uniformity of the ink in the openings 5 can be sufficiently secured .

In order to more reliably obtain the ink affinity of the openings 5, the barrier ribs 4 are formed in order to remove development residues and the like of the negative-type photosensitive resin composition that may be present in the openings 5 after heating, Ultraviolet / ozone treatment may be performed on the substrate 1 to which the substrate 1 is attached. In this case, the ink repellent layer on the partition wall obtained by using the negative photosensitive resin composition of the present invention has sufficient resistance to ultraviolet / ozone treatment.

The barrier ribs formed by the negative photosensitive resin composition of the present invention (hereinafter also referred to as barrier ribs of the present invention) are preferably, for example, 100 탆 or less in width and particularly preferably 20 탆 or less. Normally, the width is preferably 5 占 퐉 or more. The distance (width of the pattern) between adjacent barrier ribs is preferably 300 占 퐉 or less, and particularly preferably 100 占 퐉 or less. Normally, the distance between the adjacent barrier ribs (pattern width) is preferably 10 m or more.

The height of the barrier rib is preferably 0.05 to 50 탆, particularly preferably 0.2 to 10 탆.

The barrier ribs of the present invention are particularly useful as barrier ribs for organic EL devices because they have small irregularities at the edge portions when formed with the above width and are excellent in linearity and can form patterns with high precision.

The partition wall of the present invention can be used as a partition wall having an opening portion as an ink injection region when pattern printing is performed by the IJ method (inkjet method). When the pattern printing is carried out by the IJ method, when the barrier rib of the present invention is formed so as to coincide with the desired ink injection region, the upper surface of the barrier rib has good ink repellency, That is, the injection of ink into the ink injection region can be suppressed. In addition, since the opening portion surrounded by the barrier ribs has good wetting property of the ink, it is possible to uniformly print the ink in a desired region without whitening or the like.

By using the barrier rib of the present invention, pattern printing by the IJ method can be finely performed as described above. Accordingly, the barrier ribs of the present invention can be applied to an optical element having a plurality of dots and barrier ribs positioned between adjacent dots on the substrate surface formed by the IJ method, in particular, a barrier rib such as an organic EL element, a quantum dot display, .

[Optical element]

The optical element of 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 partition wall of the present invention located between a plurality of dots and adjacent dots on a substrate surface. In the organic EL device, the quantum dot display, the TFT array, or the thin film solar cell, it is preferable that the dots are formed by the IJ method.

The organic EL element is a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode. The partition of the present invention can be used for a partition wall separating an organic light emitting layer, a partition wall separating an organic TFT layer, Can be used.

The organic TFT array element is a semiconductor layer in which a plurality of dots are arranged in a matrix when viewed in a plane and TFTs are formed as pixel elements and switching elements for driving the pixel electrodes in each dot, An organic semiconductor layer is used. The organic TFT array element is provided as, for example, an organic EL element, a liquid crystal element, or the like as a TFT array substrate.

An example of forming the dots by the IJ method in the openings using the above-described partition for the organic EL element, which is the optical element of the embodiment of the present invention, will be described below.

Further, the method of forming dots in an organic EL element or the like which is an optical element of an embodiment of the present invention is not limited to the following.

Figs. 2A and 2B schematically show a method of manufacturing an organic EL device using a partition wall 4 formed on a substrate 1 shown in Fig. 1D. Here, the barrier ribs 4 on the substrate 1 are formed so that the openings 5 coincide with the dot pattern of the organic EL element to be manufactured.

The ink 10 is dropped from the ink jet head 9 into the opening 5 surrounded by the partition wall 4 and a predetermined amount of the ink 10 is injected into the opening 5 as shown in Fig. As the ink, a known ink for the organic EL element is appropriately selected and used in accordance with the function of the dot.

Next, for example, in order to remove or cure the solvent, a drying and / or heating treatment is performed depending on the kind of the ink 10 to be used, and as shown in Fig. 2B, To obtain the organic EL element 12 having the desired dot 11 formed thereon.

In particular, an organic EL device, a quantum dot display, a TFT array, or a thin film solar cell, which is an optical element of the embodiment of the present invention, uses the barrier rib of the present invention, It is possible to uniformly spread and spread, thereby making it possible to have dots formed with good precision.

The organic EL device can be manufactured, for example, as follows but is not limited thereto.

A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like. This transparent electrode is patterned as required.

Next, by using the negative-working photosensitive resin composition of the present invention, partition walls are formed in a lattice form in a plan view along the outline of each dot by a photolithography method including coating, exposure and development.

Next, the hole injecting layer, the hole transporting layer, the light emitting layer, the hole blocking layer and the electron injecting layer are applied to the dots by the IJ method, respectively, and dried, and these layers are successively laminated. The type and the number of organic layers formed in the dots are appropriately designed.

Finally, reflective electrodes such as aluminum are formed by vapor deposition or the like.

The quantum dot display can be produced in the same manner as, for example, in the production of the organic EL device except that the light emitting layer is a quantum dot layer. However, the present invention is not limited to this.

The optical element of the embodiment of the present invention can also be applied to, for example, a blue light conversion type quantum dot display manufactured as follows.

A negative photosensitive resin composition of the present invention is used for a light-transmitting substrate such as glass to form a lattice-like partition wall in a plan view along the outline of each dot.

Next, a nanoparticle solution for converting blue light into green light by a IJ method, a nanoparticle solution for converting blue light into red light, and a blue color ink, if necessary, are applied and dried in the dots to produce a module. By using a light source that emits blue light as a backlight and using the module as a substitute for a color filter, a liquid crystal display excellent in color reproducibility can be obtained.

The TFT array can be manufactured, for example, as follows, but is not limited thereto.

A gate electrode made of aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This gate electrode is patterned as 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 may be formed on the gate insulating film. The source electrode and the drain electrode can be manufactured by forming a thin metal film of aluminum, gold, silver, copper, or an alloy thereof by vacuum deposition or sputtering, for example. As a method of patterning the source electrode and the drain electrode, a resist is coated, a resist is coated, a resist is left on a portion where an electrode is to be formed by exposure and development, and then exposed to phosphoric acid or aqua regia Removing the metal to be removed, and finally removing the resist. When a metal thin film such as gold is formed, a resist is coated in advance, exposed and developed to leave a resist on a portion where the electrode is not to be formed. After that, a metal thin film is formed, There is also a method of removing the photoresist. In addition, a source electrode and a drain electrode may be formed by a method such as ink jet method using metal nano colloid such as silver or copper.

Next, by using the negative-working photosensitive resin composition of the present invention, partition walls are formed in a lattice form in a plan view along the outline of each dot by a photolithography method including coating, exposure and development.

Next, the semiconductor solution is coated in the dot by the IJ method, and the solution is dried to form the semiconductor layer. As this semiconductor solution, an organic semiconductor solution, an inorganic coated oxide semiconductor solution, or the like can be used. The source electrode and the drain electrode may be formed by using an inkjet method or the like after the semiconductor layer is formed.

Finally, a transparent electrode such as ITO is formed by a sputtering method or the like, and a protective film such as silicon nitride is formed.

Example

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

Each measurement was carried out in the following manner.

[Number average molecular weight (Mn)]

Gel permeation chromatography (GPC) of various types of monodispersed polystyrene polymers having different degrees of polymerization, which are commercially available as standard samples for measuring molecular weights, was carried out using a commercially available GPC measuring apparatus (manufactured by Tosoh Corporation, HLC-8320GPC) And a calibration curve was prepared based on the relationship between the molecular weight of the polystyrene and the retention time (retention time).

The sample was diluted with tetrahydrofuran to 1.0% by mass and passed through a 0.5 탆 filter, and the GPC of the sample was measured using the above GPC measuring device.

Using the calibration curve, the GPC spectrum of the sample was subjected to computer analysis to determine the number average molecular weight (Mn) of the sample.

[Water contact angle]

According to JIS R3257 " Wettability Test Method of Substrate Glass Surface ", water droplets were placed on three points of the measurement surface on the substrate and measured for each water droplet by the static method. The droplet was 2 占 퐇 / drop, and the measurement was carried out at 20 占 폚. The contact angle is expressed by an average value of three measured values (n = 3).

[PGMEA contact angle]

According to JIS R3257 " Wettability Test Method of Substrate Glass Surface ", the PGMEA droplets were placed at three points of the measurement surface on the substrate and measured for each PGMEA droplet by the static method. The droplet was 2 占 퐇 / drop, and the measurement was carried out at 20 占 폚. The contact angle is expressed by an average value of three measured values (n = 3).

Abbreviations of the compounds used in Synthesis Examples and Examples are as follows.

(Alkali-soluble resin (A))

Cresol novolak resin (mass average molecular weight (Mw): 11,600, dissolution rate: 164 (angstrom / sec) manufactured by Asahi Organic Materials Industry Co., Ltd.).

(Crosslinking agent (B))

MW-100LM; NIKARAK MW-100LM (methylated melamine resin having a basic skeleton of hexamethoxymethyl melamine, manufactured by Sanwa Chemical Co., Ltd.)

(Photoacid generator (C)

CPI-210S; Trade name, manufactured by SANA PRO, and represented by the formula (C2-2).

(A hydrolyzable silane compound as a raw material of the ink-repellent agent (D)),

(D-11) corresponding to the hydrolyzable silane compound (dx-1a): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃

(D-21) corresponding to the hydrolyzable silane compound (dx-2): Si (OC ₂ H ₅ ) ₄ .

Compound (d-31) corresponding to the hydrolyzable silane compound _{(dx-3): CH 3} Si (OCH 3) 3.

(D-32) corresponding to the hydrolyzable silane compound (dx-3): C ₆ H ₅ Si (OCH ₃ ) ₃ .

(A compound used in the production of a repelling ink agent (Dcf) (an addition polymer containing a structural unit derived from an unsaturated compound having a fluoroalkyl group having 4 to 6 carbon atoms) used in a 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, manufactured by Wako Pure Chemical Industries, Ltd. (2,2'-azobis (2.4 dimethylvaleronitrile) (polymerization initiator))

(Solvent (E))

PGMEA: Propylene glycol monomethyl ether acetate.

PGME: Propylene glycol monomethyl ether.

[Synthesis Example 1: Synthesis of repelling ink (D1) and preparation of (D1-1) solution]

0.38 g of the compound (d-11) and 2.35 g of the compound (d-21) were added to a 50 cm 3 three-necked flask equipped with a stirrer to obtain a raw material mixture of the repelling agent (D1). Then, 5.56 g of PGME was added to the raw material mixture to obtain a solution (raw material solution).

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

[Synthesis Example 2: Synthesis of repelling ink (D2) and preparation of (D2-1) solution]

0.38 g of the compound (d-11), 1.11 g of the compound (d-21) and 0.72 g of the compound (d-31) were placed in a 50 cm 3 three-necked flask equipped with a stirrer, To obtain a raw material mixture of (D2). Subsequently, 6.36 g of PGME was added to the raw material mixture to obtain a solution (raw material solution).

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

[Synthesis Example 3: Synthesis of repelling ink (D3) and preparation of (D3-1) solution]

0.38 g of the compound (d-11), 0.74 g of the compound (d-21) and 0.71 g of the compound (d-32) were placed in a 50 cm 3 three-necked flask equipped with a stirrer, To obtain a raw material mixture of the (D1). Subsequently, 7.18 g of PGME was added to the raw material mixture to obtain a solution (raw material solution).

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

[Synthesis Example 4: Synthesis of repeller ink (Dcf) and preparation of (Dcf-1) solution]

420.0 g of MEK, 86.4 g of C6FMA, 18.0 g of MAA, 21.6 g of GMA, 54.0 g of MMA and 0.8 g of V-65 were charged into an internal 1 L autoclave equipped with a stirrer, At 50 DEG C for 24 hours to synthesize a crude copolymer. Hexane was added to the obtained solution of the pore polymer to perform re-precipitation purification, followed by vacuum drying. To the solid obtained, 14643 g of PGMEA was added and stirred to obtain a (Dcf-1) solution which was a PGMEA solution containing 10% by mass of a repellent agent (Dcf). The fluorine content (% by mass of fluorine atoms) of the resulting composition excluding the solvent of the (Dcf-1) solution was 27.4% by mass. The composition excluding the solvent of the (Dcf-1) solution had a number average molecular weight (Mn) of 49,325.

The fluorine atom content and the number average molecular weight (Mn) of the repellent agent (D) in the solution for a repellent agent obtained in Synthesis Examples 1 to 4 were measured together with the composition (mol% Table 1 also shows.

[Example 1]

(Preparation of negative-type photosensitive resin composition)

(19.34 g of EP4020G, 4.84 g of MW-100LM, 0.73 g of CPI-210S and 74.1 g of PGMEA) of 500 cm < 3 > , And the mixture was stirred for 30 minutes to prepare a negative-working photosensitive resin composition 1.

(Production of a cured film (partition wall)

A glass substrate of 10 cm square was ultrasonically cleaned with ethanol for 30 seconds and then subjected to ultraviolet / ozone cleaning for 5 minutes. For ultraviolet / ozone cleaning, PL7-200 (Sen Engineering) was used as an ultraviolet / ozone generator. Also, with respect to all of the following ultraviolet / ozone treatment, this apparatus was used as an ultraviolet / ozone generator.

The negative photosensitive resin composition 1 was coated on the cleaned glass substrate surface using a spinner and dried on a hot plate at a temperature of 100 캜 for 2 minutes to form a dry film having a thickness of 2.5 탆 Respectively. On the surface of the obtained dried film, a 50 占 퐉 gap was provided through a photomask (photomask having light irradiation in addition to the region of the pattern portion) having an opening pattern (2.5 cm 占 5 cm) from the film side, The ultraviolet rays of the mercury lamp were irradiated at 25 mW / cm 2 for 1 second, 2 seconds, 5 seconds, or 10 seconds.

Subsequently, the exposed glass substrate was immersed in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 40 seconds to develop, and the dried film of the unexposed portions was rinsed with water and dried. Subsequently, this was heated on a hot plate at 230 占 폚 for 50 minutes to obtain four kinds of glass substrates (1) in which a cured film (partition wall) of a negative photosensitive resin composition 1 was formed in a region except for the opening pattern portion.

(evaluation)

The following evaluations were performed on the negative photosensitive resin composition 1 and the glass substrate 1 on which the cured films (partitions) were formed. The evaluation results are shown in Table 2 together with the composition of the negative-type photosensitive resin composition.

≪ ink-repellent property (partition wall), inkphilic property (dot)

The contact angle of the obtained cured film of the glass substrate 1 with respect to the PGMEA of the partition wall surface (exposed portion) and the contact angle with respect to the portion of the dried portion (unexposed portion) removed, that is, The contact angle was measured. At this time, the development residue was also evaluated by the contact angle of the dot portion with respect to water. The evaluation was carried out according to the following criteria.

(standard)

○ (Good): When the contact angle of water is less than 30 degrees

× (poor): The contact angle of water is 30 degrees or more

Thereafter, a cured film was prepared from the glass substrate 1 with an exposure time of 10 seconds. On the entire surface of the side where the cured film was formed, ultraviolet / ozone irradiation was performed for 1 minute. The contact angle of the surface of the cured film (partition wall) with respect to PGMEA and the contact angle of water on the surface of the glass substrate after 1 minute irradiation were measured. The measurement method is the same as described above.

<Storage stability>

The negative photosensitive resin composition was stored in a glass screw bottle at 23 占 폚 (room temperature) for 1 month. After preserving for one month, a negative photosensitive resin composition was applied to the surface of a 10 cm x 10 cm glass substrate cleaned in the same manner as in the production of the above-mentioned cured film (partition wall) using a spinner to form a coating film. And further dried on a hot plate at 100 DEG C for 2 minutes to form a dry film having a thickness of 2 mu m. The appearance of the dried film was visually observed and evaluated according to the following criteria.

(standard)

(Good): the number of foreign substances on the dried film is 5 or less.

X (defective): 6 or more foreign substances on the dried film, and a radial stripe pattern was observed from the center of the glass substrate.

[Example 2]

(2) in which a negative-working photosensitive resin composition 2 and a negative-working photosensitive resin composition 2 were formed was prepared in the same manner as in Example 1, except that the solution (D2-1) was used instead of the solution , And evaluated in the same manner as in Example 1.

[Example 3]

(3) in which the cured film of the negative photosensitive resin composition 3 and the negative photosensitive resin composition 3 were formed was prepared in the same manner as in Example 1, except that the solution of (D3-1) was used in place of the solution of the negative photosensitive resin composition , And evaluated in the same manner as in Example 1.

[Example 4]

(4) in which the cured film of the negative photosensitive resin composition 4 and the negative photosensitive resin composition 4 were formed was produced in the same manner as in Example 1 except that the (Dcf-1) solution was used in place of the (Dcf-1) , And evaluated in the same manner as in Example 1.

The evaluation results of Examples 2 to 4 are shown in Table 2 together with the composition of the negative-type photosensitive resin composition.

It can be seen from Table 2 that the cured films obtained in Examples 1, 2 and 3 exhibit good ink repellency even when the exposure amount is low and high ink repellency even after irradiation with ultraviolet rays / ozone, It is also understood that the surface of the glass substrate has good hydrophilicity. The storage stability is also high. On the other hand, in Example 4, since a repellent agent irrelevant to the present invention was used, it was found that the high ink repellency was not maintained after ultraviolet / ozone irradiation.

Industrial availability

The barrier ribs formed using the negative photosensitive resin composition of the present invention are excellent in ink repellency and capable of maintaining the ink repellency even after irradiation with ultraviolet rays and ozone and uniformly apply the ink to the openings divided by the partition walls, And is useful as an optical element having dots formed with good precision. In addition, the negative-working photosensitive resin composition of the present invention can be applied to various types of optical elements, in particular, an organic layer such as a light emitting layer of an organic EL element, a quantum dot layer or a hole transport layer of a quantum dot display, a conductor pattern or a semiconductor pattern of a TFT array, As a composition for forming a barrier rib when pattern printing is performed by the IJ method in an organic semiconductor layer, a gate electrode, a source electrode, a drain electrode, a gate wiring and a source wiring, a thin film solar cell, .

Further, the entire contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2014-092092 filed on April 25, 2014 are incorporated herein by reference and are to be taken as the disclosure of the specification of the present invention.

One … Board
21 ... Coat
22 ... Dry film
23 ... Exposure film
23A ... Exposure
23B ... Unexposed portion
4 … septum
4A ... Ink layer
5 ... Opening
31 ... Masking portion
30: Photomask
9 ... Inkjet head
10 ... ink
11 ... dot
12 ... Organic EL device.

Claims (15)

A method for producing a photosensitive resin composition, which comprises mixing an alkali-soluble resin (A), a crosslinking agent (B), a photo acid generator (C), and a hydrolyzable silane compound (s1) having a fluoroalkylene group and / or a fluoroalkyl group and a hydrolyzable group, (D) as a hydrolyzable (co) condensate of a negative-type photosensitive resin composition. The method according to claim 1,
, And the content of fluorine atoms in the repellent agent (D) is 1 to 40% by mass. 3. The method according to claim 1 or 2,
(D) comprises a hydrolyzable silane compound (s2) in which four hydrolyzable groups are bonded to a silicon atom as a monomer and / or a partially hydrolyzed (co) condensate. 4. The method according to any one of claims 1 to 3,
(D) comprises a hydrocarbon group and a hydrolyzable silane compound (s3) having only a hydrolyzable group as a monomer and / or a partially hydrolyzed (co) condensate. 5. The method according to any one of claims 1 to 4,
The above-mentioned repellent agent (D) is a negative resist composition which contains a cationically polymerizable group and a hydrolyzable group and contains a hydrolyzable silane compound (s4) containing no fluorine atom as a monomer and / or a partially hydrolyzed (co) Type photosensitive resin composition. 6. The method according to any one of claims 1 to 5,
Wherein the content of the alkali-soluble resin (A) is 10 to 90 mass% of the total solid content in the negative-working photosensitive resin composition. 7. The method according to any one of claims 1 to 6,
Wherein the content of the crosslinking agent (B) and the photoacid generator is 2 to 50 parts by mass and 0.1 to 20 parts by mass based on 100 parts by mass of the alkali-soluble resin (A), respectively. 8. The method according to any one of claims 1 to 7,
Wherein the content of the ink-repellent agent (D) is 0.01 to 20 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). 9. The method according to any one of claims 1 to 8,
(E) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate and 2-propanol, By weight based on the total weight of the photosensitive resin composition. 10. The method according to any one of claims 1 to 9,
Wherein the content of the solvent (E) is 50 to 99% by mass with respect to the total amount of the negative-working photosensitive resin composition. A barrier rib formed of a cured film of a negative photosensitive resin composition according to any one of claims 1 to 10, formed in such a manner that the substrate surface is divided into a plurality of sections for dot formation. 12. The method of claim 11,
A width of 100 mu m or less, a distance between barrier ribs (pattern width) of 300 mu m or less, and a height of 0.05 to 50 mu m. An optical element having a plurality of dots on a surface of a substrate and barrier ribs positioned between adjacent dots, wherein the barrier ribs are formed of barrier ribs as defined in claim 11 or 12. 14. The method of claim 13,
Wherein the dot is formed by an ink-jet method. The method according to claim 13 or 14,
Wherein the optical element is an organic EL element, a quantum dot display, a TFT array or a thin film solar cell.

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