TWI666235B - Ink repellent, negative photosensitive resin composition, partition wall and optical element - Google Patents

Abstract

Provided is an ink repellent, and the photosensitive resin composition containing the ink repellent has sufficient storage stability. At the same time, the ink repellent can form a partition wall with good ink repellency on the upper surface and openings with good ink affinity. And a negative photosensitive resin composition containing the ink repellent, a partition wall having a good ink repellency on the upper surface, and an optical element having a point, the point being The openings divided by the partition wall are uniformly coated with printing ink and accurately formed.

An ink-repellent agent is one that imparts ink-repellency to the upper surface of a partition wall, and the partition wall is formed into a shape that divides the substrate surface into a plurality of dot-forming partitions; the ink-repellent agent comprises a fluorine-containing atomic unit and A polymer composed of an isocyanate group-terminated unit and a fluorine atom content of 1 to 40% by mass. The blocked isocyanate group-containing unit can be blocked by heating to generate an isocyanate group.

Description

Ink repellent, negative photosensitive resin composition, partition wall and optical element Field of invention

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

Background of the invention

In the production of optical elements such as organic EL (Electro-Luminescence) elements, a method of pattern printing by an inkjet (IJ) method in which an organic layer such as a light-emitting layer is formed as a dot is sometimes used. In this method, a partition wall is set along the outline of the point to be formed, and a printing ink containing an organic layer material is injected into a partition surrounded by the partition wall (hereinafter also referred to as an "opening part"), and then dried or heated, etc. The point where the desired pattern is formed.

In the above method, in order to prevent mixing of ink between adjacent dots and uniformly apply dots to form ink, the upper surface of the partition wall must have ink repellency, and at the same time, the opening for dot formation surrounded by the partition wall including the side surface of the partition wall. Department must be ink-friendly.

Therefore, in order to obtain a partition wall having ink repellency on the upper surface, a method is known in which a partition wall corresponding to a dot pattern is formed by a photolithography method using a photosensitive resin composition containing an ink repellent agent. For example, Patent Document 1 or Patent Document 2 discloses a negative-type photosensitive resin containing a polysiloxane ink repellent. A silicone resin ink repellent is composed of a hydrolyzed condensate of a fluorine-containing hydrolyzable silane compound.

When a partition wall is formed using a negative photosensitive resin composition containing such an ink repellent, the portion corresponding to the partition wall in the coating film of the composition is exposed, and then the composition corresponding to the opening portion is removed by development. At this time, it is difficult to completely remove the negative photosensitive resin composition from the opening portion, and a slight amount of residue usually remains in the opening portion. The problem is that the residue of the negative photosensitive resin composition causes the ink affinity of the openings to decrease, which hinders uniform coating of the printing ink.

Prior art literature Patent literature

Patent Document 1: International Publication No. 2010/013816

Patent Document 2: International Publication No. 2014/046209

Summary of invention

Regarding the residue of the negative photosensitive resin composition in the openings, after verification by the present inventors, it is known that compared to the problem of the amount of residue, the type of negative photosensitive resin composition used, and more specifically The type of the ink repellent contained in the negative photosensitive resin composition may cause a difference in the degree of ink affinity of the opening.

Therefore, if an ink repellent blended into a negative photosensitive resin composition is selected from the viewpoint of improving the ink affinity of the openings, the problem becomes that of the negative photosensitive resin composition containing the ink repellent. Insufficient storage stability full. Moreover, the same problem exists in a positive photosensitive resin composition.

The purpose of the present invention is to provide an ink repellent which has sufficient storage stability of the photosensitive resin composition containing the ink repellent, and at the same time, the ink repellent can form a partition wall with good ink repellency on the upper surface and good ink affinity. The photosensitive resin composition of the opening.

An object of the present invention is to provide a negative photosensitive resin composition having good storage stability and capable of forming partition walls with good ink repellency on the upper surface and openings with good ink affinity.

An object of the present invention is to provide a partition wall having a good ink repellency on the upper surface.

Another object of the present invention is to provide an optical element having dots, which are formed by accurately coating ink uniformly on the opening portion divided by the partition wall.

The present invention provides an ink repellent having the following constitution, a negative photosensitive resin composition, a partition wall, and an optical element.

[1] An ink-repellent agent, which imparts ink-repellency to the upper surface of a partition wall, and the partition wall is formed into a shape that divides the substrate surface into a plurality of dot-forming partitions; the ink-repellent agent includes a fluorine-containing atomic unit And a polymer containing a blocked isocyanate group unit and a fluorine atom content of 1 to 40% by mass. The blocked isocyanate group-containing unit can be deblocked by heating to generate an isocyanate group.

[2] The ink repellent according to [1], in which the aforementioned blocked isocyanate group is unblocked and The 10-hour half-life temperature to become an isocyanate group is 60 to 180 ° C.

[3] The ink repellent according to [1] or [2], wherein the blocked isocyanate group is represented by the following formula (1): -NHC (= O) -B ... (1)

(In formula (1), B is the following: a monohydric alcohol, a phenol, a lactam, an oxime, an acetoacetic acid alkyl ester, a malonic acid alkyl ester, or phthalic acid基 A radical obtained by removing one of the active hydrogens of imines, imidazoles, or pyrazoles; a chlorine atom or a nitrile group; or a radical obtained by dehydrogenating sodium bisulfite).

[4] The ink repellent according to [3], wherein B is the following: a group obtained by removing an oxime from a hydrogen atom in a hydroxyl group; or an activity of bonding to a nitrogen atom constituting a ring of pyrazoles The radical obtained after the removal of hydrogen.

[5] The ink repellent according to any one of [1] to [4], wherein the aforementioned polymer is a polymerization having a hydrocarbon chain as a main chain and a mass average molecular weight within a range of 5 × 10 ³ to 1 × 10 ⁵ The fluorine atom-containing unit is a unit having the following group: a fluoroalkyl group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom.

[6] The ink repellent according to [5], wherein the polymer further has at least one unit selected from the group consisting of a unit having an acidic group, a unit having an ethylenic double bond, A unit having a hydroxyl group and a unit having a polyoxyalkylene chain.

[7] The ink repellent according to any one of [1] to [4], wherein the polymer is a partially hydrolyzed condensate of a hydrolyzable silane compound, and the fluorine-containing atomic unit is a bond between the following group and a silicon atom, and The resulting siloxane unit: a group having a fluoroalkylene group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom.

[8] The ink repellent according to [7], wherein the partially hydrolyzed condensate is a partially hydrolyzed condensate of a hydrolyzable silane compound mixture, and the hydrolyzable silane compound mixture includes a hydrolyzable silane compound having a fluorine atom-containing group and An isocyanate-blocked hydrolyzable silane compound, and the hydrolyzable silane compound mixture optionally contains at least one kind of hydrolyzable silane compound selected from the group consisting of the following hydrolyzable silane compounds: a silicon atom bond has 4 Hydrolyzable silane compound having a hydrolyzable group, a hydrolyzable silane compound having a vinyl double bond group and not containing a fluorine atom, a hydrolyzable silane compound having only a hydrocarbon group bonded to a silicon atom, and a mercapto group and containing no fluorine Atomically hydrolyzable silane compound.

[9] The ink repellent according to any one of [1] to [8], wherein the substrate has a functional group reactive with an isocyanate group on at least a surface on which the partition wall can be formed.

[10] A negative photosensitive resin composition, comprising: a photo-curable alkali-soluble resin or a photo-curable alkali-soluble monomer; a photopolymerization initiator; and [1] to [8] Ink repellent agent of any one.

[11] The negative photosensitive resin composition according to [10], which further contains a black colorant.

[12] A partition wall formed into a shape that divides the surface of a substrate into a plurality of dot-forming partitions, and the partition wall is formed of a hardened body of a negative photosensitive resin composition such as [10] or [11] .

[13] The partition wall according to [12], wherein the partition wall is formed on a substrate, and the substrate has a functional group reactive with an isocyanate group.

[14] An optical element having a plurality of points and positions on a substrate surface The partition wall between adjacent points is characterized in that the aforementioned partition wall is formed by a partition wall such as [12] or [13].

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

According to the present invention, an ink repellent can be provided. The photosensitive resin composition containing the ink repellent has sufficient storage stability. At the same time, the ink repellent can form a partition wall with good ink repellency on the upper surface and good ink affinity. The photosensitive resin composition of the opening.

The negative photosensitive resin composition of the present invention has good storage stability, and can be used to form a partition wall with good ink repellency on the upper surface and an opening portion with good ink affinity.

The partition wall of the present invention has good ink repellency on the upper surface.

The optical element of the present invention is an optical element having dots, and the dots are precisely formed by uniformly coating printing ink on the opening portion divided by the partition wall.

1‧‧‧ substrate

4‧‧‧ next door

4A‧‧‧Ink layer

4B‧‧‧Floor

5‧‧‧ opening

9‧‧‧ inkjet head

10‧‧‧Ink

11 o'clock

12‧‧‧ Optical Elements

21‧‧‧coating film

22‧‧‧ dry film

23‧‧‧ exposure film

23A‧‧‧Exposure Department

23B‧‧‧Unexposed

30‧‧‧Mask

31‧‧‧Mask

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

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

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

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

FIG. 2A is a schematic diagram showing a manufacturing method of an optical element according to an embodiment of the present invention; Process steps diagram.

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

Forms used to implement the invention

In this specification, "(meth) acrylfluorenyl" is a general term for "methacrylfluorenyl" and "acrylfluorenyl". (Meth) acrylic acid, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, and (meth) acrylic resin are all explained based on this.

In this specification, the base represented by the formula (x) will be described only as the base (x).

In the present specification, the compound represented by the formula (y) will be described only as the compound (y).

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

The "side chain" in this specification means a group other than a hydrogen atom and a halogen atom bonded to a carbon atom constituting a main chain in a polymer constituting a main chain composed of repeating units composed of carbon atoms. "Unit" such as a fluorine atom-containing unit means a polymerization unit.

In this specification, unless otherwise specified, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are measured by gel permeation chromatography using polystyrene as a standard substance.

The "total solid content of the photosensitive resin composition" in this specification refers to a component that forms a later-described cured film among the components contained in the photosensitive resin composition, and the photosensitive resin composition can be heated at 140 ° C for 24 hours. The residue after removal of the solvent was calculated. The total solid content can also be calculated from the feed amount.

In the present specification, a film made of a cured product of a composition containing a resin as a main component is referred to as a "resin cured film".

In this specification, a film obtained by applying a photosensitive resin composition is referred to as a "coating film", and a film obtained by drying is referred to as a "dry film". A film obtained by curing the "dry film" is a "resin cured film". In this specification, the "resin cured film" is also simply referred to as a "cured film".

The "partition wall" is a form of a resin hardened film having a predetermined area divided into a plurality of partitions. The partitions divided by the next wall, that is, the openings surrounded by the next wall, can be filled with, for example, the following “printing ink” to form “dot”.

The term "printing ink" in this specification is a generic term for a liquid that has optical and / or electrical functions after drying, hardening, and the like.

In optical elements such as an organic EL element, a color filter for a liquid crystal element, and a TFT (Thin Film Transistor) array, dots for various constituent elements are pattern-printed by an inkjet (IJ) method using the dot-forming ink. "Ink" in this manual includes inks that can be used for this purpose.

The "ink repellency" in this manual is the property of preventing the above-mentioned ink contamination, and has both water repellency and oil repellency. The ink repellency can be evaluated, for example, by the contact angle when the ink is dropped. "Ink affinity" is the opposite of the ink repellency, and can be evaluated by the contact angle when the ink is dripped as well as the ink repellency. Alternatively, the ink affinity can be evaluated by evaluating the wet spreading degree (moist spreading property of the printing ink) of the printing ink when the printing ink is dropped on a predetermined basis.

"Dots" in this manual refer to the optical modulation of optical components The smallest area. In optical elements such as organic EL elements, liquid crystal elements, color filters, and TFT arrays, if the display is black and white, 1 point = 1 pixel, and if the color display, for example, 3 points (R (red), G (green), B (blue), etc.) = 1 pixel.

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

[Ink Repellent]

The ink-repellent agent of the present invention is an ink-repellent agent that imparts ink-repellency to the upper surface of the partition wall, and the partition wall is formed into a shape that divides the surface of the substrate into a plurality of dot-forming partitions; It is composed of an atomic unit and a polymer containing a blocked isocyanate group unit and a fluorine atom content rate of 1 to 40% by mass. The blocked isocyanate group-containing unit can be deblocked by heating to generate an isocyanate group.

In this specification, the ink repellent of the present invention is also referred to as an ink repellent (C). A polymer which can be used as the ink repellent (C) and has the above characteristics is referred to as a polymer (C).

The partition wall to which the ink repellent agent (C) can be applied is not particularly limited. The ink-repellent agent (C) is preferably used in the following form: After the ink-repellent agent (C) is contained in a photosensitive resin composition and the composition is coated on a substrate, the ink-repellent agent (C) forms a partition wall in a manner described later. Transfer to the upper surface of the composition layer, and then form a densely distributed layer of ink repellent (C) (hereinafter also referred to as the "ink repellent layer") on the upper layer portion containing the upper surface of the obtained partition wall, thereby changing the ink repellency Give to the upper surface of the next wall. The photosensitive resin composition may be a positive type or a negative type.

Polymer (C) contains 1 to 40% by mass of fluorine atoms In addition, it has the property of migrating to the upper surface of the composition layer (upper surface migration) and ink repellency, so it can impart good ink repellency to the upper surface of the obtained partition wall. The fluorine atom content rate in the polymer (C) is preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. If the fluorine atom content rate of the polymer (C) is above the lower limit of the above range, good ink repellency can be imparted to the upper surface of the partition wall; if it is below the upper limit, it can interact with other components in the photosensitive resin composition. The compatibility is better.

In addition, the polymer (C) has a blocked isocyanate group (hereinafter also simply referred to as a "blocked isocyanate group") capable of generating an isocyanate group by being deblocked by heating, and can be suppressed below the temperature at which the above-mentioned deblocking occurs. From the viewpoint of reactivity, storage stability can be improved when it is stored as an ink repellent or contained in a photosensitive resin composition. In addition, it can be deblocked by heating to become an isocyanate group during use, which can improve the reactivity of the polymer (C), and can improve the binding and adhesion with other ingredients or other materials. Thereby, the openings surrounding the partition wall can suppress the residue of the photosensitive resin composition from hindering the wet diffusion of the printing ink and improving the ink affinity.

From this point of view, in the case of forming a partition wall on a substrate surface using a photosensitive resin composition containing an ink repellent (C), it is preferable that at least the surface on which the partition wall is formed have a functional group reactive with an isocyanate group. Examples include hydroxy, amine, carboxy, and mercapto. That is, for example, when the ink repellent (C) is contained in the photosensitive resin composition and used, it is particularly effective when used for a substrate having at least a partition wall surface having a functional group reactive with an isocyanate group. This is because we believe that the surface of the substrate forming the partition wall has a functional group that is reactive with the isocyanate group and can be lifted at the opening. The adhesion between the substrate surface and the ink repellent (C) can ensure the ink affinity of the openings even if the openings have residues of a photosensitive resin composition.

Specifically, the blocked isocyanate group which can generate an isocyanate group by heating and deblocking is a functional group which has reacted the isocyanate group with an active hydrogen-containing compound (blocking agent) and became inert at normal temperature. Once heated, the blocking agent dissociates and regenerates into isocyanate groups.

In addition, the 10-hour half-life temperature of the blocked isocyanate group to be blocked to become an isocyanate group is preferably 60 to 180 ° C, and more preferably 80 to 150 ° C. As long as the 10-hour half-life temperature of the blocked isocyanate group is within the above range, the ink affinity is good.

Specific examples of such a blocked isocyanate group include a group represented by the following formula (1).

-NHC (= O) -B ... (1)

(In formula (1), B is the following: a monohydric alcohol, a phenol, a lactam, an oxime, an acetoacetic acid alkyl ester, a malonic acid alkyl ester, or phthalic acid A group obtained by removing one of active hydrogens of imines, imidazoles or pyrazoles; a chlorine atom or a nitrile group; or a group obtained by dehydrogenating sodium hydrogen sulfite).

Among the above, monohydric alcohols, phenols, oximes, and the like have hydrogen having a hydroxyl group as active hydrogen. Acetyl acetate and alkyl malonate are compounds having methylene active hydrogen. Lactams, phthalimines, imidazoles, and pyrazoles are compounds with amine active hydrogen.

As for the monohydric alcohols, linear or branched monohydric alcohols having a carbon number of 1 to 10 may be mentioned, and methanol and ethanol are preferred. As far as phenols are concerned, For example, a hydrogen bonded to an aromatic ring has a phenol compound having 6 to 15 carbon atoms which is substituted with a hydroxyl group. Phenol, cresol and the like are preferred.

As for the lactamamine, for example, the number of members of 3 to 6 can be listed. As for the oxime, for example, an aldoxime having a carbon number of 1 to 6 or a ketone having a carbon number of 3 to 9 having> C = N-OH group, R ^k1 R ^k2 C = N-OH (R ^k1 and R ^k2 each independently represents an alkyl group having 1 to 4 carbon atoms) A ketone fluorene having 3 to 7 carbon atoms is preferred.

The alkyl portions of the alkyl acetoacetates and the alkyl malonates are preferably linear or branched alkyl groups having 1 to 4 carbon atoms, respectively.

As far as phthalimides are concerned, for example, phthalimide and a hydrogen atom bonded to a carbon atom of the phthalimide ring have been linear with a carbon number of 1 to 6. Or branched alkyl substituted phthalimide derivatives and the like. Examples of imidazoles include imidazole and imidazole derivatives in which a hydrogen atom bonded to a carbon atom of an imidazole ring has been substituted with a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of the pyrazoles include pyrazole and pyrazole derivatives in which a hydrogen atom bonded to a carbon atom of a pyrazole ring has been substituted with a linear or branched alkyl group having 1 to 6 carbon atoms.

Among these, oximes and pyrazoles are preferred, and pyrazoles are particularly preferred. In the case of oximes, -B is a group obtained by removing the hydrogen atom in the hydroxyl group of the oxime; in the case of pyrazoles, -B is obtained by removing the hydrogen atom bonded to the nitrogen atom constituting the ring of the pyrazole group. base. Particularly preferable examples of -B include a group represented by the following formula (b1) and a group represented by the following formula (b2).

[Chemical 1]

Here, in the group (1), for example, -B is -NHC (= O)-(b1) of the group (b1) and -B is -NHC (= O)-(b2) of the group (b2). The 10-hour half-life temperatures were 110 ° C and 140 ° C, respectively.

The polymer (C) contains the above-mentioned fluorine atom as a fluorine atom-containing unit and a blocked isocyanate group as a blocked isocyanate group-containing unit, respectively. In the polymer (C), the fluorine atom-containing unit and the blocked isocyanate group-containing unit may be the same unit, that is, the fluorine unit and the blocked isocyanate group may be contained in the same unit. However, the fluorine atom-containing unit and the blocked Isocyanate-based units are different units.

Examples of the polymer (C) include a polymer (hereinafter referred to as a polymer (C1)) composed of a partially hydrolyzed condensate of a hydrolyzable silane compound mixture containing a fluorine atom-containing group Hydrolyzable silane compounds and hydrolyzable silane compounds containing blocked isocyanate groups; and polymers having a hydrocarbon chain in the main chain and having the following units (hereinafter referred to as polymer (C2)), etc .: a side having a fluorine atom A unit of a chain and a unit having a blocked isocyanate group.

In addition, the content of the blocked isocyanate group in the polymer (C) is preferably 0.2 mmol / g to 4 mmol / g regardless of the polymer (C1) and the polymer (C2), and 0.3 mmolol / g to 4 mmol / g is more preferable. .

<Polymer (C1)>

The polymer (C1) is a partially hydrolyzed condensate of a mixture of hydrolyzable silane compounds (hereinafter also referred to as "mixture (M)"). This mixture (M) contains a hydrolyzable silane compound having a fluorine atom-containing group (hereinafter also referred to as "compound (s1)") and a hydrolyzable silane compound having a blocked isocyanate group (hereinafter also referred to as "compound (s2)") As an essential component and optionally containing a hydrolyzable silane compound other than compounds (s1) and (s2), the compound s1 is, for example, a fluoroalkylene group which may contain an etheric oxygen atom and / or a fluorine which may contain an etheric oxygen atom. A hydrolyzable silane compound having an alkyl group and a hydrolyzable group. Examples of the hydrolyzable silane compound contained in the mixture (M) include the following hydrolyzable silane compounds (s3) to (s6) (hereinafter also referred to as "compound (s3)", "compound (s4)", "Compound (s5)", "Compound (s6)"). The hydrolyzable silane compound optionally contained in the mixture (M) is particularly preferably the compound (s3).

Hydrolyzable silane compound (s3); a hydrolyzable silane compound in which a silicon atom is bonded to 4 hydrolyzable groups.

Hydrolyzable silane compound (s4): Hydrolyzable silane compound having a vinylic double bond and a hydrolyzable group and containing no fluorine atom.

Hydrolyzable silane compound (s5); a hydrolyzable silane compound having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom (except those belonging to a hydrolyzable silane compound (s4)).

Hydrolyzable silane compound (s6); Hydrolyzable silane compound having a mercapto group and a hydrolyzable group and containing no fluorine atom.

Compounds (s1) to (s6) will be described below.

<1> Compound (s1)

By using the compound (s1), the polymer (C1) has the following form Fluorine atom with excellent upper surface migration and ink repellency: fluoroalkylene group which may contain etheric oxygen atom and / or fluoroalkyl group which may contain etheric oxygen atom.

In order to advance these properties of the compound (s1) to a higher level, the compound (s1) has at least one selected from the group consisting of a fluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkyl group. Preferably, a perfluoroalkyl group is preferred. Moreover, these fluorine-containing hydrocarbon groups may also contain etheric oxygen atoms, and perfluoroalkyl groups containing etheric oxygen atoms are also preferred. That is, the most preferable compound in the compound (s1) is a compound having a perfluoroalkyl group and / or an etheric oxygen atom-containing perfluoroalkyl group.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a fluorenyl group, an isocyanate group, an amine group, and a group in which at least one hydrogen of the amine group is substituted with an alkyl group. From the viewpoint that the reaction to form a Si-O-Si bond is facilitated by a hydrolysis reaction to form a hydroxyl group (silanol group) and a condensation reaction between molecules, the alkoxy group having 1 to 4 carbon atoms or A halogen atom is preferred, a methoxy, ethoxy or chlorine atom is preferred, and a methoxy or ethoxy group is particularly preferred.

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

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

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

In the formula (cx-1), each symbol has the following meaning.

R ^F11 is a divalent organic group having 1 to 16 carbon atoms containing at least one fluoroalkylene group and may contain etheric oxygen atoms. However, the terminal atom bonded to A and the terminal atom bonded to Si of R ^F11 are all carbon atoms.

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

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

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

-Si (R ^H12 ) _c X ¹² _(3-c) … (Ia)

R ^H12 is a hydrocarbon group having 1 to 6 carbon atoms.

c is 0 or 1.

X ¹¹ and X ¹² are hydrolyzable groups.

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

When there are a plurality of X ¹² , these may be different from each other or may be the same.

When there are a plurality of AR ^F11 , these may be different from each other or may be the same.

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

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

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

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

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

TR ^F12 -Q ¹¹ -SiX ¹¹ ₃ … (cx-1a)

In the formula (cx-1a), each symbol has the following meaning.

R ^F12 is a perfluoroalkylene group which may contain etheric oxygen atoms 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 hydrolyzable groups.

The three X ¹¹ may be different from each other or may be the same.

The three X ¹² may be different from each other or may be the same.

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

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

In formula (cx-1a), when T is a group (Ib), R ^{F12 is} a perfluoroalkylene group having 3 to 15 carbon atoms or a perfluoro group having 3 to 15 carbon atoms and containing an etheric oxygen atom. The alkylene group is preferable, and the perfluoroalkylene group having 4 to 6 carbon atoms is particularly preferable.

When R ^F12 is the base exemplified above, the polymer (C1) has good ink repellency and the compound (cx-1a) has excellent solubility in a solvent.

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

Specific examples of R ^F12 include those described in paragraph [0043] in International Publication No. 2014/046209 (hereinafter referred to as WO2014 / 046209).

When Q ¹¹ and Q ¹² are respectively represented by bonding Si at the right bonding position and R ^F12 at the left bonding position, specifically, the following bases are preferred:-(CH ₂ ) _i1- (i1 Is an integer from 1 to 5), -CH ₂ O (CH ₂ ) _i2- (i2 is an integer from 1 to 4), -SO ₂ NR ^1- (CH ₂ ) _i3- (R ¹ is a hydrogen atom, methyl or Ethyl, i3 is an integer of 1 to 4, and the total number of carbon atoms of R ¹ and (CH ₂ ) _i3 is an integer of 4 or less) _or- (C = O) -NR ^1- (CH ₂ ) _i4- ( R ¹ is defined above, I4 is the integer of 1 to 4, and R ¹ and carbon atoms (CH _{2) i4} of integers of 4 or less in total). As for Q ¹¹ and Q ¹² ,-(CH ₂ ) _i1 with i1 being an integer of 2 to 4 is preferred, _and- (CH ₂ ) ₂ -is particularly preferred.

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

When R ^F12 is a perfluoroalkyl group containing an etheric oxygen atom, Q ¹¹ and Q ^{12 are} represented _by- (CH ₂ ) _i1- , -CH ₂ O (CH ₂ ) _i2- , -SO ₂ NR ^1- (CH ₂ ) _{A base represented by i3} -or- (C = O) -NR ^1- (CH ₂ ) _i4 -is preferred. In this case,-(CH ₂ ) _i1 -is still preferred, i1 is more preferably an integer of 2 to 4, and i1 is more preferably 2.

When T is a fluorine atom, specific examples of the compound (cx-1a) include those described in, for example, paragraph [0046] in WO2014 / 046209.

When T is a group (Ib), specific examples of the compound (cx-1a) include those described in, for example, paragraph [0047] in WO2014 / 046209.

In the present invention, as the compound (cx-1a), F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and 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 compound (s1) in the mixture (M) is preferably a fluorine atom content of the partially hydrolyzed condensate obtained from the mixture of 1 to 40% by mass, preferably 5 to 35% by mass, and 10 to 30% by mass. % Is better. If the content ratio of the compound (s1) is above the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film; if it is below the upper limit, it is compatible with other hydrolyzable silane compounds in the mixture Solubility is better.

<2> Compound (s2)

By containing the compound (s2) in the mixture (M) of the present invention, it is possible to improve storage stability when used as an ink repellent or in a photosensitive resin composition for storage. In addition, the isocyanate group is formed by deblocking by heating during use. Improve the reactivity of polymer (C), and improve the binding and adhesion with other ingredients or other materials. Thereby, the residue of the photosensitive resin composition can be suppressed in the opening part enclosed by the partition wall from interfering with the wet diffusion property of the printing ink, and the ink affinity is good. The compound (s2) may be used alone or in combination of two or more.

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

The compound (s2) can be represented by the following formula (cx-2).

(BI-Q ² ) _d -Si (R ^H2 ) _e X ² _(4-de) … (cx-2)

The meaning of the symbols in the formula (cx-2) is as follows.

BI is a blocked isocyanate group.

Q ² is a divalent organic group containing 1 to 6 carbon atoms and not containing a fluorine atom. However, the terminal atom of Q ² bonded to Si is a carbon atom.

R ^H2 is a hydrocarbon group having 1 to 6 carbon atoms.

X ² is a hydrolyzable group.

d is 1 or 2, e is 0 or 1, and d + e is 1 or 2.

When there are a large number of BI-Q ² , these may be different or the same.

When there are a plurality of X ² , these may be different from each other or may be the same.

R ^H2 may use the same base as the aforementioned R ^H11 and R ^H12 .

X ² may use the same base as X ¹¹ and X ¹² described above.

As far as BI is concerned, it can be exemplified by the above-mentioned base (1), and the ideal aspect is also the same as the base (1).

It is preferable that d is 1 and e is 0 or 1.

The compound (cx-2) may be used alone or in combination of two or more.

Specific examples of the compound (cx-2) include the following compounds Thing.

Relative to 1 mole of the compound (s1), the compound (s2) in the mixture (M) should preferably contain 0.5 to 6 moles, and more preferably 0.5 to 5 moles. In addition, the content of the compound (s2) in the mixture (M) is preferably a ratio such that the content of the blocked isocyanate group in the polymer (C1), which is a partially hydrolyzed condensate obtained from the mixture, becomes the above range. If the content ratio is above the lower limit of the above range, the storage stability and the ink affinity of the openings are excellent. When it is below the upper limit, the fluorine atom content rate in the polymer (C1) is high, and good ink repellency can be imparted.

<3> Compound (s3)

When the compound (s3) is contained in the mixture (M) of the present invention, for example, in a partition wall prepared using a photosensitive resin composition containing a polymer (C1), It can improve the film forming property of the polymer (C1) after moving to the upper surface. That is, from the viewpoint that the number of hydrolyzable groups in the compound (s3) is large, we believe that the polymers (C1) can condense well with each other after moving to the upper surface, and form a film on the entire upper surface to become an ink repellent layer .

Moreover, when the mixture (M) contains the compound (s3), the polymer (C1) can be easily dissolved in a hydrocarbon-based solvent.

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

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

The compound (s3) can be represented by the following formula (cx-3).

SiX ³ ₄ … (cx-3)

In the formula (cx-3), X ³ represents a hydrolyzable group, and four X ³ may be mutually different or may be the same. X ³ may use the same base as X ¹¹ and X ¹² described above.

Specific examples of the compound (cx-3) include the following compounds. In addition, a partially hydrolyzed condensate obtained by partially hydrolyzing and condensing a plurality of them in advance may be used as the compound (cx-3) as required.

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

When the mixture (M) contains the compound (s3), the content ratio of the compound (s3) in the mixture (M) is preferably 0.01 to 5 moles, particularly preferably 0.05 to 3 moles, relative to 1 mole of the compound (s1). If the content ratio is above the lower limit of the above range, the film forming property of the polymer (C1) is good; if it is below the upper limit value, the ink repellency of the polymer (C1) is good.

<4> Compound (s4)

By containing the compound (s4) in the mixture (M) of the present invention, the polymer (C1) can be (co) polymerized with each other through a group having an ethylenic double bond, or the polymer (C1) and, for example, a photosensitive resin The other component having an ethylenic double bond (co) polymerized in the composition is preferable. Thereby, as described above, it is possible to obtain the effect of improving the adhesion of the polymer (C1) to the ink repellent layer.

The compound (s4) may be used alone or in combination of two or more.

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

For the group having an ethylenic double bond, (meth) acryloxy, vinylphenyl, allyl, vinyl, Is preferred, and (meth) propenyloxy is particularly preferred.

The compound (s4) is preferably a compound represented by the following formula (cx-4).

(YQ ⁴ ) _g -Si (R ^H4 ) _h X ⁴ _(4-gh) … (cx-4)

The meaning of the symbols in the formula (cx-4) is as follows.

Y is a group having an ethylenic double bond.

Q ⁴ is a divalent organic group containing 1 to 6 carbon atoms and not containing a fluorine atom. However, the terminal atom of Q ⁴ bonded to Si is a carbon atom.

R ^H4 is a hydrocarbon group having 1 to 6 carbon atoms.

X ⁴ is a hydrolyzable group.

g is 1 or 2, h is 0 or 1, and g + h is 1 or 2.

When there are a plurality of YQ ⁴ , these may be different or the same.

When there is a plurality of X ⁴ , these may be different from each other or may be the same.

R ^H4 may use the same base as R ^H11 and R ^H12 described above.

X ⁴ may use the same base as X ¹¹ and X ¹² described above.

Y is preferably (meth) acryloxy or vinylphenyl, and (Meth) acrylic acid is particularly preferred.

Specific examples of Q ⁴ include an alkylene group having 2 to 6 carbon atoms, a phenylene group, and the like. Among these,-(CH ₂ ) ₃ -is preferred.

Preferably g is 1 and h is 0 or 1.

The compound (cx-4) may be used alone or in combination of two or more.

Specific examples of the compound (cx-4) include those described in, for example, paragraph [0057] in WO2014 / 046209.

When the mixture (M) contains the compound (s4), the content of the compound (s4) in the mixture (M) is preferably 0.1 to 5 moles, and more preferably 0.5 to 4 moles, relative to 1 mole of the compound (s1). If the content ratio is above the lower limit of the above range, the migration of the upper surface of the polymer (C1) is good, and after the migration to the upper surface, the polymer (C1) has good adhesion in the ink repellent layer including the upper surface. Moreover, the storage stability of the ink repellent (C1) is good. If it is below the upper limit, the ink repellency of the polymer (C1) is good.

<5> Compound (s5)

When the compound (s3) is used in the mixture (M) of the present invention, for example, in a partition wall obtained by curing the photosensitive resin composition, a protrusion may be formed on an end portion of the upper surface. These protrusions are minute objects that can be observed with a scanning electron microscope (SEM) or the like. The present inventors confirmed that the content of F and / or Si in the protrusion is larger than that in the other portions.

The above-mentioned protrusions do not cause a particular obstacle as a partition wall or the like, but the present inventors have found that by replacing a part of the compound (s3) with a compound (s5) having a small number of hydrolyzable groups, the occurrence of the protrusions can be suppressed.

Silanol groups generated from compounds (s3) with a large number of hydrolyzable groups This reaction improves the film forming property of the polymer (C1). However, we believe that it is precisely because of its high reactivity that the above protrusions are triggered. Therefore, we believe that by substituting a part of the compound (s3) with the compound (s5) having a small number of hydrolyzable groups, it is possible to suppress the reaction of the silanol groups, thereby suppressing the occurrence of the protrusions.

The compound (s5) may be used alone or in combination of two or more.

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

The compound (s5) is preferably a compound represented by the following formula (cx-5).

(R ^H5 ) _j -SiX ⁵ _(4-j) … (cx-5)

In the formula (cx-5), each symbol has the following meaning.

R ^H5 is a hydrocarbon group having 1 to 20 carbon atoms.

X ⁵ is a hydrolyzable group.

j is an integer from 1 to 3, ideally 2 or 3.

When there are a plurality of R ^H5 , these may be different from each other or may be the same.

When there are a plurality of X ⁵ , these may be different from each other or may be the same.

In the case of R ^H5 , when j is 1, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms can be cited, and an alkyl group having 1 to 10 carbon atoms and benzene can be cited. Basic is better. When j is 2 or 3, R ^H5 is preferably a hydrocarbon group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 3 carbon atoms is more preferred.

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

Specific examples of the compound (cx-5) include those described in, for example, paragraph [0063] in WO2014 / 046209.

When the mixture (M) contains the compound (s5), the content ratio of the compound (s5) in the mixture (M) is preferably 0.05 relative to 1 mole of the compound (s1). ~ 5 moles, especially 0.3 ~ 3 moles. If the content ratio is at least the lower limit of the above range, it is possible to suppress the protrusion of the end portion of the upper surface of the partition wall. If it is below the upper limit, the ink repellency of the polymer (C1) is good.

<6> Compound (s6)

By using the compound (s6), for example, the photosensitive resin composition can be cured at a lower exposure amount. We believe that because the thiol group in the compound (s6) has chain transferability, when the above-mentioned alkali-soluble resin or alkali-soluble monomer and the polymer (C1) have an ethylenic double bond, it is easily related to the polymer (C1) itself. Ethylene double bonds and other bonds promote light hardening.

Moreover, the pKa of the compound (s6) containing a mercapto group is about 10, and it is easy to deprotonate in an alkaline solution, that is, it is easy to dissociate. Here, it is expressed as pKa = -log ₁₀ Ka, where Ka represents an acid dissociation constant. Therefore, we think that the mercapto group can improve the alkali solubility of the photosensitive resin composition during development.

The compound (s6) may be used alone or in combination of two or more.

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

The compound (s6) is preferably a compound represented by the following formula (cx-6).

(HS-Q ⁶ ) _p -Si (R ^H6 ) _q X ⁶ _(4-pq) … (cx-6)

In the formula (cx-6), each symbol has the following meaning.

Q ⁶ is a divalent organic group containing 1 to 10 carbon atoms and not containing a fluorine atom. However, the terminal atom bonded to Si of Q ⁶ is a carbon atom.

R ^H6 is a hydrocarbon group having 1 to 6 carbon atoms.

X ⁶ is a hydrolyzable group.

p is 1 or 2, q is 0 or 1, and p + q is 1 or 2.

HS-Q ⁶ there a plurality of time, these may be the same or may be mutually exclusive.

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

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

As far as Q ^{6 is} concerned, alkylene groups having 1 to 10 carbon atoms are preferred, alkylene groups having 1 to 5 carbon atoms are preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred.

R ^H6 may use the same base as R ^H11 and R ^H12 described above.

Specific examples of the compound (cx-6) include HS- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ and HS- (CH ₂ ) ₃ -Si (CH ₃ ) (OCH ₃ ) ₂ .

When the mixture (M) contains the compound (s6), the content of the compound (s6) in the mixture (M) is preferably 0.125 to 18 moles, particularly preferably 0.125 to 8 moles, relative to 1 mole of the compound (s1). If the content ratio is above the lower limit of the above range, for example, the photosensitive resin composition can be cured at a lower exposure amount. Moreover, alkali solubility can be improved and developability is favorable. If it is below the upper limit, the ink repellency of the polymer (C1) is good.

<7> Other hydrolyzable silane compounds

The mixture (M) may optionally contain one or more types of hydrolyzable silane compounds other than the compounds (s1) to (s6).

Examples of the other hydrolyzable silane compound include a hydrolyzable silane compound having an oxyalkylene group and a hydrolyzable group and not containing a fluorine atom. Specifically, for example, CH ₃ O (C ₂ H ₄ O) _k C ₃ H ₆ Si (OCH ₃ ) ₃ (polyoxyethylene-containing trimethoxysilane) (here, k is, for example, about 10) Wait.

<8> Polymer (C1)

The polymer (C1) is a partially hydrolyzed condensate of the mixture (M).

An example of the polymer (C1) is a partially hydrolyzed condensate of the mixture (M), This mixture (M) contains compound (cx-1a) and compound (cx-2) as essential components, and optionally contains compounds (cx-3) to (cx-6), and the group T in compound (cx-1a) is The average composition formula of the fluorine atom and the polymer (C11) is shown in the following formula (II).

[TR ^F12 -Q ¹¹ -SiO _3/2 ] _n1 ‧ [(BI-Q ² ) _d -Si (R ^H2 ) _e SiO _{(4-de) / 2} ] _n2 ‧ [SiO _4/2 ] _n3 ‧ [( YQ ⁴ ) _g -Si (R ^H4 ) _h SiO _{(4-gh) / 2} ] _n4 ‧ [(R ^H5 ) _j -SiO ( _{4-j) / 2} ] _n5 ‧ [(HS-Q ⁶ ) _p -Si (R ^H6 ) _q O _{(4-pq) / 2} ] _n6 … (II)

In the formula (II), n1 to n6 represent the mole fractions of each constituent unit with respect to the total mole amount of the constituent units. n1> 0, n2> 0, n3 ≧ 0, n4 ≧ 0, n5 ≧ 0, n6 ≧ 0, and n1 + n2 + n3 + n4 + n5 + n6 = 1. The other symbols are as described above. However, T is a fluorine atom.

In addition, since the polymer (C11) is actually a product (partially hydrolyzed condensate) of a residual hydrolyzable group or a silanol group, it is difficult to express the product by a chemical formula.

The average composition formula represented by the formula (II) is a chemical formula when all the hydrolyzable groups or silanol groups in the polymer (C11) become siloxane bonds.

In addition, it is speculated that units derived from compounds (cx-1a) and (cx-2) to (cx-6) in formula (II) are randomly arranged.

N1: n2: n3: n4: n5: n6 in the average composition formula shown by formula (II), and compound (cx-1a), and (cx-2) to (cx-6) in the mixture (M) The feed composition is consistent.

The mole ratio of each component can be designed from the balance of the effects of each component.

As far as the fluorine atom content of the polymer (C11) can be made into the above-mentioned ideal range, n1 is preferably 0.02 to 0.4, and particularly preferably 0.02 to 0.3.

n2 is preferably from 0.05 to 0.6, particularly from 0.1 to 0.5.

n3 is preferably 0 ~ 0.98, especially 0.05 ~ 0.6.

n4 is preferably 0 ~ 0.8, especially 0 ~ 0.5.

n5 is preferably 0 ~ 0.5, especially 0.05 ~ 0.3.

n6 is preferably from 0 to 0.9, preferably from 0 to 0.8, and particularly preferably from 0 to 0.4.

In addition, the ideal molar ratio of each of the above components is the same as when T is the base (Ib) in the compound (cx-1a).

The ideal molar ratio of each of the components described above is also applicable to the case where the mixture (M) contains the compound (s1) and the compound (s2) and optionally contains the compounds (s3) to (s6). That is, the ideal feeding amounts of the compounds (s1) to (s6) in the mixture (M) to obtain the polymer (C1) correspond to the above-mentioned ideal ranges of n1 to n6, respectively.

The mass average molecular weight (Mw) of the polymer (C1) is preferably 5 × 10 ² or more, more preferably less than 1 × 10 ⁶ , and particularly preferably less than 1 × 10 ⁴ .

When the mass average molecular weight (Mw) is at least the lower limit value, when the photosensitive resin composition is used to form the partition wall, the ink repellent (C1) can easily move on the upper surface. If it is less than the upper limit, the solubility of the polymer (C1) in a solvent is better.

The mass average molecular weight (Mw) of the polymer (C1) can be adjusted according to manufacturing conditions.

The polymer (C1) can be produced by subjecting the mixture (M) to a hydrolysis and condensation reaction by a known method.

In this reaction, it is preferable to use a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid or an organic acid such as acetic acid, oxalic acid, or maleic acid as a catalyst. In addition, according to requirements, sodium hydroxide and tetramethylammonium hydroxide can also be used. (TMAH) and other alkali catalysts.

For the above reaction, a known solvent can be used.

The polymer (C1) obtained by the above reaction may be blended into the photosensitive resin composition in the form of a solution together with a solvent.

<Polymer (C2)>

The main chain of the polymer (C2) is a hydrocarbon chain and has the following units: a unit having a fluorine atom-containing side chain and a unit having a blocked isocyanate group. The mass average molecular weight (Mw) of the polymer (C2) is preferably 1 × 10 ² to 1 × 10 ⁶ , and particularly preferably 5 × 10 ³ to 1 × 10 ⁵ . When the mass average molecular weight (Mw) is at least the lower limit value, when the photosensitive resin composition is used to form the partition wall, the polymer (C2) can easily undergo upper surface migration. If it is lower than the upper limit, the solubility of the polymer (C2) in the solvent is better.

As for the above-mentioned unit having a fluorine atom-containing side chain, the polymer (C2) preferably has a unit having a fluoroalkylene group which may contain etheric oxygen atoms and / or a fluorine group which may contain etheric oxygen atoms. alkyl.

The fluoroalkyl group may be linear or branched.

Specific examples of the fluoroalkyl group having no etheric oxygen atom include those described in, for example, paragraph [0082] in WO2014 / 046209.

Specific examples of the fluoroalkyl group containing an etheric oxygen atom include those described in, for example, paragraph [0083] in WO2014 / 046209.

From the viewpoint of good ink repellency, a perfluoroalkyl group is preferred.

The number of carbon atoms of the fluoroalkyl group is preferably from 4 to 15, and more preferably from 4 to 12. If the number of carbon atoms of the fluoroalkyl group is 4 to 15, the ink repellency is better; In the compound (C2), the compatibility between the monomer having a fluoroalkyl group and a monomer other than the monomer described later is good.

The polymer (C2) is preferably a polymer containing a unit having a fluoroalkyl group as the above-mentioned unit having a side chain containing a fluorine atom. The unit having a fluoroalkyl group is preferably introduced into the polymer by polymerizing a polymerizable monomer having a fluoroalkyl group. In addition, the fluoroalkyl group may be introduced into the polymer by various modification methods in which a polymer having a reaction site is reacted with an appropriate compound.

As for the hydrocarbon chain constituting the main chain of the polymer (C2), specifically, for example, a main chain obtained by polymerization of a monomer having an ethylenic double bond, and -Ph-CH _2- (but "Ph" represents a phenolic backbone composed of repeating units of a benzene skeleton).

When a polymer (C2) is to be produced by polymerizing a monomer having an ethylenic double bond, the monomer having an ethylenic double bond and having a fluoroalkyl group and the monomer having an ethylenic double bond and having an end cap at the same time Isocyanate-based monomers may be polymerized, or may be polymerized with other monomers having ethylenic double bonds as required.

Hereinafter, a case where the main chain of the polymer (C2) is a main chain obtained by polymerization of a monomer having an ethylenic double bond will be described.

Examples of monomers having an ethylenic double bond and a fluoroalkyl group are CH ₂ = CR ⁴ COOR ⁵ R ^f , CH ₂ = CR ⁴ COOR ⁶ NR ⁴ SO ₂ R ^f , CH ₂ = CR ⁴ COOR ⁶ NR ⁴ COR ^f , CH ₂ = CR ⁴ COOCH ₂ CH (OH) R ⁵ R ^f , CH ₂ = CR ⁴ CR ⁴ = CFR ^f, etc.

In the above formula, R ^f represents a fluoroalkyl group, R ⁴ represents a hydrogen atom, a halogen atom or a methyl group other than a fluorine atom, R ⁵ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and R ⁶ represents carbon. Divalent 1 to 6 divalent organic groups.

As for R ^f , a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoroalkyl group having 4 to 10 carbon atoms containing an etheric oxygen atom is preferred, and a perfluoroalkyl group having 4 to 8 carbon atoms It is more preferred, and a perfluoroalkyl group having 6 carbon atoms is particularly preferred.

The halogen atom represented by R ^{4 is} preferably a chlorine atom.

As for R ⁵ and R ⁶ , an alkylene group is preferred. Specific examples of R ⁵ and R ⁶ include -CH _2- , -CH ₂ CH _2- , -CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -C (CH ₃ ) ₂ -,- CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH _2- , CH (CH ₂ CH ( CH ₃ ) ₂ )-and so on.

The said polymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

The polymer (C2) contains the above-mentioned unit having a fluorine atom-containing side chain and also a unit having a blocked isocyanate group. Since the polymer (C2) has a blocked isocyanate group, it can improve storage stability when used as an ink repellent or contained in a photosensitive resin composition for storage. In addition, the isocyanate group formed by heating and deblocking during use can improve the reactivity of the polymer (C2), and can improve the binding and adhesion with other ingredients or other materials. Thereby, the openings around the partition wall can suppress the residue of the photosensitive resin composition from hindering the wet diffusibility of the printing ink, and the ink affinity is good.

As a blocked isocyanate group, the group (1) represented by the said Formula (1) is mentioned. As described above, among them, a blocked isocyanate group obtained by reacting an isocyanate group with a pyrazole or an oxime is preferable, and a blocked isocyanate group obtained by reacting an isocyanate group with a pyrazole is particularly preferable.

Examples of the monomer having an ethylenic double bond and having a blocked isocyanate group include CH ₂ = CR ⁴ COOR ⁵ -NHC (= O) -B and the like. In the formula, when R ⁴ and R ⁵ are monomers having a fluoroalkyl group, R ⁴ and R ⁵ are synonymous, and B is synonymous with B in formula (1).

For CH ₂ = CR ⁴ COOR ⁵ -NHC (= O) -B, specifically, a monomer represented by the following formula (m1) and a monomer represented by the following formula (m2) may be mentioned.

The polymer (C2) may have, in addition to a fluorine atom-containing unit and a blocked isocyanate group-containing unit, a polymer selected from the group consisting of a unit having an acidic group, a unit having an ethylenic double bond, a unit having a hydroxyl group, and a unit having polyoxygen. At least one type of unit in the group consisting of units of an alkyl chain.

From the viewpoint of good alkali solubility, the polymer (C2) is preferably a polymer having an acidic group.

The acidic group is preferably at least one acidic group or a salt thereof selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.

The polymer (C2) has photo-crosslinking properties. In the production process of the cured film obtained by curing the photosensitive resin composition, the upper layer of the cured film is bonded to each other or contained in the photosensitive resin composition. Bonding of other components having an ethylenic double bond can improve the fixation of the polymer (C2). In this viewpoint, the polymer (C2) is preferably a polymer having an ethylenic double bond.

The group having an ethylenic double bond is (meth) acryloxy, vinylphenyl, allyl, vinyl, or Is preferred, and (meth) propenyloxy is particularly preferred.

The ethylenic double bond is suitable for polymer (C2) to be introduced after the polymer is formed. Although the ethylenic double bond undergoes a reaction during the polymerization of the monomer, a polymer having an ethylenic double bond cannot usually be produced only by the polymerization of the monomer. In this case, a polymer having a reaction site such as a hydroxyl group is first polymerized, and then a compound having an ethylenic double bond that can be bonded to the reaction site of the polymer is reacted to produce a polymer having an ethylenic double bond. . Specifically, for example, a polymer containing a unit having a fluorine atom-containing side chain, a unit having a blocked isocyanate group, and a unit having a hydroxyl group is produced first, and then an isocyanate alkyl (meth) acrylate is reacted to produce the polymer. Polymer (C2) having an ethylenic double bond.

The polymer (C2) may have a hydroxyl group or a polyoxyalkylene group.

Although the polyoxyalkylene group and hydroxyl group do not have photo-crosslinkability, the polymer (C2) having a polyoxyalkylene group or hydroxyl group and the ethylenic double bond are also bonded to each other on the upper part of the cured film or are Bonding with other components contained in the photosensitive resin composition can improve the fixing property of the polymer (C2). Moreover, a hydroxyl group can also act as a reaction site of a polymer as mentioned above. Among polyoxyalkylene groups, polyoxyethylene groups are hydrophilic, and therefore have the effect of improving the wettability of the developer.

The polymer (C2) may contain one or more of an acidic group, an ethylenic double bond, a hydroxyl group, and a polyoxyalkylene group. Two or more of these groups may be contained in one side chain of the polymer. For example, hydroxyl groups can be bonded to polyoxyalkylenes end.

As the method for introducing the above group, a method in which a monomer having a fluoroalkyl group, a monomer having a blocked isocyanate group, and a monomer having the above group can be copolymerized is preferable. The above-mentioned groups can also be introduced into the polymer by various modification methods in which a polymer having a reaction site is reacted with an appropriate compound.

Specific examples of the monomer having a carboxyl group, the monomer having a phenolic hydroxyl group, and the monomer having a sulfonic acid group include those described in paragraphs [0092], [0093], and [0094] of WO2014 / 046209.

The method for introducing a carboxyl group into a polymer having a reaction site may be exemplified by the following method: method (1), which reacts an acid anhydride with a polymer having a hydroxyl group; and method (2), which causes a compound with a hydroxyl group to react The polymer having an acid anhydride unit having an ethylenic double bond reacts.

Specific examples of the monomer having a hydroxyl group include those described in, for example, paragraph [0096] in WO2014 / 046209.

The monomer having a hydroxyl group may also be a monomer having a polyoxyalkylene chain having a hydroxyl group at its terminal.

For example, WO2014 / 046209 may be the one described in paragraph [0097].

Examples of the acid anhydride include those described in, for example, paragraph [0098] in WO2014 / 046209.

The compound having a hydroxyl group may be a compound having one or more hydroxyl groups, and examples thereof include those described in paragraph [0099] of WO2014 / 046209.

As the monomer having no hydroxyl group and acidic group and having a polyoxyalkylene group, for example, a monomer represented by the following formula (POA-1) or (POA-2) can also be used.

CH ₂ = CR ⁷¹ -COO-W- (R ⁷² -O) _K4 -R ⁷³ … (POA-1)

CH ₂ = CR ⁷¹ -OW- (R ⁷² -O) _K4 -R ⁷³ … (POA-2)

(R ⁷¹ is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with an aryl group, or an aryl group having 6 to 20 carbon atoms Or a cycloalkyl group having 3 to 20 carbon atoms.

R ⁷² is an alkylene group having 1 to 5 carbon atoms. R ⁷³ is an alkyl group having 1 to 4 carbon atoms. W is a single bond or a divalent organic group having 1 to 10 carbon atoms without a fluorine atom. k4 is an integer from 6 to 30).

In addition, according to the desired composition, well-known monomers and reactions can be appropriately selected to obtain fluorine-containing side chains and blocked isocyanate groups, and acidic groups, ethylenic double bonds, hydroxyl groups, and polyoxyalkylene groups as required. Polymer (C2).

In addition, in this case, it is preferable to appropriately adjust the blending ratio of the monomers used in such a manner that the content of the fluorine atom and the blocked isocyanate group in the polymer (C2) becomes the above-mentioned desirable range.

When the main chain of the polymer (C2) is a phenolic main chain composed of repeating units of -Ph-CH _2- , it is usually a side chain having a fluorine atom on a benzene skeleton (Ph) constituting the main chain and a A polymer having a side chain of an isocyanate group blocked and optionally bonded with a group having an acidic group, a group having an ethylenic double bond, and an oxyalkylene group is used as the polymer (C2). The side chain having a fluorine atom is preferably a side chain having a fluoroalkyl group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom. Examples of the acidic group, the group having an ethylenic double bond, and the oxyalkylene group are the same as those described above for the polymer (C2) having a main chain prepared by polymerizing an ethylenic double bond monomer Thing.

In addition, in this case, it is also preferable to design the polymer (C2) as a molecule so that the content of the fluorine atom and the blocked isocyanate group in the polymer (C2) becomes the above-mentioned desirable range.

Such a polymer (C2) can be produced by polymerizing a monomer having the above-mentioned groups introduced into the benzene skeleton in advance, or can be produced by preparing a reaction site, specifically a hydroxyl group, an amine group, a thiol group, and a sulfonic acid group. A modification method in which a polymer such as a carboxylic acid group, a carbonyl group, an ethylenic double bond, and the like is used to react the reaction site with an appropriate compound, and the aforementioned groups are introduced into the polymer.

[Negative photosensitive resin composition]

The negative photosensitive resin composition of the present invention contains a photo-curable alkali-soluble resin (hereinafter also referred to as resin (AP)) or a photo-curable alkali-soluble monomer (hereinafter also referred to as monomer (AM)), Polymerization initiator and the ink repellent (C). By containing the ink repellent (C) as the ink repellent, the negative photosensitive resin composition of the present invention can have good storage stability, and when it is made into a partition wall, the upper surface of the partition wall has excellent ink repellency, and The opening has good ink affinity.

The negative-type photosensitive resin composition of the present invention may further contain a black colorant, a cross-linking agent, a solvent, and other optional components as required.

Hereinafter, each component contained in the negative photosensitive resin composition of this invention is demonstrated.

The resin (AP) is preferably a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the resin (AP) has B in the molecule Since the ethylenic double bond is used, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator.

The exposed portion hardened in this way cannot be removed by the alkali developer. In addition, since the resin (AP) has an acidic group in the molecule, the non-exposed portion of the non-cured negative photosensitive resin composition can be selectively removed by an alkali developer. Thus, the cured film can be made into a partition shape having a predetermined area divided into a plurality of partitions.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphate group. These may be used alone or in combination of two or more.

Examples of ethylenic double bonds include addition-polymerizable double bonds such as (meth) acrylfluorenyl, allyl, vinyl, vinyloxy, and vinyloxyalkyl. These may be used individually by 1 type, and may use 2 or more types together. Moreover, a part or all of the hydrogen atoms which an ethylenic double bond has may be substituted by the alkyl group, such as a methyl group.

Examples of the resin (AP) include a resin (AP-1) having a side chain having an acidic group and a side chain having an ethylene-based double bond, and an acidic group and an ethylene-based double bond introduced into an epoxy resin. Resin (AP-2) and so on. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the resin (AP-1) include a vinyl resin having a side chain having an acidic group and a side chain having an ethylene-based double bond.

The resin (AP-2) includes a resin obtained by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, and then reacting it with a polycarboxylic acid or an anhydride thereof. The epoxy resin to be used is not particularly limited, and a conventionally known epoxy resin used as the main chain of a negative photosensitive resin can be used, such as the epoxy described in International Publication No. 2010/013816 and the like. Resin.

As for the resin (AP), the acid value is preferably from 10 to 300 mgKOH / g, and particularly from 30 to 150 mgKOH / g. The number average molecular weight (Mn) is preferably 5 × 10 ² to 2 × 10 ^{4, and particularly} preferably 2 × 10 ³ to 1.5 × 10 ⁴ . The mass average molecular weight (Mw) is preferably 1 × 10 ³ to 4 × 10 ^{4, and particularly} preferably 3 × 10 ³ to 2 × 10 ⁴ .

Resin (AP) should preferably be used for the resin (AP-) in that it can suppress the peeling of the cured film to obtain a high-resolution dot pattern during development, that the pattern is straight when the dots are straight, and that the smooth cured film surface is easy to obtain 2).

As the monomer (AM), for example, a monomer (AM-1) having an acidic group and an ethylenic double bond is suitably used. The acidic group and the ethylenic double bond are the same as those of the resin (AP). The acid value of the monomer (AM) is preferably in the same range as the resin (AP).

Examples of the monomer (AM-1) include 2,2,2-tripropenyloxymethylethyl phthalic acid and the like.

The resin (AP) and the monomer (AM) contained in the negative photosensitive resin composition may be used singly or in combination of two or more kinds.

The content ratio of the resin (AP) and the monomer (AM) in the total solid content of the negative photosensitive resin composition are preferably 5 to 80% by mass, respectively. When the negative photosensitive resin composition does not contain a black colorant described later, its content is preferably 30 to 70% by mass. When the negative photosensitive resin composition has a black colorant described later, the content thereof is particularly preferably 10 to 60% by mass. If the content ratio is within the above range, the photo-curability and developability of the negative photosensitive resin composition are better.

(Photopolymerization initiator)

The photopolymerization initiator of the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, and a compound capable of generating a radical by light is preferred.

As for the photopolymerization initiator, it can be classified into α-diketones, saponins, saponins, 9-oxosulfur, etc. Compounds, such as diphenyl ketones, acetophenones, quinones, aminobenzoic acids, peroxides, oxime esters, and aliphatic amines.

Among the photopolymerization initiators, diphenyl ketones, aminobenzoic acids, and aliphatic amines can exhibit a sensitizing effect when used together with other free radical initiators, which is ideal.

The photopolymerization initiator is preferably the following: 2-methyl-1- [4- (methylthio) phenyl] -2-N- classified as acetophenone Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-N- (Phenylphenyl) -butan-1-one; 1,2-octanedione classified as oxime esters, 1- [4- (phenylthio)-, 2- (O-benzylidene oxime) , Ethyl ketone 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamoxime); and classified as 9- Oxygen sulfur 2,4-diethyl 9-oxosulfur . In addition, combinations of these with diphenyl ketones such as 4,4'-bis (diethylamino) diphenyl ketone are particularly preferred.

The photopolymerization initiator may be used alone or in combination of two or more.

The content ratio of the photopolymerization initiator in the total solid content of the negative photosensitive resin composition is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. When the negative photosensitive resin composition does not contain the black colorant mentioned later, its content is particularly preferably 5 to 15% by mass. Negative photosensitive resin composition contains to be described later In the case of black colorants, the content is preferably 2 to 12% by mass. If the content ratio is within the above range, the photo-curability and developability of the negative photosensitive resin composition are better.

(Ink Repellent (C))

The ink-repellent agent (C) of the present invention has a function of sufficiently migrating to the upper surface during formation of the partition wall using the photosensitive resin composition and imparting good ink-repellency to the obtained upper surface of the partition wall. On the other hand, when the ink repellent (C) is contained in the photosensitive resin composition for storage, storage stability can be improved. In addition, the isocyanate group is formed by deblocking by heating during use, which can improve the reactivity of the ink repellent (C), and further improve the binding and adhesion with other ingredients or other materials. Thereby, the residue of the photosensitive resin composition can be suppressed in the opening part enclosed by the partition wall from interfering with the wet diffusion property of the printing ink, and the ink affinity is good.

The content of the ink repellent (C) in the total solid content of the negative photosensitive resin composition is preferably 0.01 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.03 to 1.5% by mass. If the content ratio is above the lower limit of the above range, the upper surface of the cured film formed of the negative photosensitive resin composition will have excellent ink repellency. When it is below the upper limit of the above range, the adhesion between the cured film and the substrate is good.

(Black colorant)

The negative-type photosensitive composition of the present invention contains a black colorant when it is desired to impart light-shielding properties to the partition wall depending on the application. Previously, when a coloring agent was blended in a negative photosensitive composition containing a conventional ink repellent, the ink repellency of the upper surface of the partition wall became insufficient, or the ink affinity of the openings became insufficient. borrow By using the ink repellent agent (C) of the present invention, even if a colorant is blended, the above-mentioned problem does not occur, and the good ink repellency of the upper surface of the partition wall and the ink affinity of the opening can be taken into consideration.

In particular, when a polymer having a hydrocarbon chain as a main chain and a fluorine atom-containing side chain was used as an ink repellent, once a negative-type photosensitive composition containing a colorant is used to make a partition, the ink affinity of the opening portion is mostly Not enough. If the polymer (C2) is used as the ink repellent (C) of the present invention to prepare a negative-type photosensitive composition, the problem of ink affinity of the opening portion can be solved, and an opening portion having sufficient ink affinity can be obtained. And the upper surface has a sufficient ink repellent partition.

Examples of the black colorant include carbon black, aniline black, anthraquinone-based black pigment, and fluorene-based black pigment, and specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31, and the like. As for the black colorant, a mixture of organic pigments such as red pigments, blue pigments, green pigments, and yellow pigments or inorganic pigments can also be used. Specific examples of the organic pigments include C.I. Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, Pigment Yellow 150, and imine-based pigments. As the black colorant, an organic pigment is preferred from the viewpoint of electrical properties, and carbon black is preferred from the viewpoint of price and light-shielding properties. Carbon black is preferably subjected to a surface treatment through a resin or the like, and in order to adjust the color tone, a blue pigment or a purple pigment may be used in combination.

As the organic pigment, from the viewpoint of the shape of the black matrix, it is preferable that the specific surface area by the BET method is 50 to 200 m ² / g. When the specific surface area is 50 m ² / g or more, the shape of the black matrix is not easily deteriorated. If it is 200 m ² / g or less, the organic pigment will not be excessively adsorbed on the dispersing aid, and it is not necessary to mix a large amount of the dispersing aid in order to develop various physical properties.

The average primary particle diameter of the organic pigment under observation with a transmission electron microscope is preferably 20 to 150 nm. If the average primary particle diameter is 20 nm or more, it can be dispersed in the photosensitive composition for negative type at a high concentration, and further, it is easy to obtain a photosensitive composition for negative type with good stability over time. If it is 150 nm or less, the shape of the partition wall is difficult to deteriorate. In addition, the average secondary particle diameter under observation by a transmission electron microscope is preferably 80 to 200 nm.

The content of the black colorant in the total solid content of the negative-type photosensitive composition is preferably 20 to 65% by mass, more preferably 25 to 60% by mass, and even more preferably 30 to 60% by mass. If the content ratio is above the lower limit of the above range, the optical density is sufficient, and the optical density is a value representing the light-shielding property of the obtained partition wall. If it is below the upper limit of the above range, the curability of the negative photosensitive composition is good, a cured film with a good appearance can be obtained, and the ink repellency is also good.

In order to improve the dispersibility of the black colorant in the negative-type photosensitive composition, it is preferable to include a basic polymer dispersant or an acidic polymer dispersant. The amine value of the basic polymer dispersant is preferably 10 to 100 mgKOH / g, and more preferably 30 to 70 mgKOH / g. The acid value of the acidic polymer dispersant is preferably 30 to 150 mgKOH / g, and more preferably 50 to 100 mgKOH / g. From the standpoint of affinity for a black colorant, the polymer dispersant is preferably a compound having a basic functional group. As for this basic functional group, if it has a primary, secondary, or tertiary amine group, dispersibility is particularly good.

Examples of the polymer dispersant include urethane-based, polyimide-based, alkyd-based, epoxy-based, unsaturated polyester-based, melamine-based, phenol-based, and acrylic Compounds such as enoic acid-based, vinyl chloride-based, vinyl chloride-vinyl acetate-based copolymer, polyamide-based, and polycarbonate-based. Among them, urethane-based and polyester-based compounds are particularly preferred.

The amount of the polymer dispersant is preferably 5 to 30% by weight, and more preferably 10 to 25% by weight relative to the black colorant. If the amount used is above the lower limit of the above range, the dispersion of the black colorant is better; if it is below the upper limit of the above range, the developability is better.

(Crosslinking agent)

The crosslinking agent arbitrarily contained in the negative photosensitive resin composition of the present invention is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. When the negative photosensitive resin composition contains a cross-linking agent, the curability of the negative photosensitive resin composition during exposure can be improved, and a cured film can be formed even at a low exposure.

Examples of the cross-linking agent include those described in paragraph [0137] of WO2014 / 046209.

From the viewpoint of photoreactivity, it is preferable to have a plurality of vinylic double bonds. For example, neopentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (methyl) Base) acrylate, ethoxylated isotricyanate tri (meth) acrylate, and urethane acrylate are preferred.

The crosslinking agent may be used singly or in combination of two or more kinds.

The content of the crosslinking agent in the total solid content of the negative photosensitive resin composition is preferably 10 to 60% by mass. When the negative photosensitive resin composition does not contain a black colorant, its content is preferably 20 to 55 mass%. Negative When the resin composition contains a black colorant, its content is particularly preferably 5 to 50% by mass.

(Solvent)

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

As the solvent (F), a known solvent can be used. The solvents may be used singly or in combination of two or more kinds.

Examples of the solvent include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, and solvent oils. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferred, and at least one solvent selected from the group consisting of propylene glycol At least one solvent in the group consisting of monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, and 2-propanol is more preferable.

The solvent content in the negative photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and most preferably 65 to 90% by mass relative to the total amount of the composition.

(Other ingredients)

The negative photosensitive resin composition of the present invention may further contain one or two or more other additives such as a thermal crosslinking agent, a dispersing aid, a silane coupling agent, fine particles (fillers), a phosphoric acid compound, a hardening accelerator, Thickener, plasticizer, defoamer, leveling agent, anti-shrinking agent and UV absorber.

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

Since the negative photosensitive resin composition of the present invention contains the ink repellent (C) having improved storage stability, it has good storage stability. As long as the negative photosensitive resin composition of the present invention is used, the obtained partition wall has good ink repellency on the upper surface, and the opening portion surrounded by the partition wall also has good ink affinity.

[next door]

The partition wall of the present invention is formed as a partition that divides the surface of the substrate into a plurality of dot-forming partitions, and is formed of the cured product of the negative photosensitive resin composition of the present invention. The partition wall can be coated on the surface of a substrate such as a substrate with the negative photosensitive resin composition of the present invention, dried if necessary to remove the solvent, etc., and then a mask is applied to the portion forming the dot-forming partition, which is developed after exposure. Prepared by heating.

By developing, the unexposed portion due to the mask can be removed, and an opening portion corresponding to the dot formation section can be formed together with the partition wall. When the partition wall is formed, the ink repellent (C) contained in the negative photosensitive resin composition migrates to the upper surface and is stored in the ink repellent layer on the upper layer of the partition at a high concentration. Furthermore, the blocked isocyanate group of the ink repellent (C) can be unblocked to become an isocyanate group by heating, and it can be firmly fixed to the ink repellent layer. In addition, even if the non-exposed portion cannot be completely removed by development and remains in the opening portion, the ink repellent (C) is still fixed on the surface of the substrate, and the ink affinity of the opening portion can be ensured.

Therefore, for the substrate forming the partition wall of the present invention, at least the surface on which the partition wall is formed should have a functional group reactive with the isocyanate group such as Hydroxyl, amine, carboxyl, mercapto and the like. Because the surface of the substrate forming the partition wall has a functional group reactive with the isocyanate group, the adhesion between the substrate surface and the ink repellent (C) can be improved in the opening portion, and even if there is a residue of the photosensitive resin composition in the opening portion , Can still ensure the ink affinity of the opening.

Specific examples of the material constituting the surface having the functional group reactive with the isocyanate group include glass, metal oxides, and organic films. Examples of the metal oxide include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), and the like. In addition, for example, when a surface having a metal oxide is formed on the surface of a metal electrode, the surface may have a surface having a functional group reactive with an isocyanate group.

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

As shown in FIG. 1A, a negative photosensitive resin composition is entirely applied to one of the main surfaces of the substrate 1 to form a coating film 21. At this time, the ink repellent (C) has been completely dissolved and uniformly dispersed in the coating film 21. In addition, in FIG. 1A, the ink repellent (C) is shown schematically, but is not actually distributed in such a particle shape.

Next, as shown in FIG. 1B, the coating film 21 is dried to form a dry film 22. Examples of the drying method include heating drying, drying under reduced pressure, and drying under reduced pressure. Although it varies according to the type of solvent, in the case of heating and drying, the heating temperature is preferably 50 to 120 ° C. Heating time is 30 seconds. About 5 to 5 minutes is preferred.

During this drying process, the ink repellent (C) will migrate to the upper part of the drying film. In addition, even if the negative photosensitive resin composition does not contain a solvent, the ink repellent (C) in the coating film can also achieve upper surface migration.

Next, as shown in FIG. 1C, the dry film 22 is exposed to light through a photomask 30, and the photomask 30 has a mask portion 31 having a shape corresponding to an opening portion surrounded by the partition wall. The film after exposing the dry film 22 is referred to as an exposure film 23. In the exposure film 23, the exposed portion 23A is already light-cured, and the non-exposed portion 23B is in the same state as the dry film 22.

In terms of irradiation light, there can be mentioned visible light; ultraviolet light; far ultraviolet light; KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, Kr ₂ excimer laser light, KrAr excimer laser light, and Ar ₂ Excimer laser light and other excimer laser light; X-rays; electron rays and so on.

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

As for the exposure method, the whole surface can be exposed simultaneously, scanning exposure, and the like. Expose multiple times for the same place. At this time, the exposure conditions for several times may be the same or different. Regardless of any of the above exposure methods, the exposure amount is preferably, for example, 5 to 1,000 mJ / cm ² , 5 to 500 mJ / cm ^{2 is more} preferable, and 5 to 300 mJ / cm ^{2 is more} preferable. The exposure amount can be appropriately optimized depending on the wavelength of the irradiation light, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the like.

There is no particular limitation on the exposure time per unit area, and it can be designed from the exposure power and required exposure amount of the exposure device used. In addition, In the case of scanning exposure, the exposure time can be calculated from the scanning speed of light. The exposure time per unit area is usually about 1 to 60 seconds.

Next, as shown in FIG. 1D, the partition wall 4 is formed by developing using an alkali developing solution, and the partition wall 4 is composed of only a portion corresponding to the exposure portion 23A of the exposure film 23. The opening 5 surrounded by the partition wall 4 is a part of the exposure film 23 where the non-exposed portion 23B was once stored. FIG. 1D shows a state where the non-exposed portion 23B is removed by development. As described above, the non-exposed portion 23B is dissolved with an alkali developer in a state where the ink repellent (C) has moved to the upper layer portion and the ink repellent (C) is hardly stored in the layer below it. It is removed, so the upper surface of the prepared partition wall has good ink repellency.

In addition, in the partition wall 4 shown in FIG. 1D, the uppermost layer including the upper surface is an ink repellent layer 4A. When the ink-repellent agent (C) does not have a side chain having a vinylic double bond, the ink-repellent agent (C) is directly stored in the uppermost layer at a high concentration during exposure to become an ink-repellent layer. More specifically, at the time of exposure, the resin (AP) or monomer (AM) stored around the ink repellent (C) or even any light-hardening component other than these will be firmly light-cured, allowing the ink repellent (C) Fixed to the ink repellent layer.

When the ink-repellent agent (C) has an ethylenic double bond, the ink-repellent agent (C) is photocured with each other and / or with the resin (AP) or monomer (AM) and other light-hardening components to form an ink-repellent agent. (C) The ink repellent layer 4A which is firmly bonded.

In any of the above cases, a layer 4B will be formed below the ink repellent layer 4A. This layer 4B is mainly formed by light curing of resin (AP) or monomer (AM) or even light curing components other than these And almost no ink repellent (C).

After the development, the partition wall 4 is further heated. The heating temperature is set to be higher than the temperature at which the blocked isocyanate group of the ink repellent (C) is deblocked to generate an isocyanate group. Although the type of the blocked isocyanate group that the ink repellent (C) has is different, the heating temperature can be set to approximately 150 to 250 ° C, and preferably 200 to 250 ° C. The heating time is preferably about 20 to 70 minutes.

The blocked isocyanate group of the ink repellent agent (C) is deblocked by heating to become an isocyanate group, so that the ink repellent agent (C) is more firmly fixed in the ink repellent layer 4A. Moreover, the hardening of the partition wall 4 can be made stronger by heating.

In addition, the non-exposed portion may not be completely removed by the above-mentioned development, and a small and partial portion of the non-exposed portion 23B may remain as a residue in the opening portion. In this case, the ink repellent (C) can be immobilized on the surface of the substrate by the action of the deblocked isocyanate group to ensure the ink affinity of the opening.

Even if the partition wall 4 of the present invention obtained by the above method is exposed at a low exposure amount, the upper surface has good ink repellency. In addition, after development and heating in the partition wall 4, the hydrophilic property of the opening portion 5 is good, and the uniform coating property of the ink on the opening portion 5 can be sufficiently ensured.

In addition, in order to obtain the ink affinity of the opening 5 more reliably, the substrate 1 with the partition wall 4 may be subjected to ultraviolet / ozone treatment after the above-mentioned heating to remove the development of the negative photosensitive resin composition that may be present in the opening 5. Residues, etc.

The partition wall made of the negative photosensitive resin composition of the present invention is preferably, for example, 100 μm or less in width, and more preferably 20 μm or less. The distance (pattern width) between adjacent partition walls is preferably 300 μm or less, and is preferably 100 μm. The following is particularly preferred. The height of the partition wall is preferably 0.05 to 50 μm, and more preferably 0.2 to 10 μm.

When the partition wall of the present invention is subjected to pattern printing by the IJ method, the opening portion can be used as a partition wall in which the ink is injected. When pattern printing is performed by the IJ method, as long as the partition wall of the present invention is used in a state in which the opening is consistent with the desired ink injection area, the upper surface of the partition wall has good ink repellency, so that the ink can be suppressed from exceeding The partition wall is injected into an undesired opening, which is an ink injection region. In addition, since the printing ink in the opening portion surrounded by the partition wall has good moist diffusivity, the printing ink can be uniformly printed on a desired area without generating voids or the like.

With the partition wall of the present invention, pattern printing using the IJ method can be performed cleverly as described above. Therefore, the partition wall of the present invention can be effectively used as a partition wall of an optical element using the IJ method to form dots, and the optical element has a plurality of points on the substrate surface and partition walls between adjacent points.

[Optical element]

The optical element of the present invention is an optical element having a plurality of points on the substrate surface and the partition wall of the present invention located between adjacent points. In the optical element of the present invention, the dots are preferably formed by the IJ method.

Hereinafter, a case where an optical element according to an embodiment of the present invention is manufactured by the IJ method will be described as an example. In addition, the manufacturing method of the optical element of this invention is not limited to the following.

FIGS. 2A to 2B are schematic views showing a method for manufacturing an optical element using the partition wall 4 shown in FIG. 1D that has been formed on the substrate 1. Here, the partition wall 4 on the substrate 1 is formed as a dot pattern between the opening 5 and the optical element to be manufactured. Consistent.

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

Next, according to the type of the printing ink 10 used, drying and / or heating may be performed to remove and harden the solvent, for example, and then, as shown in FIG. 2B, a desired point 11 is formed in a form adjacent to the partition 4. The optical element 12.

The optical element of the present invention is an optical element having dots, and by using the partition wall of the present invention, the printing ink can be uniformly wetted and diffused in the opening portion divided by the partition during the manufacturing process, so as to be accurately formed. By.

In terms of optical elements, examples include organic EL elements, color filters for liquid crystal elements, TFT array elements, quantum dot displays, and thin-film solar cells.

A TFT array element is an element in which a plurality of dots are arranged in a matrix shape in plan view, and TFTs are provided at each point as a pixel electrode and a switching element for driving the pixel electrode.

The TFT array element may be provided as an TFT array substrate on an organic EL element or a liquid crystal element.

The TFT array can be manufactured, for example, by the following method, but is not limited thereto.

A gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The gate electrode can be patterned as required.

Next, gate insulation such as silicon nitride is formed by a plasma CVD method. membrane. A source electrode and a drain electrode can also be formed on the gate insulating film. The source electrode and the drain electrode can be formed by, for example, forming a metal thin film of aluminum, gold, silver, copper, or an alloy thereof by vacuum evaporation or sputtering. The method of patterning the source electrode and the drain electrode includes the following methods: after forming a metal thin film, applying a resist, exposing, and developing the resist to remain on the portion where the electrode is to be formed, and then using phosphoric acid or aqua regia Wait until the exposed metal is removed, and finally remove the resist. In the case where a metal thin film such as gold is formed, a resist is pre-coated, and after the exposure and development, the resist is left on the portion where the electrode is not to be formed, and then the photoresist is formed after the metal thin film is formed. Remove the agent together with the metal film. Further, a metal nano colloid such as silver or copper may be used to form a source electrode and a drain electrode by a method such as inkjet.

Next, using the composition of the present invention, the partition wall is formed into a plan lattice shape along the outline of each dot by a photolithography method including coating, exposure, and development.

Next, a semiconductor solution is applied in the spot by the IJ method and the solution is dried to form a semiconductor layer. The semiconductor solution may be an organic semiconductor solution or an inorganic coating oxide semiconductor solution. The source electrode and the drain electrode may be formed by a method such as inkjet after the semiconductor layer is formed.

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

An organic EL element can be manufactured by the following method, for example.

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

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

Next, the materials of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are respectively coated and dried by IJ method in the points to sequentially laminate the layers. The type and number of organic layers formed in the dots can be appropriately designed.

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

The quantum dot display can be manufactured by, for example, the following method, but is not limited thereto.

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

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

Next, the materials of the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer are respectively coated and dried by IJ method in the points to sequentially laminate the layers. The type and number of organic layers formed in the dots can be appropriately designed.

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

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

On a light-transmitting substrate such as glass, the composition of the present invention is used along each The dot outline forms a partition in a plan view.

Next, a nano-particle solution that can convert blue light to green light, a nano-particle solution that can convert blue light to red light, and a blue color printing ink according to demand are applied by dots by IJ method. Wait for drying to make the module. A blue light source is used as a backlight and the aforementioned module is used instead of a color filter, whereby a liquid crystal display having excellent color reproducibility can be obtained.

Examples

The present invention will be described below based on examples, but the present invention is not limited thereto. Examples 1, 2, 5-8, Examples 10-16 are examples, and Examples 3, 4, 9, and 17-19 are comparative examples.

Each measurement was performed by the following method.

[Number average molecular weight (Mn), mass average molecular weight (Mw)]

Gel permeation chromatography was used to measure number average molecular weight (Mn) and mass average molecular weight (Mw) using polystyrene as a standard material. As the gel permeation chromatography system, HPLC-8220 GPC (manufactured by Tosoh Corporation) was used. For the column, three shodex LF-604 were connected. The detector uses an RI detector. As the standard substance, EasiCal PS1 (manufactured by Polymer Laboratories) was used. In addition, when measuring the number average molecular weight and the mass average molecular weight, the column was maintained at 37 ° C, and tetrahydrofuran was used as an eluent, and a flow rate of 0.2 mL / min was injected into 40 μL of a 0.5% tetrahydrofuran solution of the measurement sample.

[Fluorine atom content rate]

The fluorine atom content rate (% by mass) was calculated by ¹⁹ F NMR measurement using 1,4-bis (trifluoromethyl) benzene as a reference material.

[Content of blocked isocyanate group]

The content of the blocked isocyanate group is calculated from the blending ratio of the raw materials.

[Content of ethylenic double bond (C = C)]

The content of ethylenic double bonds is calculated from the blending ratio of the raw materials.

[Acid value]

The acid value is calculated theoretically from the blending ratio of the raw materials.

The abbreviations of the compounds used in the following examples are shown below.

(Alkali soluble resin (AP))

Alkali-soluble resin (AP1) composition: It is made by reacting cresol novolac epoxy resin with acrylic acid, and then reacting with 1,2,3,6-tetrahydrophthalic anhydride, and then introducing propylene with hexane A composition (resin 70% by mass, 30% by mass of PGMEA) of a resin (alkali-soluble resin (A1), acid value 60 mgKOH / g) prepared by purifying a resin having a base and a carboxyl group.

(Photopolymerization initiator)

IR907: IRGACURE907, trade name, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-N- Phenylpropan-1-one.

OXE02: trade name; IRGACURE OXE 02, ethyl ketone 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-ethylfluorenyl Oxime) (manufactured by BASF).

EAB: 4,4'-bis (diethylamino) diphenyl ketone.

(Raw material of polymer (C1))

Compound (cx-11) equivalent to compound (cx-1): F (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ .

Compound (cx-21) equivalent to compound (cx-2): A compound obtained by capping 3-isocyanatepropyltriethoxysilane with 3,5-dimethylpyrazole A 50% by mass solution of toluene (manufactured by a known method).

Compound (cx-31) equivalent to compound (cx-3): Si (OC ₂ H ₅ ) ₄ .

Compound (cx-41) equivalent to compound (cx-4): CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ .

Compound (cx-51) equivalent to compound (cx-5): (CH ₃ ) ₃ -Si-OCH ₃ .

Compound (cx-61) equivalent to compound (cx-6): HS- (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ .

(Raw material of polymer (C2))

C6FMA: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F

MAA: methacrylic acid

2-HEMA: 2-hydroxyethyl methacrylate

PME400: CH ₂ = C (CH ₃ ) COO (C ₂ H ₄ O) ₉ CH ₃

MOI-BP: KARENZ MOI-BP (trade name, manufactured by Showa Denko Corporation, a compound represented by the above formula (m1))

MOI-BM: KARENZ MOI-BM (trade name, manufactured by Showa Denko Corporation, compound represented by the above formula (m2))

V-65: (2,2'-azobis (2,4-dimethylvaleronitrile))

AOI: KARENZ AOI (trade name, manufactured by Showa Denko Corporation, 2-propenyloxyethyl isocyanate)

DBTDL: Dibutyltin dilaurate

TBQ: tertiary butyl-p-benzoquinone

MEK: 2-butanone

(Black colorant)

Black colorant (D-1): PGMEA dispersion of black organic pigment Imine-based black organic pigment: 12% by mass, polymer dispersant: 7.2% by mass, PGMEA: 80.8% by mass, and solid component acid value: 7.2 mgKOH / g).

(Crosslinking agent)

DPHA: Dinepentaerythritol hexaacrylate

(Solvent)

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

[Synthesis of Polymer (C)]

The polymer (C1) and the polymer (C2) were synthesized in the following manner. A polymer (Cf) of a comparative example was synthesized.

(Example 1; Synthesis of polymer (C1-1))

In a 300 cm ³ three-neck flask equipped with a stirrer, 3.87 g of compound (cx-11), 13.30 g of compound (cx-21), 4.16 g of compound (cx-31), and 1.28 g of compound (cx-51) were added to obtain a hydrolyzable silane Compound mixture. Next, 71.1 g of PGME was put into this mixture to prepare a raw material solution.

To the prepared raw material solution, 6.30 g of a 1% nitric acid aqueous solution was dropped. After completion of the dropping, the solution was stirred at 40 ° C. for 12 hours to obtain a PGME solution of the polymer (C1-1) (concentration of the polymer (C1-1): 10% by mass; hereinafter also referred to as “polymer (C1-1) solution”). .

In addition, after the reaction was completed, the components of the reaction solution were measured using gas chromatography, and it was confirmed that each compound as a raw material was below the detection limit.

Table 1 shows the feed amount and the like of the raw material hydrolyzable silane compound used in the production of the obtained polymer (C1-1). In Table 1, the silane compound table Shows hydrolyzable silane compounds. The results of measuring the number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, and C = C content of the obtained polymer (C1-1) are shown in Table 1.

(Examples 2 to 4: Synthesis of polymers (C1-2), (Cf-1), (Cf-2))

Except that the raw material composition was set as shown in Table 1, in the same manner as in Example 1, PGME was added to the mixture of each silane compound shown in Table 1 to prepare a raw material solution, and the acid shown in Table 1 below was dropped thereinto. After the aqueous solution was stirred in the same manner as in Example 1, a solution of the polymers (C1-2), (Cf-1), and (Cf-2) was obtained (all compound concentrations: 10% by mass; below, each solution was also (Referred to as "polymer (C1-2), (Cf-1), (Cf-2) solution").

Table 1 shows the feed amounts and molar ratios of the hydrolyzable silane compounds as raw materials used in the production of the polymers (C1-2), (Cf-1), and (Cf-2) obtained at the time of production. In Table 1, the silane compound represents a hydrolyzable silane compound. The results obtained by measuring the number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, and C = C content of the obtained polymer are shown in Table 1 together.

[Table 1]

(Example 5; Synthesis of polymer (C2-1))

In a 1L autoclave equipped with a mixer, feed MEK (466.7g), C6FMA (94.0g), MOI-BP (66.0g), PME-400 (40.0g), and polymerization initiator V-65 (0.91g) Polymerization was performed at 50 ° C for 24 hours while stirring under a nitrogen environment to obtain a polymer (C2-1) solution. The obtained polymer (C2-1) solution was added to hexane for reprecipitation and purification, and then vacuum-dried to obtain a polymer (C2-1) (169.2 g). The number average molecular weight of the polymer (C2-1) was 35,900, and the mass average molecular weight was 71,600.

(Example 6: Synthesis of polymer (C2-2))

A polymer (C2-2) was obtained in the same manner as in Synthesis Example 5 except that MOI-BP was changed to MOI-BP. The number average molecular weight of the polymer (C2-2) was 34,500, and the mass average molecular weight was 72,300.

(Example 7: Synthesis of polymer (C2-3))

Feed MEK (466.7) into an autoclave with an internal volume of 1L equipped with a mixer g), C6FMA (94.0g), 2-HEMA (46.0), MOI-BP (20.0g), PME-400 (40.0g) and polymerization initiator V-65 (1.2g), while stirring under a nitrogen atmosphere Polymerization was performed at 50 ° C for 24 hours to obtain a solution of a polymer (C2-3) precursor.

Feed the solution (500.0g) of the polymer (C2-3) precursor, AOI (37.5g), DBTDL (0.15g), and TBQ (1.87g) into an autoclave with an internal volume of 1L equipped with a stirrer, while stirring It was made to react at 40 degreeC for 24 hours, and the solution of the polymer (C2-3) was obtained. The obtained polymer (C2-3) solution was added to hexane for reprecipitation and purification, and then dried under vacuum to obtain a polymer (C2-3) (143.1 g). The number average molecular weight of the polymer (C2-3) was 41,200, and the mass average molecular weight was 85,700.

(Examples 8 and 9: Synthesis of polymers (C2-4) and (Cf-3))

In the polymer (C2-3), polymers (C2-4) and (Cf-3) were synthesized by the same reaction except that the blending of the raw materials was changed as shown in Table 2.

Table 2 shows the number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, blocked isocyanate group content, ethylenic double bond content, and acid value of the polymers prepared in Examples 1 to 4.

[Table 2]

[Manufacture of negative photosensitive resin composition and manufacture of partition wall]

(Example 10; Production of negative photosensitive resin composition)

Put 12.66 g of alkali-soluble resin (AP1) composition, 1.907 g of IR907, 1.00 g of EAB, 1.61 g of polymer (C1-1) solution, 8.96 g of A9530, and 74.7 g of PGMEA in a stirring container of 200 cm ³ for 3 hours Then, a negative-type photosensitive resin composition 1 was produced.

(Made next door)

A 10 cm square glass substrate was washed with ethanol as an ultrasonic wave for 30 seconds, and then subjected to UV / O ₃ treatment for 5 minutes. For UV / O ₃ treatment, PL2001N-58 (manufactured by Senengineering Co., Ltd.) was used as a UV / O ₃ generating device. The optical power (light output) converted at 254 nm was 10 mW / cm ² .

The obtained negative photosensitive resin composition 1 was coated on the surface of the cleaned glass substrate using a spinner, and then dried on a hot plate at 100 ° C for 2 minutes to form a dry film having a thickness of 2.4 µm. The obtained dry film was irradiated with UV light of an ultra-high pressure mercury lamp with an exposure power (exposure output) of 25 mW / cm ² converted at 365 nm through a mask having a mask portion (non-exposed portion) of 2.5 cm × 5 cm ( The exposure amount was 250 mJ / cm ² ). The light below 330nm has been cut off during exposure. The distance between the dry film and the photomask is set to 50 μm.

Next, the glass substrate after the exposure treatment was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 40 seconds for development, and then the non-exposed portion was rinsed with water and then dried. Next, it was heated on a hot plate at 230 ° C. for 60 minutes, thereby forming a cured film having an opening portion corresponding to the mask portion of the photomask, thereby forming a partition wall.

The obtained negative photosensitive resin composition 1 and the partition walls were evaluated as follows. The evaluation results are shown in Table 3.

(Evaluation)

<Film thickness of the partition>

The measurement was performed using a laser microscope (manufactured by Keynes Corporation, device name: VK-8500).

<Next to the ink repellency>

The PGMEA contact angle on the upper surface of the partition wall obtained above was measured by the following method as an evaluation of ink repellency.

According to JIS R3257 "Test method for wettability of substrate glass surface", PGMEA droplets were dropped on the upper surface of the cured film in accordance with JIS R3257, and measurement was performed for each PGMEA droplet. The droplet system was set to 2 μL / drop, and the measurement was performed at 20 ° C. The contact angle was calculated from the average of 3 measured values.

<Ink affinity of openings>

The above method was measured by the same method as the above evaluation of ink repellency. The PGMEA contact angle of the opening surrounded by the next wall was used as the evaluation of ink affinity.

In addition, if the PGMEA contact angle is above 40 degrees, it can be said that the ink repellency is good. In addition, if the PGMEA contact angle is less than 5 degrees, it can be said that the ink affinity is good.

<Storage stability of negative photosensitive resin composition>

The negative photosensitive resin composition 1 was stored at room temperature (20 to 25 ° C) for 20 days. Then, the state (transparent or cloudy) of the negative photosensitive resin composition 1 was visually observed, and then a partition wall and a cured film were produced in the same manner as described above (however, the size of the glass substrate was set to 7.5 cm square). In addition, during the manufacturing process, the presence or absence of foreign matter on the film surface was observed with a visual inspection and a laser microscope in the state of the coating film.

The external appearance of the partition wall and the cured film and the presence of foreign matter on the film surface were observed with a visual inspection and a laser microscope, and the partition wall and the cured film formed from the negative photosensitive resin composition 1 before storage in the same manner as described above (however, the glass The size of the substrate was changed to a 7.5 cm square) for comparison, and evaluation was performed based on the following criteria.

：: Neither the laser microscope nor the visual observation of the coating film confirmed the presence of foreign matter, and the appearance was the same as that of the partition wall and the cured film formed from the negative photosensitive resin composition before storage.

○: When the coating film was observed with a laser microscope, granular foreign matter was confirmed.

△: When the coating film was visually observed, granular foreign matter was confirmed.

X: The negative-type photosensitive resin composition after storage was cloudy.

(Examples 11 to 19)

With the compositions shown in Table 3, the negative photosensitive resin compositions of Examples 11 to 19 were produced in the same manner as in Example 10. Using the obtained negative photosensitive resin The composition produced a partition wall in the same manner as in Example 10. The obtained negative photosensitive resin composition, the partition walls, and the openings were evaluated in the same manner as in Example 10. The results are shown in Table 3.

Industrial availability

The ink repellent of the present invention is contained in, for example, a photosensitive resin composition, and is suitable for use in forming an optical element such as an organic EL element, a color filter of a liquid crystal element, and a TFT array. Next door.

The negative photosensitive resin composition of the present invention is suitable for use as a composition for forming a partition wall or the like in pattern printing by the IJ method in optical elements such as organic EL elements, color filters for liquid crystal elements, and TFT arrays.

The partition wall of the present invention can be used in organic EL elements as a partition wall (convex bank) for forming organic layers such as a light-emitting layer by IJ method pattern printing, or in a liquid crystal element as a color filter by IJ method pattern printing. Light barrier A wall (the partition wall can also serve as a black matrix (BM)) and the like are used.

The partition wall of the present invention can also be used in a TFT array as a partition wall for forming a conductor pattern or a semiconductor pattern by IJ pattern printing.

The partition wall of the present invention can be used as a partition wall for forming an organic semiconductor layer, a gate electrode, a source electrode, a drain electrode, a gate wiring, a source wiring, and the like, such as a channel layer constituting a TFT, by IJ pattern printing.

In addition, the entire contents of the specification, patent application scope, abstract, and drawings of Japanese Patent Application No. 2014-118475, which has been filed on June 9, 2014, are incorporated herein as a disclosure of the specification of the present invention.

Claims (14)

An ink-repellent agent is one that imparts ink-repellency to the upper surface of a partition wall, and the partition wall is formed into a shape that divides the substrate surface into a plurality of dot-forming partitions; the ink-repellent agent comprises a fluorine-containing atomic unit and An isocyanate group-terminated unit and a polymer having a fluorine atom content of 1 to 40% by mass. The blocked isocyanate group-containing unit can be deblocked by heating to form an isocyanate group; the aforementioned blocked isocyanate group is represented by the following formula ( 1): -NHC (= O) -B ... (1) (In formula (1), B is the following: a monohydric alcohol, a phenol, a lactam, an oxime, or an acetamidine acetate A group obtained by removing one of the active hydrogens of the base ester, alkyl malonate, phthalimide, imidazole or pyrazole; a chlorine atom or a nitrile group; or Base obtained after removing hydrogen with sodium hydrogen sulfate). For example, the ink repellent of claim 1, wherein the 10-hour half-life temperature of the aforementioned blocked isocyanate group to be unblocked to become an isocyanate group is 60 to 180 ° C. For example, the ink repellent of claim 1 or 2, wherein B is the following: a radical obtained by removing the oxime from a hydrogen atom in a hydroxyl group; or an active hydrogen bonded to a nitrogen atom constituting a ring of pyrazoles The base obtained after removal. For example, the ink repellent of claim 1 or 2, wherein the aforementioned polymer is a polymer having a hydrocarbon chain as a main chain and having a mass average molecular weight in a range of 5 × 10 ³ to 1 × 10 ⁵ , and the aforementioned fluorine atomic unit is A unit having the following group: a fluoroalkyl group which may contain an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom. The ink repellent according to claim 4, wherein the aforementioned polymer further has at least one unit selected from the group consisting of a unit having an acidic group, a unit having an ethylenic double bond, and a unit having a hydroxyl group. Units and units with polyoxyalkylene chains. For example, the ink repellent of claim 1 or 2, wherein the aforementioned polymer is a partially hydrolyzed condensate of a hydrolyzable silane compound, and the aforementioned fluorine atom-containing unit is a siloxane unit obtained by bonding the following group with a silicon atom: A fluoroalkyl group containing an etheric oxygen atom and / or a fluoroalkyl group which may contain an etheric oxygen atom. The ink repellent according to claim 6, wherein the aforementioned partially hydrolyzed condensate is a partially hydrolyzed condensate of a hydrolyzable silane compound mixture, the hydrolyzable silane compound mixture comprising a hydrolyzable silane compound having a fluorine atom-containing group and a blocked isocyanate Hydrolyzable silane compound based on the base, and the mixture of hydrolyzable silane compounds arbitrarily contains at least one hydrolyzable silane compound selected from the group consisting of the following hydrolyzable silane compounds: the silicon atom has 4 hydrolyzability Hydrolyzable silane compound having a base, a hydrolyzable silane compound having a group having an ethylenic double bond and not containing a fluorine atom, a hydrolyzable silane compound having only a hydrocarbon group bonded to a silicon atom, and hydrolysis having a mercapto group and not containing a fluorine atom Sex silane compound. The ink repellent according to claim 1 or 2, wherein the substrate has a functional group reactive with an isocyanate group on at least a surface on which the partition wall can be formed. A negative-type photosensitive resin composition, comprising: an alkali-soluble resin having photo-hardening property or an alkali-soluble monomer having photo-hardening property; a photopolymerization initiator; and any one of claims 1 to 7 Repellent. The negative photosensitive resin composition according to claim 9, further comprising a black colorant. A partition wall is formed by dividing the surface of a substrate into a plurality of dot-forming partitions, and the partition wall is made of a hardened material of a negative photosensitive resin composition according to claim 9 or 10. The partition wall according to claim 11, wherein the partition wall is formed on a substrate, and the substrate has a functional group reactive with an isocyanate group. An optical element has a plurality of points on a substrate surface and a partition wall between adjacent points, and is characterized in that the partition wall is formed by a partition wall as claimed in claim 11 or 12. The optical element according to claim 13, wherein the aforementioned dots are formed by an inkjet method.