CN104684994B - Refuse ink compositions, negative light-sensitive resin combination, cured film, partition wall and optical element - Google Patents

Abstract

The present invention provides an ink repellent composition having good ink repellency and its UV/ _O3 resistance, and provides a cured composition which has good ink repellency on the upper surface and which can maintain good ink repellency even after UV/ _O3 irradiation treatment film and partition walls, and provide an optical element capable of uniformly coating ink within a dot. An ink repellent composition comprising a first compound and a second compound, the first compound being a mixture comprising a first hydrolyzable silane compound having a fluoroalkylene group and/or a fluoroalkyl group and a hydrolyzable group The partial hydrolysis condensate of the second compound, the main chain of the second compound is a hydrocarbon chain and includes side chains with fluorine atoms, and the mass average molecular weight (Mw) is 1 million to 1 million.

Description

Ink repellent composition, negative photosensitive resin composition, cured film, partition wall and Optical element

technical field

The present invention relates to an ink repellent composition, a negative photosensitive resin composition, and a cured film, a partition, and an optical element using the negative photosensitive resin composition.

Background technique

For an organic EL (Electro-Luminescence, organic electroluminescence) element, there is a method of pattern-printing an organic layer such as a light-emitting layer by an inkjet (IJ) method. In the method, a partition wall is provided along the outline of dots, ink containing a material of a layer to be formed is injected into the interior thereof, dried and/or heated, etc., thereby forming a desired pattern film.

In the above-mentioned method, in order to prevent ink color mixing between adjacent dots and apply ink uniformly within the dots, it is necessary that the upper surface of the partition wall has ink repellency and the side surface of the partition wall has ink affinity.

The said partition is patterned by the photolithography method using a photosensitive resin composition, for example.

For example, when an ink repellent with a small surface free energy is included in the photosensitive resin composition, the repulsion of the ink repellent to the air side due to the repulsive force acting between the ink repellent and other solid components is utilized during the solvent evaporation process when the coating film is dried. (The upper surface side of the coating film) moves, and ink repellency can be provided to the upper surface of the obtained partition. In the method, the upper surface mobility of the ink repellent is important. Moreover, it is important that the ink repellent agent does not remain in the dot after image development.

In an organic EL element, organic layers such as a light-emitting layer tend to deteriorate due to residues of the photosensitive resin composition remaining in dots after image development. Therefore, in order to remove the development residue in the dots, the entire surface of the substrate is generally subjected to UV (ultraviolet ray)/O ₃ (ozone) irradiation treatment before ink injection. Therefore, it is important for the organic EL element that the ink repellency of the upper surface of the partition be well maintained even after the UV/O ₃ irradiation treatment.

Conventionally, as an ink repellent agent, the acrylic polymer containing the main chain mainly containing a carbon-carbon bond, and the side chain which has a fluorine atom is known (for example, refer the [Example] section of patent documents 1-4).

However, the UV/ _O3 resistance of the ink repellency of the ink repellent agent containing an acrylic polymer is low, and it is not sufficient as a partition wall use of an organic EL element.

Patent Document 5 discloses a negative photosensitive resin composition, the surface free energy of which is sufficiently small, and the formed partition wall has good ink repellency on the upper surface, and even after UV/ _O3 irradiation treatment, its repellency Ink properties are maintained well, and this negative photosensitive resin composition contains a silicone-based ink repellent containing a hydrolysis condensate of a fluorine-containing hydrolyzable silane compound.

prior art literature

patent documents

Patent Document 1: International Publication No. 2004/042474

Patent Document 2: International Publication No. 2007/069703

Patent Document 3: International Publication No. 2011/081151

Patent Document 4: International Publication No. 2010/001976

Patent Document 5: International Publication No. 2010/013816

Contents of the invention

The problem to be solved by the invention

In an organic EL element, it is preferable that the line width of the part of the partition that does not originally participate in display be as thin as possible. In order to well prevent ink color mixing between adjacent dots even if the line width of the partition is narrowed, it is preferable that the ink repellency of the upper surface of the partition is higher.

The object of the present invention is to provide an ink repellent composition capable of producing a partition wall having good ink repellency and its UV/ _O3 resistance, and an ink repellent composition containing the ink repellent composition and having an ink repellent composition that does not easily remain in dots. A negative-type photosensitive resin composition with specific characteristics, a cured film and a partition obtained by using the negative-type photosensitive resin composition.

Furthermore, the object of this invention is to provide the optical element which has a partition which has favorable ink repellency on the upper surface, does not easily remain an ink repellent agent in a dot, and can apply ink uniformly in a dot.

solutions to problems

This invention provides the ink repellent composition, negative photosensitive resin composition, cured film, partition, and optical element which have the invention of following [1]-[17].

[1] An ink repellent composition characterized in that it comprises a first compound and a second compound, the first compound comprising a fluoroalkylene group and/or a fluoroalkyl group and a hydrolyzable group. Partially hydrolyzed condensates of mixtures of hydrolyzable silane compounds,

The main chain of the second compound is a hydrocarbon chain and includes side chains having fluorine atoms, and its mass average molecular weight (Mw) is 1 million to 1 million.

[2] The ink repellent composition according to the above [1], wherein the first hydrolyzable silane compound is a compound represented by the following formula (cx-1).

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

(R ^F11 is a divalent organic group with 1 to 16 carbon atoms containing at least one fluoroalkylene group or a divalent organic group with 2 to 16 carbon atoms containing an etheric oxygen atom. R ^H11 is carbon A hydrocarbon group with 1 to 6 atoms.

X ¹¹ is a hydrolyzable group. When a plurality of X ¹¹ exists, they may be different from each other or may be the same.

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 (I).

-Si(R ^H12 ) _c X ¹² _(3-c) ···(I)

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

c is 0 or 1.

X ¹² is a hydrolyzable group. When a plurality of X ¹² exists, they may be different from each other or may be the same. )

When a plurality of AR ^F11 exists, they may be different from each other or may be the same. )

[3] The ink repellent composition as described in said [2] whose said mixture contains the 2nd hydrolyzable silane compound represented by following formula (cx-2) further.

SiX ² ₄ ···(cx-2)

(X ² represents a hydrolyzable group, and 4 X ² may be different from each other or the same.)

[4] The ink repellent composition according to any one of the above [1] to [3], wherein the mixture further contains a third hydrolyzable silane compound represented by the following formula (cx-3).

(YQ ³ ) _g -Si(R ^H3 ) _h X ³ _(4-gh) ···(cx-3)

(Y is a group having an ethylenic double bond.

Q ³ is a divalent organic group having 1 to 6 carbon atoms that does not contain a fluorine atom.

R ^H3 is a hydrocarbon group having 1 to 6 carbon atoms.

X ³ is a hydrolyzable group. When a plurality of X ³ exists, they may be different from each other or may be the same.

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

When a plurality of YQ ³ exists, they may be different from each other or may be the same. )

[5] The ink repellent composition according to any one of [1] to [4] above, wherein the second compound is a polymer containing a halothane optionally containing an etheric oxygen atom. group and/or a side chain having a fluoroalkyl group optionally containing an etheric oxygen atom.

[6] The ink repellent composition according to the above [5], wherein the second compound is a polymer having a side chain having an acidic group.

[7] The ink repellent composition according to the above [5] or [6], wherein the second compound is a polymer having a side chain having an ethylenic double bond.

[8] The ink repellent composition according to any one of the above [5] to [7], wherein the second compound is a polymer containing a side chain having an oxyalkylene group.

[9] The ink repellent composition according to any one of the above [1] to [8], wherein the mass ratio of the second compound to the first compound is 0.01 to 10.

[10] The ink repellent composition as described in any one of said [1]-[9] whose content rate of a fluorine atom is 5-40 mass %.

[11] A negative photosensitive resin composition comprising the ink repellent composition according to any one of [1] to [10] above, and a photocurable alkali-soluble resin or alkali-soluble monomer (A), photopolymerization initiator (B) and solvent (D).

[12] The negative photosensitive resin composition according to the above [11], further comprising a crosslinking agent (E) having two or more ethylenic double bonds in one molecule and having no acidic group.

[13] The negative photosensitive resin composition according to the above [11] or [12], wherein the content ratio of the first compound in the total solid content is 0.05 to 10% by mass, and the content ratio of the second compound is 0.01 to 5% by mass.

[14] The negative photosensitive resin composition according to any one of the above [11] to [13], wherein the content ratio of the ink repellent composition in the total solid content is 0.06 to 15% by mass.

[15] A cured film characterized by applying the negative photosensitive resin composition described in any one of [11] to [14] on the surface of a substrate, removing the solvent (D) and exposing made.

[16] A partition characterized by comprising the cured film described in [15] above.

[17] An optical element comprising a plurality of dots and the partition wall described in [16] above.

The effect of the invention

The ink repellency composition of the present invention can prepare a negative photosensitive resin composition capable of forming a partition wall with good ink repellency and UV/O resistance _on the upper surface, and has the advantage of using the negative photosensitive resin composition. The obtained optical element of the partition has favorable ink repellency on the upper surface of the partition and has the characteristics that the ink repellent component does not easily remain in the dots, so ink can be uniformly applied to the dots and a pattern film can be easily formed.

Description of drawings

FIG. 1A is a process diagram schematically showing a method of manufacturing a partition formed from a cured film of the present invention.

FIG. 1B is a process diagram schematically showing a method of manufacturing a partition formed from a cured film of the present invention.

Fig. 1C is a process diagram schematically showing a method of manufacturing a partition formed from a cured film of the present invention.

FIG. 1D is a process diagram schematically showing a method of manufacturing a partition formed from a cured film of the present invention.

FIG. 1E is a process diagram schematically showing a method of manufacturing a partition formed from a cured film of the present invention.

2A is a process diagram schematically showing a method of manufacturing a patterned film using a partition formed from a cured film of the present invention.

2B is a process diagram schematically showing a method of manufacturing a patterned film using a partition formed from a cured film of the present invention.

detailed description

In this specification, "(meth)acryloyl" is a generic term for "methacryloyl" and "acryloyl". (Meth)acrylates, (meth)acrylamides, and (meth)acrylic resins also comply with this regulation.

In this specification, the group represented by formula (x) may be abbreviated as group (x).

In this specification, the compound represented by formula (y) may be abbreviated as compound (y).

Here, formula (x) and formula (y) represent arbitrary formulas.

The "side chain" in the present specification refers to a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which repeating units constitute the main chain.

The "total solid content of the photosensitive resin composition" in this specification refers to the components used to form the cured film described later among the components contained in the photosensitive resin composition. Hours and remove the residue of the solvent. It should be noted that the total solid content can also be calculated from the feed amount.

In this specification, the film obtained by applying the photosensitive resin composition is called "coated film", the film obtained by drying the coated film is called "dried film", and the film obtained by curing the dried film is called "coating film". as "cured film".

The cured film may be a patterned film or an unpatterned film.

In this specification, the "upper surface" of a partition does not include the side surface of a partition.

The "ink" in this specification includes all liquids having optical functions and/or electrical functions.

The "ink" in this specification includes all inks used for pattern printing by the inkjet (IJ) method.

For optical elements such as organic EL elements, color filters of liquid crystal elements, and organic TFT (Thin Film Transistor, thin film transistor) arrays, various constituent elements can be pattern-printed by the IJ method. The "ink" in this specification includes inks used in the above-mentioned uses.

"Ink repellency" in this specification refers to the property of repelling the ink described above, and includes both water repellency and oil repellency. Ink repellency can be evaluated, for example, by the contact angle when ink is dripped.

The "UV/ _O3 resistance" in this specification means the characteristic which maintains ink repellency favorably even after performing UV/ _O3 irradiation process.

A "spot" in this specification means the smallest area in an optical element where light modulation can be performed. For optical elements such as organic EL elements, color filters of liquid crystal elements, and organic TFT arrays, 1 dot = 1 pixel when displaying black and white, for example, 3 dots (R (red), G (green), B (blue, etc.) = 1 pixel.

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

[Ink repellent composition]

In the ink repellent composition (Hereinafter, it may be referred to as an ink repellent composition (C)) of this invention, the following 1st compound and 2nd compound are contained as an ink repellent compound. In addition, the raw material of an unreacted 1st compound and a 2nd compound is considered to be contained in this ink repellent composition (C).

It is preferable that the ink repellent composition (C) of this invention consists only of a 1st compound and a 2nd compound.

The ink repellent composition of this invention can be applied to the ink repellent agent contained in a negative photosensitive resin composition, a positive photosensitive resin composition, etc. It is especially preferably applied to a negative photosensitive resin composition. This composition is suitable as a composition for partition formation in the pattern formation by the IJ method of various components of an optical element.

In the formation process of the partition, the ink repellent composition moves to the upper surface, forms a thin ink repellent layer on the partition upper surface, and provides ink repellency to the partition upper surface. In addition, the ink repellent composition of this invention can also be used for other uses.

According to the studies of the present inventors, it has been clarified that the first compound and the second compound exhibit ink repellency on the surface of the partition alone, but when the first compound and the second compound are used in combination under the condition of the same fluorine atom content , the ink repellency of the upper surface of the partition wall can be improved more than when they are used alone. The reason for this is considered as follows.

Even if the first compound is used alone, a certain degree of crosslinking reaction occurs to form a thin ink repellent layer on the upper surface of the partition wall. However, the molecular weight of the first compound is, for example, about 1000 to 2000, and the expansion of each molecule is not large, so gaps are likely to be generated between molecules. It is thought that ink repellency improves by filling this gap with a 2nd compound.

According to the studies of the present inventors, the following points are also considered to be effects of combining the first compound and the second compound.

(1) Removal of the ink repellent layer on the partition upper surface at the time of alkali image development is suppressed and ink repellency improves compared with using a 2nd compound alone.

(2) Compared with using the 1st compound alone, the storage stability of a negative photosensitive resin composition improves.

(3) Swelling of the end portion of the upper surface of the partition wall is less likely to occur than when the first compound is used alone.

The reason why the effect (1) can be expressed is considered as follows.

When using a 2nd compound alone, when the mass average molecular weight (Mw) of a 2nd compound exceeds 100,000, high ink repellency can be provided to a partition upper surface, but the solubility to alkaline developing solution exists in the tendency for a fall. That is, it can be considered that a part of the ink repellent layer on the partition upper surface is removed at the time of alkali image development, and the ink repellency falls. It is considered that removal of the ink repellent layer on the partition upper surface at the time of alkali image development is suppressed and ink repellency improves by using together the 1st compound which does not produce this tendency.

The reason why the effect (2) can be expressed is considered as follows.

When the 1st compound is used independently, since the reactivity of silanol groups is high, the storage stability of the photosensitive resin composition containing a 1st compound exists in the tendency for it to become insufficient. It is thought that the reaction of silanol groups is suppressed and the storage stability of a photosensitive resin composition improves by using the 2nd compound with low reactivity in combination.

The reason why the effect (3) can be expressed is considered as follows.

When the first compound is used alone, there may be a case where a horizontal microprotrusion that can be observed with a scanning electron microscope (SEM) or the like is formed on the end of the upper surface of the partition wall. This swelling does not particularly hinder as a partition etc. However, if this swelling falls off for some reason, ink repellency is given to the side wall of a partition, etc., and it is unpreferable.

Since the first compound has high reactivity between silanol groups, it is considered that a crosslinking reaction occurs to some extent even in the non-exposed portion to form the above-mentioned bumps. It is considered that the reaction of the silanol groups in the non-exposed part is inhibited by using the second compound with low reactivity in combination, and the generation of the above-mentioned swelling is suppressed.

It should be noted that the inventors of the present invention confirmed that the content of F and/or Si is larger in the protrusion than in other parts.

(first compound)

The first compound is a partially hydrolyzed condensate of a mixture (hereinafter also referred to as a hydrolyzable silane compound mixture) containing a first hydrolyzable silane compound. This hydrolyzable silane compound mixture contains the 1st hydrolyzable silane compound as an essential component, and optionally contains the 2nd - 5th hydrolyzable silane compound mentioned later. Hydrolyzable silane compounds other than the 2nd - 5th hydrolyzable silane compounds may also be included.

The first compound is a composition having a molecular weight distribution.

<First hydrolyzable silane compound>

The first hydrolyzable silane compound in the present invention is a compound having a fluoroalkylene group and/or a fluoroalkyl group and a hydrolyzable group.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, and a group in which at least one hydrogen in the amino group is substituted with an alkyl group. From the viewpoint that the reaction of forming a hydroxyl group (silanol group) through a hydrolysis reaction and further intermolecular condensation reaction to form a Si-O-Si bond proceeds smoothly, an alkoxy group or an alkoxy group having 1 to 4 carbon atoms is preferred. A halogen atom is more preferably a methoxy group, an ethoxy group or a chlorine atom, particularly preferably a methoxy group or an ethoxy group.

The first hydrolyzable silane compound may be used alone or in combination of two or more.

By using the first hydrolyzable silane compound containing a fluoroalkylene group and/or a fluoroalkyl group, the first compound has a fluoroalkylene group and/or a fluoroalkyl group. When using the negative photosensitive resin composition containing a 1st compound, favorable ink repellency can be provided to the upper surface of a partition. Furthermore, good ink repellency can be maintained even after UV/ _O3 irradiation treatment.

It should be noted that, in order to further exhibit the above-mentioned effects of the first hydrolyzable silane compound, the first hydrolyzable silane compound more preferably has a fluoroalkyl group, a perfluoroalkylene group or a perfluoroalkyl group, and particularly preferably has a perfluoroalkyl group. . In addition, perfluoroalkyl groups containing etheric oxygen atoms are also preferred. That is, the most preferable compound as the first hydrolyzable silane compound is a compound having a perfluoroalkyl group and/or a perfluoroalkyl group containing an etheric oxygen atom.

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

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

In the formula (cx-1), R ^F11 is a divalent organic group with 1 to 16 carbon atoms containing at least one fluoroalkylene group or a divalent organic group with 2 to 16 carbon atoms containing an etheric oxygen atom. group.

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

X ¹¹ is a hydrolyzable group. When a plurality of X ¹¹ exists, they may be different from each other or may be the same.

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 (I).

-Si(R ^H12 ) _c X ¹² _(3-c) ···(I)

In formula (I), R ^H12 is a hydrocarbon group having 1 to 6 carbon atoms.

c is 0 or 1.

X ¹² is a hydrolyzable group. When a plurality of X ¹² exists, they may be different from each other or may be the same.

In addition, when there are a plurality of AR ^F11 , they may be different from each other or may be the same.

Compound (cx-1) is a fluorine-containing hydrolyzable silane compound having one or two bifunctional or trifunctional hydrolyzable silyl groups.

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

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

Specific examples and preferred embodiments of ^X11 and ^X12 as hydrolyzable groups are as described above.

As a 1st hydrolyzable silane compound, the compound represented by following formula (cx-1a) is especially preferable.

DR ^F12 -Q ¹¹ -SiX ¹¹ ₃ ···(cx-1a)

In formula (cx-1a), R ^F12 is a perfluoroalkylene group optionally containing an etheric oxygen atom having 2 to 15 carbon atoms.

Q ¹¹ is a divalent organic group having 1 to 10 carbon atoms that does not contain a fluorine atom.

X ¹¹ is a hydrolyzable group. The three X ^11s may be different or the same.

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

-Q ¹² -SiX ¹² ₃ ···(Ia)

In formula (Ia), X ¹² is a hydrolyzable group. The 3 X ^12s may be different or the same.

^Q12 is a divalent organic group having 1 to 10 carbon atoms that does not contain a fluorine atom.

In formula (cx-1a), when D is a fluorine atom, R ^F12 is preferably a perfluoroalkylene group having 4 to 8 carbon atoms or a perfluoroalkylene group containing etheric oxygen atoms having 4 to 10 carbon atoms, It is more preferably a perfluoroalkylene group having 4 to 8 carbon atoms, particularly preferably a perfluoroalkylene group having 6 carbon atoms.

In addition, in the formula (cx-1a), when D is the group (Ia), R ^F12 is preferably a perfluoroalkylene group with 3 to 15 carbon atoms or a perfluoroalkylene group with 3 to 15 carbon atoms containing an etheric oxygen atom. The fluoroalkylene group is particularly preferably a perfluoroalkylene group having 4 to 6 carbon atoms.

When R ^F12 is the above group, the ink repellency composition of the present invention can be used to obtain a negative photosensitive resin composition that can form a partition wall with good ink repellency and UV/O resistance _on the upper surface, and Compound (cx-1a) has excellent solubility in solvents.

Examples of the structure of ^RF12 include linear structures, branched structures, ring structures, structures partially having rings, and the like, and linear structures are preferred.

Specific examples of R ^F12 include the following groups.

-(CF ₂ ) ₄ -, -(CF ₂ ) ₆ -, -(CF ₂ ) ₈ -, -CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ -, -CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, -CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ -, -CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -. -CF ₂ CF ₂ CF ₂ OCF ₂ -, -CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ OCF(CF ₃ )-, -CF ₂ CF ₂ CF ₂ OCF(CF ₃ ) CF ₂ -, -CF ₂ CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-, -CF ₂ CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )CF ₂ -,-CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-,-CF ₂ CF ₂ OCF(CF ₃ )CF ₂ OCF(CF ₃ )-.

Among Q ¹¹ and Q ¹² , when expressed in the form that Si is bonded to the atomic bond on the right side and R ^F12 is bonded to the atomic bond on the left side, specifically, -(CH ₂ ) _i1 is preferable. -(i1 is an integer of 1 to 5.), -CH ₂ O(CH ₂ ) _i2 -(i2 is an integer of 1 to 4.), -SO ₂ NR ¹ -(CH ₂ ) _i3 -(R ¹ is 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 - A group represented by (CH ₂ ) _i4 - (R ¹ is the same as above, i4 is an integer of 1 to 4, and the total number of carbon atoms of R ¹ and (CH ₂ ) _i4 is an integer of 4 or less.). Q ¹¹ and Q ¹² are more preferably -(CH ₂ ) _i1 - in which i1 is an integer of 2 to 4, particularly preferably -(CH ₂ ) ₂ -.

When R ^F12 is a perfluoroalkylene group, Q ¹¹ and Q ¹² are preferably groups represented by -(CH ₂ ) _i1 -. i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.

When R ^F12 is a perfluoroalkylene group containing an etheric oxygen atom, Q ¹¹ and Q ¹² are preferably -(CH ₂ ) _i1 -, -CH ₂ O(CH ₂ ) _i2 -, -SO ₂ NR ¹ - A group represented by (CH ₂ ) _i3 -, or -(C=O)-NR ¹ -(CH ₂ ) _i4 -. Among them, -(CH ₂ ) _i1 - is more preferable, i1 is more preferably an integer of 2 to 4, and i1 is particularly preferably 2.

When D is a fluorine atom, specific examples of the compound (cx-1a) include the following compounds. F(CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₆ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₈ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , F(CF ₂ ) ₂ O(CF ₂ ) ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

When D is a group (Ia), specific examples of the compound (cx-1a) include the following compounds. (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₄ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) _3. (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ (CF ₂ ) ₂ OCF ₂ CF(CF ₃ ) O(CF ₂ ) ₂ OCF(CF ₃ )CF ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

Among them, F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ or F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ O(CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) is particularly preferable. ₃ .

In the present invention, the compound (cx-1a) is particularly preferably F(CF ₂ ) ₆ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , or F(CF ₂ ) ₃ OCF(CF ₃ )CF ₂ O( CF ₂ ) ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ .

The content ratio of the first hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably such that the fluorine atom content in the partially hydrolyzed condensate obtained from the mixture is 5 to 55% by mass, more preferably 10 to 40% by mass, especially It is preferable to achieve a ratio of 15 to 30% by mass. When the content ratio of the first hydrolyzable silane compound is more than the lower limit value of the above-mentioned range, good ink repellency can be imparted to the upper surface of the cured film, and when it is below the upper limit value, the content ratio of the first hydrolyzable silane compound in the mixture can be compatibility becomes good.

<Second Hydrolyzable Silane Compound>

The second hydrolyzable silane compound in the present invention is a compound represented by the following formula (cx-2).

SiX ² ₄ ···(cx-2)

In formula (cx-2), X ² represents a hydrolyzable group, and four X ² may be different or the same. As X ² , the same groups as the aforementioned X ¹¹ and X ¹² can be used.

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. In addition, as the compound (cx-2), if necessary, a partial hydrolysis condensate obtained by partially hydrolyzing and condensing a plurality of these compounds may be used.

As specific examples, Si(OCH ₃ ) ₄ , Si(OCH ₂ CH ₃ ) ₄ , and partial hydrolysis condensates of Si(OCH ₃ ) ₄ (for example, Methyl Silicate 51 (trade name) manufactured by COLCOAT CO., Ltd.), Partial hydrolysis condensate of Si(OCH ₂ CH ₃ ) ₄ (for example, Ethyl Silicate 40 and Ethyl Silicate 48 (both trade names) manufactured by COLCOAT CO., Ltd.) and the like.

By including the compound (cx-2) in the hydrolyzable silane compound mixture, the movement of the ink repellent composition (C) can be improved for the cured film obtained by curing the negative photosensitive resin composition containing the first compound. Film-forming properties after reaching the upper surface. That is, it is considered that the number of hydrolyzable groups in the compound (cx-2) is large, so after moving to the upper surface, the partial hydrolyzed condensates are well condensed with each other, and a thin film can be formed on the entire upper surface (excellent film-forming property) .

In addition, by including the compound (cx-2) in the hydrolyzable silane compound mixture, the first compound is easily soluble in the hydrocarbon solvent.

The content ratio of the second hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 0.01 to 5 mol, particularly preferably 0.05 to 3 mol, based on 1 mol of the first hydrolyzable silane compound. The film-forming property of an ink repellent composition (C) becomes favorable that a content ratio is more than the lower limit of the said range, and when it is below an upper limit, favorable ink repellency can be provided to the upper surface of a cured film.

<The third hydrolyzable silane compound>

The 3rd hydrolyzable silane compound in this invention is a hydrolyzable silane compound represented by following formula (cx-3).

(YQ ³ ) _g -Si(R ^H3 ) _h X ³ _(4-gh) ···(cx-3)

In formula (cx-3), Y is a group having an ethylenic double bond.

Q ³ is a divalent organic group having 1 to 6 carbon atoms that does not contain a fluorine atom.

R ^H3 is a hydrocarbon group having 1 to 6 carbon atoms.

X ³ is a hydrolyzable group. When a plurality of X ³ exists, they may be different from each other or may be the same.

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

When a plurality of YQ ³ exists, they may be different from each other or may be the same.

As R ^H3 , the same groups as the aforementioned R ^H11 and R ^H12 can be used.

As X ³ , the same groups as the aforementioned X ¹¹ and X ¹² can be used.

Y is preferably a (meth)acryloyloxy group or a vinylphenyl group, and is particularly preferably a (meth)acryloyloxy group.

Specific examples of ^Q3 include alkylene groups having 2 to 6 carbon atoms, phenylene groups, and the like. Among them, -(CH ₂ ) ₃ - is preferable.

Preferably, g is 1 and h is 0 or 1.

Compound (cx-3) may be used alone or in combination of two or more.

Specific examples of the compound (cx-3) include the following compounds.

CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ,

CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ,

CH ₂ =CHCOO(CH ₂ ) ₃ Si(OCH ₃ ) ₃ ,

CH ₂ =CHCOO(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ,

[CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ ]SiCH ₃ (OCH ₃ ) ₂ ,

[CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ ]SiCH ₃ (OC ₂ H ₅ ) ₂ .

By making the compound (cx-3) containing the group Y with an ethylenic double bond contained in the hydrolyzable silane compound mixture, in the manufacture of the partition wall which hardened the negative photosensitive resin composition, ink repellency can be improved Fixability of the permanent composition (C) on the upper surface of the partition wall.

The compound (cx-3) has a group Y with an ethylenic double bond, so when the negative photosensitive resin composition is exposed, the ink repellent compounds or the ink repellent compound and the negative photosensitive resin composition Further components having ethylenic double bonds can be copolymerized via this group. It is considered that the ink repellent composition (C) is chemically bonded to the cured film upper surface after exposure by these operation effects, and fixability improves.

The content ratio of the third hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 0.1 to 5 mol, particularly preferably 0.5 to 4 mol, based on 1 mol of the first hydrolyzable silane compound. The upper surface mobility and fixability of an ink repellent composition (C) are favorable that a content rate is more than the lower limit of the said range, and the storage stability of an ink repellent composition is favorable. The ink repellency of the ink repellent composition (C) is favorable that it is below an upper limit.

<Fourth hydrolyzable silane compound>

The 4th hydrolyzable silane compound in this invention is a compound represented by following formula (cx-4).

(R ^H4 ) _j -SiX ⁴ _(4-j) ···(cx-4)

In formula (cx-4), R ^H4 is a hydrocarbon group having 1 to 6 carbon atoms. When a plurality of R ^H4 exists, they may be different or the same.

X ⁴ is a hydrolyzable group. When there are a plurality of X ⁴ , they may be different or the same.

j is 2 or 3.

As R ^H4 , the same groups as the aforementioned R ^H11 and R ^H12 can be used.

As X ⁴ , the same groups as the aforementioned X ¹¹ and X ¹² can be used.

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

Specific examples of the compound (cx-4) include the following compounds.

(CH ₃ ) ₃ -Si-OCH ₃ , (CH ₃ CH ₂ ) ₃ -Si-OCH ₂ CH ₃ , (CH ₃ ) ₃ -Si-OCH ₂ CH ₃ , (CH ₃ CH ₂ ) ₃ -Si-OCH _3. (CH ₃ ) ₂ -Si-(OCH ₃ ) ₂ , (CH ₃ ) ₂ -Si-(OCH ₂ CH ₃ ) ₂ , (CH ₃ CH ₂ ) ₂ -Si-(OCH ₂ CH ₃ ) ₂ , (CH ₃ CH ₂ ) ₂ -Si-(OCH ₃ ) ₂ .

When a compound (cx-2) is used for a hydrolyzable silane compound mixture, a bump may be formed in the edge part of the upper surface about the partition which hardened the negative photosensitive resin composition. These are microscopic protrusions at a level that can be observed with a scanning electron microscope (SEM) or the like. The inventors of the present invention have confirmed that the content of F and/or Si is larger in this bump than in other parts.

The above-mentioned bulging does not particularly hinder the partition wall, etc., and the present inventors found that the above-mentioned bulging can be suppressed by substituting a part of the compound (cx-2) with a compound (cx-4) having a small number of hydrolyzed groups. occur.

The film-forming property of an ink repellent composition (C) increases by the reaction of the silanol group which generate|occur|produced from the compound (cx-2) with many hydrolyzed groups. However, it is considered that the above-mentioned swelling occurs due to its high reactivity.

On the other hand, it is considered that by substituting part of the compound (cx-2) with the compound (cx-4) having a small number of hydrolyzed groups, the reaction of silanol groups is suppressed and the occurrence of the above-mentioned swelling is suppressed.

The content ratio of the fourth hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 0.05 to 5 mol, particularly preferably 0.3 to 3 mol, based on 1 mol of the first hydrolyzable silane compound. When the content ratio is equal to or more than the lower limit of the above-mentioned range, it is possible to suppress the swelling of the end portion of the upper surface of the partition wall. The ink repellency of the ink repellent composition (C) is favorable that it is below an upper limit.

<Fifth Hydrolyzable Silane Compound>

The fifth hydrolyzable silane compound in the present invention is a compound having a mercapto group and a hydrolyzable group but not having a fluoroalkylene group and a fluoroalkyl group.

As the hydrolyzable group, the same group as that of the first hydrolyzable silane compound can be used.

The fifth hydrolyzable silane compound may be used alone or in combination of two or more.

By using the fifth hydrolyzable silane compound containing a mercapto group, the negative photosensitive resin composition can be exposed with a lower exposure amount. It is considered that the reason is that the mercapto group in the fifth hydrolyzable silane compound has chain transfer properties and is easily linked to the ethylenic double bond of the alkali-soluble resin or alkali-soluble monomer (A) described later, thereby promoting photocuring.

In addition, the fifth hydrolyzable silane compound containing a mercapto group has a pKa of about 10, and is easily deprotonated, that is, easily dissociated in an alkaline solution.

Here, it is represented by pKa=-log ₁₀ Ka, where Ka represents an acid dissociation constant. Therefore, it is thought that a mercapto group can improve the alkali solubility at the time of image development of a negative photosensitive resin composition.

As the fifth hydrolyzable silane compound, a compound represented by the following formula (cx-5) is preferable.

(HS-Q ⁵ ) _p -Si(R ^H5 ) _q X ⁵ _(4-pq) ···(cx-5)

In the formula (cx-5), Q ⁵ is a divalent organic group having 1 to 10 carbon atoms that does not contain a fluorine atom.

R ^H5 is a hydrocarbon group having 1 to 6 carbon atoms.

X ⁵ is a hydrolyzable group. When a plurality of X ⁵ exists, they may be different from each other or may be the same.

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

When a plurality of HS-Q ⁵ exists, they may be different from each other or may be the same.

As X ⁵ , the same groups as the aforementioned X ¹ and X ² can be used.

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

As R ^H5 , the same groups as the aforementioned R ^H11 and R ^H12 can be used.

Specific examples of the compound (cx-5) include HS-(CH ₂ ) ₃ -Si(OCH ₃ ) ₃ , HS-(CH ₂ ) ₃ -Si(CH ₃ )(OCH ₃ ) ₂ and the like.

The content ratio of the fifth hydrolyzable silane compound in the hydrolyzable silane compound mixture is preferably 0.125 to 18 mol, particularly preferably 0.125 to 8 mol, based on 1 mol of the first hydrolyzable silane compound. When the content ratio is more than the lower limit of the said range, a negative photosensitive resin composition can be exposed with a lower exposure amount. The ink repellency of the ink repellent composition (C) is favorable that it is below an upper limit.

<Other hydrolyzable silane compounds>

The hydrolyzable silane compound mixture may contain 1 type, or 2 or more types of arbitrary hydrolyzable silane compounds other than the 1st - 5th hydrolyzable silane compound.

As another hydrolyzable silane compound, the hydrolyzable silane compound which has an oxyalkylene group and a hydrolyzable group but does not have a fluoroalkylene group and a fluoroalkyl group is mentioned. Specifically, for example, CH ₃ O(C ₂ H ₄ O) _k Si(OCH ₃ ) ₃ (polyoxyethylene group-containing trimethoxysilane) (here, k is, for example, about 10.) etc. .

<Preferred combination of hydrolyzable silane compounds>

When the first compound is a partially hydrolyzed condensate of a mixture including compound (cx-1a), optionally including compounds (cx-2) to (cx-5), and the group D in compound (cx-1a) is a fluorine atom , and its average composition formula is shown in the following formula (II).

[DR ^F12 -Q ¹¹ -SiO _3/2 ] _n1 ·[SiO ₂ ] _n2 ·[(YQ ³ ) _g -Si(R ^H3 ) _h SiO _(4-gh)/2 ] _n3 [(R ^H4 ) _j - SiO _(4-j)/2 ] _n4 ·[(HS-Q ⁵ ) _p -Si(R ^H5 ) _q O _(4-pq)/2 ] _n5 ···(II)

In formula (II), n1-n5 are the mole percentages of each structural unit with respect to the total molar weight of structural units. n1>0, n2≥0, n3≥0, n4≥0, n5≥0, n1+n2+n3+n4+n5=1. The other symbols are as above. In addition, D is a fluorine atom.

Since it is actually a product (partially hydrolyzed condensate) in which a hydrolyzable group or a silanol group remains, it is difficult to represent this product with a chemical formula. The average composition formula represented by the formula (II) is a chemical formula assuming that all the hydrolyzable groups or silanol groups in the first compound form siloxane bonds. In addition, in formula (II), it is presumed that units derived from compounds (cx-1a) and (cx-2) to (cx-5) are arranged randomly.

The average composition formula shown in formula (II): n1:n2:n3:n4:n5 and compound (cx-1a) and (cx-2)～(cx-5) feed composition in the hydrolyzable silane compound mixture unanimous.

The molar ratio of each component is designed based on the balance of the effects of each component.

n1 is preferably 0.05 to 0.4.

n2 is preferably 0 to 0.8, particularly preferably 0.05 to 0.6.

n3 is preferably 0 to 0.8, particularly preferably 0.2 to 0.5.

n4 is preferably 0 to 0.5, particularly preferably 0.05 to 0.3.

n5 is preferably 0.05 to 0.9, particularly preferably 0.05 to 0.4.

In addition, the preferable molar ratio of each said component is the same when D in compound (cx-1a) is a group (Ia).

The mass average molecular weight (Mw) of the first compound is preferably 500 or more, more preferably 1,000 or more. In addition, it is preferably less than 1 million, and more preferably less than 10,000. Particularly preferably, it is 6000 or less.

When the mass average molecular weight (Mw) is more than the lower limit, the 1st compound which is an ink repellent agent will be hard to migrate to an upper surface. When less than the upper limit, the solubility of the first compound in the solvent becomes favorable. Furthermore, when it is less than the upper limit, the solubility of the first compound in the solvent becomes favorable.

The mass average molecular weight (Mw) of the first compound can be adjusted by production conditions.

<Manufacture of partial hydrolysis condensate>

The first compound can be produced by subjecting the above-mentioned hydrolyzable silane compound mixture to hydrolysis and condensation reactions by known methods.

In this reaction, generally used inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids such as acetic acid, oxalic acid, and maleic acid are preferably used as catalysts. In addition, inorganic bases such as sodium hydroxide, organic bases such as tetramethylammonium hydroxide, metal complexes such as dibutyltin dilaurate, and the like are also preferably used as catalysts.

A known solvent can be used for the above reaction.

(second compound)

The second compound is a compound whose main chain is a hydrocarbon chain and includes a side chain having a fluorine atom, and has a mass average molecular weight (Mw) of 1 million to 1 million. The mass average molecular weight (Mw) is preferably 3000 or more, more preferably 5000 or more. In addition, it is preferably 300,000 or less, more preferably 200,000 or less.

The second compound is preferably a polymer containing a fluoroalkyl group optionally containing an etheric oxygen atom and/or a side chain having a fluoroalkyl group optionally containing an etheric oxygen atom.

The second compound is preferably a polymer having a polymerized unit containing a fluoroalkyl group. The polymerized unit having a fluoroalkyl group is preferably introduced into the polymer by polymerizing a polymerizable monomer having a fluoroalkyl group.

In addition, a fluoroalkyl group can also be introduced into a polymer by various modification methods in which a suitable compound is reacted with a polymer having a reactive site.

The fluoroalkyl group may be linear or branched.

Specific examples of the fluoroalkyl group include the following structures.

-CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₃ CF ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ 、-(CF ₂ ) ₆ CF ₃ 、-(CF ₂ ) ₇ CF ₃ 、-(CF ₂ ) ₈ CF ₃ 、-(CF ₂ ) ₉ CF ₃ 、-(CF ₂ ) ₁₁ CF ₃ 、-(CF ₂ ) ₁₅ CF ₃ .

The fluoroalkyl group optionally contains etheric oxygen atoms.

Specific examples of the case where the fluoroalkyl group contains an etheric oxygen atom include the following structures.

-CF(CF ₃ )O(CF ₂ ) ₅ CF ₃ ,

-CF ₂ O(CF ₂ CF ₂ O) _r1 CF ₃ ,

-CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _r2 C ₆ F ₁₃ ,

-CF(CF ₃ )O(CF ₂ CF( _{CF 3} )O _{) r3C3F7} .

In the above formula, r1 is an integer of 1-8, r2 is an integer of 1-4, and r3 is an integer of 1-5.

It is preferable that a fluoroalkyl group is a perfluoroalkyl group from a viewpoint that ink repellency becomes favorable.

The number of carbon atoms in the fluoroalkyl group is preferably 4-15. It is excellent in ink repellency, and when manufacturing a 2nd compound, the compatibility of the monomer which has a fluoroalkyl group and the monomer other than this monomer mentioned later becomes favorable.

Examples of monomers having a fluoroalkyl group include 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 and the like.

In the above formula, R ^f is a fluoroalkyl group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a single bond or a divalent organic group with 1 to 6 carbons, and R ⁶ is a divalent organic group with 1 to 6 carbons. 2-valent organic group.

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 - and -CH(CH ₂ CH(CH ₃ ) ₂ )-.

The above-mentioned polymerizable monomers may be used alone or in combination of two or more.

The second compound is preferably a polymer including a side chain having an acidic group from the viewpoint of improving the alkali solubility of the second compound.

In addition, the side chain which has a fluoroalkyl group may contain an acidic group. In addition, a side chain which has an acidic group but does not have a fluoroalkyl group may exist other than the side chain which has a fluoroalkyl 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 second compound is preferably a polymer containing a side chain having an ethylenic double bond from the viewpoint of having photocrosslinkability, curing in the upper layer during the partition formation process, and maintaining ink repellency.

Particularly preferred are polymers containing two or more ethylenic double bonds in one side chain.

In addition, the side chain which has a fluoroalkyl group may contain an ethylenic double bond.

In addition, a side chain having an ethylenic double bond and not having a fluoroalkyl group may exist other than a side chain having a fluoroalkyl group.

The second compound may be a polymer including a side chain having an oxyalkylene group. The oxyalkylene group may be contained in the form of a polyoxyalkylene chain (POA chain) in which a plurality of oxyalkylene groups are connected. As an oxyalkylene group, an oxyethylene group and an oxypropylene group are mentioned, Preferably it is an oxyethylene group.

The oxyalkylene group itself does not have photocrosslinkability, but the second compound having the oxyalkylene group cures in the upper layer during the formation of the partition as in the case of having an ethylenic double bond, and ink repellency continues. Since the oxyalkylene group has hydrophilicity, it also has the effect of improving the wettability with respect to a developing solution.

In addition, the side chain which has a fluoroalkyl group may contain an oxyalkylene group. In addition, a side chain having an oxyalkylene group and not having a fluoroalkyl group may exist other than a side chain having a fluoroalkyl group.

The second compound may contain one or more types of side chains among side chains having an acidic group, side chains having an ethylenic double bond, and side chains having an oxyalkylene group. Two or more of an acidic group, an ethylenic double bond, and an oxyalkylene group may be included in one side chain.

The second compound may include a side chain having an arbitrary group other than a side chain having an acidic group, a side chain having an ethylenic double bond, and a side chain having an oxyalkylene group.

As a method for introducing a side chain having an acidic group and not having a fluoroalkyl group, a method of copolymerizing a monomer having a fluoroalkyl group and a monomer having an acidic group and not having a fluoroalkyl group is preferable. In addition, acidic groups can also be introduced into polymers by various modification methods in which appropriate compounds are reacted with polymers having reactive sites.

Examples of the monomer having a carboxyl group include (meth)acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used individually or in combination of 2 or more types.

As a monomer which has a phenolic hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc. are mentioned. In addition, one or more hydrogen atoms on their benzene rings are replaced by alkyl groups such as methyl, ethyl, and n-butyl groups, alkoxy groups such as methoxy, ethoxy, and n-butoxy, halogen atoms, A compound in which one or more hydrogen atoms of an alkyl group are substituted with a haloalkyl group, a nitro group, a cyano group, or an amide group substituted by a halogen atom.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropanesulfonic acid, 2-(methyl) Acrylamide-2-methylpropanesulfonic acid, and their salts.

As a method of introducing a carboxyl group into a polymer by various modification methods of reacting a suitable compound with a polymer having a reactive site, for example, (1) copolymerizing a monomer having a hydroxyl group in advance, and then using A method in which it reacts with an acid anhydride; (2) a method in which an acid anhydride having an olefinic double bond is copolymerized in advance, and then reacted with a compound having a hydroxyl group.

Specific examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) 4-Hydroxybutyl Acrylate, 5-Hydroxypentyl (Meth)acrylate, 6-Hydroxyhexyl (Meth)acrylate, 4-Hydroxycyclohexyl (Meth)acrylate, Neopentyl Glycol Mono(Meth) Acrylates, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol Monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth)acrylamide, N,N-bis(hydroxymethyl)(meth)acrylamide, etc. These may be used individually or in combination of 2 or more types.

The monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain (POA chain) whose terminal is a hydroxyl group.

For example, CH ₂ =CHOCH ₂ C ₆ H ₁₀ CH ₂ O(C ₂ H ₄ O) _k1 H, CH ₂ =CHOC ₄ H ₈ O(C ₂ H ₄ O) _k1 H, CH ₂ =CHCOOC ₂ H ₄ O(C ₂ H ₄ O) _k1 H, CH ₂ ＝C(CH ₃ )COOC ₂ H ₄ O(C ₂ H ₄ O) _k1 H, CH ₂ ＝CHCOOC ₂ H ₄ O(C ₂ H ₄ O) _k2 (C ₃ H ₆ O) _k3 H, CH ₂ =C(CH ₃ )COOC ₂ H ₄ O(C ₂ H ₄ O) _k2 (C ₃ H ₆ O) _k3 H, etc. These may be used individually or in combination of 2 or more types.

In the above formula, k1 is an integer of 1-100, k2 is an integer of 0-100, k3 is an integer of 1-100, and k2+k3 is 1-100.

As an acid anhydride, the acid anhydride of the compound which has 2 or more carboxyl groups in 1 molecule is mentioned. Examples thereof include pivalic anhydride and trimellitic anhydride. In addition, maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methylphthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3 , 4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc. have ethylenic double bonds of acid anhydride. These may be used individually or in combination of 2 or more types.

As the compound having a hydroxyl group, as long as it is a compound having one or more hydroxyl groups, specific examples of the above-mentioned monomers having a hydroxyl group include ethanol, 1-propanol, 2-propanol, and 1-butanol. , ethylene glycol and other alcohols, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and other cellosolves, 2-(2-methoxyethoxy)ethanol, 2- Carbitols such as (2-ethoxyethoxy)ethanol and 2-(2-butoxyethoxy)ethanol. Among these, compounds having one hydroxyl group in the molecule are preferred. These may be used individually or in combination of 2 or more types.

According to the method described above, a side chain containing an acidic group, a side chain containing an acidic group and an ethylenic double bond, or a side chain containing an acidic group and an oxyalkylene group can be introduced.

A monomer having a polyoxyalkylene chain (POA chain) that does not contain a hydroxyl group and an acidic group, for example, monomers represented by the following formulas (POA-1) and (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)

( ^R71 is hydrogen atom, chlorine atom, bromine atom, iodine atom, cyano group, alkyl group with 1 to 20 carbons, alkyl group substituted with aryl group with 7 to 20 carbons, aryl group with 6 to 20 carbons , or a cycloalkyl group having 3 to 20 carbon atoms.

^R72 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 and not having a fluorine atom.

k4 is an integer of 6-30. )

In addition, by appropriately selecting known monomers and reactions according to the desired composition, one of the side chains having an acidic group, the side chain having an ethylenic double bond, and the side chain having an oxyalkylene group can be obtained. A second compound of one or more side chains.

The mass ratio (mass of the second compound/mass of the first compound) of the second compound in the ink repellent composition (C) to the first compound is preferably 0.01 to 10, more preferably 0.02 to 5, particularly preferably 0.05～2.

Moreover, the content rate of the fluorine atom in an ink repellent composition (C) becomes like this. Preferably it is 5-40 mass %, More preferably, it is 10-35 mass %, More preferably, it is 13-32 mass %. When it is this range, characteristics, such as the ink repellency of an ink repellent composition (C) and the compatibility with other components in a negative photosensitive resin composition, become favorable.

[Negative Photosensitive Resin Composition]

The negative photosensitive resin composition of the present invention contains a photocurable alkali-soluble resin or alkali-soluble monomer (A), a photopolymerization initiator (B), the above-mentioned ink repellent composition (C), and a solvent (D) . A crosslinking agent (E), a coloring agent (F), etc. may also be contained as needed.

(alkali-soluble resin or alkali-soluble monomer (A))

The symbol (AP) is given to the alkali-soluble resin, and the symbol (AM) is given to the alkali-soluble monomer, and it demonstrates separately.

As alkali-soluble resin (AP), the photosensitive resin which has an acidic group and an ethylenic double bond in 1 molecule is preferable. By having an ethylenic double bond in the molecule of alkali-soluble resin (AP), the exposure part of a negative photosensitive resin composition polymerizes and hardens|cures by the radical which arises from a photoinitiator (B). The exposed portion cured in this way is not removed by an alkali developing solution.

Moreover, since an alkali-soluble resin (AP) has an acidic group in a molecule|numerator, the non-exposed part of an uncured negative photosensitive resin composition can be selectively removed with an alkali developing solution. As a result, a cured film having a desired pattern, that is, a partition can be formed.

A carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group etc. are mentioned as an acidic group, These may be used individually by 1 type, and may use 2 or more types together.

Examples of the ethylenic double bond include addition polymerizable double bonds such as a (meth)acryloyl group, an allyl group, a vinyl group, a vinyloxy group, and a vinyloxyalkyl group. These may be used individually by 1 type, and may use it in combination of 2 or more types.

In addition, some or all of the hydrogen atoms in the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

Examples of the alkali-soluble resin (AP) include a resin (A-1) containing a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin in which an acidic group and an ethylenic double bond are introduced. bonded resin (A-2), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

Resin (A-1) can be synthesize|combined by the method of following (i) or (ii), for example.

(i) Copolymerize monomers having reactive groups other than acidic groups in the side chains, such as reactive groups such as hydroxyl groups and epoxy groups, and monomers having acidic groups in the side chains, so as to obtain A copolymer of a side chain with an acidic group and a side chain with an acidic group. Next, this copolymer is reacted with a compound having a functional group capable of bonding to the above-mentioned reactive group and an ethylenic double bond. Alternatively, after copolymerizing a monomer having an acidic group such as a carboxyl group in the side chain, a compound having a functional group capable of bonding to the acidic group and an ethylenic double bond is reacted in an amount such that the acidic group remains after the reaction.

(ii) A monomer having a side chain having a reactive group other than the same acidic group as in (i) above, and a compound having a functional group capable of bonding to the reactive group and a protected ethylenic double bond react. Next, after copolymerizing this monomer with a monomer having an acidic group in the side chain, the protection of the ethylenic double bond is removed. Alternatively, after copolymerizing a monomer having an acidic group in the side chain and a monomer having a protected ethylenic double bond in the side chain, the protection of the ethylenic double bond is removed.

In addition, (i) and (ii) are preferably implemented in a solvent.

Among the above methods, the method (i) is preferably used. Hereinafter, the method of (i) is demonstrated concretely.

As the monomer having a hydroxyl group as a reactive group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, glycerin Mono(meth)acrylate, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl(meth)acrylamide, N,N-bis(hydroxymethyl)( Meth)acrylamide etc.

When using a monomer having a hydroxyl group as a reactive group, the monomer having an acidic group to be copolymerized, in addition to the monomer having a carboxyl group described later, as a monomer having a phosphoric acid group, 2-(methyl base) acryloyloxyethyl phosphate, etc. Copolymerization of a monomer having a hydroxyl group as a reactive group and a monomer having an acidic group can be performed according to a conventionally known method.

Examples of the compound having a functional group capable of bonding to a hydroxyl group and an ethylenic double bond to react with the obtained copolymer include acid anhydrides having an ethylenic double bond, compounds having an isocyanate group and an ethylenic double bond, acid chlorides Compounds with radicals and ethylenic double bonds, etc.

Examples of acid anhydrides having ethylenic double bonds include maleic acid, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetra Hydrogen phthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, etc.

Examples of compounds having an isocyanate group and an ethylenic double bond include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, etc. .

(meth)acryloyl chloride etc. are mentioned as a compound which has an acid chloride group and an ethylenic double bond.

Glycidyl (meth)acrylate, 3, 4- epoxy cyclohexyl methyl acrylate, etc. are mentioned about the monomer which has an epoxy group as a reactive group.

As the monomer having an acidic group to be copolymerized with the monomer having an epoxy group as a reactive group, the same monomers as those described above for the monomer having a hydroxyl group as a reactive group can be used, The copolymerization of the monomer having an epoxy group as a reactive group and the monomer having an acidic group can also be carried out according to a conventionally known method.

Examples of the compound having a functional group capable of bonding to an epoxy group and an ethylenic double bond to react with the obtained copolymer include compounds having a carboxyl group and an ethylenic double bond. Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and their salts. In the case of dibasic acids The monoester etc. are mentioned. It should be noted that the carboxyl group may be introduced into the resin (A-1) by reacting the hydroxyl group generated here with an acid anhydride in which the dehydration condensation portion of the carboxylic acid forms a part of the ring structure.

As for monomers having a carboxyl group as a reactive group, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salts are listed. In the case of an acid, its monoester etc. are mentioned. In addition, these monomers can also be used as the above-mentioned monomer which has an acidic group.

When using a monomer having a carboxyl group as a reactive group, the monomer is polymerized as described above. Examples of the compound having a functional group capable of bonding to a carboxyl group and an ethylenic double bond to react with the obtained polymer include compounds having an epoxy group and an ethylenic double bond. Glycidyl (meth)acrylate, 3, 4- epoxycyclohexyl methyl acrylate, etc. are mentioned as said compound. It should be noted that at this time, the amount of the compound having a functional group capable of bonding to a carboxyl group and an ethylenic double bond to be reacted with the polymer having a carboxyl group is set as the amount of the carboxyl group in the polymer as an acidic group after the reaction. Form the amount remaining in the side chain.

The resin (A-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond described later, and then reacting with a polyvalent carboxylic acid or an anhydride thereof.

Specifically, an ethylenic double bond is introduced into an epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduced by reacting a polyvalent carboxylic acid or an anhydride thereof with an epoxy resin having an ethylenic double bond introduced therein.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, and bisphenol novolak type epoxy resin. An epoxy resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (A-2a), a fluorene-substituted bisphenol A type epoxy resin represented by the following formula (A-2b), An epoxy resin having a biphenyl skeleton represented by the following formula (A-2c), or the like.

(v is an integer of 1 to 50, preferably an integer of 2 to 10. In addition, the hydrogen atoms of the benzene ring are each independently optionally replaced by an alkyl group with 1 to 12 carbon atoms, a halogen atom, or a part of hydrogen atoms. Substituent substituted phenyl.)

(R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group with 1 to 5 carbon atoms, and w is an integer of 0 or 1 to 10.)

(The hydrogen atoms of the benzene ring are each independently optionally substituted by an alkyl group with 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which a part of the hydrogen atoms are optionally substituted by a substituent. z is an integer of 0 or 1 to 10 .)

It should be noted that when the epoxy resin represented by the formulas (A-2a) to (A-2c) is reacted with a compound having a carboxyl group and an ethylenic double bond and then reacted with a polycarboxylic anhydride, as a polycarboxylic anhydride, Preference is given to using mixtures of dicarboxylic anhydrides and tetracarboxylic dianhydrides.

Acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and these salts are mentioned as a compound which has a carboxyl group and an ethylenic double bond. In the case of dibasic acids, this compound is preferably a monoester, particularly preferably (meth)acrylic acid.

As an alkali-soluble resin (AP), from the viewpoint that peeling of the cured film during development is suppressed, a high-resolution pattern can be obtained, the linearity of the line pattern is good, and a smooth cured film surface is easily obtained, Resin (A-2) is preferably used.

As the resin (A-2), it is particularly preferable to introduce an acidic group and an ethylenic double bond into a bisphenol A type epoxy resin, or a resin into which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin. Resins with double bonds, resins with acid groups and ethylenic double bonds introduced into phenol novolak epoxy resins, resins with acid groups and ethylenic double bonds introduced into cresol novolak type epoxy resins, A resin having an acidic group and an ethylenic double bond introduced into a trisphenolmethane type epoxy resin, or an acidic group and an ethylenic double bond introduced into an epoxy resin represented by formulas (A-2a) to (A-2c) A resin with a double bond.

As the alkali-soluble monomer (AM), for example, a monomer (A-3) including a side chain having an acidic group and a side chain having an ethylenic double bond is preferably used. The acidic group and ethylenic double bond are the same as the alkali-soluble resin (AP).

As a monomer (A-3), 2,2,2- triacryloxymethyl ethyl phthalic acid etc. are mentioned.

The alkali-soluble resin (AP) or alkali-soluble monomer (AM) contained in a negative photosensitive resin composition may be used individually by 1 type, and may use it in combination of 2 or more types.

The content rate of the alkali-soluble resin or alkali-soluble monomer (A) in the total solid content in a negative photosensitive resin composition becomes like this. Preferably it is 5-80 mass %, Especially preferably, it is 10-60 mass %. When the content ratio is the above range, the photocurability and developability of the negative photosensitive resin composition are favorable.

(Photopolymerization Initiator (B))

The photopolymerization initiator (B) in the present invention will not be particularly limited as long as it is a compound having a function as a photopolymerization initiator, but is preferably a compound that generates radicals using light.

Examples of the photopolymerization initiator (B) include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; azoins such as benzoin; benzoin methyl ether, benzoin Azoin ethers such as ethyl ether, benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone Ketones and other thioxanthones; benzophenones, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and other benzophenones; Acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4 -Morpholinylphenyl)-butan-1-one and other acetophenones; anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone and other quinones; 2-dimethylaminobenzoic acid Aminobenzoic acids such as ethyl ester and (n-butoxy)ethyl 4-dimethylaminobenzoate; Halogen compounds such as phenacyl chloride and trihalogenated methylphenyl sulfone; Acyl phosphine oxides Classes; di-tert-butyl peroxide and other peroxides; {1-[4-(phenylthio)-2-(O-benzoyl oxime)]}1,2-octanedione, acetyl oxime and other oximes Esters; triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate and other aliphatic amines; 2-mercaptobenzimidazole, 2 -Mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis(3-mercaptobutyrate), tris(2-mercaptopropionyloxyethyl)isocyanurate, pentaerythritol tetra (3-mercaptobutyrate) and other thiol compounds, etc.

Among the photopolymerization initiators (B), benzophenones, aminobenzoic acids, aliphatic amines, thiol compounds, etc. are preferred because they may show a sensitizing effect when used together with other radical initiators. of.

As the photopolymerization initiator (B), 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan-1-one, {1-[4-(phenylthio)-2-(O-benzoyl oxime)]}1,2-octanedione, 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, or 2,4-diethylthio xanthone. Furthermore, combinations of these with benzophenones such as 4,4'-bis(diethylamino)benzophenone are particularly preferred.

A photoinitiator (B) may be used individually by 1 type, and may use it in combination of 2 or more types.

The content rate of the photoinitiator (B) in the total solid content in a negative photosensitive resin composition becomes like this. Preferably it is 0.1-50 mass %, More preferably, it is 0.5-30 mass %, Especially preferably, it is 5-15 mass %. When the content ratio is the above range, the photocurability and developability of the negative photosensitive resin composition are favorable.

(ink repellent composition (C))

The content rate of the 1st compound in the total solid content in a negative photosensitive resin composition becomes like this. Preferably it is 0.05-10 mass %, More preferably, it is 0.1-3 mass %, Especially preferably, it is 0.2-1 mass %.

The content rate of the second compound in the total solids in the negative photosensitive resin composition is preferably 0.01 to 5% by mass, more preferably 0.03 to 2% by mass, particularly preferably 0.05 to 0.5% by mass.

The content rate of the ink repellent composition (C) in the total solid content in a negative photosensitive resin composition becomes like this. Preferably it is 0.06-15 mass %, More preferably, it is 0.13-5 mass %, Especially preferably, it is 0.25-1.5 mass % .

In the negative photosensitive resin composition, the mass ratio of the second compound to the first compound (mass of the second compound/mass of the first compound) is preferably 0.01 to 10, more preferably 0.02 to 5, particularly preferably 0.05 ~2. When it is the range of the said mass ratio, the storage stability of a negative photosensitive resin composition, ink repellency, its UV/ _O3 resistance, photocurability, and developability are favorable.

(Solvent (D))

When the negative photosensitive resin composition in this invention contains a solvent (D), the viscosity will be reduced, and it will become easy to apply a negative photosensitive resin composition to the surface of a base material. As a result, the coating film of the negative photosensitive resin composition of uniform film thickness can be formed.

As the solvent (D), known solvents can be used.

The content rate of the solvent (D) in a negative photosensitive resin composition becomes like this. Preferably it is 50-99 mass %, More preferably, it is 60-95 mass %, Especially preferably, it is 65-90 mass %.

(Crosslinking agent (E))

As a crosslinking agent (E) in this invention, the compound which has 2 or more ethylenic double bonds in 1 molecule, but does not have an acidic group is preferable. When a negative photosensitive resin composition contains a crosslinking agent (E), the hardening property of the negative photosensitive resin composition at the time of exposure improves, and even if it is a low exposure amount, a partition can be formed.

Examples of the crosslinking agent (E) include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ) acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated isocyanurate triacrylate, ε -Caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, aminomethyl Acrylic acid ester etc.

From the viewpoint of photoreactivity, it is preferable to have a plurality of ethylenic double bonds. For example, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxy Isocyanuric acid triacrylate, urethane acrylate, etc.

The crosslinking agent (E) may be used alone or in combination of two or more.

The content rate of the crosslinking agent (E) in the total solid content in a negative photosensitive resin composition becomes like this. Preferably it is 10-60 mass %, Especially preferably, it is 20-55 mass %.

(colorant (F))

Examples of the colorant (F) in the present invention include carbon black, aniline black, anthraquinone-based black pigments, perylene-based black pigments, specifically, C.I. Pigment Black 1, 6, 7, 12, 20, and 31. Mixtures of organic and/or inorganic pigments such as red, blue and green pigments may also be used.

The content rate of the coloring agent (F) in the total solid content in the negative photosensitive resin composition of this invention becomes like this. Preferably it is 15-65 mass %, Especially preferably, it is 20-50 mass %. When it is the said range, the sensitivity of the negative photosensitive resin composition obtained is favorable, and the light-shielding property of the partition formed is excellent.

(other ingredients)

The negative photosensitive resin composition of the present invention may also contain thermal crosslinking agents, polymer dispersants, dispersion aids, silane coupling agents, microparticles, phosphoric acid compounds, curing accelerators, thickeners, and plasticizers as needed. , defoaming agent, leveling agent, anti-shrinkage agent, ultraviolet absorber and other additives of one or more kinds.

[partition wall]

The partition wall of the present invention is a cured film having a pattern obtained by applying the above-mentioned negative photosensitive resin composition on the surface of a substrate, exposing and developing it.

Hereinafter, although an example of the manufacturing method of a partition is demonstrated using FIGS. 1A-1E, the manufacturing method of a partition is not limited to the following description.

As shown in FIG. 1A , the negative photosensitive resin composition is applied to the entire surface of the substrate 10 to form a coating film 21 . At this time, in the coating film 21, the first compound and the second compound having ink repellency are entirely dissolved and uniformly dispersed. In addition, in a figure, although the ink repellent composition (C) is shown schematically, it does not exist in such particle form actually.

Next, as shown in FIG. 1B , the coating film 21 is dried to form a dry film 22 . As a drying method, heat drying, reduced-pressure drying, and reduced-pressure heating drying etc. are mentioned.

Although it also depends on the kind of solvent (D), when drying by heating, heating temperature is preferably 50-120 degreeC, More preferably, it is 70-120 degreeC, More preferably, it is 80-120 degreeC.

In this drying process, the ink repellent composition (C) moves to the upper surface of a dry film and its vicinity.

Next, as shown in FIG. 1C , the dry film 22 is irradiated with light L through a photomask 30 having openings 31 in a predetermined pattern to expose. The film after exposing the dry film 22 is called the exposure film 23 . In the exposure film 23, 23A is an exposure part, and 23B is a non-exposure part. In this step, the exposed portion 23A is photocured.

Examples of light L to be irradiated include visible light; _ultraviolet light; far _ultraviolet light _; Molecular lasers; X-rays; electron beams, etc.

The light L to be irradiated is preferably light with a wavelength of 100 to 600 nm, more preferably light with a wavelength of 300 to 500 nm, and particularly preferably light including i-rays (365 nm), h-rays (405 nm) or g-rays (436 nm).

As an exposure method, whole-surface collective exposure, scanning exposure, etc. are mentioned. Multiple exposures can also be performed on the same part. In this case, the conditions of the multiple exposures may be the same or different.

In any of the above-mentioned exposure methods, the exposure amount is, for example, preferably 5 to 1000 mJ/cm ² , more preferably 5 to 500 mJ/cm ² , even more preferably 5 to 300 mJ/cm ² , particularly preferably 5 to 200 mJ/cm ² , Most preferably, it is 5 to 50 mJ/cm ² . In addition, exposure amount is optimized suitably according to the wavelength of the light to irradiate, the composition of a negative photosensitive resin composition, the thickness of a coating film, etc.

The exposure time per unit area is not particularly limited, and is determined by the exposure power of the exposure device used, the necessary exposure amount, and the like. In addition, in scanning exposure, exposure time is calculated|required 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 , development is performed using an alkali developing solution to form a cured film 24 having a desired pattern. In the cured film 24, the exposed part 23A in the previous exposure becomes the convex part 24A, and the non-exposed part 23B becomes the pattern opening part 24B.

In addition, in this process, the ink repellent composition (C) of the non-exposure part 23B dissolves favorably in alkali developing solution, and does not remain in pattern opening part 24B.

The patterned cured film 24 may be further heated as shown in FIG. 1E. The heating temperature is preferably 130 to 250°C, more preferably 180 to 250°C, even more preferably 200 to 230°C. The ink repellent composition (C) is firmly bonded in the cured film by heating, and forms a thin layer closer to the surface.

After the above-mentioned heating, it is usually used to remove the development residue of the negative photosensitive resin composition remaining in the pattern opening 24B for applications such as partition walls for pattern printing of organic layers such as the light emitting layer of the organic EL element by the IJ method. , and the substrate 10 is subjected to UV/O ₃ irradiation treatment.

According to the negative photosensitive resin composition of the present invention, it is possible to form a partition having the following characteristics: the upper surface has good ink repellency and even after UV/ _O3 irradiation treatment, its ink repellency is also well maintained, and the dots are not damaged. Ink repellent will remain.

The partition wall of the present invention can be used as a partition wall for defining an ink injection region when pattern printing is performed by the IJ method.

Since the upper surface of the partition of this invention has favorable ink repellency, when performing pattern printing by the IJ method, ink can be apply|coated uniformly in the area|region surrounded by a partition. In addition, it is possible to prevent ink from being poured into an unintended region beyond the partition wall, and it is possible to print ink satisfactorily in a desired pattern.

As shown in FIG. 2A , after the cured film 24 is formed ( FIG. 1E ), the ink 51 is dripped from the inkjet head 40 , and the ink 51 is injected into the pattern opening 24B of the cured film 24 . Next, drying and/or heating are performed to remove the solvent, and as shown in FIG. 2B , a desired pattern film 52 can be obtained.

[Optical element]

The optical element of the present invention includes a plurality of dots and the above-mentioned partition wall of the present invention.

As an optical element, an organic EL element, the color filter of a liquid crystal element, an organic TFT array element, etc. are mentioned.

An organic TFT array element refers to an element in which a plurality of dots are arranged in a matrix form in a plan view, a pixel electrode and a TFT as a switching element for driving it are provided in each dot, and an organic semiconductor layer is used as a semiconductor including a channel layer of the TFT. layer.

The organic TFT array element is provided as a TFT array substrate in an organic EL element, a liquid crystal element, or the like.

An organic EL element can be manufactured as follows, for example.

A light-transmitting electrode such as tin-doped indium oxide (ITO) is deposited on a light-transmitting substrate such as glass by sputtering or the like. This translucent electrode is patterned as needed.

Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in plan view along the outline of each point by photolithography including application, exposure, and development.

Next, ink affinity treatment is performed on the dots surrounded by the partition wall by a known method as needed.

Next, materials for the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are applied and dried in the dots by the IJ method, and these layers are sequentially stacked. The kind and number of organic layers formed in the dots can be appropriately designed.

Finally, a reflective electrode made of aluminum or the like is formed by vapor deposition or the like.

Example

The present invention is explained based on examples, and the present invention is not limitedly interpreted by them. Examples 1-10, Example 14 and Example 15 are examples, and Examples 11-13 are comparative examples.

Each measurement was performed by the following method.

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

The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance. As the gel permeation chromatography, HPLC-8220GPC (manufactured by Tosoh Corporation) was used. As the column, a column obtained by connecting three Shodex LF-604 pieces was used. As a detector, an RI (Refractive Index, refractive index) detector is used. As a standard substance, EasiCal PS1 (manufactured by Polymer Laboratories) was used. Furthermore, when measuring the number average molecular weight and mass average molecular weight, the column was held at 37° C., tetrahydrofuran was used as an eluent, and 40 μL of a 0.5 mass % tetrahydrofuran solution of the measurement sample was injected at a flow rate of 0.2 mL/min.

[Fluorine atom content rate]

The fluorine atom content (mass %) in the first compound and the second compound was calculated by ¹⁹ F NMR measurement using 1,4-bistrifluoromethylbenzene as a standard substance. Moreover, the fluorine atom content rate of an ink repellent composition (C) is computed from content of a 1st compound and a 2nd compound, and the fluorine atom content rate of a 1st compound and a 2nd compound.

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

The content of the ethylenic double bond (C=C) in the 1st compound and the 2nd compound was calculated theoretically from the compounding ratio of a raw material.

[acid value]

The acid value in the second compound is theoretically calculated from the compounding ratio of the raw materials.

The abbreviations of the compounds used in each example are shown below.

(Raw material of the first compound)

Compound (cx-11) corresponding to compound (cx-1): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si(O CH ₃ ) ₃ (manufactured by Asahi Glass Co., Ltd.), compound (cx-12): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ ,

Compound (cx-21) corresponding to compound (cx-2): Si(OC ₂ H ₅ ) ₄ (manufactured by COLCOAT CO., Ltd), compound (cx-22): part of Si(OC ₂ H ₅ ) ₄ Hydrolysis condensate (manufactured by COLC OAT CO., Ltd., trade name: Ethyl Silicate 48),

Compound (cx-31) corresponding to compound (cx-3): CH ₂ =CHCOO(CH ₂ ) ₃ Si(O CH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.),

Compound (cx-41) corresponding to compound (cx-4): (CH ₃ ) ₃ SiOCH ₃ (manufactured by Tokyo Chemical Industry Co., Ltd.),

Compound (cx-51) corresponding to compound (cx-5): SH(CH ₂ ) ₃ Si(OCH ₃ ) ₃ (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803),

Other hydrolyzable silane compounds (cx-61): CH ₃ O(C ₂ H ₄ O) _k Si(OCH ₃ ) ₃ (polyoxyethylene-containing trimethoxysilane, where k is about 10.) .

DBTDL: dibutyltin dilaurate

(Raw material of the second compound)

C6FMA: _CH2 =C( _CH3 ) _COOCH2CH2 ( _{CF2 ) 6F} .

MAA: methacrylic acid.

2-HEMA: 2-Hydroxyethyl methacrylate.

PME-400: CH ₂ ＝C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ (α-methyl-ω-methacryloyloxypoly(oxyethylene), k in the formula represents intermolecular The average value of k is about 9. NOF Co., Ltd., trade name: BLEMMER PME-400).

IBMA: Isobornyl methacrylate.

V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.).

n-DM: n-dodecylmercaptan.

BEI: 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko Co., Ltd., brand name: Karenz BEI).

AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., brand name: Karenz AOI).

DBTDL: dibutyltin dilaurate.

TBQ: tert-butyl-p-benzoquinone.

MEK: 2-butanone.

(Alkali soluble resin (AP))

A-11: Reaction of cresol novolac type epoxy resin with acrylic acid, followed by reaction with 1,2,3,6-tetrahydrophthalic anhydride to introduce acryloyl group and carboxyl group, after that, purification with hexane The resulting resin had a solid content of 70% by mass and an acid value of 60 mgKOH/g.

A-12: Resin obtained by introducing carboxyl groups and olefinic double bonds into bisphenol A epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD ZAR-2002H, solid content 70% by mass, acid value 60mgKOH/ g).

A-13: A resin obtained by introducing an ethylenic double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the upward formula (A-2a) (manufactured by Nippon Kayaku Co., Ltd., trade name: ZCR-1642H , mass average molecular weight (Mw): 5800, acid value: 100 mgKOH/g, solid content: 70% by mass).

A-14: Resin (solid content: 70 mass %, PGMEA: 30 mass %. Acid value 70mgKOH/g.).

(Photopolymerization Initiator (B))

IR907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by BASF Corporation, brand name: IRGACURE907).

OXE02: 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (manufactured by BASF Corporation, brand name: OXE02 ETHANON ).

OXE01: {1-[4-(phenylthio)-2-(O-benzoyl oxime)]} 1,2-octanedione (manufactured by BASF Corporation, brand name: OXE01).

(sensitizer)

EAB: 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).

NR1: Tris(2-mercaptopropionyloxyethyl)isocyanurate (manufactured by Showa Denko Co., Ltd., brand name: KarenzMT NR1).

PE1: pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., brand name: Karenz MTPE1).

BTT: 2-Mercaptobenzothiazole

(Solvent (D))

PGMEA: Propylene Glycol Monomethyl Ether Acetate.

PGME: Propylene Glycol Monomethyl Ether.

EDM: diethylene glycol methyl ethyl ether.

EDGAC: Diethylene glycol monoethyl ether acetate.

(Crosslinking agent (E))

A9550W: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name: NK ESTER A-9550W).

UX5002D: polyfunctional urethane acrylate oligomer (manufactured by Nippon Kayaku Co., Ltd., brand name: KAYARAD UX-5002D-P20).

ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name: NK ESTER A-DPH).

ABPEF: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name: NK ESTER A-BPEF).

(colorant (F))

Mixed organic pigment: 10:5:5:5 mixture of C.I. Pigment Blue 15:6, C.I. Pigment Red 254, C.I. Pigment Yellow 139 and polymer dispersant (solid content: 25% by mass, PGMEA: 75% by mass.) .

(other)

BHT: Inhibitor (2,6-di-tert-butyl-p-cresol).

XD1000: multifunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., brand name: XD1000).

[Synthesis Example 1: Synthesis of Compound (CX-1)]

^14.5g of compound (cx-11), 32.9g of compound (cx-21), 21.9g of compound (cx-31), 21.9g of compound (cx-41), and 21.9g of compound (cx-41) and compound ( cx-51) 8.8 g to obtain a hydrolyzable silane compound mixture. Next, 320.2 g of PGMEA was thrown into this mixture to prepare a raw material solution.

98.7 g of 1 mass % nitric acid aqueous solution was dripped at the obtained raw material solution. After completion of the dropwise addition, it was stirred at 40° C. for 5 hours to obtain a solution of compound (CX-1) (compound concentration: 10% by mass, hereinafter also referred to as (CX-1) solution.).

It should be noted that after the reaction was completed, the reaction solution was measured using a gas chromatograph, and it was confirmed that each compound used as a raw material was below the detection limit.

Table 1 shows the raw material composition and evaluation results (number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, and ethylenic double bond content).

[Synthesis Examples 2 to 6: Compounds (CX-2) to (CX-6)]

Except that the raw material composition was set as shown in Table 1, the same operation was performed as in Synthesis Example 1 to obtain solutions of compounds (CX-2) to (CX-6) (both compound concentrations: 10% by mass, and each solution was also hereinafter referred to as Called (CX-2) ~ (CX-6) liquid.).

Table 1 shows the evaluation results (number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, and ethylenic double bond content).

[Table 1]

[Synthesis Example 7: Synthesis of Compound (CY-1)]

420.0 g of MEK, 81.0 g of C6FMA, 18.0 g of MAA, 81.0 g of 2-HEMA, 5.0 g of polymerization initiator V-65, and 4.7 g of n-DM were put into an autoclave with an internal volume of 1000 cm ³ equipped with a stirrer, and the The polymerization was carried out at 50° C. for 24 hours while stirring under an atmosphere. Furthermore, the polymerization initiator was deactivated by heating at 70 degreeC for 5 hours, and the solution of the copolymer 1 was obtained. The number average molecular weight (Mn) of the copolymer 1 was 5540, and the mass average molecular weight (Mw) was 13200.

Next, 130.0 g of the solution of the above-mentioned copolymer 1, 30.5 g of BEI, 0.12 g of DBTDL, and 1.5 g of TBQ were put into an autoclave with an internal volume of 300 cm ³ equipped with a stirrer, and reacted at 40° C. for 24 hours while stirring to synthesize a crude polymer. thing. Hexane was added to the solution of the obtained crude polymer to carry out reprecipitation purification, and vacuum drying was performed to obtain 65.6 g of compound (CY-1).

Table 2 shows raw material compositions, yields, and evaluation results of the obtained compounds (number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, ethylenic double bond content, and acid value).

[Synthesis Example 8: Synthesis of Compound (CY-2)]

Compound (CY-2) was obtained in the same manner as in Synthesis Example 7, except that the above-mentioned solution of copolymer 1, AOI, DBTDL, and TBQ were used in the composition shown in Table 2.

[Synthesis Example 9: Synthesis of Compound (CY-3)]

MEK, C6FMA, MAA, 2-HEMA, PME-400, and polymerization initiator V-65 were charged with the composition shown in Table 2 in an autoclave with an internal volume of 1000 cm ³ equipped with a stirrer, and stirred under a nitrogen atmosphere. Polymerization was carried out at 50°C for 24 hours. Furthermore, it heated at 70 degreeC for 5 hours, the polymerization initiator was deactivated, and the solution of compound (CY-3) was obtained. The solvent was distilled off at a temperature of 50° C. using a rotary evaporator, and then vacuum-dried to obtain compound (CY-3).

[Synthesis Examples 10-11: Synthesis of Compounds (CY-4)-(CY-5)]

Compounds (CY-4) to (CY-4) were obtained in the same manner as in Synthesis Example 9 except that the raw material composition was shown in Table 2.

[Synthesis Example 12: Compound (CY-6)]

As a compound (CY-6), a trade name: Megafac RS10 ₂ manufactured by Dainippon Ink Co., Ltd. was prepared.

This compound is a polymer having the following repeating units. In addition, m2/m1=3-4.

[Synthesis Example 13: Synthesis of Compound (CY-7)]

A solution of Copolymer 2 was obtained in the same manner as Copolymer 1 in Synthesis Example 7, except that MEK, C6FMA, MAA, 2-HEMA, and polymerization initiator V-65 were used in the raw material composition shown in Table 2. The number average molecular weight (Mn) of the copolymer 2 was 32400, and the mass average molecular weight (Mw) was 69320.

Compound (CY-7) was obtained in the same manner as in Example 5, except that the solution of copolymer 2, AOI, DBTDL, and TBQ were used in the raw material composition shown in Table 2.

The raw material composition, yield and evaluation results (number average molecular weight (Mn), mass average molecular weight (Mw), fluorine atom content, olefinic double bond content, and Acid value) is shown in Table 2.

[Table 2]

[Example 1: Manufacture of Negative Photosensitive Resin Composition and Partition Wall]

(Manufacture of negative photosensitive resin composition)

1.5 g of compound (CX-1) obtained in Synthesis Example 1 (containing 0.15 g of compound (CX-1) in terms of solid content, and the remainder being solvent PGMEA), 0.015 g of compound (CY-1) obtained in Synthesis Example 7, g, A-11 16.07g (solid content is 11.25g, the remainder is solvent PGMEA), IR907 1.21g, EAB 1.125g, A9550W 11.25g, PGMEA 55.0g, and EDM 20.0g were put into a 200cm ³ stirring container, It stirred for 5 hours, and produced the negative photosensitive resin composition. Table 3 shows the raw material composition.

In the table|surface, solid content total amount means the quantity (mass %) of all solid content with respect to the negative photosensitive resin composition whole quantity except a solvent (D).

The solid content composition is represented by the amount (% by mass) of each solid raw material relative to the total solid content.

The solvent (D) composition is represented by the amount (% by mass) of each solvent (D) relative to the total amount of the composition.

Table 3 also shows the mass of the second compound/mass of the first compound.

(manufacturing of partition walls)

A 10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, followed by UV/O ₃ treatment for 5 minutes. UV/O ₃ treatment used PL2001N-58 (manufactured by Sen Engineering Co., Ltd.) as a UV/O ₃ generator. The optical power converted to 254 nm is 10 mW/cm ² . It should be noted that this device was used in all of the following UV/O ₃ treatments.

The above-mentioned negative photosensitive resin composition was coated on the surface of the above-mentioned cleaned glass substrate using a spin coater, and then dried on a hot plate at 100° C. for 2 minutes to form a dry film with a film thickness of 2.4 μm.

Through a photomask having an opening pattern (2.5 cm x 5 cm), the entire surface was exposed at an exposure dose of 100 mJ/cm ² to the obtained dried film by irradiating ultra-high voltage with an exposure power of 25 mW/cm ² in terms of 365 nm. UV light from a mercury lamp. During exposure, light below 330nm is cut off. In addition, the separation distance between the dry film and the photomask was set to 50 μm.

Next, the glass substrate after the said exposure process was immersed and developed for 40 second in 2.38 mass % tetramethylammonium hydroxide aqueous solution, and the non-exposed part was rinsed with water, and it was made to dry. Next, this was heated on a hot plate at 230° C. for 60 minutes to obtain a partition (cured film) having a pattern corresponding to the opening pattern of the photomask.

The following evaluation was implemented about the obtained partition. The evaluation results are shown in Table 3.

<Compatibility of Negative Photosensitive Resin Composition>

Using the negative photosensitive resin composition immediately after production, a dry film was obtained under the above-mentioned formation conditions of the dry film. The obtained dried film was observed with the naked eye, and evaluated according to the following criteria.

○ (good): The film was transparent and colorless. Δ (possible): The film was clouded white, but no foreign matter was seen. × (poor): The film was clouded white, and foreign matter was seen in the film.

<Storage Stability of Negative Photosensitive Resin Composition>

Using the negative photosensitive resin composition stored at 60° C. for 30 days, a dry film was obtained under the above-mentioned formation conditions of the dry film. The obtained dried film was observed with the naked eye, and evaluated according to the following criteria.

If there are large foreign matter in the negative photosensitive resin composition, the foreign matter will be dragged to the outer periphery during spin coating, and radial streaks will be generated on the obtained film.

○ (good): No foreign matter and radial streaks. Δ (possible): Foreign matter is seen but no radial streaks. x (poor): Radial streaks exist.

<Film thickness of cured film>

Measurement was performed using a laser microscope (manufactured by Keyence Corporation, device name: VK-8500).

<Ink repellency and UV/O ₃ resistance on the upper surface of the partition wall>

The PGMEA contact angle of the upper surface of the obtained cured film was measured by the following method.

According to JIS R3257 "Wettability Test Method of Substrate Glass Surface" by the static drop method, PGMEA droplets were placed on three places on the upper surface of the cured film, and each PGMEA droplet was measured. The droplet size was 2 µL/drop, and the measurement was performed at 20°C. The contact angle was obtained from the average value of three measured values. It should be noted that PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.

The entire surface of the glass substrate on which the cured film was formed was irradiated with UV/O ₃ for 3 minutes (1800 mJ/cm ² in terms of light intensity at 254 nm), and then the PGMEA contact angle on the upper surface of the cured film was measured again by the method described above.

<SEM Observation of Upper Surface of Partition Wall>

SEM observation (5000 magnification, manufactured by Keyence Corporation, device name: 3D Real Surface Observation Microscope VE-9800) was performed on the upper surface of the partition wall obtained, and the presence or absence of bumps at the end of the upper surface of the partition wall was observed, and evaluation was performed according to the following criteria .

◯ (good): No swelling was observed at the end portion of the upper surface of the partition wall.

Δ (possible): Swelling was observed at the end portion of the upper surface of the partition wall.

[Example 2-15]

Except having changed the negative photosensitive resin composition into the composition shown in Table 3 in Example 1, the negative photosensitive resin composition and the partition were produced and evaluated by the same method. The evaluation results are shown in Table 3.

[table 3]

In Table 3, "%" is "mass %".

(summary of results)

In Examples 1 to 10, 14, and 15 in which the first compound and the second compound were used in combination, that is, the ink repellent composition (C), the upper surface of the partition wall had excellent ink repellency, and the ink repellency was excellent even at It is also well maintained after UV/ _O3 treatment.

In the evaluation before UV/O ₃ irradiation treatment, the ink repellency of the upper surface of the partition wall of Examples 1 to 10, Examples 14 and 15 was compared with that of the example using only the second compound with a mass average molecular weight (Mw) exceeding 100,000. The partition wall upper surfaces of 13 are equal.

In the evaluation before UV/O ₃ irradiation treatment, the ink repellency of the upper surface of the partition wall of Examples 1 to 10, Example 14, and Example 15 was higher than that of Example 11 using only the first compound, and using only the mass average molecular weight. Example 12 of the second compound whose (Mw) is 50,000 or less.

The storage stability of the negative photosensitive resin composition of Examples 1-10 which combined the 1st compound and the 2nd compound was also favorable. Improvement was seen relative to Example 11 using only the first compound.

In Examples 1 to 10 in which the first compound and the second compound were used in combination, no swelling was observed at the end of the upper surface of the partition wall, and a regular partition wall could be formed. Improvement was seen relative to Example 11 using only the first compound.

In the negative photosensitive resin compositions of Examples 12 and 13 using only the second compound, the ink repellency of the upper surface of the partition wall after UV/O ₃ treatment was significantly reduced.

Industrial availability

The ink repellent composition of the present invention can be suitably used as a photosensitive resin composition for forming partitions in optical elements such as organic EL elements, color filters of liquid crystal elements, and organic TFT arrays when pattern printing is performed by an inkjet method substances, or the ink repellent contained therein.

In addition, the partition formed by the photosensitive resin composition containing the ink repellent composition of the present invention can be used as a partition (protrusion) for pattern-printing organic layers such as a light-emitting layer by the IJ method in an organic EL element, Alternatively, it can be used as a partition wall for pattern printing of color filters by the IJ method in liquid crystal elements (this partition wall can also be used as a black matrix (BM).), and in turn can be used as a pattern pattern by the IJ method in an organic TFT array. Partition walls for printing conductor patterns or semiconductor patterns can also be used as partition walls for pattern-printing organic semiconductor layers, gate electrodes, source electrodes, drain electrodes, gate wirings, and source wirings to be channel layers of TFTs by the IJ method.

In addition, all the content of the Japanese patent application 2012-209084 for which it applied on September 24, 2012, a claim, drawing, and abstract are referred here, and it incorporates it as an indication of the specification of this invention.

Explanation of reference signs

10: Substrate, 21: Coated film, 22: Dry film, 23: Exposure film, 23A: Exposed part, 23B: Non-exposed part, 24: Cured film, 24A: Convex part, 24B: Pattern opening part, 30: Light Mask, 40: inkjet head, 51: ink, 52: pattern film, L: light.

Claims (15)

1. a negative light-sensitive resin combination, it is characterised in that it is refused ink compositions for comprising and have photocuring The alkali soluble resin of property or base soluble monomer (A), Photoepolymerizationinitiater initiater (B) and the negative photosensitive resin group of solvent (D) Compound,

Described ink compositions of refusing comprises the first compound and the second compound, and described first compound has fluorine alkylene for comprising The partial hydrolysis condensate of the mixture of the first hydrolysable silanes compound of base and/or fluoroalkyl and hydrolization group, institute State the main chain of the second compound be hydrocarbon chain and comprise there is the side chain of fluorine atom, matter average molecular weight (Mw) is 100～1,000,000,

Described second compound is the polymer comprising the side chain with acidic-group.

Negative light-sensitive resin combination the most according to claim 1, wherein, described first hydrolysable silanes compound is Compound shown in following formula (cx-1),

(A-R^F11)_a-Si(R^H11)_bX¹¹ _(4-a-b)···(cx-1)

R^F11For comprising at least 1 fluorine alkylidene, the divalent organic group of carbon number 1～16 or comprise etheric oxygen atom The divalent organic group of carbon number 2～16, R^H11For the alkyl of carbon number 1～6,

X¹¹For hydrolization group, X¹¹When existing multiple, they each other can difference can also be identical；

A is 1 or 2, b is 0 or 1, a+b is 1 or 2,

A is the group shown in fluorine atom or lower formula (I),

-Si(R^H12)_cX¹² _(3-c)···(I)

R^H12For the alkyl of carbon number 1～6,

C is 0 or 1,

X¹²For hydrolization group, X¹²When existing multiple, they each other can difference can also be identical,

A-R^F11When existing multiple, they each other can difference can also be identical.

Negative light-sensitive resin combination the most according to claim 2, wherein, described mixture also comprises following formula (cx-2) The second shown hydrolysable silanes compound,

SiX² ₄···(cx-2)

X²Represent hydrolization group, 4 X²Each other can difference can also be identical.

4. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described mixture also wraps Containing the 3rd hydrolysable silanes compound shown in following formula (cx-3),

(Y-Q³)_g-Si(R^H3)_hX³ _(4-g-h)···(cx-3)

Y is the group with olefinic double bond,

Q³For the divalent organic group without fluorine atom of carbon number 1～6,

R^H3For the alkyl of carbon number 1～6,

X³For hydrolization group, X³When existing multiple, they each other can difference can also be identical,

G is 1 or 2, h is 0 or 1, g+h is 1 or 2,

Y-Q³When existing multiple, they each other can difference can also be identical.

5. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described second compound For polymer, described polymer comprises the fluoroalkyl optionally containing etheric oxygen atom and/or has optionally containing etheric oxygen atom The side chain of fluoroalkyl.

Negative light-sensitive resin combination the most according to claim 5, wherein, described second compound has alkene for comprising Belong to the polymer of the side chain of double bond.

Negative light-sensitive resin combination the most according to claim 5, wherein, described second compound has oxygen for comprising The polymer of the side chain of alkylidene.

8. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, described second compound It is 0.01～10 relative to the mass ratio of described first compound.

9. described according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, refuse ink combination The containing ratio of the fluorine atom of thing is 5～40 mass %.

10., according to the negative light-sensitive resin combination according to any one of claims 1 to 3, it is also included in 1 molecule tool There are more than 2 olefinic double bonds and not there is the cross-linking agent (E) of acidic-group.

11. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, in all solids composition The first compound be 0.05～10 mass % containing ratio, the second compound is 0.01～5 mass % containing ratio.

12. according to the negative light-sensitive resin combination according to any one of claims 1 to 3, wherein, in all solids composition Described in refuse ink compositions is 0.06～15 mass % containing ratio.

13. 1 kinds of cured film, it is characterised in that it is by the negative photosensitive resin according to any one of claim 1～12 Compositions coats substrate surface, removal solvent (D) exposure.

14. 1 kinds of partition walls, it is characterised in that it comprises the cured film described in claim 13.

15. 1 kinds of optical elements, it is characterised in that it possesses the partition wall described in multiple point and claim 14.