TWI494687B - Photosensitive composition, partition, color filter and organic EL element (2) - Google Patents

Description

Photosensitive composition, partition, color filter, and organic EL device (2) Field of invention

The present invention relates to a photosensitive composition, a partition wall using the same, and a color filter and an organic EL element having the partition wall.

Background of the invention

In recent years, the photosensitive composition is used as a partition between pixels forming a color filter, a partition between pixels of an organic EL (Electro-Luminescence) display element, and an organic TFT (Thin Film Transistor). The material of the permanent film of each of the TFTs of the crystal array, the partition walls of the ITO electrodes of the liquid crystal display element, and the partition walls of the circuit wiring board is attracting attention. For example, when a color filter is manufactured, a partition pattern is formed by lithography (the effect of achieving a black matrix is also obtained), and then R (red) and G (green) are applied to the opening between the partition walls by an inkjet method. And B (blue) ink to form a pixel. In the production of the organic EL device, a partition pattern is formed by using lithography, and a solution such as a hole transport material or a light-emitting material is applied to the opening between the partition walls by an inkjet method to form a hole transport layer and emit light. Pixels such as layers.

In order to prevent color mixture between adjacent pixels of such a color filter and an organic EL element, it is necessary to have ink-repellent properties (i.e., liquid repellency) on the upper surface of the partition wall. Further, in order to prevent white spots from occurring in the color filter and the organic EL element, it is necessary to have a wet property to the ink (that is, lyophilic property) in the opening between the partition walls.

In order to obtain the characteristics required for such a partition, it has been proposed to disclose a photosensitive resin composition containing a copolymer obtained by introducing a fluoroalkyl chain into a system.

Patent Document 1 describes a composition for a partition wall (alkaline development type photosensitive photoresist) containing a vinyl polymer having an ethylenically unsaturated double bond and a fluoroalkyl group. However, it has been found that, depending on the composition of the partition wall composition, the liquid repellency of the surface is extremely high, and the bubbles generated in the developing step are adsorbed on the surface to hinder the development of the unexposed portion, resulting in the final development of the image defect. The form of residual form.

On the other hand, in order to improve the affinity with the developing solution, Patent Document 2 describes a negative photosensitive composition containing a polyoxyalkylene chain to enhance hydrophilicity. Fluoropolymer. It is known that according to the length of the polyoxyalkylene chain exemplified herein, there is a case where the development defect is completely ineffective, and on the other hand, because it increases the affinity of the developing solution, the liquid repellency on the surface of the partition wall Some parts are easily cut off, resulting in a problem of low liquid repellency.

Next, Patent Document 3 describes a composition for a partition wall (alkaline developing type photosensitive resist) containing a vinyl polymer which is introduced into the terminal of the polyoxyalkylene chain. It has a saturated double bond and has a fluoroalkyl group. However, since the polyoxyalkylene chain having a double bond moiety at the terminal is easily fixed to the surface of the partition by exposure and hardening, the behavior of the side chain is restricted, and a sufficient hydrophilic effect is not exhibited.

Patent Document 4 describes a vinyl polymer having an ethylenic unsaturated double bond moiety, a fluoroalkyl group, and an oxyalkylene group. However, these materials are aimed at improving the embossability of the ink on the printing plate in the field of lithography, and the exemplified compounds have no sufficient effect on the development defects.

Prior technical literature

Patent literature

Patent Document 1: International Publication No. 2007/69703

Patent Document 2: Japanese Patent Laid-Open Publication No. 2009-168948

Patent Document 3: International Publication No. 2007/111356

Patent Document 4: Japanese Patent Laid-Open Publication No. 2001-312053

The present invention has been made in order to solve the problems of the prior art, and aims to provide a photosensitive composition capable of forming a non-developing defect and having liquid repellent even after a developing step. The partition wall of the upper surface having good properties and the lyophilic property of the side surface of the partition wall are good, and an opening portion in which the ink is easily wetted and expanded can be formed. Moreover, the present invention has an object of providing a partition wall having good performance by curing the photosensitive composition, and a color filter and an organic EL element having the partition wall.

The present invention provides a photosensitive composition, a partition wall, a color filter, and an organic EL element having the following constitution.

[1] A photosensitive composition comprising a polymer (A), a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond, the polymer (A) At least

a side chain having a group represented by the following formula (1),

-CFXR ^f ...(1)

a side chain having a group represented by the following formula (2),

-(R ¹¹ -O) _n -R ¹² ...(2)

And a side chain having an ethylenic double bond, wherein the symbol in the formula represents the following meaning, X: a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f : may also have an etheric oxygen atom having a carbon number of 1 The above is a fluoroalkyl group or a fluorine atom of 20 or less, R ^{11 is} an alkylene group having 1 to 5 carbon atoms, R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 6 to 30.

[2] The photosensitive composition according to [1], wherein the polymer (A) has a mass average molecular weight of 1.2 × 10 ⁴ or more and 15 × 10 ⁴ or less.

[3] The photosensitive composition according to [1] or [2], wherein the content of the fluorine atom in the polymer (A) is 5% by mass or more and 35% by mass or less.

[4] The photosensitive composition according to any one of [1] to [3] wherein the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) is 5 mass. % or more and 50% by mass or less.

[5] The photosensitive composition according to any one of [1] to [4] wherein the polymer (A) further contains a side chain having an acidic group.

[6] The photosensitive composition according to any one of [1] to [5], which further comprises a crosslinking agent having two or more ethylenic double bonds (D)

[7] The photosensitive composition according to any one of [1] to [6] which further contains a coloring agent (E).

The photosensitive composition of any one of [1] to [7], wherein the content of the polymer (A) is 0.07% by mass or more and 1 mass with respect to the total solid content of the photosensitive composition. %the following.

[9] A partition wall formed by separating a substrate into a plurality of pixel formation intervals, characterized by coating of the photosensitive composition according to any one of [1] to [8] It is composed of a cured film.

[10] A color filter comprising a color filter on a substrate having a complex pixel and a partition wall between adjacent pixels, wherein the partition wall is formed using a partition wall of [9].

[11] An organic EL device is an organic EL device having a complex pixel and a partition wall between adjacent pixels on a substrate, wherein the partition wall is formed using a partition wall of [9].

According to the photosensitive composition of the present invention, it is possible to form a partition wall having a side surface having good liquid repellency and a liquid repellency which is excellent in liquid repellency, and an opening portion in which the ink is easily wetted and spread. Moreover, according to the present invention, it is possible to provide a partition wall having excellent performance by curing the photosensitive composition, and a color filter and an organic EL element having the partition wall.

Form for implementing the invention

The mode for carrying out the invention will be described below, but the invention is not limited by the following embodiments.

In addition, in this specification, unless otherwise indicated, % shows the mass %. Further, the fluorenyl (meth) acrylate group means a general term for both of an acryloyl group and a methacryl fluorenyl group. The (meth) acrylate means a general term for both acrylate and methacrylate. The (meth)acrylic acid means a general term for both of acrylic acid and methacrylic acid. The (meth) acrylamide system means a general term for both of acrylamide and methacrylamide. The (meth)allyl group means a general term for both of an allyl group and a methallyl group. The group represented by the formula (1) is also referred to as a group (1). The other bases are the same.

<1> Photosensitive composition

The photosensitive composition of the present invention is characterized by comprising a polymer (A), a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond, the polymer (A) a side chain having a group represented by the following formula (1), a side chain having a group represented by the following formula (2), and a side chain having an ethylenic double bond,

-CFXR ^f ...(1)

(In the formula (1), X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f is a fluoroalkyl group or a fluorine atom which may have an etheric oxygen atom of 1 or more and 20 or less)

a side chain of a group represented by the following formula (2),

-(R ¹¹ -O) _n -R ¹² ...(2)

(In the formula (2), R ¹¹ is an alkylene group having 1 to 5 carbon atoms, R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 6 to 30)

(1) Polymer (A)

Since the polymer (A) contained in the photosensitive composition of the present invention contains the side chain having the above-mentioned group (1), the coating film formed by applying the photosensitive composition of the present invention on the substrate is dried. It is easy to move to the vicinity of the surface of the film. Further, since the polymer (A) contains a side chain having an ethylenic double bond, hardening proceeds during exposure, and is easily immobilized in the vicinity of the surface of the coating film. Further, since the side chain having the above-mentioned group (2) is contained, the bubbles generated during development are prevented from being adsorbed on the surface of the coating film, and the development defects considered to be caused by bubble adsorption can be prevented. Therefore, the partition wall formed by developing the exposed coating film has no development defects and only exhibits liquid repellency on the partition walls. Therefore, when the ink is applied to the opening surrounded by the partition wall by the inkjet method, color mixing can be suppressed between the adjacent openings. Moreover, since the lyophilic property of the side wall and the opening of the partition wall can be ensured, the ink wettability in the opening portion is good, and white spots can be suppressed.

Here, the mass average molecular weight (Mw) of the polymer (A) is preferably 1.2 × 10 ⁴ to 15 × 10 ^{4 , more} preferably 3.0 × 10 ⁴ to 12 × 10 ⁴ , and more preferably 5.5 × 10 ⁴ to 11 ×10 ⁴ is especially good. The number average molecular weight (Mn) of the polymer (A) is preferably 1.0 × 10 ⁴ to 7.0 × 10 ^{4 , more} preferably 2.5 × 10 ⁴ to 6.0 × 10 ⁴ .

Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification mean values measured by using gel permeation chromatography and using polystyrene as a standard substance.

When the mass average molecular weight of the polymer (A) is less than 1.2×10 ⁴ , the lyophilicity of the opening between the partition walls may be insufficient, and when the ink is applied by the inkjet method, the ink may not sufficiently wet and expand. When the mass average molecular weight is more than 15 × 10 ⁴ , the alkali solubility and developability may be insufficient. Further, when the number average molecular weight of the polymer (A) is less than 1.0 × 10 ⁴ , the lyophilicity of the opening between the partition walls may be insufficient, and when the ink is applied by the inkjet method, the ink may not sufficiently wet and expand. Sex. Further, when the mass average molecular weight (Mw) is from 3.0 × 10 ⁴ to 12 × 10 ⁴ , regardless of the type and concentration of the alkali and the spray conditions, it is easy to keep the liquid repellency high, and the manufacturing margin is expanded. Preferably. Further, it is also preferable in terms of ease of production of the polymer (A).

The molecular weight distribution (mass average molecular weight / number average molecular weight) of the polymer (A) is preferably 8 or less, more preferably 4 or less. In this range, the developability is good. The lower limit of the molecular weight distribution is not particularly limited, and from the viewpoint of easy synthesis and affinity with a developing solution, it is preferably 1.5 or more.

Further, the adjustment of the molecular weight of the polymer (A) will be described in the method for producing the polymer (A) to be described later.

The content of the fluorine atom in the polymer (A) is preferably 5 to 35% by mass, more preferably 10 to 30% by mass. When the content of the fluorine atom is less than 5% by mass, the liquid repellency of the upper surface of the partition wall may be insufficient. When it exceeds 35% by mass, the adhesion between the partition wall and the substrate may be lowered. Further, the content of the fluorine atom in the polymer (A) can be adjusted by the amount of introduction of the side chain having the group (1) mainly described below in the polymer (A).

The polymer (A) used in the present invention has a fluorine atom-containing group (1) represented by the above formula (1) in a side chain. In the case where the group (1) and the ^Rf group may have a fluoroalkyl group having 1 to 20 carbon atoms of an etheric oxygen atom, the ^Rf group may have a halogen atom other than the fluorine atom. As such a halogen atom, a chlorine atom is preferred.

In addition, the structure of the fluoroalkyl group is not particularly limited, and examples thereof include a linear structure, a branching structure, a ring structure, and a partial structure having a ring, and a linear structure is preferred. Further, when R ^f is a fluoroalkyl group having an etheric oxygen atom, the etheric oxygen atom may be present between the carbon-carbon bonds of the fluoroalkyl group or may be present at the terminal of the fluoroalkyl group.

R ^f as the group (1) is preferably a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom. Further, X is particularly preferred as a fluorine atom.

In the above-mentioned group (1), when R ^f is a fluoroalkyl group having 1 to 20 carbon atoms of an etheric oxygen atom, R ^f is not particularly limited as long as it has such a configuration. Specific examples of R ^f include -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 , -CF(CF ₃ )O(CF ₂ ) ₅ CF ₃ , -CF ₂ O(CF ₂ CF ₂ O) _p CF ₃ (p system 1~8 Integer), -CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _q C ₆ F ₁₃ (q is an integer from 1 to 4), -CF(CF ₃ )O(CF ₂ CF(CF _{3 )} )O) _r C ₃ F ₇ (r is an integer of 1 to 5) and the like.

When R ^f is a fluoroalkyl group having an etheric oxygen atom having 1 or more carbon atoms and 20 or less carbon atoms, R ^f is a perfluoroalkyl group having no etheric oxygen atom and a perfluoro group having an etheric oxygen atom. An alkyl group is preferred, and a perfluoroalkyl group having no etheric oxygen atom is more preferred. The carbon number is preferably from 1 to 11, and particularly preferably from 3 to 5.

Among the above groups (1), in the present invention, a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferred, and a perfluoroalkyl group is particularly preferred. Further, the perfluoroalkyl group and the polyfluoroalkyl group also include those having an etheric oxygen atom. Further, as the polyfluoroalkyl group having one hydrogen atom, a compound in which X is a hydrogen atom is preferred. As a result, the partition wall formed by using the photosensitive composition of the present invention has a good liquid repellency on the upper surface.

Further, the base (1) is preferably a carbon number of 4 to 6. Specific examples of such a group (1) include -(CF ₂ ) ₃ CF ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -CF ₂ O(CF ₂ ) ₂ OCF. ₃ , -CF ₂ O(CF ₂ ) ₂ O(CF ₂ ) ₂ OCF ₃ and the like. When the number of carbon atoms of the group (1) in the side chain of the polymer (A) is 4 to 6, the compatibility between the polymer (A) and other components constituting the photosensitive composition can be improved, so that it is possible to suppress borrowing. The aggregation of the polymer (A) in the coating film formed by applying the photosensitive composition can result in formation of a partition wall having a good appearance.

Further, in the polymer (A), the number of introductions of the group (1) having the side chain of the group (1) was 1. In the side chain having the group (1) of each of the polymers (A), the groups (1) may be the same or different. In other words, the polymer (A) may have one type of the group (1) in the side chain, or a combination of two or more types. Further, in the polymer (A) used in the present invention, the group (1) may be introduced into all of the side chains, but it is preferred to appropriately adjust the introduced group so as to have the above fluorine atom content. The ratio of the side chain to the entirety of the polymer (A). Specifically, when the polymer (A) is produced by polymerization of a raw material monomer to be described later, the amount of the monomer having the group (1) with respect to the entire raw material monomer is adjusted. Further, the side chain having the group (1) may be directly formed by a polymerization reaction or may be formed by chemical conversion after the polymerization reaction.

Further, the polymer (A) used in the present invention has a group (2) having a polyoxyalkylene chain represented by the above formula (2) in a side chain. The polyoxyalkylene chain means a moiety represented by -(R ¹¹ -O) _n -. The polyoxyalkylene chain is preferably a chain having hydrophilicity, and particularly preferably 50 to 100% of the number of n oxygen-extended alkyl groups present is an oxyethylene group. The polyoxyalkylene chain having an oxygen-extended ethyl group can exert good hydrophilicity.

In addition, the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) used in the present invention is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. It is particularly good at 15 to 35 mass%. When the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) is less than 5% by mass, the adsorption of bubbles generated during development cannot be sufficiently suppressed on the surface of the coating film, resulting in Finally, the partition wall and the partition opening portion which are obtained have a large number of development defects. Further, when the ratio of the polymerization unit is more than 50% by mass, the liquid repellency may be lowered. When the ratio of the polymerized unit containing the group represented by the above formula (2) is in this range, the position of the group (2) (the group having a polyoxyalkylene group) around the polymer (A) is uniformly distributed. And the performance is stable.

In the above group (2), R ¹¹ is an alkylene having 1 to 5 carbon atoms, and preferably 50 to 100% of the number of n of R ¹¹ present is an ethylene group. The R ¹¹ group other than the ethyl group is preferably a C 3-5 alkylene group, particularly preferably a propyl group. Further, the structure of the alkyl group having 3 to 5 carbon atoms may be a linear structure or a branched structure. Among the n R ¹¹ , when the ratio of the number of alkyl groups other than the ethyl group is large, the effect as a hydrophilic group is reduced, and the effect that the bubbles are not easily adsorbed at the time of development is lowered, resulting in an increase in development defects. Of the n number of R ¹¹ present, 80 to 100% of the ethyl group is more preferably ethylidene, and particularly 100% of the ethyl group is particularly preferred. That is, the polyoxyalkylene chain is particularly preferred as a polyoxyalkylene chain.

-(R ¹¹ -O) _n - is an oxygen-extended alkyl group other than an oxygen-extended ethyl group and an oxygen-extended ethyl group. The group (2) is a block copolymer chain of an oxygen-extended ethyl group and another oxygen-extended alkyl group. It is better.

Further, in the group (2), the number of repetitions of the oxygen-extended alkyl group represented by -R ¹¹ -O- is 6 to 30, preferably 8 to 25. When n is 6 or more, since it has a hydrophilic effect, the wettability of the developing liquid can be improved, and bubble adsorption and stabilization can be suppressed. When n is 30 or less, the base (2), that is, the polyoxyalkylene chain is uniformly distributed in the surface of the film.

Here, n in the group (2) is a value used as an average value between the polymerization units containing the group (2) of the polymer (A).

Further, in the group (2), a terminal group bonded to the polyoxyalkylene chain: -(R ¹¹ -O) _n -: R ¹² is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. When it is bonded to a reactive group such as a hydroxyl group at the terminal group of the polyoxyalkylene chain, the other reactive groups are modified at the same time, and the effect of introducing the polyoxyalkylene chain is reduced. Sex. Further, when the carbon number of the terminal group: R ¹² is 5 or more, since the hydrophobicity is increased, the effect of introducing an oxygen-extended alkyl chain of the hydrophilic group is lowered.

The ethylenic double bond which the polymer (A) used in the present invention has in the side chain is not particularly limited, and examples thereof include a (meth)acryl fluorenyl group, an allyl group, a vinyl group, a vinyloxy group, and the like. Addition polymerizable group.

The content of the ethylenic double bond in the polymer (A) is preferably 1.0 to 5.0 mmol/g, more preferably 1.2 to 2.5 mmol/g. In this range, the immobilization and development of the polymer (A) to the partition walls are good.

The polymer (A) may further contain a side chain having an acidic group as necessary. Thereby, the polymer (A) which is not hardened at the time of exposure is easily removed from the upper surface of the partition wall at the time of development. Therefore, it is possible to suppress the unhardened polymer (A) from flowing out to the opening portion during post-baking, and it is possible to improve the lyophilicity of the opening portion. Further, the acid group of the polymer (A) in the side chain may be one type or two or more types.

The acidic group to be introduced into the polymer (A) is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. In the polymer (A) used in the present invention, when the polymer (A) is produced by polymerization of a raw material monomer, the obtained polymer can be obtained by polymerization with respect to the entire raw material monomer. The amount of the monomer (A) to be adjusted to the following preferable acid value is appropriately adjusted by adjusting the amount of the monomer having an acidic group.

The acid value of the polymer (A) is preferably 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. When the acid value is in this range, the polymer (A) which is not immobilized at the time of exposure is easily removed from the upper surface of the partition wall during development. Here, the acid value is the mass [mg] of potassium hydroxide necessary for neutralizing 1 g of the sample, and in the present specification, the unit is described as mgKOH/g.

Further, the side chain system having an acidic group can be directly formed by a polymerization reaction or can be formed by chemical conversion after the polymerization reaction.

(Manufacture of polymer (A))

In the present invention, the polymer (A) can be obtained by using a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, and a monomer having an acidic group as necessary. And/or other monomers are copolymerized to obtain a copolymer (precursor of the polymer (A)), and the copolymer has a functional group and an ethyl group having a reactive group capable of bonding to the copolymer. The compound of the double bond is reacted to synthesize.

The monomer having the above-mentioned group (1) used for the production of the polymer (A) is preferably a compound represented by the following formula (3). These may be used alone or in combination of two or more.

CH ₂ =CR ⁴ -COO-Y-CFXR ^f ...(3)

(wherein R ⁴ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a trifluoromethyl group, a Y-based single bond or a divalent organic group having a carbon number of 1 to 6 and having no fluorine atom; -CFXR ^f is a group corresponding to the above group (1), that is, an X-based hydrogen atom, a fluorine atom or a trifluoromethyl group, and the R ^f system may have an etheric oxygen atom and a carbon number of 1 to 20 fluorocarbon. Base or fluorine atom)

Further, the preferred aspect of the above-mentioned compound (3)-CFXR ^f is the same as that described above for the group (1).

Among the groups represented by the above formula (3) and Y, Y which is a divalent organic group having no fluorine atom and having 1 to 6 carbon atoms is -R ⁵ -, -R ⁵ -NR ⁶ -SO ₂ -, -R ⁵ -NR ⁶ -CO-, -CH ₂ CH(OH)-R ⁷ - (R ⁵ is an alkylene group having 1 to 6 carbon atoms, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a A single bond or an alkylene group having 1 to 4 carbon atoms. However, when R ⁶ is a methyl group, the carbon number of R ⁵ bonded to NR ⁶ is 1 to 5).

Specific examples of R ⁵ include -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH. (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH ₂ -, -CH(CH ₂ CH(( CH ₃ ) ₂ )-etc. Specific examples of R ⁷ 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 )-, and the like.

Among these, as the Y of the compound (3), an alkylene group having 2 to 4 carbon atoms is preferred from the viewpoint of easy availability.

Further, as R ^{4 of the} compound (3), a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group is preferred, and a hydrogen atom or a methyl group is particularly preferred. That is, the compound (3) is particularly preferably a (meth) acrylate.

The compound represented by the formula (3) is preferably a (meth) acrylate in which -CFXR ^f is a perfluoroalkyl group having 4 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms. . Specific examples thereof include 2-(perfluorohexyl)ethyl (meth)acrylate and 2-(perfluorobutyl)ethyl (meth)acrylate.

As the monomer having the above-mentioned group (2) used for the production of the polymer (A), a compound represented by the following formula (4a) or (4b) is preferred. These may be used alone or in combination of two or more.

CH ₂ =CR ¹⁰ -COO-(WO) _q -(R ¹¹ -O) _n -R ¹² (4a)

CH ₂ =CR ¹⁰ -O-(WO) _q -(R ¹¹ -O) _n -R ¹² (4b)

(In the formulae (4a) and (4b), R ¹⁰ is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group substituted with an aromatic group having 7 to 20 carbon atoms. a group, an aromatic group having 6 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. W is a divalent organic group having 1 to 10 carbon atoms and having no fluorine atom. q is 0 or 1. (R ¹¹ -O) _{n -} R ¹² is a group corresponding to the above-mentioned group (2).

The preferred aspects of (R ¹¹ -O) _n -R ¹² in the above compounds (4a) and (4b) are the same as those described in the above group (2).

When -(WO) _q -, q of the compounds (4a) and (4b) is 0, it means a single bond. When q is 1, -(WO) _q - is an organic group having an oxygen atom on the R ¹¹ side. When q is 1, W is preferably a divalent hydrocarbon group having 2 to 10 carbon atoms, an alkylene group having 2 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, and a stretching ratio of 5 or 6 carbon atoms. It is preferred that the alkyl group having a carbon number of 1 to 2 on both sides or one side of the cycloalkyl group has a total of from 6 to 10 carbon atoms of the cycloalkyl group. However, when the W system and R ¹¹ are the same alkylene group, the q system is regarded as 0.

Further, R ^{10 of the} compounds (4a) and (4b) is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

In the production of the polymer (A), a commercially available product can be used as the above-mentioned compounds (4a) and (4b) used for the purpose of introducing the group (2) into the side chain. As such a commercial item, for example, BLEMMER-PME-400 (trade name, manufactured by Nippon Oil & Fats Co., Ltd., CH ₂ = C(CH ₃ )COO(CH ₂ CH ₂ O) _n CH ₃ : n-type in the formula The average value between the molecules is shown, n is about 9), NK ESTER M-230G: (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., CH ₂ = C(CH ₃ )COO(CH ₂ CH ₂ O) _n CH ₃ : In the formula, n represents an average value between molecules, and n is about 23).

The monomer having a reactive group used for the production of the polymer (A) is not particularly limited, and examples thereof include a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, and an epoxy group. Monomers, etc. These may be used alone or in combination of two or more. Further, a single system having a reactive group is preferably substantially free of the group (1).

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4- Hydroxybutyl ester, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 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-methylol (meth) acrylamide, N, N-bis(hydroxymethyl) (meth) acrylamide, and the like.

Further, the monomer having a hydroxyl group may have a polyoxyalkylene chain having a terminal hydroxyl group, and examples thereof include CH ₂ =CHOCH ₂ C ₆ H ₁₀ CH ₂ O(CH ₂ CH ₂ O) _k H, CH ₂ =CHOC ₄ H ₈ O(CH ₂ CH ₂ O) _k H, CH ₂ =CHCOOCH ₂ CH ₂ O(CH ₂ CH ₂ O) _k H,CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ O(CH ₂ CH ₂ O) _k H, CH ₂ =CHCOOCH ₂ CH ₂ O(CH ₂ CH ₂ O) _m (C ₃ H ₆ O) _j H,CH ₂ =C(CH ₃ )COOC ₂ H ₄ O(CH ₂ CH ₂ O _m (C ₃ H ₆ O) _j H (k is an integer of 1 to 100, m is an integer of 0 to 100, j is an integer of 1 to 100, m + j is 1 to 100). Further, the above C ₆ H ₁₀ is a cyclohexyl group, the C ₄ H ₈ is an exobutyl group, and the C ₃ H ₆ is a propyl group.

k is preferably an integer of 1 to 30, m is preferably an integer of 0 to 30, j is preferably an integer of 1 to 30, and m+j is preferably an integer of 1 to 30.

Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, and methyl-5-nor. Aceene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl-succinic anhydride Wait.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and the like.

Examples of the monomer having an epoxy group include glycidyl (meth)acrylate and methyl 3,4-epoxycyclohexylmethacrylate.

In the production of the polymer (A), a monomer having a carboxyl group as required, a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, and the like can be given. These may be used alone or in combination of two or more. Further, as the monomer having an acidic group, a monomer having a carboxyl group is used, and when a monomer having a reactive group is used, a monomer having a carboxyl group is also used, and finally, an ethylenic double bond is not introduced and a carboxyl group is used. The residue is considered as a monomer.

Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene; and one or more hydrogen atoms of the benzene ring of the substance are methyl, ethyl, and n-butyl An alkoxy group such as an alkyl group, a methoxy group, an ethoxy group or a n-butoxy group, a halogen atom, a haloalkyl group having one or more halogen atoms, a nitro group, a cyano group or a decylamino group. Compounds and the like.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, and 2-hydroxy-3-(methyl)allyloxypropanesulfonic acid. 2-sulfonic acid ethyl (meth)acrylate, 2-sulfonic acid propyl (meth)acrylate, 2-hydroxy-3-(meth)acryloxypropane sulfonic acid, 2-(methyl) Acrylamide-2-methylpropane sulfonic acid and the like.

Examples of the monomer other than the above which can be arbitrarily used in the production of the polymer (A) include hydrocarbon olefins, vinyl ethers, isopropylene ethers, allyl ethers, vinyl esters, and allyl esters. , (meth) acrylates, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes, and wires modified with one end using a (meth) acrylonitrile group When considering the heat resistance of the partition wall, it is preferable to use a (meth) acrylate or a (meth) acrylamide. Further, these compounds may have a functional group such as a carbonyl group or an alkoxy group.

To produce the polymer (A) used in the present invention, it is possible to appropriately select a monomer which provides polymerization from the monomer described above and copolymerize it at an appropriate ratio. Further, a preferred blending ratio of the various monomers used in the production of the polymer (A) is as follows.

The ratio of the mass ratio of the monomer having the group (1) to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably from 5 to 80% by mass, more preferably from 25 to 60% by mass. When the ratio is too low, the polymer (A) is difficult to move to the vicinity of the upper surface of the partition wall formed by using the photosensitive composition of the present invention, and the liquid repellency on the partition wall is insufficient. When the ratio is too high, the adhesion between the partition walls and the substrate is lowered.

The ratio of the mass ratio of the monomer having the group (2) to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass. When it is in this range, the wettability of the developing liquid can be improved, and bubble adsorption and stabilization can be suppressed. Further, in the surface of the film, the position where the group (2) (i.e., the polyoxyalkylene chain) exists is uniformly distributed.

The ratio of the mass ratio of the monomer having a reactive group to the ratio of the polymer (A) into which the ethylenic double bond is introduced by the reactive group described later is converted to the total mass of the monomer to be copolymerized. It is preferably 5 to 50% by mass, more preferably 10 to 35% by mass. In this range, the ethylenic double bond system introduced through the reactive group and introduced by the method described later may have an appropriate amount in the polymer (A), specifically, 1.0 to 5.0 mmol/g, and 1.2. The amount of ～2.5 mmol/g is more preferable, and the immobilization and development of the polymer (A) to the partition walls become good.

In the case of copolymerization, when a monomer having an acidic group is used as necessary, the mass ratio of the monomer having an acidic group is the acid of the finally obtained polymer (A) with respect to the total mass of the copolymerized monomer. The value is preferably in the above preferred range, specifically, in the range of 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. Such a ratio depends on the type of the monomer having an acidic group, and is preferably 2 to 20% by mass, more preferably 4 to 12% by mass. In this range, the polymer (A) which is not hardened upon exposure is easily washed away from the partition wall during development.

In the case of the copolymerization, if a monomer other than the above is used as necessary, the other monomer mass ratio is converted into an ethylene double in terms of the total amount of the monomer copolymerized. The ratio of the polymer (A) of the bond is preferably 50% by mass or less, more preferably 30% by mass or less. When the ratio of the mass exceeds 50% by mass, the basic developability may be lowered.

a copolymer containing a side chain having a group (1), a side chain having a group (2), a side chain having a reactive group, and optionally containing a side chain having an acidic group and/or another side chain, can be borrowed Heating by dissolving a monomer having a group (1), a monomer having a group (2), a monomer having a reactive group, a monomer having an acidic group as necessary, and/or other monomer in a solvent, and The polymerization initiator is added and copolymerized to synthesize. Further, in the case of copolymerization, it is preferred to add a chain transfer agent as necessary. Further, a monomer, a polymerization initiator, a solvent, and a chain transfer agent may be continuously added.

Examples of the solvent used in the copolymerization include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; acetone, methyl isobutyl ketone, and cyclohexanone. Ketones such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; 2-(2-methoxyethoxy)ethanol, 2-(2) - ethoxylated alcohols such as ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl propionate, Esters of n-butyl alkanolate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, triacetin, etc.; diethylene glycol Methyl ether, diethylene glycol ethyl methyl ether, and the like.

As a polymerization initiator, a well-known organic peroxide, an inorganic peroxide, an azo compound, etc. are mentioned. An organic peroxide or an inorganic peroxide may be used in combination with a reducing agent as a redox catalyst. These polymerization initiators may be used alone or in combination of two or more.

Examples of the organic peroxide include benzammonium peroxide, laurel peroxide, isobutylammonium peroxide, t-butyl hydroperoxide, and tert-butyl-α-isopropylbenzene peroxide. Examples of the inorganic peroxide include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonate. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis (2,4-). Dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-dimethyl azobisbutyrate, 2,2'-azobis(2-amidinopropane) dihydrochloride, and the like.

Examples of the chain transfer agent include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl acetate, 2-ethylhexyl acetate, 2-hydrogenthioethanol, and the like. Mercaptans; alkyl halides such as chloroform, carbon tetrachloride, and carbon tetrabromide.

The polymer (A) is a copolymer which can be obtained as a precursor of the polymer (A), a functional group having a reactive group capable of bonding to the copolymer, and ethylene. The compound of the double bond is reacted to synthesize.

The combination of the reactive group of the above-mentioned copolymer and a compound having a functional group capable of bonding the reactive group to an ethylenic double bond may, for example, be the following combination.

(a) a hydroxyl group, an anhydride having an ethylenic double bond,

(b) a compound having a hydroxyl group, an isocyanate group, and an ethylenic double bond,

(c) a compound having a hydroxyl group, an acyl chloride group and an ethylenic double bond,

(d) an acid anhydride, a compound having a hydroxyl group and an ethylenic double bond,

(e) a compound having a carboxyl group, an epoxy group, and an ethylenic double bond,

(f) a compound having an epoxy group, a carboxyl group, and an ethylenic double bond.

As the acid anhydride having an ethylenic double bond in the above (a) combination, those exemplified as the above-mentioned monomer having a reactive group can be used. Examples of the compound having an isocyanate group and an ethylenic double bond in the above (b) combination include ethyl 2-(methyl) propylene oxy isocyanate and 1,1-bis ((meth) propylene oxyfluoride). Methyl) isocyanate ethyl ester or the like. Examples of the compound having a fluorenyl group and an ethylenic double bond in the above (c) combination include (meth) acrylonitrile and the like.

As the compound having a hydroxyl group and an ethylenic double bond in the above (d) combination, those exemplified as the monomer having a hydroxyl group can be used. As the compound having an epoxy group and an ethylenic double bond in the above (e) combination, those exemplified as the above-mentioned monomer having an epoxy group can be used. As the compound having a carboxyl group and an ethylenic double bond in the above (f) combination, those exemplified as the monomer having a carboxyl group can be used. In addition, as the reaction of the above (f), a reactive group such as a hydroxyl group generated after the reaction may be used, and if necessary, an acid anhydride or the like may be used.

Further, a copolymer containing a side chain having a group (1), a side chain having a group (2), a side chain having a reactive group, and a side chain having an acidic group as necessary, and a reaction capable of reacting When the compound having a functional group bonded to the ethylenic double bond is reacted with a compound having a functional group capable of bonding the reactive group and a compound having an ethylenic double bond with respect to the reactive group of the copolymer The ratio is preferably 0.5 to 2.0, more preferably 0.8 to 1.5. When the equivalent ratio is in this range, the content of the ethylenic double bond in the polymer (A) is sufficient to be the above preferred range, specifically 1.0 to 5.0 mmol/g, more preferably 1.2 to 2.5 mmol/ The amount of g. When the equivalent ratio is less than 0.5, the content of the ethylenic double bond in the polymer (A) cannot be an appropriate amount, and the polymer (A) is hardly immobilized in the vicinity of the upper surface of the partition wall, and the lyophilic portion of the opening surrounded by the partition wall is lyophilic. In the case where the properties are insufficient, when the amount exceeds 2.0, the amount of unreacted compounds increases, and the appearance of the partition wall is low.

The polymer (A) is a copolymer capable of containing a side chain having a side chain of the group (1), a side chain having a group (2), a side chain having a reactive group, and a side chain having an acidic group as necessary And a compound having a functional group capable of bonding the reactive group of the copolymer and an ethylenic double bond, dissolved in a solvent according to the combination of the above (a) to (f), and used in accordance with each combination The previously known conditions allow the reaction to be synthesized.

The content of the polymer (A) in the total solid content of the photosensitive composition of the present invention is preferably from 0.07 to 1% by mass, more preferably from 0.1 to 0.5% by mass. When the content of the polymer (A) is less than 0.07% by mass, the liquid repellency of the upper surface of the partition wall formed by using the photosensitive composition of the present invention may be insufficient. When the content exceeds 1% by mass, the partition wall and the substrate are dense. There is a low level of sexuality.

(2) Photopolymerization initiator (B)

The photopolymerization initiator (B) contained in the photosensitive composition of the present invention can be used without any particular limitation as a photopolymerization initiator used in a general radical-curable photosensitive composition.

The photopolymerization initiator (B) is not particularly limited as long as it is a compound which generates a radical by irradiation with light, and examples thereof include benzoin, acetonide, methylphenyl glyoxylate, 9,10- A-diketones such as phenanthrene; acyloin of benzoin; acetoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (acyloin ether) class; 9-oxygen sulfur (thioxanthone), 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur 9-oxosulfuric acid such as 4-sulfonic acid Diphenyl ketones such as diphenyl ketone, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone; Ketone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, pair Methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2- Phenyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)-butan-1-one; anthraquinones such as hydrazine, 2-ethylhydrazine, camphorquinone, and 1,4-naphthoquinone; 2-dimethylaminobenzoic acid Ethyl ester, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzene Aminobenzoic acid such as 2-ethylhexyl formate; halogen compound such as phenacyl chloride or trihalomethylphenylhydrazine; fluorenylphosphine oxide; a peroxide such as butyl; 1-[4-(phenylthio)-1,2-octanedione 2-(0-benzamide)], 1-[9-ethyl-6-(2) -Methylbenzylidene)-9H-carbazolyl-3-yl]-ethanone-1-(O-acetamidine), or two or more types may be used in combination.

Among these, the photopolymerization initiator (B) used in the present invention is preferably a compound represented by the following formula (5).

[Chemical 1]

(wherein R ²¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group substituted or unsubstituted with 6 to 6 carbon atoms; A phenyl group of 20 is a phenoxy group having 6 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group, a hydrogen atom of R ²² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a phenyl group. a phenyl group having 6 to 20 carbon atoms substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, a benzamidine group having 7 to 20 carbon atoms substituted or unsubstituted, or a carbon number of 2 to 12 The alkoxycarbonyl group is an alkyl group substituted or unsubstituted phenyloxycarbonyl group having 7 to 20 carbon atoms, R ²³ is an alkyl group having 1 to 12 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each Independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group having 3 to 8 carbon atoms substituted or unsubstituted with an alkyl group, a phenyl group having 6 to 20 carbon atoms substituted or unsubstituted, or carbon 2 to 20 alkyl alkane groups, alkyl substituted or unsubstituted benzylidene groups having 7 to 20 carbon atoms, alkyl substituted or unsubstituted benzylcarbonyl groups having 7 to 20 carbon atoms, substituted by alkyl groups Or an unsubstituted alkoxycarbonyl group having 2 to 12 carbon atoms, an alkyl group substituted or unsubstituted, and having 7 to 20 carbon atoms Phenoxycarbonyl group, acyl group or nitro group having a carbon number 1 to 20)

The compound represented by the formula (5), preferably R ²¹ , is an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted, and a methyl group is exemplified. , ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, phenyl, and the like. Among these, an alkyl group having 1 to 4 carbon atoms is preferred, an alkyl group having 1 or 2 carbon atoms is more preferred, and a methyl group is particularly preferred.

The compound represented by the formula (5), preferably R ²² , is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group or a butyl group. Base, pentyl, hexyl, heptyl, octyl, decyl, decyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl. Among them, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is particularly preferred.

The compound represented by the formula (5), and the alkyl group having 1 to 12 carbon atoms represented by R ²³ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group. Octyl, decyl, decyl, undecyl, dodecyl and the like. Among these, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 2 to 6 carbon atoms is more preferred, and ethyl is particularly preferred.

In the compound represented by the formula (5), as R ²⁴ , R ²⁶ and R ²⁷ , a hydrogen atom is preferred.

The compound represented by the formula (5), as R ²⁵ , is an alkyl substituted or unsubstituted benzylidene group having 7 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 7 to 20 carbon atoms. The benzylcarbonyl group is preferably a 2-methylbenzhydryl group, a benzylcarbonyl group or a 1,3,5-trimethylbenzylcarbonyl group.

The compound (O-anthracene compound) represented by the formula (5) is not particularly limited, and in the formula (5), R ²¹ is a phenyl group, R ²² is an octyl group, and R ²³ is an alkyl group. a compound wherein R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom and R ²⁵ is a benzamidine group; R ²¹ is a methyl group; R ²² is a butyl group, a heptyl group or an octyl group, and R ²³ is an ethyl group; R ²⁴ R ²⁶ and R ²⁷ are a hydrogen atom, and R ²⁵ is a benzamidine group; R ²¹ is a phenyl group; R ²² is an octyl group; R ²³ is an ethyl group; and R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom; R ²⁵ is a 2-methylbenzhydryl group; R ²¹ is a methyl group; R ²² is a methyl group or an octyl group; R ²³ is an ethyl group; R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom, and R ²⁵ is a compound of 2-methylbenzhydryl; R ²¹ and R ²² are methyl, R ²³ is ethyl, R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom, and R ²⁵ is a 2-methyl-5-tetrahydrofuranyl group. A compound of methoxybenzimidyl, 2-methyl-4-tetrahydrofurylmethoxybenzylidene or 2-methyl-5-tetrahydrofuranylmethoxybenzylidene.

A commercially available product can be used as the photopolymerization initiator (B). As a commercial item, for example, OXE02 (trade name, manufactured by CIBA SPECIALTY CHEMICALS, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl) -Ethyl ketone-1-(O-acetamidine): in the above formula (5), R ²¹ and R ²² are a methyl group, R ²³ is an ethyl group, and R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom. R ²⁵ is a compound of 2-methylbenzhydryl group).

The content of the photopolymerization initiator (B) in the total solid content of the photosensitive composition of the present invention is preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass. In this range, the hardenability is good, and the pattern and line width close to the mask pattern can be formed by exposure and development.

Further, 2-hydroxythiobenzimidazole and 2-hydrothiobenzoate are simultaneously used together with the photopolymerization initiator (B). Azole, 2-hydrothiobenzothiazole, 1,4-butanol bis(3-hydrothiobutyrate), ginseng (2-methylhydrothiopropenyloxyethyl)isocyanuric acid When a thiol compound such as an ester or neopentyl sterol (3-hydrogenthiobutyrate) exhibits sensitization effect.

(3) Photosensitive resin (C)

The photosensitive resin (C) contained in the photosensitive composition of the present invention is a photosensitive resin having an acidic group and an ethylenic double bond, and is a radical generated by the photopolymerization initiator (B). The film is cured and hardened to form a cured film, and the cured film is capable of alkaline development.

Since the photosensitive resin (C) has an acidic group and an ethylenic double bond in one molecule, it is possible to selectively remove the unexposed portion of the photosensitive composition which is not cured by using an alkaline developing solution. Form the next door. Further, the compound other than the photosensitive resin (C)-based polymer (A) preferably contains no group (1).

The acidic group having the photosensitive resin (C) is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group, and two or more kinds thereof may be used in combination.

The ethylenic double bond of the photosensitive resin (C) is not particularly limited, and examples thereof include an addition polymerizable group such as a (meth)acryl fluorenyl group, an allyl group, a vinyl group, or a vinyloxy group. Two or more types of double bonds can be used in combination. Further, part or all of the hydrogen atoms of the addition polymerizable group may be substituted with a hydrocarbon group, preferably a methyl group.

The photosensitive resin (C) is not particularly limited, and specific examples thereof include a resin (C-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an ethylenic double bond introduced into the epoxy resin. And an acid-based resin (C-2). These may be used alone or in combination of two or more.

The resin (C-1) can be synthesized in the same manner as the polymer (A) except that the monomer having the monomer having the group (1) is not used. In addition, the monomer having a phosphate group is not particularly limited, and examples thereof include 2-(meth)acryloxymethoxyethane phosphate.

The resin (C-2) can be synthesized, for example, by reacting an epoxy group with a compound having a carboxyl group and an ethylenic double bond, and then reacting it with a polyvalent carboxylic acid or an anhydride thereof. Specifically, an epoxy resin can be reacted with a compound having a carboxyl group and an ethylenic double bond, and a carboxyl group can be reacted with an epoxy group of the epoxy resin to introduce an ethylenic double bond. Subsequently, the carboxyl group can be introduced by reacting a hydroxyl group of the resin into which the ethylenic double bond is introduced with a polyvalent carboxylic acid or an anhydride thereof.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and phenolic methane ring. An epoxy resin, an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (6), an epoxy resin represented by the following formula (7), and the following formula (8) ) The epoxy resin represented by the like.

[Chemical 2]

(In the formula, s is 1 to 50, preferably 2 to 10)

[Chemical 3]

(wherein R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10)

[Chemical 4]

(In the formula (8), the hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent. The system is 0 to 10)

Further, when an epoxy resin represented by the formula (6), the formula (7) or the formula (8) is reacted with a compound having a carboxyl group and an ethylenic double bond, and then reacted with a polyvalent carboxylic anhydride, The polyvalent carboxylic anhydride is preferably a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. At this time, the molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride to the tetracarboxylic dianhydride.

Commercial products of a resin (C-2) obtained by introducing an acidic group and an ethylenic double bond into an epoxy resin include KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, and CCR-1163H. , CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR -1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H (above, manufactured by Nippon Kayaku Co., Ltd.).

The photosensitive resin (C) used in the present invention preferably has a mass average molecular weight of from 1.5 × 10 ³ to 20 × 10 ^{3 and more} preferably from 2.0 × 10 ³ to 15 × 10 ³ . When the mass average molecular weight is less than 1.5 × 10 ³ , the curing at the time of exposure is insufficient, and when it exceeds 20 × 10 ³ , the development property may be lowered.

The number of the ethylenic double bonds of the photosensitive resin (C) is preferably 3 or more in an average of 1 molecule, and more preferably 6 or more. When the number of the ethylenic double bonds is three or more, the difference in alkali solubility between the exposed portion and the unexposed portion is easily increased, and a fine pattern can be formed with a small amount of exposure.

The photosensitive resin (C) preferably has an acid value of 10 to 300 mgKOH/g, more preferably 30 to 150 mgKOH/g. When the acid value is in this range, the developability of the photosensitive composition is good.

The content of the photosensitive resin (C) in the total solid content of the photosensitive composition of the present invention is preferably from 5 to 80% by mass, more preferably from 10 to 60% by mass. When the content of the photosensitive resin (C) is within this range, the developability of the photosensitive composition is good.

(4) arbitrary ingredients

In the photosensitive composition of the present invention, the polymer (A), the photopolymerization initiator (B), and the photosensitive resin (C) having an acidic group and an ethylenic double bond are contained as essential components. However, it is possible to include any component described below for the purpose of improving various functions without impairing the effects of the present invention.

(crosslinking agent (D))

The photosensitive composition of the present invention may contain a crosslinking agent (D) having two or more ethylenic double bonds as necessary. Thereby, the curability of the photosensitive resin is improved, and the amount of exposure when the partition walls are formed can be reduced.

The crosslinking agent (D) is not particularly limited, and a compound having 2 to 10 (meth) acryloxy groups is preferred. Specific examples thereof include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and neopentyl glycol di( Methyl) acrylate, 1,9-nonanediol di(meth) acrylate, trimethylolpropane di(meth) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol Tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated iso-cyanuric acid triacrylate, amine A Two or more kinds of ester acrylates and the like may be used in combination.

The commercially available product of the above-mentioned crosslinking agent (D) includes KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK. Ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ε-己Lactone modified isocyanuric acid (2-propenyloxyethyl) ester, BANI-M (trade name, Maruzen Petrochemical Co., Ltd., bis [4-(allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxylimenine)phenyl]methane), BANI-X (trade name, Maruzen Petrochemical Co., Ltd., N,N'-m-xylylene-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine)) and the like.

Further, the urethane acrylate may be a KAYARADUX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, and UXE-3501. , UX-5000, UX-5002D-P20 and so on.

The content of the crosslinking agent (D) in the total solid content of the photosensitive composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the crosslinking agent (D) is in this range, the pattern shape of the photosensitive composition becomes good.

(colorant (E))

The photosensitive composition of the present invention may have a coloring agent (E) added thereto. For example, when the cured product of the photosensitive composition of the present invention is used for applications in which a black matrix is required to have light shielding properties, a black coloring agent (E) can be used in accordance with the optical density of a desired partition wall. The black coloring agent (E) is not particularly limited, and examples thereof include carbon black, aniline black, an anthraquinone black pigment, and a perylene black pigment. Specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be mentioned. Further, the black colorant (E) may be a mixture of an organic pigment such as a red pigment, a blue pigment, or a green pigment, and an inorganic pigment. Among these, carbon black is preferred in consideration of the light-shielding property. Further, carbon black may be treated with a surface treatment such as a resin. Further, in order to adjust the color tone of the black colorant (E), carbon black can be used in combination with a blue pigment and a violet pigment.

Further, the carbon black used as the colorant (E) is preferably 50 to 200 m ² /g by the specific surface area of the BET method. When the specific surface area is too small, the shape of the partition wall is deteriorated. When the specific surface area is too large, the dispersing aid described later is excessively adsorbed on the black coloring agent (E), and a large amount of dispersing aid must be added.

Further, in consideration of the exposure sensitivity of the photosensitive composition, the carbon black used as the colorant (E) preferably has an oil absorption of dibutyl phthalate of 120 cc/100 g or less, more preferably a smaller one. .

Further, the carbon black used as the colorant (E) preferably has an average primary particle diameter of 20 to 50 nm. When the average primary particle diameter is too small, it is difficult to disperse it at a high concentration, and it is difficult to obtain a photosensitive composition having good stability over time. When the average primary particle diameter is too large, the shape of the partition wall is deteriorated. situation. Further, the carbon black-based average secondary particle diameter is preferably from 80 to 200 nm. Here, the particle diameter of carbon black can be measured using a transmission electron microscope.

The content of the coloring agent (E) in the total solid content of the photosensitive composition of the present invention can be appropriately selected in accordance with the function required for the coloring agent (E) insofar as the effects of the present invention are not impaired. For example, when the coloring agent (E) for imparting a black color-blocking black coloring agent (E) to the cured film of the coating film is prepared by the photosensitive film formed of the photosensitive composition of the present invention, the content of the coloring agent (E) It is also preferably 15 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 40% by mass, based on the required light-shielding property and optical density. . In this case, when the content of the black coloring agent (E) is too small, the optical density of the partition wall may be insufficient. When the content is too large, the curing property of the photosensitive composition is lowered, the appearance of the partition wall is lowered, and the liquid repellency is lowered. situation.

(polymer dispersant - dispersing aid)

The photosensitive composition of the present invention preferably contains a polymer dispersant for enhancing the dispersibility of the black colorant (E). The polymer dispersant is not particularly limited, and examples thereof include an urethane type, a polyimide type, an alkyd type, an epoxy type, a polyester type, a melamine type, a phenol type, an acrylic type, and a polyether type. Examples of the vinyl chloride-based, vinyl chloride-vinyl acetate-based copolymer, polyamine-based, and polycarbonate-based compounds are preferably urethane-based or polyester-based. Further, the polymer dispersant may have an oxygen-extended ethyl group and an oxygen-extended propyl group.

In consideration of the affinity for the coloring agent (E) such as the above black coloring agent, the polymer dispersing agent preferably has a basic group. The basic group is not particularly limited, and examples thereof include amine groups of the first, second or third stage.

As a commercial product of a polymer dispersing agent, for example, DISPARLON DA-7301 (manufactured by Nanben Chemical Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (above, BYK-Chemie), SOLSPERSE 5000, SOLSPERSE 17000 (above, ZENECA company) and so on.

The amount of the polymer dispersant to be added is preferably from 5 to 30% by mass, more preferably from 10 to 25% by mass, based on the coloring agent (E) of the black colorant or the like. When the amount of addition is too small, the effect of improving the dispersibility may be insufficient, and when the amount of addition is too large, the development property may be lowered.

Further, the photosensitive composition of the present invention may further contain a phthalocyanine-based pigment derivative and a metal phthalocyanine sulfonamide compound as a dispersing aid. It is considered that the dispersing agent is adsorbed to the coloring agent (E) such as the black coloring agent and the polymer dispersing agent, and has a function of improving dispersion stability.

(microparticles)

The photosensitive composition of the present invention may contain fine particles as necessary. Thereby, it is possible to suppress the shape change of the partition wall at the time of post-baking described later.

The fine particles are not particularly limited, and examples thereof include inorganic fine particles such as cerium oxide, zirconium oxide, magnesium fluoride, ITO (tin-doped indium oxide), and ATO (yttrium-doped tin oxide); polyethylene and PMMA ( Organic fine particles such as polymethyl methacrylate. When the heat resistance is considered as the fine particles, inorganic fine particles are preferable, and in view of ease of availability and dispersion stability, cerium oxide or zirconium oxide is preferred. Further, when the photosensitive composition contains the coloring agent (E) such as the above black coloring agent and the polymer dispersing agent for improving the dispersibility, the fine particles are negatively charged in consideration of the adsorption ability of the polymer dispersing agent. It is better. Further, in consideration of the exposure sensitivity of the photosensitive composition, the fine particles are preferably not absorbed by the light irradiated during exposure, so as not to absorb the main emission wavelength of the ultrahigh pressure mercury lamp, that is, i-ray (365 nm), h-ray (405 nm). ), g-ray (436 nm) is particularly good.

The surface smoothness of the partition walls is good, and the average particle diameter of the fine particles is preferably 1 μm or less, more preferably 200 nm or less.

The content of the fine particles in the total solid content of the photosensitive composition of the present invention is preferably from 3 to 20% by mass, more preferably from 5 to 15% by mass. When the content is too small, the shape of the partition wall may change during post-baking, and when the content is too large, the dispersion stability of the photosensitive composition may be lowered.

(decane coupling agent)

The photosensitive composition of the present invention may contain a decane coupling agent as necessary. Thereby, the adhesion between the partition wall and the substrate can be improved.

The decane coupling agent is not particularly limited. Specific examples thereof include tetraethoxydecane, 3-glycidoxypropyltrimethoxydecane, methyltrimethoxydecane, vinyltrimethoxydecane, and 3-methylpropenyloxypropyltrimethyl. Oxydecane, 3-chloropropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, heptadecafluorooctyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxy Further, two or more kinds may be used in combination with a decyl alkane, a polyoxyethylene having a triethoxyalkylene group, an imidazolium or the like.

(phosphoric acid compound)

The photosensitive composition of the present invention may contain a phosphoric acid compound as necessary. Thereby, the adhesion between the partition wall and the substrate can be improved.

Examples of the phosphoric acid compound include mono(meth)acryloxyethyl phosphate, di(meth)acryloxyethyl phosphate, and tris(meth)acryloxyethyl phosphate.

(hot hardener)

The photosensitive composition of the present invention may contain a thermosetting agent as necessary. Thereby, the heat resistance and water permeability of the partition walls can be improved.

The thermosetting agent is not particularly limited, and examples thereof include an amine-based resin, a compound having two or more epoxy groups, a compound having two or more mercapto groups, a polycarbodiimide compound, and two or more. A compound having an oxazoline group, a compound having two or more indole cyclopropanes, a polyvalent metal, a compound having two or more hydrogenthio groups, a polyisocyanate compound, or the like may be used in combination of two or more kinds. In the case of considering the chemical resistance of the partition wall, an amine-based resin, a compound having two or more epoxy groups, or two or more compounds may be used. The compound of oxazoline is preferred.

(other optional ingredients)

Further, in the photosensitive composition of the present invention, in addition to the above various components, a curing accelerator, a tackifier, a plasticizer, an antifoaming agent, a leveling agent, an anti-shrinking agent, and an ultraviolet absorber may be contained as necessary. Wait.

The photosensitive composition of the present invention can be prepared by uniformly mixing the various essential components described above and any necessary components in accordance with the above-described blending amount by a usual method.

(diluting solvent)

When a partition film is formed by using the photosensitive composition of the present invention, a coating film (wet film) is formed by using a diluent obtained by diluting the photosensitive composition with a solvent, and then the solvent is volatilized and removed to form a coating film of the photosensitive composition. It is better.

The solvent system for diluting the photosensitive composition is not particularly limited. Specific examples thereof include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol; and ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Cypresses such as oxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy) Carbitol such as ethanol, 2-(2-butoxyethoxy)ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl propionate, n-butyl propionate, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Ethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, 3-ethoxypropionic acid Ethyl ester, cyclohexanol acetate, ethyl lactate, n-butyl lactate, γ-butyrolactone, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, glycerol Esters such as acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, three Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, diethylene glycol methyl ethyl ether, etc. The ethers may be used in combination of two or more.

In addition, it is preferable to prepare a dilution liquid in which the photosensitive composition is diluted with a solvent, and the concentration of the photosensitive component is 5 to 40% by mass, and is adjusted to 10 to 25% by mass. Better.

<2> Next door

In the partition wall of the present invention, the cured film of the photosensitive composition of the present invention is used, and the substrate is formed into a plurality of pixel formation intervals, and can be applied to a color filter and an organic EL element. Black matrix and so on.

Hereinafter, as an example of a method of producing the partition wall of the present invention, a method of producing a partition wall by a lithography step using the photosensitive composition of the present invention will be described.

(coating step)

First, a diluent of the photosensitive composition of the present invention is applied onto a substrate. The substrate is not particularly limited, and examples thereof include various glass plates, inorganic substrates such as SiC substrates and tantalum, inorganic oxide substrates such as ITO, polyester (polyethylene terephthalate or the like), and polyolefin (polyethylene). , polypropylene, etc.), thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, polyfluorene, polyimine, poly(meth)acrylic resin, etc.; thermosetting of epoxy resin, unsaturated polyester, etc. Hardened sheet of resin, etc. When heat resistance is considered, it is preferable to use a heat resistant resin such as a glass plate or a polyimide. Further, since the surface of the substrate on which the partition wall is not formed can be exposed, the substrate is preferably transparent. Further, the substrate may be a substrate obtained by forming an organic film, an inorganic oxide film such as TFT, ITO or SiO ₂ on a transparent substrate such as a glass substrate, or a patterned substrate, or may be laminated on the substrate. The laminated substrate.

The coating method is not particularly limited, and examples thereof include a spin coating method, a spray method, a slit coating method, a roll coating method, a spin coating method, and a bar coating method.

(drying step)

Subsequently, the coating film formed on the substrate is dried. Thereby, since the solvent is volatilized, a coating film of the non-adhesive photosensitive composition can be obtained. The drying method is not particularly limited, and examples thereof include vacuum drying and heat drying. In order to prevent the appearance of the coating film from being uneven and to dry it efficiently, it is preferred to use vacuum drying and heat drying in combination. The drying conditions vary depending on the type and composition of the components contained in the photosensitive composition, and vacuum drying is preferably carried out at 10 to 500 Pa (absolute pressure) for 10 to 300 seconds, and heat drying is carried out at 50 to 120 ° C. ~ 2000 seconds is better.

(exposure step)

Subsequently, the coating film is exposed through a mask of a predetermined pattern. The light to be irradiated is not particularly limited, and examples thereof include visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, and KrAr Excimer lasers such as molecular lasers, Ar ₂ excimer lasers, X-rays, electron beams, and the like. The wavelength is preferably 100 to 600 nm, and the wavelength is preferably 300 to 500 nm, and particularly preferably i rays (365 nm), h rays (405 nm), and g rays (436 nm). Further, as the light source, a well-known ultrahigh pressure mercury lamp or the like can be used.

The exposure amount is usually 5 to 1000 mJ/cm ² on an i-ray basis, preferably 10 to 400 mJ/cm ² , more preferably 20 to 200 mJ/cm ² , and particularly preferably 50 to 100 mJ/cm ² . When the amount of exposure is less than 5 mJ/cm ² , the curing of the coating film is insufficient, and the development property is lowered. When the amount is more than 1000 mJ/cm ² , a high resolution cannot be obtained.

(development step)

Subsequently, the unexposed portion of the coating film was removed using a developing solution to develop. The developing liquid system is not particularly limited, and examples thereof include an aqueous solution of an alkali such as an inorganic base, an amine, an alkanolamine or a fourth-order ammonium salt. The development time is preferably 5 to 180 seconds even if it is in contact with the developing solution. The development method is not particularly limited, and examples thereof include a liquid holding method, a dipping method, and a shower method.

Further, after development, the running water was washed, and air was dried by using compressed air and compressed nitrogen gas to remove moisture on the substrate.

(post exposure step)

Subsequently, post-exposure of the partition wall after development can also be performed. At this time, exposure may be performed from any of the side on which the partition wall is formed and the side on which the partition wall is not formed, and exposure may be performed from both surfaces. The light that is irradiated during exposure is preferably ultraviolet light.

As the light source, a well-known ultrahigh pressure mercury lamp, a high pressure mercury lamp, or the like can be used. These light sources emit light having a wavelength of 600 nm or less which contributes to the hardening of the partition walls, and the light having a wavelength of 200 nm or less which causes oxidative decomposition of the partition walls is less likely to emit light. Further, it is preferable that the quartz tube glass used in the light source has a function of blocking light of 200 nm or less.

The exposure amount is usually 50 mJ/cm ² or more, preferably 200 mJ/cm ² or more, more preferably 1000 mJ/cm ² or more, and particularly preferably 2,000 mJ/cm ² or more.

Further, as the light source, a low-pressure mercury lamp can be used. Since the low-pressure mercury lamp emits a large amount of light having a wavelength of 200 nm or less, the exposure amount is preferably 500 mJ/cm ² or less, and more preferably 300 mJ/cm ² or less.

(post-baking step)

After the development (after the post-exposure, after the post-exposure), it is preferred to heat the partition walls. The heating conditions are preferably 150 to 250 ° C for 5 to 90 minutes, and the heating temperature is preferably 180 ° C or higher. When the heating temperature is too low, there is a case where the chemical resistance is insufficient, and when the ink is applied to the partition wall, the partition wall is swollen or the ink is infiltrated. On the other hand, when the heating temperature is too high, there is a case where the partition wall is thermally decomposed.

As the heating device, a hot plate, an oven, or the like can be used.

The partition wall of the present invention can be formed by curing the photosensitive composition of the present invention by the lithography step as described above. In the partition wall of the present invention, a black colorant (E) can be formed by a photosensitive composition used for the production as necessary, thereby forming a black matrix in black. At this time, a black matrix is formed by forming a partition wall using a photosensitive composition.

The partition wall of the present invention preferably has a width (average value) of 100 μm or less and more preferably 20 μm or less. Further, the distance between the adjacent partition walls, that is, the width (average value) of the opening portion is preferably 300 μm or less, more preferably 100 μm or less. Further, the height (average value) of the partition walls is preferably 0.05 to 50 μm, more preferably 0.2 to 10 μm.

In general, the liquid repellency (ink repellency) of the partition wall composed of the cured film of the photosensitive composition is water repellency and oil repellency, and each of them can be water and PGMEA (propylene glycol monomethyl ether B). The contact angle of the acid ester: mostly used as an organic solvent of a solvent for the ink was evaluated. The water contact angle of the upper surface of the partition wall of the present invention is preferably 90 to 150, and more preferably 95 to 120. Further, the PGMEA contact angle of the upper surface of the partition wall is preferably 35 to 55, and more preferably 40 to 50.

<3>Color filter

The color filter of the present invention has a plurality of pixels on a substrate and a partition wall between adjacent pixels, and the partition wall is formed by using the partition wall of the present invention. Further, in the color filter of the present invention, the partition wall is preferably a black matrix having an optical density of about 2 to 7.

As described above, the color filter of the present invention can be produced by forming a partition wall, for example, a black matrix on a substrate, and then forming an ink by applying ink to the opening of the partition wall by, for example, an inkjet method.

The inkjet method is not particularly limited, and examples thereof include a method of continuously ejecting charged ink and controlling by a magnetic field, a method of intermittently ejecting ink using a piezoelectric element, and heating and foaming the ink. A method of intermittently spraying, and the like.

The arrangement of the pixels is not particularly limited, and examples thereof include well-known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.

The ink system mainly contains a coloring component, a binder resin component, and a solvent, and may be any of an aqueous ink and an oil ink. As the coloring component, a pigment and/or a dye excellent in heat resistance and light resistance are preferred. The resin component which is excellent in transparency and heat resistance is preferable as the binder resin component, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and/or a water-dispersible resin as a binder resin component. Further, the oil-based ink contains an organic solvent as a solvent and contains a resin soluble in an organic solvent as a binder resin component.

Further, after the ink is applied to the partition walls, for example, the openings of the black matrix by the inkjet method, the pixels can be formed by drying, heat curing, ultraviolet curing, or the like as necessary.

Further, after the pixels are formed in the openings of the partition walls (black matrix), the protective film can be formed as necessary. Thereby, while the surface smoothness of the color filter is improved, it is possible to isolate the eluted substances from the partition walls (black matrix) and the pixels from reaching the adjacent liquid crystal layer.

At this time, it is preferable to remove the liquid repellency on the partition wall (black matrix) before forming the protective film. Thereby, it is possible to suppress the case where the coating liquid for the protective film is not stained on the upper surface of the partition wall (black matrix). The method for removing the liquid repellency of the upper surface of the partition wall (black matrix) is not particularly limited, and examples thereof include a plasma ashing treatment and a light ashing treatment.

Further, in order to improve the quality of the liquid crystal panel manufactured by using the color filter of the present invention, a light spacer may be formed on a partition wall such as a black matrix as necessary.

<4> Organic EL element

The organic EL device of the present invention has a plurality of pixels on a substrate and a partition wall between adjacent pixels, wherein the partition wall is formed using the partition wall of the present invention, and the pixel is formed by an inkjet method. By.

The organic EL device of the present invention can be produced as follows. First, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate by a sputtering method or the like, and the transparent electrode is etched into a desired pattern as necessary. Subsequently, in the same manner as in the case of the color filter, after forming a partition wall, for example, a black matrix on the substrate, for example, a solution of the hole transporting material as an ink is applied in order to the opening of the partition (black matrix) by an inkjet method. The solution of the luminescent material is dried to form a hole transport layer and a luminescent layer. Further, an organic EL device can be obtained by forming an electrode such as aluminum by a vapor deposition method or the like and forming a pixel.

Example

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Also, the parts mean parts by mass.

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

[1] A compound used for producing a polymer (A) and a polymer (R)

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

MAA: Methacrylic acid

MMA: Methyl methacrylate

2-HEMA: 2-hydroxyethyl methacrylate

PME-200: BLEMMER-PME-200 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH ₂ = C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ : The k series in the formula represents the average value between molecules, and the value of k is 4)

PME-400: BLEMMER-PME-400 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH ₂ = C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ : The k series in the formula represents the average value between molecules, and the value of k is 9)

PME-4000: BLEMMER-PME-4000 (manufactured by Nippon Oil Co., Ltd.: α-methyl-ω-methacryl oxime (oxygen extension ethyl): CH ₂ = C(CH ₃ )COO(CH ₂ CH ₂ O) _k CH ₃ : The k series in the formula represents the average value between molecules, and the value of k is 90)

PE-350: BLEMMER-PME-350 (manufactured by Nippon Oil & Fats Co., Ltd.: α-hydrogen-ω-methacryl oxime (oxygen extension ethyl): CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) _k The k series in the formula H represents the average value between molecules, and the value of k is 8)

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

AOI: KARENZ AOI (manufactured by Showa Denko, 2-(methyl) propylene oxime ethoxylate)

DBTDL: Dibutyltin dilaurate

TBQ: tert-butyl-p-benzoquinone

MEK: 2-butanone

[2] Photosensitive composition

OXEO2: OXEO2 (manufactured by CIBA SPECIALTY CHEMICALS, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazolyl-3-yl]-ethanone-1-(O-) Ethylene (in the formula (5), R ²¹ and R ²² are methyl, R ²³ is ethyl, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, and R ²⁵ is 2-methylbenzhydryl Compound)

ZCR1569H: ZCR-1569H (a solution of a resin obtained by introducing a vinyl double bond and an acidic group into an epoxy resin having a biphenyl skeleton represented by the formula (6), manufactured by Nippon Kayaku Co., Ltd., and having a solid content of 70% by mass %, mass average molecular weight is 4710)

DPHA: KAYARAD DPHA (manufactured by Nippon Kagaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

PGMEA: propylene glycol monomethyl ether acetate

CB: carbon black dispersion (average secondary particle diameter: 120 nm, dispersion medium: PGMEA, carbon black: 20% by mass, and polyurethane-based polymer dispersant having an amine value of 18 mgKOH/g: 5% by mass)

Ceria: cerium oxide dispersion (average particle size 20 nm, dispersion medium PGMEA, solid content 30% by mass)

<Synthesis of Polymer (A)> [Synthesis of Polymer (A-1)]

In an autoclave having a 1 L internal volume of a stirrer, 420.0 g of MEK, 81.0 g of C6FMA, 36.0 g of 2-HEMA, 54.0 g of PME-400, 9.0 g of MMA, and 1.1 g of a polymerization initiator V-65 were added, and nitrogen gas was added thereto. The mixture was polymerized at 50 ° C for 24 hours while stirring to obtain a solution of the copolymer 1. The copolymer 1 coefficient had an average molecular weight of 34,200 and a mass average molecular weight of 63,900.

Into an autoclave having a 1 L internal volume of a stirrer, 500 g of the solution of the above copolymer 1, 32.6 g of AOI, 0.13 g of DBTDL, 1.6 g of TBQ, and 17.1 g of MEK were added, and the mixture was reacted at 40 ° C for 24 hours while stirring to synthesize it. Crude polymer. After adding hexane to the solution of the obtained crude polymer and reprecipitating and purifying, it was dried under vacuum to obtain 165.0 g of the polymer (A-1) corresponding to the polymer (A). The polymer (A-1) has a coefficient average molecular weight of 34,900, a mass average molecular weight of 69,300, an F atom content of 21.1% by mass, an ethylenic double bond content of 1.26 × 10 ^-3 mol/g, and an acid value of 26.8 mg KOH. /g.

[Synthesis of Polymers (A-2) to (A-5)]

In the synthesis of the polymer (A-1), in addition to the modification of the raw materials as shown in Table 1, the copolymers 2 to 5 were synthesized by the same reaction. The polymer (A-2) to (A-5) corresponding to the polymer (A) obtained in the same manner as above was prepared by using the obtained copolymers 2 to 5 in the same manner as described above.

<Synthesis of Comparative Polymer (R) Not Compatible with Polymer (A)> [Synthesis of Polymer (R-1), (R-3) to (R-5)]

In the synthesis of the polymer (A-1), in addition to the modification of the raw materials as shown in Table 1, the copolymers 6, 8 to 10 were synthesized by the same reaction. Using the obtained copolymers 6, 8 to 10, and mixing the raw materials according to Table 2, the comparative polymer (R-1) and (R-) which did not satisfy the polymer (A) of the present invention were obtained in the same manner as above. 3) ~ (R-5).

[Synthesis of Polymer (R-2)]

In an autoclave having a 1 L internal volume of a stirrer, 420.0 g of MEK, 99.0 g of C6FMA, 18.0 g of 2-HEMA, 27.0 g of PME-400, 18.0 g of MAA, 18.0 g of MMA, and 1.1 g of a polymerization initiator V-65 were added. Further, the mixture was polymerized at 50 ° C for 24 hours while stirring under a nitrogen atmosphere to obtain a solution of the copolymer 7.

After adding hexane to the obtained solution and reprecipitating and purifying, it was dried under vacuum to obtain 170.0 g of a polymer (R-2) which did not correspond to the polymer (A) of the present invention. The polymer (R-2) coefficient had an average molecular weight of 26,600, a mass average molecular weight of 57,600, an F atom content of 31.4% by mass, and an acid value of 65.2 mg KOH/g.

The yield of each of the polymer (A) and the comparative polymer (R) obtained above, the ratio of the polymer unit having the group (2) in the polymer, and the number average molecular weight (Mn) and mass measured by the following method The average molecular weight (Mw), the molecular weight distribution (Mw/Mn), the content of the fluorine atom (F), the content of the ethylenic double bond (C=C), and the acid value are shown in Table 2.

<molecular weight>

The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography, and polystyrene was used as a standard substance. As a gel permeation chromatograph, HPLC-8220GPC (manufactured by TOSOH Co., Ltd.) was used. As the column, three shodex LF-604 were used. As the detector, an RI detector is used. As a standard substance, EasiCal PS1 (manufactured by Polymer Laboratories Co., Ltd.) was used. Further, when the number average molecular weight and the mass average molecular weight were measured, the column was kept at 37 ° C and tetrahydrofuran was used as the eluent, and the flow rate was set to 0.2 mL/min to inject 40 μL of the 0.5% tetrahydrofuran solution of the measurement sample. .

<Fluorine content>

The fluorine atom content in the polymer was calculated by performing ¹⁹ F NMR measurement using 1,4-bistrifluoromethylbenzene as a standard material.

<Content of ethylenic double bond>

The content of the ethylenic double bond in the polymer was calculated by ¹ H NMR measurement using 1,4-bistrifluoromethylbenzene as a standard material.

<acid value>

The acid value is a theoretical value calculated from the ratio of the raw materials, that is, the monomer.

[Example 1]

0.06 parts of the polymer (A-1), 1.3 parts of OXE02 as a photopolymerization initiator (B), 12.9 parts of ZCR1569H as a dispersion of the photosensitive resin (C), and 3.9 parts as a crosslinking agent (D) DPHA, 38.6 parts of CB as a dispersion of black colorant (E), 15.0 parts of cerium oxide as a cerium oxide dispersion, and 28.24 parts of PGMEA as a solvent were mixed to obtain a diluted solution of a photosensitive composition. The content of the polymer (A-1) in the total solid content of the diluted solution of the photosensitive composition was 0.20% by mass.

The diluted solution of the photosensitive composition was applied onto a glass substrate using a spin coater, and then dried on a hot plate at 100 ° C for 2 minutes to form a coating film of a photosensitive composition having a film thickness of 2.0 μm. Subsequently, light having an exposure amount of 100 mJ/cm ² on the basis of i-ray (365 nm) was irradiated with an ultra-high pressure mercury lamp, and the coating film was irradiated through a photomask to perform exposure. Further, the mask-shielding portion was a lattice pattern of 150 μm × 400 μm and the light-transmitting portion was 20 μm, and the volume of the opening formed was 40 pL, and the area of the pattern was 10 cm ² . Subsequently, the development is performed using a video camera. In this case, a 10-fold diluted aqueous solution of an inorganic alkali-based developing solution SEMICLEAN DL-A4 (trade name, manufactured by Yokohama Oil & Fats Co., Ltd.) is used as the developing solution, and the nozzle is used to shrink the angle of the substrate to 8 degrees or less. Further, rotation development was performed by applying a pressure of 0.15 MPa to discharge the substrate to generate bubbles. Subsequently, the unexposed portion was washed with water and dried to obtain a glass substrate sample (1) of Example 1 in which the partition walls were formed.

In addition, exposure was performed in the same manner as described above except that exposure was carried out without using a photomask, and then the glass substrate was immersed in a 10-fold diluted aqueous solution of an inorganic alkali-type developing liquid SEMICLEAN DL-A4, and developed and dried. . The glass substrate sample (2) of Example 1 in which the cured film of the photosensitive film of the photosensitive composition after image formation was formed was obtained.

Further, the glass substrate sample (2) was produced in the same manner as in the above-described glass substrate sample (2), and the glass plate sample (3) of Example 1 was obtained by heating the glass plate at 220 ° C for 30 minutes on a hot plate.

[Examples 2 to 5 and Comparative Examples 1 to 5]

The glass substrate sample (1) of Examples 2 to 5 and Comparative Examples 1 to 5 in which the partition walls were formed was obtained in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 3. The glass substrate sample (2) of the cured product of the photosensitive film of the photosensitive composition after development, and the same procedure as the glass substrate sample (2), and finally heat-treated to form a photosensitive composition The glass substrate sample (3) of the cured film of the film contains the polymers (A-2) to (A-5) and the comparative polymer (R-1) obtained in the above-mentioned synthesis examples. The composition of the cured film of the photosensitive composition of (R-5).

[Evaluation method and evaluation result]

The glass substrate samples (1), (2), and (3) of Examples 1 to 5 and Comparative Examples 1 to 5 were used, and the development property, water and oil repellency, and ink wetness in the opening portion were evaluated by the following methods. Scalability. The evaluation results are shown in Table 4 together with the content % of each component of the total solid content of the photosensitive composition.

In the table, ◎ indicates that it is the best, ○ is good, △ is OK, and × is not good. In the present invention, all of the evaluations are ◎ or ○, which is good.

[developability]

In the glass substrate (1), if the number of development defects per area is less than 30, it is judged as ○, the number of development defects is 30 or more, less than 50 is judged as Δ, and the number of development defects is determined to be 50 or more. For ×. Further, this evaluation method is a method for intentionally causing a large amount of bubbles to be generated. When the evaluation is less than 30, it means that there is almost no development defect in the actual production line.

[water repellency]

The water repellency was evaluated by measuring the contact angle of water on the surface of the cured film of the glass substrate (2). The contact angle is the angle formed by the tangent to the liquid surface at the point of contact of the solid with the liquid and the solid surface, and is defined by the angle of the side containing the liquid. Therefore, the larger the contact angle is, the more excellent the water repellency of the cured film of the coating film is.

In addition, when the contact angle of water is 95° or more, it is judged as ○, and when it is 90° or more and less than 95°, it is Δ, and when it is less than 90°, it is judged as ×.

[oil repellency]

The oil repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured film of the glass substrate (3). The contact angle is defined as the water repellency, and the larger the contact angle is, the more excellent the oil repellency of the cured film is.

In addition, when the contact angle of PGMEA is 40° or more and 50° or less, it is judged as ○, and when it is 35° or more and less than 40°, it is Δ, and when it is less than 35°, it is judged as ×.

<Ink wet spreadability in the opening between partitions>

6.25 g of liquid EPOXY ME-562 (manufactured by PELNOX Co., Ltd.), 6.25 g of hardener HV-562 (manufactured by PELNOX Co., Ltd., Japan), 12.5 g of diethyl adipate, and 25.0 g of diethyl malonate were stirred. The mixture was stirred and mixed for 1 hour to prepare an ink.

About 10 pL or about 20 pL of the ink prepared above was applied to the opening of the glass substrate (1) by an inkjet method, and was observed by using an ultra-depth shape measuring microscope VK-8500 (manufactured by KEYENCE). Photograph to evaluate the wet spreadability of the ink in the opening.

Regarding the position of the opening portion between the ten partitions in the photograph obtained as described above, the portion where the ink does not adhere to the zero position is determined to be ◎, the position of 1 to 2 positions is ○, and the position of 3 to 5 positions is Δ, 5 The number of ~10 locations is ×.

As shown in Table 4, when the photosensitive resin compositions of Examples 1 to 5 were used, it was found that the development defects were small, and the water repellency, the oil repellency, and the wet spreading of the liquid to the partition walls were sufficiently exhibited. On the other hand, Comparative Example 1 in which the polyoxyalkylene chain was not introduced into the group (2) showed very good results in terms of water repellency, oil repellency, and wettability. However, many imaging defects occur. Further, in Comparative Example 2 in which the side chain of the ethylenic double bond was not introduced into the polymer (A), the development defect was improved, but the water repellency and oil repellency after development were greatly lowered. In Comparative Example 3 in which the polyoxyalkylene chain was short, many development defects were produced without effect. On the other hand, in the case of the polyoxyalkylene group of the length of the range used in Examples 1 to 5, Comparative Example 4 in which the polyoxyalkylene alkyl chain was long was increased in developmental defects. In Comparative Example 5, although the liquid repellency was good, since it had a double bond at the terminal of the polyoxyalkylene chain, it was fixed by photocuring, and it had no effect on development defects.

Industrial availability

The photosensitive composition of the present invention has sufficient liquid repellency, but has no development defects, and can form a partition wall having a good liquid repellency and a side surface having good lyophilicity even after a development step. An opening portion in which the ink is easily wetted and expanded is formed. The photosensitive composition of the present invention is suitable for forming a partition wall, and is, for example, a manufacturer of an organic EL display element for producing a color filter using an ink jet recording technique. Further, it is suitable to use a material which is a permanent film which forms a partition wall of each TFT which separates an organic TFT (Thin Film Transistor) array, a partition wall of an ITO electrode of a liquid crystal display element, and a partition of a circuit wiring board.

In addition, the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2009-298960, filed on Dec.

Claims (11)

A photosensitive composition comprising a polymer (A), a photopolymerization initiator (B), and a photosensitive resin (C) having an acidic group and an ethylenic double bond, the polymer (A) comprising at least: a side chain having a group represented by the following formula (1), -CFXR ^f (1) having a side chain of a group represented by the following formula (2), -(R ¹¹ -O)nR ¹² ... ( 2) and a side chain having an ethylenic double bond, wherein the symbol in the formula represents the following meaning: X: a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ^f : a carbon number which may also have an etheric oxygen atom A fluoroalkyl group or a fluorine atom of 1 or more and 20 or less, R ¹¹ : an alkylene group having 1 to 5 carbon atoms, R ¹² : an alkyl group having 1 to 4 carbon atoms, and n: an integer of 6 to 30. The photosensitive composition of claim 1, wherein the polymer (A) has a mass average molecular weight of 1.2 × 10 ⁴ or more and 15 × 10 ⁴ or less. The photosensitive composition according to claim 1 or 2, wherein the content of the fluorine atom in the polymer (A) is 5% by mass or more and 35% by mass or less. The photosensitive composition of the first aspect or the second aspect of the invention, wherein the ratio of the polymer unit containing the group represented by the above formula (2) in the polymer (A) is 5% by mass or more and 50% by mass or less. . The photosensitive composition of claim 1 or 2, wherein the polymer (A) further contains a side chain having an acidic group. The photosensitive composition of claim 1 or 2 further contains a crosslinking agent (D) having two or more ethylenic double bonds. The photosensitive composition of claim 1 or 2 further contains a coloring agent (E). The photosensitive composition of the first or second aspect of the invention, wherein the content of the polymer (A) is 0.07% by mass or more and 1% by mass or less based on the total solid content of the photosensitive composition. A partition wall is formed by dividing a substrate into a plurality of pixel formation intervals, and is characterized by a cured film of a photosensitive composition according to any one of claims 1 to 8. Composition. A color filter comprising a plurality of pixels on a substrate and a partition wall between adjacent pixels, wherein the partition wall is formed by using the partition wall of the ninth aspect of the patent application. An organic EL device having a plurality of pixels on a substrate and a spacer between adjacent pixels, wherein the partition wall is formed by using the partition wall of the ninth aspect of the patent application.