KR20120124397A - Photosensitive composition, partition wall, color filter and organic el element - Google Patents

Abstract

Although it is an ink repellent component which does not have an ethylenic double bond, good ink repellency in the upper part of a partition, developer resistance which does not erode to a developing solution, and the wettability of the ink to a partition opening part can be given to the partition obtained. A photosensitive composition containing an ink repellent component is provided.
A polymer having a side chain having a group represented by the following General Formula (1) and not having a side chain having an ethylenic double bond, and having a mass average molecular weight (Mw) of 4.2 × 10 ⁴ <Mw ≦ 20 × 10 ⁴ ( A photosensitive composition containing A), a photocuring initiator (B), and binder resin (C).
-CFXR ^f . (One)
(Wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group or fluorine atom having 1 to 20 carbon atoms which may have an ether oxygen atom)

Description

PHOTOSENSITIVE COMPOSITION, PARTITION WALL, COLOR FILTER AND ORGANIC EL ELEMENT}

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

In recent years, barrier ribs between pixels of color filters, barrier ribs between pixels of organic EL (Electro-Luminescence) display elements, barrier ribs that divide respective TFTs of organic TFT (Thin Film Transistor) arrays, barrier ribs of ITO electrodes of liquid crystal display elements, The photosensitive composition is attracting attention as a material which forms a permanent film, such as a partition of a circuit wiring board. For example, when manufacturing a color filter, after forming a partition pattern (sometimes serving as a black matrix) using photolithography, R (red), G (green) and Ink of B (blue) is applied to the opening between the partition walls to form a pixel. In forming an organic EL device, after forming a partition pattern using photolithography, a solution such as a hole transport material, a light emitting material, or the like is applied to the openings between partition walls by using the inkjet method, and the hole transport layer, the light emitting layer, and the like are applied. The pixel which has is formed.

In order to prevent the color mixture between such color filters and adjacent pixels of the organic EL element, the upper surface of the partition wall must have a property of splashing ink or so-called liquid repellency. Moreover, in order to prevent the whitening of a color filter or an organic EL element, the partition opening part needs to have wet property with ink, so-called lyophilic.

In order to acquire the characteristic requested | required of such a partition, adding a ink repellent component to the photosensitive composition for partition formation is proposed. For example, Patent Document 1 describes an alkali developing photosensitive coloring composition containing a fluorine-containing block copolymer in which A segment is a fluorine-containing segment and B segment is a non-fluorine segment. The mass average molecular weights of the fluorine-containing block copolymer described in the Example of patent document 1 are 33,000, 36,000, 37,000, 38,000, 40,000, 42,000.

Patent Document 2 has 4 to 4 carbon atoms. A liquid-repellent resist composition containing an α-substituted acrylate having a fluoroalkyl group of 6, an unsaturated organic acid, and a fluorine-based polymer having a high softening point monomer as a repeating unit is described. The mass average molecular weight of the fluorine-containing copolymer described in the Example of patent document 2 is 10,100 at the maximum.

Patent Literature 3 describes a technique relating to a partition wall made of an ink repellent material containing a resin binder, an ink repellent agent having a site having compatibility with the resin binder and a site having ink repellency. The number average molecular weight of the ink repellent agent in patent document 3 is 40,000? 100,000, and an Example has a number average molecular weight of 40,000? A fluorine-containing block polymer of 70,000 is exemplified.

In patent document 4, it has a monomeric unit formed from the monomer represented by following formula 1, and a fluorine atom content rate is 7? Fluorine-containing resin which is 35 mass%, and wavelength 100? Resist compositions containing photosensitive components that react to 600 nm light are described.

CH ₂ = CH (R ^x ) COOY ¹ R ^F ... Equation 1

(Wherein, R ^x is a hydrogen atom, a methyl group or a trifluoromethyl group, Y ¹ represents an organic group which does not contain a divalent fluorine atom with a carbon number of 1? 6, R ^F is a perfluoroalkyl group having a carbon number of 4? 6 Indicates)

In Patent Document 4, there is a description that the fluorine-containing resin preferably has a group having an ethylenic double bond, a carboxyl group and / or a hydroxyl group, depending on the kind of the photosensitive component. In the fluorine-containing resin described in the Example of patent document 5, the mass mean molecular weight of the fluorine-containing resin which does not contain an ethylenic double bond is 8,100 at most, and the mass average molecular weight of the fluorine-containing resin which has an ethylenic double bond is maximum. Is up to 11,600.

However, in the conventional ink repellent component, when the fluorine-containing resin which has an ethylenic double bond is used, the said required performance in the obtained partition, ie, good ink repellency in the upper part of a partition, and a developer which does not erode to a developing solution The performances such as resistance and wet ink diffusion property of the ink against the partition openings are sufficiently obtained. However, when fluorine-containing resins without ethylenic double bonds are used, partitions sufficiently satisfying all of these performances have not been obtained. It was the present situation.

In addition, in the fluorine-containing resin having an ethylenic double bond having sufficient performance as the ink repellent component, there are disadvantages in terms of manufacturing, such as increasing the number of steps in order to introduce a group having an ethylenic double bond into the fluorine-containing resin. there was.

International Publication No. 2007/10918 Japanese Unexamined Patent Publication No. 2008-287251 Japanese Unexamined Patent Publication No. 2007-25427 Japanese Laid-Open Patent Publication 2005-315984

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and is an ink repellent component having no ethylenic double bond, and has good ink repellency in the upper part of the partition, developer resistance not eroded into the developer, and an opening between partition walls. An object of the present invention is to provide a photosensitive composition containing a repellent ink component that can impart wettability of a good ink to a partition to be obtained. Another object of the present invention is to provide a partition having good performance obtained from an economically advantageous material, a color filter having the partition, and an organic EL device.

This invention provides the photosensitive composition, partition, color filter, and organic electroluminescent element which have the following structures.

[1] A polymer (A), a photocuring initiator (B), and a binder resin (C) having a side chain having a group represented by the following General Formula (1) and not having a side chain having an ethylenic double bond; As a photosensitive composition to contain,

-CFXR ^f . (One)

(Wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group or a fluorine atom having 1 to 20 carbon atoms which may have an ether oxygen atom)

The mass average molecular weight (Mw (A)) of the said polymer (A) is 4.2 * 10 < ⁴ <Mw (A) <= 20 * 10 <^4> , The photosensitive composition characterized by the above-mentioned.

[2] The photosensitive composition according to [1], wherein the number average molecular weight (Mn (A)) of the polymer (A) is 1.5 × 10 ⁴ ≦ Mn (A) ≦ 6 × 10 ⁴ .

[3] The photosensitive composition as described in [1] or [2], in which the polymer (A) has an acidic group.

[4] The fluorine atom content ratio in the polymer (A) is 20? 50 mass% [1]? The photosensitive composition in any one of [3].

[5] The ratio of the polymer (A) in the total solid of the photosensitive composition is 0.07? [1] which is 1 mass%? The photosensitive composition in any one of [4].

[6] [1], wherein the polymer (A) further has at least one member selected from the group consisting of an epoxy group, a mercapto group and a hydroxyl group. The photosensitive composition in any one of [5].

[7] [1], wherein the polymer (A) further has a side chain having a group represented by the following General Formula (2): The photosensitive composition in any one of [6].

[Formula 1]

(In formula, R <^1> and R <^2> is respectively independently the alkyl group, the cycloalkyl group, or the aryl group which may be substituted by the hydrogen atom or the fluorine atom, R <^3> is a hydrogen atom or a C1-C10 organic group, n Represents an integer of 1 or more and 200 or less, respectively)

[8] A polymer (A) having no side chain having a group represented by the general formula (1), a side chain having a group represented by the general formula (2), and no side chain having an ethylenic double bond. [1] which further contains the polymer (A) 'whose mass mean molecular weight (Mw (A)') is 4.2x10 < ⁴ <Mw (A) '<20x10 < ⁴ >? The photosensitive composition in any one of [7].

[9] The photocuring initiator (B) is a photopolymerization initiator, and the binder resin (C) is a photosensitive resin having an acidic group and an ethylenic double bond. The photosensitive composition in any one of [8].

[10] The photosensitive composition according to [9], further comprising a crosslinking agent (D) having two or more ethylenic double bonds.

[11] Furthermore, [1] containing a black coloring agent (E). The photosensitive composition in any one of [10].

[12] A partition wall formed in a form in which a substrate is divided into a plurality of sections for pixel formation, [1]? The partition which consists of a coating film hardened | cured material of the photosensitive composition in any one of [11].

[13] A color filter having a partition located between a plurality of pixels and adjacent pixels on a substrate, wherein the partition is formed by the partition described in [12], wherein the pixel is formed by an inkjet method. Color filter.

[14] An organic EL device having barrier ribs positioned between a plurality of pixels and adjacent pixels on a substrate, wherein the barrier ribs are formed by barrier ribs as described in [12], and the pixels are formed by an inkjet method. An organic EL element.

In addition, in this specification, the term "photocuring initiator" is used as a generic term of the compound which generate | occur | produces active species by light irradiation and starts hardening reaction of the said binder resin (C).

According to the photosensitive composition of the present invention, an economically advantageous ink repellent ink component is used for the resulting partition wall to have good ink repellency in the upper part of the partition wall, developer resistance not to be eroded into the developer, and good wetting of the partition wall openings. Diffusion can be provided. According to the present invention, by using the photosensitive composition of the present invention, a partition which is economically advantageous and excellent in performance, a color filter having the partition and an organic EL element are obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a photograph which shows the result of evaluating the wettightness of the ink in an opening between partition walls about the board | substrate sample which has a partition obtained by the Example and the comparative example.

EMBODIMENT OF THE INVENTION Although the form for implementing this invention is demonstrated below, this invention is not limited to the following embodiment.

In addition, in this specification, unless otherwise indicated,% shows the mass%. In addition, a (meth) acryloyl group is used as a generic term meaning both acryloyl group and methacryloyl group. (Meth) acrylate is used as a generic term which means both an acrylate and a methacrylate. (Meth) acrylic acid is used as a generic term meaning both acrylic acid and methacrylic acid. (Meth) acrylamide is used as a generic term which means both acrylamide and methacrylamide. (Meth) allyl is used as a general term which means both allyl and metallyl. The group represented by General formula (1) is also called group (1). The other prayer is the same.

<1> photosensitive composition

The photosensitive composition of this invention has a side chain which has a group represented by following General formula (1), and does not have a side chain which has an ethylenic double bond, The mass mean molecular weight (Mw (A)) is 4.2x10 <^4> It is a photosensitive composition containing the polymer (A) of <Mw (A) <= 20x10 <^4> , a photocuring initiator (B), and binder resin (C).

-CFXR ^f . (One)

(Wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group or a fluorine atom having 1 to 20 carbon atoms which may have an ether oxygen atom)

The photosensitive composition of this invention is a photosensitive composition containing the said polymer (A), a photocuring initiator (B), and a binder resin (C), and is binder resin (C) in the light irradiation part at the time of exposure in photolithography etc. It is a negative photosensitive composition hardened | cured by the action of a photocuring initiator (B). In photolithography or the like, a portion (unexposed portion) to which light is not irradiated is selectively removed at the time of alkali development subsequent to exposure, and as a result, a partition wall formed of a cured product of the photosensitive composition is formed. .

A negative photosensitive composition is classified into several types, such as a radical curing type and an acid hardening type, depending on the kind of hardening, for example, The photocuring initiator (B) and binder resin (C) to be used according to the kind of hardening. ) Is selected. If the photosensitive composition of this invention is applicable to any hardening type as long as it is a negative photosensitive composition, it is especially preferable for the radical curable photosensitive composition. EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the photosensitive composition of this invention is described as an example of a radical curable photosensitive composition and an acid-curable photosensitive composition.

(1) radically curable photosensitive composition

When the photosensitive composition of the present invention is a radical curable type, the photosensitive composition is photosensitive having a polymer (A), a photopolymerization initiator (B1) as a photocuring initiator (B), and an acidic group as a binder resin (C) and an ethylenic double bond. It contains resin (C1). In such a radically curable photosensitive composition, the photosensitive resin (C1) is radically polymerized by the action of the photopolymerization initiator (B1) in the light irradiation part during exposure in photolithography or the like, and curing is accelerated to form a coating film cured product.

Each component which the radically curable photosensitive composition which concerns on this invention contains is demonstrated below.

(1-1) Polymer (A)

Polymer (A) is a fluorine-containing polymer which has a side chain which has a group represented by the said General formula (1), and does not have a side chain which has an ethylenic double bond, The mass mean molecular weight (Mw (A)) is 4.2 10 ⁴ <Mw (A) ≤ 20 x 10 ⁴ .

Since the polymer (A) has the side chain which has the said fluorine atom containing group (1), and has a high molecular weight as mass mean molecular weight shows in the said range, it forms by apply | coating the photosensitive composition of this invention on a board | substrate. When drying the coating film used, it is easy to shift to the surface vicinity of a coating film. Moreover, although a polymer (A) does not have ethylenic double bond in a side chain, since it is high molecular weight like the said mass average molecular weight range, even when hardening of the photosensitive composition advances by exposure after coating film drying, the said coating film is carried out. It stays in the vicinity of the coating film surface shifted at the time of drying, and is easy to fix at that position. In the polymer (A), the developer solubility is also sufficiently secured by setting the mass average molecular weight within the above range. As a result, in the partition formed by developing the coating film after exposure, liquid repellency can be expressed on the upper surface, and lyophilic property can be expressed in the opening part between partitions. In addition, the migration of the polymer (A) to the openings can be suppressed at the time of heating after the development (post-baking), and the lyophilic properties can be expressed at the openings between the partition walls. For this reason, when the ink is applied to the openings surrounded by the partition walls using the inkjet method, the generation of mixed color between adjacent openings and the occurrence of whitening in the openings can be suppressed.

The mass mean molecular weight (Mw (A)) of the polymer (A) used in the present invention is 4.2 × 10 ⁴ <Mw (A) ≦ 20 × 10 ⁴ . More preferably, 4.5x10 <^4> Mw (A) <= 12x10 <^4> , Especially preferably, it is 5.0x10 <^4><Mw (A) <10x10 <^4> .

When the mass average molecular weight of the polymer (A) is 4.2 × 10 ⁴ or less, the lyophilic properties of the partition wall openings are insufficient, and when the ink is applied by the inkjet method, the ink is sufficiently wetted in the openings and does not diffuse. Moreover, when mass average molecular weight exceeds 20x10 < ⁴ >, alkali solubility and developability will become inadequate.

The polymer (A) also preferably has a number average molecular weight (Mn (A)) of 1.5 × 10 ⁴ ≦ Mn (A) ≦ 6.0 × 10 ⁴ , with 1.8 × 10 ⁴ ≦ Mn (A) ≦ 5.0 × 10 ⁴ It is more preferable that it is 2.0x10 <^4> Mn (A) <= 4.0x10 <^4> . If the number average molecular weight of the polymer (A) is less than 1.5 × 10 ⁴ , the lipophilic properties of the partition wall openings are insufficient, and when the ink is applied using the inkjet method, the ink may not be sufficiently wetted and diffused in the openings. When number average molecular weight exceeds 6.0x10 < ⁴ >, alkali solubility and developability may become inadequate.

In addition, in this specification, mass average molecular weight (Mw) and number average molecular weight (Mn) say the value which measured polystyrene as a reference substance by the gel permeation chromatography method.

The relationship between the mass average molecular weight and the number average molecular weight of the polymer (A) and the lyophilic property in the opening between the partition walls is uncertain. Generally, since the photosensitive composition, especially the photosensitive composition containing a black coloring agent, may not fully advance hardening reaction at the time of exposure, the polymer (A) which is not immobilized at the time of exposure is normally performed after exposure and development. At the time of the heat processing (to be described later) called post-baking, it may shift to the side surface of a partition, or may flow out to the opening part between partitions. If the mass average molecular weight of the polymer (A) exceeds 4.2 x 10 ⁴ , and more preferably, the number average molecular weight is 1.5 x 10 ⁴ or more, the migration and outflow phenomenon of the polymer (A) at the time of the post-baking is suppressed. It seems to be.

Moreover, it is preferable that the molecular weight distribution represented by the mass mean molecular weight (Mw (A)) / number average molecular weight (Mn (A)) in the polymer (A) used for this invention is 1.5 or more and 8.0 or less, It is 2.0 or more 4.0 or less are more preferable. If the molecular weight distribution in a polymer (A) is this range, the production process of a polymer (A) can be simplified, it is economically advantageous, and developability is also favorable.

The polymer (A) used for this invention has group (1) containing the fluorine atom represented by the said General formula (1) in a side chain. In the group (1), the carbon number in which R ^f may have an ether oxygen atom is 1? If the alkyl group in the 20-fluoro, R ^f is, it may have a halogen atom other than a fluorine atom. As such a halogen atom, a chlorine atom is preferable.

Moreover, it does not specifically limit as a structure of this fluoroalkyl group, Although a linear structure, a branched structure, a ring structure, the structure which has a ring partially, etc. are mentioned, A linear structure is preferable. In addition, when R <^f> is a fluoroalkyl group which has an ether oxygen atom, an ether oxygen atom may exist between the carbon-carbon bonds of a fluoroalkyl group, and may exist in the terminal of a fluoroalkyl group.

As R ^f in the group (1), the carbon number which may have the said etheric oxygen atom is 1? Preference is given to fluoroalkyl groups which are 20. Moreover, it is especially preferable that X is a fluorine atom.

When the above groups (1) of, R ^f is an ether group having the carbon number of 1 or less in St. fluoro-over 20 which may have an oxygen atom, R ^f roneun not particularly limited if they have the configuration. Specifically as R ^f , -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 is 1 ~ 8 -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).

When R ^f is a fluoroalkyl group having 1 to 20 carbon atoms which may have an ether oxygen atom, R ^f is a perfluoroalkyl group having no ether oxygen atom and a perfluoroalkyl group having ether oxygen atom It is preferable that the perfluoroalkyl group having no etheric oxygen atom is more preferable. The carbon number is 1? 11 is preferable, and 3? 5 is particularly preferred.

Among such groups (1), in the present invention, a perfluoroalkyl group or a polyfluoroalkyl group having one hydrogen atom is preferable, and a perfluoroalkyl group is particularly preferable. In addition, the thing which has an ether oxygen atom is contained in a perfluoroalkyl group and a polyfluoroalkyl group. Moreover, as a polyfluoroalkyl group which has one said hydrogen atom, the compound whose X is a hydrogen atom is preferable. Thereby, the liquid-repellent property of the upper surface becomes favorable for the partition formed using the photosensitive composition of this invention.

Moreover, group (1) has 4? 6 is preferred. As such group (1), specifically,-(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. 4 to 4 carbon atoms of group (1) which polymer (A) has in a side chain. If it is 6, the compatibility of the polymer (A) and the other component which comprises the photosensitive composition can be improved. Thereby, aggregation of the polymer (A) in the coating film formed by apply | coating a photosensitive composition can be suppressed, As a result, the partition with favorable external appearance can be formed.

In addition, in the polymer (A), the number of introduction of the group (1) in the side chain which has group (1) is 1. In each side chain which has group (1) of a polymer (A), group (1) may be same or different. That is, only 1 type may be sufficient as the group (1) which a polymer (A) has in a side chain, and 2 or more types of combinations may be sufficient as it. In addition, in the polymer (A) used for this invention, although the group (1) may be introduce | transduced in all the side chains, Preferably it is the group (1) with respect to the whole polymer (A) so that it may become the following fluorine atom content. The ratio of the side chains to be introduced is appropriately adjusted. Specifically, when producing a polymer (A) by superposition | polymerization of a raw material monomer as mentioned later, the compounding quantity with respect to the whole raw material monomer of the monomer which has group (1) is adjusted.

Moreover, the introduction position of the side chain which has group (1) in a polymer (A) is not restrict | limited, Preferably it is regular interval with regularity so that it may become the following fluorine atom content, Or randomly, the side chain which has group (1) can be introduce | transduced into the main chain which comprises a polymer (A). Thus, as long as the polymer (A) is in the range of the mass average molecular weight of the said invention, the side chain which has group (1) may be introduce | transduced in the form of an alternating copolymer, a block copolymer, and a random copolymer. However, it is preferable that it is a random copolymer from a viewpoint of manufacture efficiency, the intramolecular uniformity of a liquid repellent component, and compatibility with components other than a liquid repellent component. Moreover, it is preferable to introduce | transduce randomly by the random copolymerization similarly to introduction of the side chain which has group (1) also about the side chain which has the various groups introduce | transduced arbitrarily described below.

In the polymer (A) used for this invention, content of the fluorine atom in a polymer (A) by mainly having a side chain which has group (1) is 20? It is preferable that it is 50 mass%, and it is 25? It is more preferable that it is 42 mass%, and it is 25? It is especially preferable that it is 35 mass%. When content of the fluorine atom in this polymer (A) is less than 20 mass%, there exists a tendency for sufficient image development tolerance not to be obtained, and as a result, the liquid repellency of the upper surface of a partition may become inadequate. Moreover, when content of the fluorine atom in a polymer (A) exceeds 50 mass%, there exists a tendency for polymer (A) to self-aggregate, and as a result, the liquid repellency of the upper surface of a partition may become inadequate. Moreover, the adhesiveness of a partition and a board | substrate may fall.

In addition, the fluorine atom content in a polymer (A) is content derived from the fluorine atom which the said group (1) which a polymer (A) has in a side chain mainly. For example, when the polymer (A) has a fluorine atom which does not originate in the said group (1), such as a fluorine atom which directly bonds to the carbon of a main chain, or the fluorine atom derived from the monomer which has group (2) When it has, the content of the fluorine atom which combined the fluorine atom which the said group (1) has and the fluorine atom which a polymer (A) has other than group (1) is said.

The polymer (A) which the photosensitive composition of this invention contains can have a side chain which has a functional group according to various objectives other than the side chain which has the said group (1) in the range which does not impair the effect of this invention. As an example of introduction of a functional group to such a polymer (A) side chain, for example, a group having a siloxane bond represented by the following general formula (2) for the purpose of improving ink decay and UV ozone resistance (hereinafter, group ( 2) may be introduced into the side chain of the polymer (A).

[Formula 2]

(In formula, R <^1> and R <^2> is respectively independently the alkyl group, the cycloalkyl group, or the aryl group which may be substituted by the hydrogen atom or the fluorine atom, R <^3> is a hydrogen atom or an organic group of 1-10 or more, n is , An integer of 1 or more and 200 or less, respectively)

In the said group (2), R <^1> and R <^2> may be the same for every structural unit, and may differ. When R <^1> , R <^2> is an alkyl group, preferable carbon number is 1? 10, and more preferable carbon number is 1? 6 The alkyl group may have a linear structure or a branched structure. When R <^1> , R <^2> is a cycloalkyl group, preferable carbon number is 3? 10 and a more preferable carbon number is 5 or 6. When R <^1> , R <^2> is an aryl group, preferable carbon number is 6? 15 and more preferable carbon number is 6? 10 is. Some or all of the hydrogen atoms of R ¹ and R ² may be substituted with fluorine atoms. Moreover, when the liquid repellency of the partition formed using the photosensitive composition containing a polymer (A) is considered, it is preferable that R <^1> and R <^2> are respectively independently a hydrogen atom, a methyl group, a trifluoromethyl group, or a phenyl group. It is particularly preferable that R ¹ and R ² of all the siloxane units are a methyl group. Moreover, when R <^3> is a C1-C10 organic group, R <^3> may have a nitrogen atom, an oxygen atom, a fluorine atom, etc. In this invention, R <^3> is a hydrogen atom, C1-C? 1 to 5 carbon atoms substituted with an alkyl group or a fluorine atom; It is preferable that it is an alkyl group of 5, More preferably, it is a trifluoromethyl group or a methyl group. In group (2), n is 2? It is preferable that it is an integer of 100.

When the polymer (A) has a side chain which has group (2), group (2) may be used individually by 1 type and 2 or more types may be used together. Moreover, content of the silicon atom derived from group (2) in a polymer (A) is 0.1? It is preferable that it is 25 mass%, and is 0.5? It is more preferable that it is 20 mass%. When content of a silicon atom exists in this range, the said effect can be provided to a polymer (A), without impairing the effect of this invention. In addition, adjustment of the silicon atom content in a polymer (A) makes the compounding quantity with respect to the whole raw material monomer of the monomer which has group (2) when manufacturing a polymer (A) by superposition | polymerization of a raw material monomer as mentioned later. It is performed by adjusting suitably.

It is preferable that a polymer (A) further has a side chain which has an acidic group. Introduction of the side chain which has an acidic group in a polymer (A) is performed in order to improve developability. The developing solution used for the developing photosensitive composition is generally an alkaline developing solution, and the developer solubility of a polymer (A) becomes favorable by introducing an acidic group. As a result, good development can be performed. In addition, 1 type may be sufficient as the acidic group which a polymer (A) has in a side chain, and 2 or more types may be sufficient as it.

Although it does not specifically limit as an acidic group introduce | transduced into a polymer (A), A carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, etc. are mentioned. In addition, in the polymer (A) used for this invention, when manufacturing a polymer (A) by superposition | polymerization of a raw material monomer, it is a polymer (A) obtained by obtaining the compounding quantity with respect to the whole raw material monomer of the monomer which has an acidic group as mentioned later. It is implemented by adjusting suitably so that A) becomes the following preferable acid value.

It is preferable that acid value of a polymer (A) is 100 mgKOH / g or less, and it is 10? 50 mgKOH / g is more preferable. If the acid value is within this range, the development of the unexposed portion can also be performed satisfactorily, and the liquid repellency of the exposed portion is also likely to be maintained high. In addition, an acid value is the mass [mg] of potassium hydroxide required in order to neutralize 1 g of samples, and in this specification, a unit is described as mgKOH / g.

It is preferable that a polymer (A) also has a side chain which has the functional group which can crosslink-react with the functional group which the matrix which comprises a partition by heat and light, such as an epoxy group, a mercapto group, and a hydroxyl group, has. These functional groups introduced into a polymer (A) may be used individually by 1 type, and may use 2 or more types together.

The photosensitive composition of this invention contains a photocuring initiator (B) and binder resin (C) other than a polymer (A). This binder resin (C) is hardened | cured by the effect | action of a photocuring initiator (B) by exposing. When producing a partition using a photosensitive composition, unexposed parts other than the part hardened | cured by pattern exposure are removed with a developing solution. When performing photolithography using the negative photosensitive composition like the photosensitive composition of this invention, the combination of the binder resin (C) which has an acidic group, and alkaline developing solution is used normally.

When the polymer (A) has a functional group capable of thermal crosslinking with an acidic group such as an epoxy group, a hydroxyl group, and the like, the acidity derived from the binder resin (C) that these functional groups of the polymer (A) have in the partition matrix by post-baking treatment after exposure and development. By thermal crosslinking with the group, the polymer (A) is sufficiently fixed to the partition wall. In addition, in the case where the polymer (A) has the acidic group and the thermally crosslinkable functional group together with the acidic group, the polymers (A) are thermally crosslinked with each other in a portion where the polymer (A) on the upper surface of the partition wall has a high density, thereby polymerizing more polymerized. It becomes a state fixed enough to a partition. Moreover, when a polymer (A) has a mercapto group, it is carried out similarly to the above, and crosslinks with the ethylenically unsaturated double bond derived from binder resin (C) by a postbaking process, and is fully fixed to a partition. Thereby, after that, it becomes possible to prevent the outflow or elution of the polymer (A) from the partition to the ink which is concerned at the time of ink injection into the partition opening by inkjet.

In addition, introduction of the side chain which has the functional group which the partition matrix has to the polymer (A), and the functional group which can be thermally crosslinked, will be mentioned later, when manufacturing a polymer (A) by superposition | polymerization of a raw material monomer, The amount of the monomer having the functional group and the thermally crosslinkable functional group to the entire raw material monomer is not spilled or elution of the polymer (A) at the time of the ink injection into the polymer (A) without impairing the effect of the present invention. It adjusts suitably so that it may be a compounding quantity which can provide the effect to suppress.

(Production of Polymer (A))

About the polymer (A) used for this invention, it is set as the structure which has a side chain which has the said group (1), and also optionally has the side chain which has the said group (2), the side chain which has an acidic group, and the partition matrix In order to set it as the structure which has a side chain which has a functional group and the functional group which can be bridge | crosslinked by heat or light, the method of forming the side chain which has these groups directly by a polymerization reaction, or by chemical conversion after a polymerization reaction is mentioned. have.

In order to form the side chain which has the group (1) which a polymer (A) has essentially, and the side chain which has said each group which has optionally, by a polymerization reaction, the monomer which has group (1), and if needed, What is necessary is just to copolymerize the monomer which has group (2), the monomer which has an acidic group, the monomer which has a functional group which a partition matrix has, and the functional group which can be thermally crosslinked, and / or other monomer, selecting suitable conditions.

In addition, examples of the type of copolymerization include alternating copolymerization, block copolymerization, random copolymerization, and the like, and copolymerization can be carried out by conventionally known methods, respectively. In the present invention, the polymer (A) is copolymerized by random copolymerization. It is preferable that it is a random copolymer obtained.

It is preferable that it is a compound represented by following General formula (3) as a monomer which has the said group (1) used for manufacture of a polymer (A). These may be used individually by 1 type and may use 2 or more types together.

CH ₂ = CR ⁴ -COO-Y-CFXR ^f . (3)

(In formula (3), R <^4> is a C1-C20 fluoroalkyl group and cyano group which may have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, and an ether oxygen atom. Or an alkyl group substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, Y being a single bond or a fluorine atom having 1 to 6 carbon atoms. A divalent organic group having no -CFXR ^f is a group corresponding to the above group (1), that is, X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents an etheric oxygen atom. Fluoroalkyl group having 1 to 20 carbon atoms or fluorine atom)

Preferable embodiments of -CFXR ^f in the compound (3) are the same as those described for the group (1).

In the formula (3), among the groups represented by Y, the carbon number is 1? Y, which is a divalent organic group having no fluorine atom, 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 single bond or an alkylene group having 1 to 4 carbon atoms, provided that when R ⁶ is a methyl group, NR ^Carbon number of R <^5> bonded to ⁶ is 1-5.) Etc. are mentioned. Specifically as R ⁵ , —CH ₂ —, —CH ₂ CH ₂ —, —CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH _2- , -CH (CH ₂ CH (CH ₃ ) ₂ )-and the like. 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 —, and —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 Y in the compound (3), the carbon number is 2? Preference is given to alkylene groups of four.

Among the groups represented by R ⁴ in the compound (3), a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a benzyl group, etc. are preferable, and a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, Or a trifluoromethyl group is more preferable. As R ⁴ , a hydrogen atom or a methyl group is particularly preferable. That is, it is especially preferable that compound (3) is (meth) acrylate.

As a compound represented by General formula (3), 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, etc. are mentioned preferably.

It is preferable that it is a compound represented by following General formula (4) as a monomer which has the said group (2) used for manufacture of a polymer (A) as needed. These may be used individually by 1 type and may use 2 or more types together.

(3)

(In formula (4), R <^8> is a hydrogen atom or a methyl group, Z is a single bond or a divalent organic group having 1 to 6 carbon atoms. In addition, a group having a siloxane bond bonded to Z is the group (2). That is, R ¹ and R ² are each independently an alkyl group, a cycloalkyl group, or an aryl group which may be substituted with a hydrogen atom or a fluorine atom, and R ³ is a hydrogen atom or a carbon number of 1 to 10; Organic group, n is an integer of 1 to 200)

Preferable embodiments of R ¹ , R ² , R ³ and n in the compound (4) are the same as those described for the group (2).

Among the groups represented by Z, as Z contained in the compound (4), the carbon number is 1? A divalent hydrocarbon group of 6 is preferable, and specifically, -CH _2- , -CH ₂ CH _2- , -CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -C (CH ₃ ) _2- , -CH (CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH ₂ ) ₃ CH _2- , -CH (CH ₂ CH (CH ₃ ) ₂ )-and the like. As Z, C2? Particularly preferred is a linear alkylene group of 4.

As a monomer which has the said acidic group used as needed for manufacture of a polymer (A), if it has an acidic group, it will not specifically limit, The monomer which has a carboxyl group, the monomer which has a phenolic hydroxyl group, the monomer which has a sulfonic acid group, etc. are mentioned. have. These may be used individually by 1 type and may use 2 or more types together.

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 salts thereof.

As a monomer which has a phenolic hydroxyl group, 1 or more hydrogen atoms of o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, and these benzene rings, alkyl groups, such as a methyl group, an ethyl group, n-butyl group, Alkoxy groups, such as a methoxy group, an ethoxy group, and n-butoxy group, a halogen atom, the compound substituted by the haloalkyl group which has one or more halogen atoms, a nitro group, a cyano group, and an amide group, etc. are mentioned.

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid 2-sulfoethyl, and (meth) acrylic acid 2-sulfo Propyl, 2-hydroxy-3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, and the like.

As a monomer which has a functional group which can be bridge | crosslinked with the said partition wall matrix used as needed for manufacture of a polymer (A), and a crosslinkable functional group (henceforth a "crosslinkable functional group" hereafter), it has a crosslinkable functional group especially. It is not limited. Specifically, the monomer which has an epoxy group, the monomer which has a hydroxyl group, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Moreover, it is preferable that the monomer which has a crosslinkable functional group does not have group (1) and group (2) substantially.

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

As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N -Hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, and the like.

Moreover, about the side chain which has the mercapto group illustrated above as a crosslinkable functional group, a thiocarboxylic acid ester can be introduce | transduced into a polymer terminal by using a thiocarboxylic acid ester compound as a chain transfer agent. Furthermore, by treating the polymer with an acid or an alkali, a thiocarboxylic acid ester can be decomposed to obtain a polymer having a mercapto group at its terminal. A thiocarboxylic acid ester compound is a compound which substituted the carboxyl group of thioacetic acid, thiopropionic acid, thiobutyric acid, and thiobenzoic acid with -COSH group, for example.

As monomers other than the above which can be arbitrarily used for manufacture of a polymer (A), hydrocarbon type olefins, vinyl ether, isopropenyl ether, allyl ether, vinyl ester, allyl ester, (meth) acrylic acid Esters, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes, and the like, and in consideration of heat resistance of partition walls, (meth) acrylic acid esters or (meth) acrylamides are preferable. Do. In addition, these compounds may have functional groups, such as a carbonyl group and an alkoxy group.

In order to manufacture the polymer (A) used for this invention, the monomer used for superposition | polymerization is selected suitably from the above-mentioned monomer, and it copolymerizes in an appropriate ratio. In addition, the preferable compounding ratio of the various monomers used when manufacturing a polymer (A) is as follows.

As for the ratio of the monomer mass which has group (1) with respect to the total mass of the monomer to copolymerize, the fluorine atom content in a polymer (A) is the said preferable range, specifically, it is 25? 50 mass%, More preferably, it is 30? It is preferable to set it as the ratio used as 42 mass%. As such a ratio, although depending also on the kind of monomer which has group (1), specifically, it is 20? It is preferable that it is 80 mass%, and it is 30? 60 mass% is more preferable. When this ratio is too low, sufficient fluorine atom content cannot be ensured, sufficient development resistance will not be obtained, and a polymer (A) will be in the vicinity of the upper surface of the partition formed using the photosensitive composition of this invention. It becomes difficult to implement, and as a result, the liquid repellency of the upper surface of a partition may become inadequate. Moreover, when this ratio is too high, the fluorine atom content exceeds the preferable range, and the polymers (A) tend to self-aggregate, and as a result, the liquid repellency of the upper surface of a partition may become inadequate. Moreover, the adhesiveness of a partition and a board | substrate may fall.

In addition, when using the monomer containing a fluorine atom other than the monomer which has group (1) as a raw material monomer at the time of manufacture of a polymer (A), the fluorine atom content in the polymer (A) obtained has the said preferable range. What is necessary is just to adjust the ratio of each raw material monomer suitably so that it may be.

In the case of the superposition | polymerization of a polymer (A), when using the monomer which has group (2) as needed, the ratio of the mass of the monomer which has group (2) with respect to the total mass of the monomer to copolymerize is in a polymer (A). Silicon atom content of the said preferable range, specifically, 0.1? 25 mass%, More preferably, it is 0.5? It is preferable to set it as the ratio used as 20 mass%. As such a ratio, although depending on the kind of monomer which has group (2), it is specifically 0.5? It is preferable that it is 30 mass%, and 2? 20 mass% is more preferable. If the ratio of the monomer which has group (2) in all the monomers to copolymerize is this range, the silicon atom content in a polymer (A) will become the said preferable range generally, and ink fallability, UV ozone resistance, etc. will become favorable. .

When using the monomer which has an acidic group as needed at the time of superposition | polymerization of a polymer (A), as for the ratio of the mass of the monomer which has an acidic group with respect to the total mass of the monomer to copolymerize, the acid value of a polymer (A) is the said preferable range, Specifically, it is 100 mgKOH / g or less, More preferably, it is 10? It is preferable to set it as the ratio used as 50 mgKOH / g. As such a ratio, although depending on the kind of monomer which has an acidic group, it is specifically 2? It is preferable that it is 20 mass%, and 4? 12 mass% is more preferable. If the ratio of the monomer which has an acidic group in all the monomers to copolymerize is this range, the image development of an unexposed part can also be performed favorably, without impairing the effect of this invention.

In the case of superposition | polymerization of a polymer (A), when using the monomer which has the said crosslinkable functional group as needed, the ratio of the monomer mass which has a crosslinkable functional group with respect to the total mass of the monomer to copolymerize is 1? It is preferable that it is 40 mass%, and 5? 20 mass% is more preferable. If the ratio of the monomer which has a crosslinkable functional group in all the monomers to copolymerize is this range, immobilization to the partition of a polymer (A) will be attained and developability will be favorable, without impairing the effect of this invention.

In the case of superposition | polymerization of a polymer (A), when using other monomers other than the above as needed, it is preferable that the ratio of the other monomer mass with respect to the total mass of the monomer to copolymerize is 70 mass% or less, and 50 mass% The following is more preferable. When the ratio of this mass exceeds 70 mass%, alkali developability may fall.

The polymer (A) used for this invention has a side chain which has the said group (1) as an essential structure, and also optionally, the side chain which has the said group (2), the side chain which has an acidic group, and a crosslinkable functional group. As a copolymer which has a side chain which has, etc., the monomer which has group (1), the monomer which has group (2), the monomer which has an acidic group, the monomer which has a crosslinkable functional group, and / or other monomer as needed It can synthesize | combine by melt | dissolving in a solvent and heating, and adding and copolymerizing a polymerization initiator. In addition, when copolymerizing, it is preferable to add a chain transfer agent as needed. Moreover, you may add a monomer, a polymerization initiator, a solvent, and a chain transfer agent continuously. Here, adjustment of the mass average molecular weight of a polymer (A) can be performed by adjustment of conditions, such as polymerization temperature and time, the quantity of a polymerization initiator, the addition amount of a chain transfer agent, etc.

Although the polymer (A) manufactured in this way is random copolymerization, a block copolymer can also be manufactured using conventional methods, such as changing the introduction timing of a raw material monomer to a copolymerization reaction system according to the kind of monomer.

As a solvent used for the superposition | polymerization of the said polymer (A), For example, alcohol, such as ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol; Acetone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; cellosolves such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2 Carbitols such as-(2-butoxyethoxy) ethanol; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Esters such as ethylene glycol diacetate and glycerin triacetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl 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 and an inorganic peroxide can also be used as a redox catalyst in combination with a reducing agent. These polymerization initiators may be used independently and may use 2 or more types together.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, t-butyl-α-cumyl peroxide, and the like. Examples of the inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonates. 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'-azobisisobutyric acid Dimethyl, 2,2'- azobis (2-amidinopropane) dihydrochloride, etc. are mentioned.

Examples of the chain transfer agent include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-thiohexyl 2-ethylhexyl and 2-mercaptoethanol; chloroform, Alkyl halides, such as carbon tetrachloride and carbon tetrabromide, are mentioned.

Here, the side chain which has the said various group in the polymer (A) used for this invention, especially the side chain which has an acidic group, a side chain which has a heat crosslinkable functional group, etc. can be formed also by the chemical conversion after a polymerization reaction. For example, an acidic group is produced by producing a copolymer having a side chain having a group (1) and a side chain having a hydroxyl group by the polymerization, and reacting a polybasic anhydride (maleic anhydride or the like) with the hydroxyl group of the copolymer. As a polymer (A) having a side chain having a carboxyl group can be produced.

In the radically curable photosensitive composition according to the present invention, the polymer (A) is 0.07? To the total solid of the composition. It is preferable to contain in the ratio of 1 mass%, and is 0.1? It is more preferable to contain in the ratio of 0.5 mass%. When this content is too small, the liquid repellency of the upper surface of the partition formed using the photosensitive composition of this invention may become inadequate, and when there is too much content, the adhesiveness of a partition and a board | substrate may fall.

Moreover, in the radical curable photosensitive composition which concerns on this invention, in addition to the said polymer (A), it can contain the component which can provide a liquid repellent effect to a partition. As such a component, specifically, the polymer which has a side chain which has a group represented by the said General formula (2) which does not have a side chain which has the said group (1), and does not have a side chain which has an ethylenic double bond ( 'as, weight average molecular weight (Mw (a)' a) there may be mentioned a) ^{a, 4.2 × 10 4 <Mw (} a) '≤ 20 × 10 4 a polymer (a) ".

In other words, the polymer (A) 'is a polymer having essentially the side chain having the group (2) instead of the side chain having the group (1) in the polymer (A). Moreover, in the said polymer (A), in addition to the side chain which has group (1), the structure was described about the polymer (A) which has a side chain which has group (2), and polymer (A) ', Except not having the side chain which has group (1), it can be set as the structure similar to the structure.

Specifically, the silicon atom content in the polymer (A) 'is preferably 0.1? 25 mass%, 0.5? It is more preferable that it is 20 mass%. When content of a silicon atom exists in this range, the effect of improving the liquid repellency of the partition surface obtained using this will be provided to the photosensitive composition of this invention, without impairing the effect of this invention. The polymer (A) 'may have a side chain optionally having a side chain having an acidic group, a functional group possessed by the partition matrix and a side chain having a functional group crosslinkable by heat or light, and the like as the polymer (A). Also about the polymerization reaction for making a structure which has the structure which does not have a monomer, it has the said polymer (A) and it does not use the monomer which has group (1) as a raw material monomer, and uses the monomer which has group (2) as an essential raw material monomer. The same can be done.

Moreover, in the radical curable photosensitive composition which concerns on this invention, when using the said polymer (A) ', it is 0.5-about the total solid of a composition. It is preferable to contain in the ratio of 30 mass%, and it is 2? It is more preferable to contain in the ratio of 20 mass%. By using it in this content, the effect which improves the liquid repellency of the partition surface obtained using this can be provided to the photosensitive composition of this invention, without impairing the effect of this invention. Moreover, when using the said polymer (A) ', even if it uses the polymer (A) which does not have a side chain which has group (2) as a polymer (A) used together, it can exhibit the same effect as the above. have.

(1-2) Photocuring initiator (B) (photoinitiator (B1))

When the photosensitive composition of this invention is a radical curing type, as a photocuring initiator (B), the photoinitiator (B1) which generate | occur | produces a radical by irradiation of light is used.

It will not specifically limit, if it is a compound which generate | occur | produces a radical by light irradiation as a photoinitiator (B1). Specifically, α-diketones such as benzyl, diacetyl, methylphenylglyoxylate, 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Acyloin ethers, such as an ether; Thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2, 4- dimethyl thioxanthone, isopropyl thioxanthone, 2, 4- diethyl thioxide Thioxanthones, such as a tontone, a 2, 4- dichloro thioxanthone, a 2, 4- diisopropyl thioxanthone, and a thioxanthone-4- sulfonic acid; benzophenone, 4, 4'-bis (dimethylamino) benzo; Benzophenones such as phenone and 4,4'-bis (diethylamino) benzophenone; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2, 2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2- Dimethylamino-1- (4-morpholino Acetophenones such as nil) -butan-1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate and 4-dimethylaminobenzoic acid Aminobenzoic acids such as ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoamyl and 4-dimethylaminobenzoic acid 2-ethylhexyl; phenacyl chloride, trihalomethylphenylsulfone, etc. Halogen compounds; acylphosphine oxides; peroxides such as di-t-butylperoxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone Oxime esters, such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl oxime), etc. are mentioned, It uses 2 or more types together. You may also

Among these, as a photoinitiator (B1) used for this invention, the compound represented by following General formula (5) is preferable.

[Formula 4]

(In formula, R <^21> is a hydrogen atom, a C1-C12 alkyl group, a C3-C8 cycloalkyl group, a C2-C5 alkenyl group, an alkyl group substituted or unsubstituted C6-C20 phenyl group, or a substituted or unsubstituted 6? 20 of the phenoxy group with an alkyl group, R ²² is a hydrogen atom, a carbon number of 1? 20 alkyl group, the carbon number is 3? 8, a cycloalkyl group, a substituted or unsubstituted C 6 alkyl groups? A phenyl group having 20 carbon atoms, alkanoyl group having 2 to 20 carbon atoms, a substituted or unsubstituted benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkyl group substituted or unsubstituted having 7 to 20 carbon atoms A phenoxycarbonyl group, 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, or an alkyl group; or Unsubstituted cyclohexyl having 3 to 8 carbon atoms Substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, alkanoyl group having 2 to 20 carbon atoms, substituted or unsubstituted benzoyl group having 7 to 20 carbon atoms, unsubstituted carbon group having 7 to 20 carbon atoms. A benzylcarbonyl group having 20 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms substituted or unsubstituted or substituted with an alkyl group, an amide group having 1 to 20 carbon atoms, or a nitro group)

In the compound represented by the general formula (5), as R ²¹ , a carbon number is 1? 6 to 6 carbon atoms substituted or unsubstituted or substituted with an alkyl group or alkyl group; The phenyl group which is 12 is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a phenyl group, etc. are mentioned. Among these, carbon number 1? An alkyl group of 4 is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

In the compound represented by the general formula (5), as R ²² , the carbon number is 1? An alkyl group having 10 or 2? 5 is alkoxycarbonyl group is preferable, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group Etc. can be mentioned. Especially, carbon number is 1? 6 is preferably an alkyl group, and the carbon number is 1? The alkyl group which is 3 is more preferable, and a methyl group is especially preferable.

In the compound represented by General Formula (5), the number of carbon atoms represented by R ²³ is 1? Examples of the 12 phosphorus alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. Among these, carbon number 1? The alkyl group which is 8 is preferable, and carbon number is 2? The alkyl group which is 6 is more preferable, and an ethyl group is especially preferable.

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

In the compound represented by the general formula (5), R ²⁵ is an alkyl group substituted or unsubstituted with 7 to 7 carbon atoms. Substituted or unsubstituted benzoyl or alkyl group having 20 carbon atoms of 7? A benzylcarbonyl group of 20 is preferable, and 2-methylbenzoyl group, benzylcarbonyl group, or 1,3,5-trimethylbenzylcarbonyl group is particularly preferable.

Although it does not specifically limit as a compound (O-acyl oxime type compound) represented by General formula (5), In general formula (5), R <^21> is a phenyl group, R <^22> octyl group, R <^23> ethyl group, R <^24> , R ²⁶ and R ²⁷ are hydrogen atoms, R ²⁵ is a benzoyl group; R ²¹ is a methyl group, R ²² is a butyl group, a heptyl group or an octyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, A compound in which R ²⁵ is a benzoyl group; R ²¹ is a phenyl group, R ²² is an octyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom, R ²⁵ is a 2-methylbenzoyl group; R ²¹ is a methyl group, R ²² is methyl or octyl, R ²³ is ethyl, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, R ²⁵ is 2-methylbenzoyl group; R ²¹ and R ²² are methyl, R ²³ is ethyl, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, R ²⁵ is 2-methyl-5-tetrahydrofuranylmethoxybenzoyl group, 2-methyl-4-tetrahydropyranylmethoxybenzoyl group or 2-methyl-5-tet The compound etc. which are a lahydropyranyl methoxy benzoyl group are mentioned.

A commercial item can be used as a photoinitiator (B1). As a commercial item, it is OXE02 (brand name, the Chiba Specialty Chemicals company make, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (for example). O-acetyl oxime): A compound in which R ²¹ and R ²² are a methyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are a hydrogen atom, and R ²⁵ is a 2-methylbenzoyl group in the general formula (5).) Can be mentioned.

Content of the photoinitiator (B1) in the radical curable photosensitive composition which concerns on this invention is 1-1 with respect to the total solid of a composition. It is preferable that it is 10 mass%, and 2? 5 mass% is more preferable. One ? If it is 10 mass%, sclerosis | hardenability is favorable and a pattern and line | wire width | variety which are close to a mask pattern can be formed by exposure and image development.

Furthermore, with a photoinitiator (B1), 2-mercapto benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1, 4- butanol bis (3-mercapto butyrate), and tris When thiol compounds, such as (2-mercapto propanoyloxyethyl) isocyanurate and pentaerythritol tetrakis (3-mercaptobutylate), are used, a sensitizing effect may be expressed.

(1-3) Binder Resin (C) (Photosensitive Resin (C1))

When the photosensitive composition of this invention is a radical curing type, as binder resin (C), the photosensitive resin (C1) which has an acidic group and ethylenic double bond superposed | polymerized by the radical which the said photoinitiator (B1) generate | occur | produced is used.

Since the photosensitive resin (C1) has an ethylenic double bond which participates in the said photopolymerization in one molecule, and also has an acidic group, it can selectively remove the unexposed part of the uncured photosensitive composition using alkaline developing solution, As a result, a partition can be formed. Moreover, it is preferable that the photosensitive resin (C1) does not have group (1) and group (2) substantially.

Although it does not specifically limit as an acidic group which photosensitive resin (C1) has, A carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, You may use 2 or more types together.

Although it does not specifically limit as ethylenic double bond which photosensitive resin (C1) has, The double bond which addition polymerizable groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyloxy group, has is mentioned, 2 You may use together a species or more. In addition, one part or all part of the hydrogen atom which these addition polymeric groups have may be substituted by the hydrocarbon group, Preferably the methyl group.

Although it does not specifically limit as photosensitive resin (C1), Specifically, ethylenic double bond and an acidic group are introduce | transduced into resin (C1-1) which has a side chain which has an acidic group, and a side chain which has an ethylenic double bond, and an epoxy resin. Resin (C1-2) etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Resin (C1-1) reacts with the side chain which has a reactive group, and the copolymer which has a side chain which has an acidic group obtained by copolymerizing the monomer which has a reactive group, such as a hydroxyl group, a carboxyl group, an epoxy group, and the monomer which has an acidic group, for example, It can synthesize | combine by dissolving the compound which has an ethylenic double bond, and the functional group which can couple | bond with respect to a genus group by making it react in a solvent. Moreover, although it does not specifically limit as a monomer which has a phosphoric acid group as an acidic group, 2- (meth) acryloyloxyethane phosphoric acid etc. are mentioned.

Resin (C1-2) can be synthesize | combined, for example by making an epoxy resin react with the compound which has a carboxyl group and ethylenic double bond, and then making polybasic carboxylic acid or its anhydride react. Specifically, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, the epoxy group of the carboxyl group and the epoxy resin reacts to introduce an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the hydroxyl group of resin in which ethylenic double bond was introduce | transduced.

Examples of the epoxy resin include, but are not particularly limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, trisphenol methane type epoxy resins, epoxy resins having a naphthalene skeleton, The epoxy resin which has a biphenyl skeleton represented by following General formula (6), the epoxy resin represented by following General formula (7), the epoxy resin represented by following General formula (8), etc. are mentioned.

[Chemical Formula 5]

(In formula (6), s is 1-50, and 2-10 are preferable.)

[Formula 6]

(In formula (7), R <^31> , R <^32> , R <^33> and R <^34> are respectively independently a hydrogen atom, a chlorine atom, or a C1-C5 alkyl group, and t is 0-10.)

[Formula 7]

(In Formula (8), the hydrogen atom of a benzene ring may respectively independently be substituted by the C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent. U is 0-10.)

Moreover, when making the polybasic carboxylic anhydride react after making the epoxy resin represented by General formula (6), General formula (7), or General formula (8) react with the compound which has a carboxyl group and ethylenic double bond, As the polybasic carboxylic anhydride, it is preferable to use a mixture of dicarboxylic anhydride and tetracarboxylic dianhydride. At this time, molecular weight can be controlled by changing the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride.

A commercial item can be used as resin (C1-2) which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin. As such a commercial item, all are brand names, KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, 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 Manufacture), EX1010 (made by Nagase Chemtex), etc. are mentioned.

The said photosensitive resin (C1) used for this invention has a mass mean molecular weight of 1.5 * 10 <^3> ? It is preferable that it is 30 * 10 <^3> , and it is 2.0 * 10 <^3> ? 15x10 ³ is more preferable. When this mass average molecular weight is less than 1.5x10 <^3> , hardening at the time of exposure may become inadequate, and when it exceeds 30x10 < ³ >, developability may fall.

It is preferable that it is three or more in 1 molecule on average, and, as for the number of the ethylenic double bond which the photosensitive resin (C1) has, 6 or more are more preferable. When the number of these ethylenic double bonds is three or more, a difference will arise easily in the alkali solubility of an exposure part and an unexposed part, and the fine pattern formation with a smaller exposure amount is attained.

The photosensitive resin (C1) has an acid value of 10? It is preferable that it is 300 mgKOH / g, and it is 30? 150 mgKOH / g is more preferable. 10? When it is 300 mgKOH / g, the developability of the photosensitive composition is favorable.

Content of the said photosensitive resin (C1) in the radical curable photosensitive composition which concerns on this invention is 5-5 with respect to the total solid of a composition. It is preferable that it is 80 mass%, and it is 10? 60 mass% is more preferable. 5? When it is 80 mass%, the developability of the photosensitive composition is favorable.

(1-3) Optional Ingredient

The radical curable photosensitive composition which concerns on this invention is a photosensitive resin (C1) which has the said polymer (A), the photoinitiator (B1) as a photocuring initiator (B), and the acidic group as a binder resin (C) and ethylenic double bond. Is contained as an essential component, but the component described below can be contained for the purpose of improvement of various functions, etc. in the range which does not impair the effect of this invention.

(Crosslinking agent (D) having two or more ethylenic double bonds)

It is preferable that the radical curable photosensitive composition which concerns on this invention contains the crosslinking agent (D) which has 2 or more of ethylenic double bonds as an arbitrary component which accelerates radical hardening. Thereby, sclerosis | hardenability of the said photosensitive resin (C1) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced. Moreover, it is preferable that the said crosslinking agent (D) does not have an acidic group substantially.

It does not specifically limit as a crosslinking agent (D) which has 2 or more of ethylenic double bonds. Specifically, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanedi Oldi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, an ethoxy isocyanuric acid triacrylate, a urethane acrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

In this invention, a commercial item can be used as a crosslinking agent (D) which has two or more ethylenic double bonds. Such commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), and NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Industries, Ltd.) Isooxycyanuric acid triacrylate), NK ester A-9300-1CL (brand name, the Shin-Nakamura Chemical Co., Ltd. make, (epsilon) -caprolactone modified tris- (2-acryloxyethyl) isocyanurate), BANI-M ( Brand name, Maruzen petrochemical company make, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane), BANI-X (brand name, Maruzen petrochemical company And N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)).

Moreover, as urethane acrylate, KAYARAD UX series by Nippon Kayaku Co., Ltd. is mentioned, As a specific brand name, UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D- P20 etc. are mentioned. A-9300, BANI-M, and BANI-X are preferable from the viewpoint of providing hardness to the coating film and suppressing heat sagging. A-9300-1CL is preferable from the viewpoint of providing flexibility to the coating film. Since urethane acrylate can implement | achieve an appropriate image development time, and developability becomes favorable, it is preferable.

Content of the said crosslinking agent (D) in the radical curable photosensitive composition which concerns on this invention is 1-1 with respect to the total solid of a composition. It is preferable that it is 50 mass%, and 5? 30 mass% is more preferable. One ? If it is 50 mass%, developability of the photosensitive composition will become favorable.

(Black colorant (E))

When the hardened | cured material is used for the application which requires light-shielding property like a black matrix, the radical curable photosensitive composition which concerns on this invention contains a black coloring agent (E) according to the optical density of the partition which is requested | required.

Although it does not specifically limit as a black coloring agent (E), Metal particles, such as carbon black, aniline black, anthraquinone type black pigment, titanium black, silver tin alloy, a perylene type black pigment, etc. are mentioned. Specifically, C.I. Pigment black 1, 6, 7, 12, 20, 31, etc. are mentioned. Moreover, the black coloring agent (E) may be a mixture of organic pigments and inorganic pigments such as red pigments, blue pigments and green pigments. Among these, carbon black is preferable in consideration of the magnitude of light shielding properties. In addition, carbon black may be surface-treated with resin etc. Moreover, in order to adjust the color tone of a black coloring agent (E), carbon black can be used together with a blue pigment and a purple pigment.

Moreover, the carbon black used as a black coloring agent (E) has a specific surface area of 50? It is preferable that it is 200 m <2> / g. If the specific surface area is too small, deterioration of the shape of the partition wall may occur. If the specific surface area is too large, the dispersion aid described later is excessively adsorbed to the black colorant (E), and it is necessary to add a large amount of the dispersion aid. May occur.

Moreover, when the exposure sensitivity of the photosensitive composition is considered, it is preferable that the oil absorption amount of dibutyl phthalate is 120 cc / 100 g or less, and, as for carbon black used as a black coloring agent (E), it is more preferable that it is small.

Moreover, the carbon black used as a black coloring agent (E) has an average primary particle of 20? It is preferable that it is 50 nm. When this average primary particle size is too small, it becomes difficult to disperse | distribute to high concentration, the photosensitive composition with favorable time-lapse stability may not be obtained well, and when average primary particle size is too large, deterioration of the shape of a partition may be caused. have. Moreover, this carbon black has an average secondary input of 80? It is preferable that it is 200 nm. In addition, the particle size of carbon black can be measured using a transmission electron microscope.

In the radically curable photosensitive composition according to the present invention, the content of the black colorant (E) in the case of blending the black colorant (E) in order to impart light shielding properties such as a black matrix to the cured film of the coating is required. Although it depends on light intensity and optical density, with respect to the total solid of a composition, it is 15? It is preferable that it is 60 mass%, and it is 20? 50 mass% is more preferable, and 25? 40 mass% is especially preferable. When this content is too small, the optical density of a partition may be insufficient when it is set as a black matrix, etc., and when there is too much content, the curability of a photosensitive composition will fall, the external appearance of a partition will fall, and liquid repellency will fall There is.

(Polymer dispersant and dispersing aid)

When the radical curable photosensitive composition which concerns on this invention contains dispersible materials, such as said black coloring agent (E), in order to improve the dispersibility, it is preferable to contain a polymeric dispersing agent. The polymer dispersant is not particularly limited, and may be a urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride vinyl copolymer copolymer, Although polyamide type | system | group, a polycarbonate type, etc. are mentioned, Urethane type or Polyester type is preferable. In addition, the polymer dispersant may have a structural unit derived from ethylene oxide and / or propylene oxide.

When using a polymeric dispersant for dispersion of a black coloring agent (E), it is preferable to use the polymeric dispersing agent which has a basic group in consideration of affinity with respect to a black coloring agent (E). Basic groups include, but are not limited to, primary, secondary or tertiary amino groups.

A commercial item can be used as such a polymeric dispersing agent, As a commercial item, Disparon DA-7301 (brand name, the product made by Kusumoto Chemical Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all are brand names, BYK- above) Chemie Co., Ltd.), the sopase 5000, the sopase 17000 (all of the above are trade names, manufactured by Geneca), and the like.

The addition amount of the polymer dispersant is 5? With respect to dispersible materials such as a black colorant (E). It is preferable that it is 30 mass%, and it is 10? 25 mass% is more preferable. When this addition amount is too small, the effect of improving dispersibility may become inadequate, and when there is too much addition amount, developability of the photosensitive composition may fall.

Moreover, the radical curable photosensitive composition which concerns on this invention may contain a phthalocyanine pigment derivative and a metal phthalocyanine sulfonamide compound as a dispersion adjuvant. A dispersal auxiliary agent is considered to have a function which adsorb | sucks to dispersible materials, such as a black coloring agent (E), and a polymeric dispersing agent, and improves dispersion stability.

(Fine particles)

The radical curable photosensitive composition which concerns on this invention may contain microparticles | fine-particles as needed. Thereby, it can suppress that the shape of a partition is changed at the time of post-baking mentioned later.

The fine particles are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin dope indium oxide (ITO), and antimony-doped tin oxide (ATO); organic fine particles such as polyethylene and polymethyl methacrylate (PMMA) Can be mentioned. As microparticles | fine-particles, when considering heat resistance, inorganic type microparticles | fine-particles are preferable, and when considering availability and dispersion stability, silica or zirconia is preferable. Moreover, when the photosensitive composition contains a black coloring agent (E) and a polymeric dispersing agent in order to improve the dispersibility, when the adsorption ability of this polymeric dispersing agent is considered, it is preferable that microparticles | fine-particles are negatively charged. . In consideration of the exposure sensitivity of the photosensitive composition, it is preferable that the fine particles do not absorb light irradiated at the time of exposure, i-line (365 nm), h-line (405 nm), g, which are the main emission wavelengths of an ultrahigh pressure mercury lamp. It is particularly preferable not to absorb the line (436 nm).

The particle size of the fine particles is preferably 1 µm or less, more preferably 200 nm or less, from the viewpoint that the surface smoothness of the partition becomes good.

Content of the microparticles | fine-particles in the radical curable photosensitive composition which concerns on this invention is 3-3 with respect to the total solid of a composition. It is preferable that it is 30 mass%, and 5? 20 mass% is more preferable. When this content is too small, the shape of a partition may change at the time of postbaking, and when there is too much content, the dispersion stability of the photosensitive composition may fall.

(Silane coupling agent)

The radical curable photosensitive composition which concerns on this invention may contain the silane coupling agent as needed. Thereby, adhesiveness of a partition and a board | substrate can be improved.

It does not specifically limit as a silane coupling agent. Specifically, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, polyoxyalkylene having a triethoxysilyl group, already A dazol silane etc. are mentioned and you may use 2 or more types together.

(Thermosetting agent)

The radical curable photosensitive composition which concerns on this invention may contain the thermosetting agent as needed. Thereby, heat resistance and water permeability of a partition can be improved. Moreover, when the said polymer (A) has a heat crosslinkable functional group, the polymer (A) and a thermosetting agent chemically bond, and the effect which fixes a polymer (A) to a partition by this is also acquired.

Although it does not specifically limit as a thermosetting agent, Amino resin (melamine compounds, such as hexamethoxymethylol melamine, etc.), the compound which has 2 or more of epoxy groups, the compound which has 2 or more of hydrazino groups, a polycarbodiimide compound, an oxa The compound which has two or more sleepy groups, the compound which has two or more aziridine groups, a polyvalent metal, the compound which has two or more mercapto groups, a polyisocyanate compound, etc. are mentioned, You may use 2 or more types together. Among these, in consideration of the chemical resistance of the partition, an amino resin, a compound having two or more epoxy groups, or a compound having two or more oxazoline groups is preferable.

(Phosphate compound)

The radical curable photosensitive composition which concerns on this invention may contain the phosphoric acid compound as needed. This is preferable because the adhesion with the substrate can be improved. Examples of the phosphoric acid compound include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.

(Other optional ingredients)

Moreover, the radical curable photosensitive composition which concerns on this invention may contain the hardening accelerator, the thickener, the plasticizer, the antifoamer, the leveling agent, the anti-cratering agent, the ultraviolet absorber, etc. as needed in addition to the various components other than the above.

The radical curable photosensitive composition which concerns on this invention can be prepared by mixing the above-mentioned various essential components and arbitrary components added as needed uniformly according to the said compounding quantity by a conventional method.

(2) acid-curable photosensitive composition

In the case where the photosensitive composition of the present invention is an acid curing type, the photosensitive composition includes a polymer (A), a photo acid generator (B2) as a photocuring initiator (B), and a carboxyl group and / or phenolic hydroxyl group as a binder resin (C). It contains alkali-soluble resin (C21) which has, and crosslinkable resin (C22) which is a compound which has 2 or more of groups which can react with a carboxyl group and / or a phenolic hydroxyl group. Such an acid-curable photosensitive composition includes an alkali-soluble resin (C21) having an carboxylic group and / or a phenolic hydroxyl group, in which an acid is generated from a photoacid generator (B2) in a light irradiation part during exposure in photolithography or the like; The crosslinkable resin (C22) which is a compound which has a 2 or more group which can react with a carboxyl group and / or a phenolic hydroxyl group crosslinks-reacts, and forms cured film.

Each component which the acid-curable photosensitive composition which concerns on this invention contains is demonstrated below.

(2-1) Polymer (A)

The polymer (A) which the acid-curable photosensitive composition which concerns on this invention contains is a characteristic component in the photosensitive composition of this invention, including the preferable aspect, and the polymer (A) demonstrated in the said radical curable photosensitive composition is It is applicable in the acid-curable photosensitive composition. Moreover, content in the photosensitive composition of a polymer (A) can also be made to the same as the above. In addition to the polymer (A), the polymer (A) 설명한 described above can be used in the same manner as in the case of the radical curable photosensitive composition as a component capable of imparting a liquid repellent action to the partition wall.

(2-2) Photocuring initiator (B) (photoacid generator (B2))

When the photosensitive composition of this invention is an acid curing type, as a photocuring initiator (B), the photoacid generator (B2) which is a compound which generate | occur | produces an acid by light is used. As a photoacid generator (B2), a diaryl iodonium salt, a triaryl sulfonium salt, a triazine type compound, a sulfonyl compound, sulfonic acid ester, etc. are mentioned, for example.

As a specific example of the cation part of a diaryl iodonium salt, diphenyl iodonium, 4-methoxyphenylphenyl iodonium, bis (4-t- butylphenyl) iodonium, etc. are mentioned. Specific examples of the anion moiety of the diaryl iodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate and tetrafluoroborate And hexafluoroantimonate. Diaryl iodonium salt consists of a combination of 1 type of the said cation part, and 1 type of the said anion part. For example, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate etc. are mentioned.

Specific examples of the cation moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, and the like. Specific examples of the anion moiety of the triarylsulfonium salt include specific examples of the anion moiety of the diaryl iodonium salt. The triarylsulfonium salt consists of a combination of one kind of the cation moiety and one kind of the anion moiety. For example, triphenylsulfonium trifluoromethanesulfonate etc. are mentioned.

Specific examples of the triazine-based compound include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloro) Rhomethyl) -1,3,5-triazine, 2- (2-pril) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-pril) Ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxyphenyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine and the like Can be mentioned.

Specific examples of the sulfonyl compound include bis (phenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane and bis (p-toluenesulfonyl) Diazomethane etc. are mentioned.

Specific examples of the sulfonic acid esters include 2-nitrobenzyl p-toluenesulfonate, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, and the like.

The content of the photoacid generator (B2) in the acid-curable photosensitive composition according to the present invention is 0.1? To the total solid of the composition. 30 mass% is preferable and 1? 20 mass% is more preferable. The developability of the photosensitive composition becomes it favorable that it is the said range.

(2-2) Binder Resin (C) (Alkali-Soluble Resin (C21)? Crosslinkable Resin (C22))

When the photosensitive composition of this invention is an acid hardening type, as binder resin (C), alkali-soluble resin which has a carboxyl group and / or phenolic hydroxyl group crosslinked-polymerized by the action of the acid which the said photoacid generator (B2) generate | occur | produced ( The combination of C21) and crosslinkable resin (C22) which is a compound which has 2 or more of groups which can react with a carboxyl group and / or a phenolic hydroxyl group is mentioned.

(Alkali Soluble Resin (C21))

Alkali-soluble resin (C21) has a carboxyl group and / or phenolic hydroxyl group. It has a carboxyl group and / or phenolic hydroxyl group, crosslinked with crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution and has two or more groups which can react with a carboxyl group and / or phenolic hydroxyl group, and cured coating film Can be formed. Alkali-soluble resin (C21) can be used without restriction | limiting as long as it is soluble resin with respect to the alkaline solution which comprises the developing solution used for photolithography etc. of the photosensitive composition, For example, the monomer which has a carboxyl group and ethylenic double bond, and And / or a resin (C21-1) obtained by polymerizing a monomer having an phenolic hydroxyl group and an ethylenic double bond as essential, a phenol resin and the like. It is preferable that these resin does not have group (1) and group (2) substantially.

Resin (C21-1) obtained by superposing | polymerizing a monomer which has a carboxyl group and ethylenic double bond, and / or a phenolic hydroxyl group and an monomer which has ethylenic double bond as an essential component is a monomer which has a carboxyl group and ethylenic double bond, and / or a phenol The monomer which has a hydroxyl group and ethylenic double bond can be obtained by copolymerizing with another monomer as needed. Moreover, in this alkali-soluble resin (C21-1), the ratio of the monomeric unit based on another monomer is 30? 95 mass% or less is preferable and 50? 90 mass% or less is more preferable. The alkali solubility and developability of a photosensitive composition are favorable in it being this range.

Moreover, as a monomer which has a carboxyl group and ethylenic double bond used when producing said alkali-soluble resin (C21-1), acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid Or their salts. As a monomer which has a phenolic hydroxyl group and ethylenic double bond, 1 or more hydrogen atoms of these benzene rings, such as o-hydroxy styrene, m-hydroxy styrene, and p-hydroxy styrene, methyl, ethyl, n- A compound in which an alkyl group such as butyl, an alkoxy group such as methoxy, ethoxy, n-butoxy, a halogen atom or one or more hydrogen atoms of the alkyl group is substituted with a haloalkyl group, a nitro group, a cyano group, an amide group substituted with a halogen atom, and the like Can be mentioned. As another monomer, the same monomer as the other monomer used for manufacture of the said polymer (A) can be used.

As the phenol resin, at least one phenol selected from aromatic hydroxy compounds such as phenol, cresol, xenol, resorcinol, hydroquinone, and alkyl substituted or halogen substituted aromatic compounds thereof is selected from formaldehyde, acetaldehyde and benzaldehyde. It is obtained by polycondensation with aldehyde compounds, such as these, and a phenol formaldehyde resin, a cresol formaldehyde resin, a phenol cresol formaldehyde cocondensation resin, etc. are mentioned, for example.

The acid value of alkali-soluble resin (C21) is 10? 600 mgKOH / g is preferable and 50? 300 mgKOH / g is more preferable. The developability of the photosensitive composition becomes it favorable that it is the said range.

The number average molecular weight of alkali-soluble resin (C21) is 200? 20000 is preferable, and 2000? 15000 is more preferable. If it is the said range, alkali solubility and developability of a photosensitive composition will become favorable. Moreover, the mass mean molecular weight of alkali-soluble resin (C21) is 1.5 * 10 <^3> ? It is preferable that it is 30 * 10 <^3> , and it is 2.0 * 10 <^3> ? 15x10 ³ is more preferable. When this mass average molecular weight is less than 1.5x10 <^3> , hardening at the time of exposure may become inadequate, and when it exceeds 30x10 < ³ >, developability may fall.

In the acid-curable photosensitive composition according to the present invention, the content of the alkali-soluble resin (C21) having a carboxyl group and / or phenolic hydroxyl group is 10? To the total solid of the composition. 90 mass% is preferable and 30? 80 mass% is more preferable. The developability of the photosensitive composition of this invention is favorable in it being the said range.

(Crosslinkable resin (C22))

Crosslinkable resin (C22) is a compound which has 2 or more groups which can react with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups which can react with a carboxyl group and / or a phenolic hydroxyl group, it can crosslink with alkali-soluble resin (C21) which has a carboxyl group and / or a phenolic hydroxyl group, and can form a coating film hardened | cured material. Moreover, when the said polymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge | crosslink with a polymer (A), and can form a coating film hardened | cured material. It is preferable that crosslinkable resin (C22) is a compound which does not have group (1) and group (2) substantially.

As crosslinkable resin (C22), it is preferable that it is at least 1 sort (s) chosen from the group which consists of an amino resin, an epoxy compound, and an oxazoline compound. These may be used alone or in combination of two or more.

As the amino resin, a compound in which a part or all of the amino groups such as melamine compound, guanamine compound or urea compound is hydroxymethylated, or a part or all of the hydroxyl groups of the hydroxymethylated compound is methanol, ethanol, n The compound etherified by -butyl alcohol, 2-methyl-1- propanol, etc., for example, hexamethoxy methyl melamine etc. are mentioned.

Examples of the epoxy compound include glycidyl ethers such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, trisphenol methane type epoxy resins, and brominated epoxy resins. Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, diglyci Glycidyl esters, such as diltetrahydrophthalate and diglycidyl phthalate, Glycidyl amines, such as tetraglycidyl diamino diphenylmethane and triglycidyl paraaminophenol, and triglycidyl isocyanurate, etc. Heterocyclic epoxy resin etc. are mentioned.

Examples of oxazoline compounds include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxa The copolymer of polymerizable monomers, such as a sleepy and 2-isopropenyl 4-methyl- 2-oxazoline, is mentioned.

In the acid-curable photosensitive composition according to the present invention, the content of the crosslinkable resin (C22), which is a compound having two or more groups capable of reacting with a carboxyl group and / or phenolic hydroxyl group, is 1? 50 mass% is preferable and 5? 30 mass% is more preferable. The developability of the photosensitive composition becomes it favorable that it is the said range.

(2-3) Optional Ingredient

The acid-curable photosensitive composition according to the present invention is an alkali-soluble resin having a carboxyl group and / or phenolic hydroxyl group as the polymer (A), the photoacid generator (B2) as the photocuring initiator (B), and the binder resin (C). (C21) and crosslinkable resin (C22) which is a compound which has 2 or more of groups which can react with a carboxyl group and / or a phenolic hydroxyl group. Moreover, various arbitrary components can be contained for the purpose of the improvement of various functions, etc. in the range which does not impair the effect of this invention.

As such an optional component, all components other than the crosslinking agent (D) which has two or more ethylenic double bonds in the arbitrary components demonstrated by the said radical curable photosensitive composition are the same as the case of a radical curable photosensitive composition, An acid-curable photosensitive composition Can be used for

The acid-curable photosensitive composition according to the present invention can be prepared by uniformly mixing various essential components described above and optional components added as necessary in accordance with the blending amount in a conventional manner.

[Solvent for dilution]

When forming a partition using the photosensitive composition of this invention, such as the radical hardening type photosensitive composition and acid hardening type photosensitive composition mentioned above, after forming a coating film (wet film) using the diluent which diluted the photosensitive composition with the solvent, It is preferable to volatilize and to form the coating film of the photosensitive composition.

It does not specifically limit as a solvent which dilutes a photosensitive composition. Specifically, Alcohol, such as ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol; Ketones, such as acetone, methyl isobutyl ketone, cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol And cellosolves such as 2-butoxyethanol; Carr such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol Bitols; methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacete , Ethyl 3-ethoxypropionate, cyclohexanol acetate, ethyl lactate, n-butyl lactate, γ-butyrolactone, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, glycerin triacetate Esters; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutyl ether And ethers such as diethylene glycol methyl ethyl ether, cyclohexanone, 4-butyrolactone, and the like, may be used in combination.

Moreover, the dilution liquid which diluted the said photosensitive composition with the solvent has the photosensitive composition concentration, ie, solid content concentration of 5? It is preferable to prepare so that it may be 40 mass%, and it is 10? It is more preferable to prepare so as to be 25 mass%.

<2> partition

The partition of this invention is a partition formed in the form which divides the board | substrate image into several division for pixel formation by the coating film hardened | cured material of the said photosensitive composition of this invention, and is applicable to a color filter, a black matrix of an organic EL element, etc. Can be.

Hereinafter, as an example of the method of manufacturing the partition of this invention, the method of manufacturing a partition by a photolithography process using the photosensitive composition of this invention is demonstrated.

(Coating step)

First, the dilution liquid of the photosensitive composition of this invention is apply | coated to a board | substrate. The substrate is not particularly limited, and various glass plates; inorganic substrates such as SiC substrates and silicon; inorganic oxide substrates such as ITO; polyesters (polyethylene terephthalate, etc.), polyolefins (polyethylene, polypropylene, etc.), polycarbonates, poly Thermoplastic resin sheets such as methyl methacrylate, polysulfone, polyimide, and poly (meth) acrylic resins; and cured sheets of thermosetting resins such as epoxy resins and unsaturated polyesters. In consideration of heat resistance, heat resistant resins such as a glass plate and polyimide are preferable. Moreover, it is preferable that a board | substrate is transparent from the point which the exposure from the surface on the side where the partition wall of a board | substrate is not formed is possible. The substrate may be formed on a transparent substrate such as a glass substrate, or a substrate on which an organic oxide film or an inorganic oxide film such as TFT (Thin Film Transistor), ITO, SiO ₂ or the like is formed, or a patterned substrate, silicon nitride, polyimide, or the like. The board | substrate with which the insulating film was formed, and the laminated board | substrate with which these board | substrates are laminated | stacked may be sufficient.

Although it does not specifically limit as a coating method, A spin coating method, a spray method, the slit coating method, the roll coating method, the rotation coating method, the bar coating method, etc. are mentioned.

(Drying step)

Next, the coating film formed in the board | substrate is dried. Thereby, since a solvent volatilizes, the coating film of the photosensitive composition without adhesiveness is obtained. It does not specifically limit as a drying method, Vacuum drying and heat drying are mentioned. In order to dry efficiently, without using the nonuniformity of the external appearance of a coating film, it is preferable to use vacuum drying and heat drying together. Drying conditions differ depending on the kind, composition, etc. of components contained in the photosensitive composition, but vacuum drying is 10? 10 at 500 ㎩ (absolute pressure) It is preferable that it is 300 second, and heat drying is 50? 10? It is preferable that it is 2000 seconds.

(Exposure step)

Next, a coating film is exposed through the mask of a predetermined pattern. Light to be irradiated at the time of exposure is not particularly limited, visible light, ultraviolet rays, far ultraviolet ray, KrF excimer laser, ArF excimer laser, F ₂ excimer such as an excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser Laser, X-ray, an electron beam, etc. are mentioned. 100 wavelength? Light of 600 nm is preferable, and the wavelength is 300? Light of 500 nm is more preferable, and i line (365 nm), h line (405 nm), and g line (436 nm) are especially preferable. Moreover, a well-known ultrahigh pressure mercury lamp etc. can be used as a light source.

The exposure dose is usually 5? 1000 mJ / cm 2, 10? 400 mJ / cm <2> is preferable and 20? 200 mJ / cm <2> is more preferable and 50? 100 mJ / cm 2 is particularly preferred. When the exposure amount is less than 5 mJ / cm 2, curing of the coating film may be insufficient, and developability may decrease. When the exposure amount exceeds 1000 mJ / cm 2, high resolution may not be obtained.

(Developing step)

Next, the unexposed part of a coating film is removed and developed using a developing solution. Although it does not specifically limit as a developing solution, The aqueous solution of alkali, such as inorganic alkali, amine, alcohol amine, quaternary ammonium salt, is mentioned. The developing time, that is, the time for contacting the developer is 5? It is preferable that it is 180 second. Although it does not specifically limit as a image development method, The mounting method, the dipping method, the shower method, etc. are mentioned.

In addition, after development, running water washing is performed, and the air on the substrate can be removed by air drying with compressed air or compressed nitrogen.

(Post exposure process)

Next, you may post-expose the developed partition. At this time, you may expose from either the surface of the side in which the partition is formed, and the surface of the side in which the partition is not formed, or may expose from both surfaces. It is preferable that the light irradiated at the time of exposure is an ultraviolet-ray.

As a light source, a well-known ultrahigh pressure mercury lamp, a high pressure mercury lamp, etc. can be used. In general, these light sources emit light having a wavelength of 600 nm or less that contributes to hardening of the partition walls, and emits light having a wavelength of 200 nm or less that causes oxidative decomposition of the partition walls. Moreover, it is preferable that the quartz tube glass used for the light source has a function of the optical filter which cuts the light whose wavelength is 200 nm or less.

An exposure dose is 50 mJ / cm <2> or more normally, 200 mJ / cm <2> or more is preferable, 1000 mJ / cm <2> or more is more preferable, 2000 mJ / cm <2> or more is especially preferable.

Moreover, although a low pressure mercury lamp may be used as a light source, since a low pressure mercury lamp has many light emission with a wavelength of 200 nm or less, it is preferable that an exposure amount is 500 mJ / cm <2> or less, and 300 mJ / cm <2> or less is more preferable.

(Post Bake Process)

It is preferable to heat a partition after development (after post exposure, when performing post exposure). Heating conditions are 150? 5 at 250 ℃? It is preferable that it is 90 minutes, and 180 degreeC or more of heating temperature is more preferable. When heating temperature is too low, chemical resistance may become inadequate, and when ink is apply | coated to a partition, a partition may swell and ink may spread. On the other hand, when heating temperature is too high, a partition may thermally decompose.

As a heating apparatus, a hot plate, oven, etc. can be used.

The partition of this invention is formed by hardening the photosensitive composition of this invention through the above photolithography process. In the partition of this invention, the black matrix which shows black can be comprised by mix | blending a black coloring agent (E) with the photosensitive composition used for the preparation as needed. In this case, a black matrix is formed by forming a partition using a photosensitive composition.

It is preferable that the width | variety (average value) of the partition of this invention is 100 micrometers or less, and 20 micrometers or less are more preferable. Moreover, it is preferable that the distance between adjacent partitions, ie, the width | variety (average value) of an opening part, is 300 micrometers or less, and 100 micrometers or less are more preferable. In addition, the bulkhead has a height (average) of 0.05? It is preferable that it is 50 micrometers, and is 0.2? 10 micrometers is more preferable.

Generally, as the liquid repellency (ink repellency) of the partition which consists of a coating film hardened | cured material of a photosensitive composition, water repellency and oil repellency are mentioned, and water and PGMEA (propylene glycol monomethyl ether acetate: a lot of solvents of an ink, respectively) are mentioned, respectively. It can evaluate by the contact angle of the organic solvent used). As for the upper surface of the partition of this invention, the contact angle of water is 90 degrees? It is preferable that it is 150 degrees, and 95 degrees? It is more preferable that it is 120 degrees. In addition, the contact angle of PGMEA is 35 degrees in the upper surface of a partition. It is preferable that it is 55 degrees, and 40 degrees? It is more preferable that it is 50 degrees.

<3> color filter

The color filter of the present invention is a color filter having a partition located between a plurality of pixels and adjacent pixels on a substrate, wherein the partition is formed of the partition of the present invention, and the pixel is formed by an inkjet method. It features. In the color filter of the present invention, the partition has an optical density of 2? It is preferable that it is a black matrix which is about 7 degrees.

The color filter of this invention can be manufactured by forming a partition, for example, a black matrix, on a board | substrate, after apply | coating ink to the opening part of a partition, and forming a pixel using the inkjet method as mentioned above. .

Although it does not specifically limit as an inkjet method, The method of spraying charged ink continuously and controlling by a magnetic field, The method of spraying intermittent ink using a piezoelectric element, The ink is heated, and spraying intermittently using the foaming And the like can be mentioned.

The array of pixels is not particularly limited, and known arrays such as stripe type, mosaic type, triangle type, 4 pixel arrangement type and the like can be given.

The ink mainly contains a coloring component, a binder resin component, and a solvent, and any of an aqueous ink and an oil ink may be used. As a coloring component, the pigment and / or dye which are excellent in heat resistance, light resistance, etc. are preferable. As a binder resin component, resin which is transparent and excellent in heat resistance is preferable, and an acrylic resin, a melamine resin, a urethane resin, etc. are mentioned. The aqueous ink contains water as a solvent, a water-soluble organic solvent if necessary, and a water-soluble resin and / or a water-dispersible resin as a binder resin component. The oil ink contains an organic solvent as a solvent and a resin soluble in an organic solvent as a binder resin component.

In addition, a pixel can be formed by applying ink to a partition, for example, an opening of a black matrix, using an inkjet method, and then performing drying, heat curing, ultraviolet curing, or the like as necessary.

Moreover, after forming a pixel in the opening part of a partition, a protective film can be formed as needed. Thereby, while improving the surface smoothness of a color filter, it can block that the eluate from a partition and a pixel reach | attains the liquid crystal layer adjacent to a protective film.

At this time, before forming a protective film, it is preferable to remove the liquid repellency of the upper surface of a partition. Thereby, it can suppress that the upper surface of a partition splashes the coating liquid for protective films. Although it does not specifically limit as a method of removing the liquid repellency of the upper surface of a partition, A plasma ashing process, an optical ashing process, etc. are mentioned.

In addition, in order to refine the liquid crystal panel manufactured using the color filter of this invention, you may form a photospacer on a partition, for example, a black matrix, as needed.

<4> organic EL element

The organic EL element of the present invention is an organic EL element having a partition located between a plurality of pixels and an adjacent pixel on a substrate, wherein the partition is formed by the partition of the present invention, and the pixel is formed by an inkjet method. It is characterized by that.

The organic EL element of this invention can be manufactured as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched in a desired pattern as necessary. Next, in the same manner as in the case of the color filter, after forming a partition, for example, a black matrix, on the substrate, a solution of a hole transporting material as ink in the openings of the partition (black matrix) using the inkjet method, and A solution of the light emitting material is applied and dried sequentially to form a hole transport layer and a light emitting layer. Furthermore, an organic EL element is obtained by forming electrodes, such as aluminum, and forming a pixel using a vapor deposition method or the like.

Example

EMBODIMENT OF THE INVENTION Although this invention is demonstrated based on an Example below, this invention is not limited to these. In addition, a part means a mass part.

The symbol of the compound used in each following examples is shown below.

[1] the compound used for the preparation of the polymer (A) and the polymer (R)

(Monomer)

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

X-24-8201: Dimethyl silicone chain-containing methacrylate X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.) (In General Formula (4), R ⁸ is a methyl group, Z is a trimethylene group, R ¹ , R ² , Each of R ³ is a methyl group and n is 24 as an average value between molecules;

MAA: methacrylic acid

2-HEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate

MMA: Methyl methacrylate

(Polymerization initiator)

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

(Chain transfer agent)

n-DM: n-dodecyl mercaptan

(menstruum)

MEK: 2-butanone

[2] photosensitive composition components

(Photocuring Initiator (B): Photopolymerization Initiator (B1))

OXE02: OXE02 (manufactured by Chiba Specialty Chemicals, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl oxime) In formula (5), R <^21> and R <^22> is a methyl group, R <^23> is an ethyl group, R <^24> , R <^26> and R <^27> are a hydrogen atom, and R <^25> is a 2-methylbenzoyl group)

(Binder Resin (C): Photosensitive Resin (C1))

EX1010: EX-1010 (A solution of a resin in which an ethylenic double bond and an acid group are introduced into an epoxy resin represented by Nagase Chemtex Co., Ltd., (7), a solid content of 70% by mass, and a mass average molecular weight: 3,020).

ZCR1569H: ZCR-1569H (a solution of a resin in which an ethylenic double bond and an acid group are introduced into an epoxy resin having a biphenyl skeleton represented by Nippon Kayaku Co., Ltd., General Formula (6); solid content 70 mass%, mass average molecular weight: 4,710)

(Cross-linking system (D))

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

A9300: NK ester A-9300 (made by Shin-Nakamura Chemical Co., Ltd., ethoxy isocyanuric acid triacrylate)

(menstruum)

PGMEA: Propylene glycol monomethyl ether acetate

(Black colorant (E), fine particles)

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

Silica: Silica dispersion (average particle diameter 20 nm, dispersion medium PGMEA, solid content 30 mass%)

Synthesis Example 1 of Polymer (A)

In a 1 liter autoclave with a stirrer, MEK (420.0 g), C6FMA (86.4 g), MAA (18.0 g), GMA (21.6 g), MMA (54.0 g) and polymerization initiator V-65 (0.8 g) was injected and polymerized at 50 ° C for 24 hours while stirring in a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the solution of the obtained crude copolymer, reprecipitated and purified, and then dried in vacuo to give a polymer (A-1) (162.7 g) corresponding to the polymer (A). The number average molecular weight was 49,325 and the mass average molecular weight of the polymer (A-1) was 125,152.

[Synthesis example 2 of polymer (A)? 5]

In the synthesis | combination of the said polymer (A-1) WHEREIN: The polymer (A-2) equivalent to a polymer (A) by the same reaction except having changed the compounding | mixing of a raw material like Table 1? (A-5) was obtained.

Comparative Synthesis Example 1? 3]: Synthesis of Comparative Example Polymer (R) Not Suitable for Polymer (A)

In the synthesis | combination of the said polymer (A-1) WHEREIN: The polymer (R-1) which is not suitable for the polymer (A) in this invention by the same reaction except having changed the compounding | mixing of a raw material like Table 1? (R-3) was obtained.

About each polymer (A) and comparative polymer (R) obtained above, content of the number average molecular weight (Mn), the mass average molecular weight (Mw), Mw / Mn, and the fluorine atom (F) measured by the following method, Content of a silicon atom (Si), an acid value, and developing solution solubility are shown in Table 1 with a polymer yield.

<Molecular weight>

The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by the gel permeation chromatography method using polystyrene as a standard substance. As the gel permeation chromatography, HPLC-8220GPC (manufactured by Tosoh Corporation) was used. As a column, what connected three shodex LF-604 was used. RI detector was used as a detector. EasiCal PS1 (manufactured by Polymer Laboratories) was used as a standard substance. In addition, when measuring a number average molecular weight and a mass average molecular weight, the column was hold | maintained at 37 degreeC, the tetrahydrofuran was used as an eluent, the flow rate was 0.2 ml / min, and 0.5 mass% tetrahydrofuran of a measurement sample was used. 40 μl of solution was injected.

<Fluorine atom content>

Content of the fluorine atom in a polymer was computed from the injection value of a polymerization reaction.

<Silicon atom content>

Content of the silicon atom in a polymer was computed from the injection value of a polymerization reaction.

<Acid value>

An acid value is a theoretical value computed from the compounding ratio of the monomer which is a raw material.

<Development solution solubility>

Each polymer obtained above was added to 0.1% NaCO ₃ aqueous solution (pH 11, temperature 23 degreeC), stirring conditions: the ratio (mass%) of the polymer melt | dissolved at 50 rpm, was calculated | required, and the solubility of the polymer in aqueous alkali solution was It was taken as an index.

Example 1

Polymer (A-1) (0.09 parts) obtained in the above synthesis example, CB (31.5 parts) as dispersion of black colorant (E), OXE02 (0.75 parts) as photopolymerization initiator (B1), as dispersion of photosensitive resin (C1) EX1010 (6.3 parts), DPHA (1.9 parts) as a crosslinking agent (D), PGMEA (34.8 parts) as a solvent, and cyclohexanone (24.7 parts) were mixed to obtain a dilute solution of the photosensitive composition. Content of the polymer (A-1) in the total solid of the dilution liquid of the photosensitive composition was 0.60 mass%.

After using the spinner, after apply | coating the dilution liquid of the photosensitive composition on a glass substrate, it dried on 100 degreeC for 2 minutes on the hotplate, and formed the coating film of the photosensitive composition whose film thickness is 2.0 micrometers. Next, using the ultrahigh pressure mercury lamp, the light of 40 mJ / cm <2> of exposure amount on the basis of i line | wire (365 nm) was irradiated to the coating film through the mask, and was exposed. In addition, the mask is a lattice pattern of 150 micrometers x 400 micrometers, and 20 micrometers light transmission parts, and the volume of the partition opening part formed is 120 pL. Next, the glass substrate was immersed in a 10-fold diluted aqueous solution of the inorganic alkali type developer Semiclean DL-A4 (trade name, manufactured by Yokohama Oil and Fat Industries, Ltd.), developed, and the unexposed portion was washed with water and dried. Next, the glass substrate sample (1) of Example 1 with a partition was obtained by heating a glass plate at 220 degreeC for 30 minutes in oven.

Moreover, the glass substrate sample (2) of Example 1 in which the hardened | cured material of the coating film of the photosensitive composition was formed like the above except having exposed without using a mask.

Example 2 6]

Except having changed the compounding of each component as shown in Table 2, it carried out similarly to Example 1, and obtained the polymer (A-2)? Example 2 with a partition which consists of coating film hardened | cured material of the photosensitive composition containing (A-6), respectively? Example 2 which the hardened | cured material of the glass substrate sample (1) of 6 and the coating film of this photosensitive composition was formed? 6 glass substrate samples (2) were obtained.

[Comparative Example 1? 3]

Except having changed the compounding of each component as shown in Table 2, it carried out similarly to Example 1, and obtained the polymer (R-1)? Comparative example 1 which formed the partition which consists of coating film hardened | cured material of the photosensitive composition containing (R-3), respectively? Comparative example 1? In which the glass substrate sample 1 of 3 and hardened | cured material of the coating film of this photosensitive composition were formed. 3 glass substrate samples (2) were obtained.

[Evaluation Method and Evaluation Result]

By the method demonstrated below, using the glass substrate sample 2 produced by each said Example and the comparative example, the liquid repellency and the glass substrate sample 1 produced by each said Example and the comparative example are used The wet diffusion property of the ink in the partition openings was evaluated. An evaluation result is shown in Table 3 with containing mass% of each component in the total solid component of the photosensitive composition.

<Liquid repellency>

The liquid repellency was evaluated by measuring the contact angle of PGMEA of the surface of the coating film hardened | cured material of the glass substrate sample (2). A contact angle is an angle which a tangent line with respect to the liquid surface and a solid surface make at the point which a solid and a liquid contact, and are defined by the angle of the side containing a liquid. For this reason, it means that the liquid repellency of the coating film hardened | cured material is excellent, so that a contact angle is large.

<Wet Diffusion of Ink in Bulkhead Openings>

Liquid epoxy ME-562 (manufactured by Nippon Pernox Co., Ltd.) (6.25 g), hardener HV-562 (manufactured by Nippon Pernox Co., Ltd.) (6.25 g), diethyl adipic acid (12.5 g) and diethyl malonate (25.0 g) The mixture was stirred and mixed for 1 hour using a stirrer to prepare an ink.

By using the inkjet method, about 20 pL of the ink prepared above was apply | coated to the opening part of the partition of the glass substrate sample 1, and observing the photograph | photographed using the super depth shape measuring microscope VK-8500 (made by Keyence Corporation). , The wettability of the ink in the openings between the partition walls was evaluated (see FIG. 1). In addition, in FIG. 1, (a), (b), (c), (d) are the inside of the partition opening part in the glass substrate samples 1 of Examples 2 and 3 and Comparative Examples 1 and 2, respectively. It is a photograph showing the wettability of ink.

In the obtained photograph, it was determined that the inside of the partition wall opening part was covered with ink, and there was no part where ink was splashed, and that there was a part where ink was splashed as x.

(Circle) is good and x is impossible.

As can be seen from Table 3, the mass average molecular weight Mw (A) is applied even when about 20 pL of ink is applied to the partition opening having a volume of 120 pL, that is, when the coating amount of the ink is small with respect to the volume of the opening. ^{this, 4.2 × 10 4 <Mw (} a) polymer (a-1) corresponding to the polymer (a) in the range of ≤ 20 × 10 ^4? Example 1 which has a partition obtained using the photosensitive composition of this invention containing (A-6), respectively. In the glass substrate sample 1 of 6, ink wetted and spread | diffused in the opening part of a partition, and there was no whitening. This is Example 1? The photosensitive composition of 6 WHEREIN: It is developable and shows that there was no movement of the polymer (A) component from the partition surface to the partition opening part.

On the other hand, when the weight average molecular weight of 4.2 × 10 ⁴ outside the scope of the <Mw (A) ≤ 20 × 10 4 of the polymer (A) The weight average molecular weight Mw (A) of to the present invention, specifically, more than 4.2 × 10 ⁴ The glass substrate samples 1 of Comparative Examples 1 and 2 having the partitions obtained by using the photosensitive compositions containing the polymers (R-1) and (R-2), respectively, are small portions where ink does not get wet and diffuse in the openings. Was present. In addition, in the polymer (R-1) whose mass average molecular weight is extremely smaller than 4.2 × 10 ⁴ , the liquid repellency is ensured by increasing the amount of the polymer blended into the photosensitive composition. It is thought that the diffusivity becomes insufficient. However, when the compounding quantity of a polymer is small, liquid repellency becomes inadequate and it is a problem.

Moreover, the mass average molecular weight is outside the range of the mass average molecular weight Mw (A) of the polymer (A) which concerns on this invention, specifically, using the photosensitive composition containing polymer (R-3) which is more than 20x10 < ⁴ >. In the glass substrate sample 1 of Comparative Example 3 having the obtained partition wall, the ink was wetted and diffused in the opening between the partition walls, and there was no whitening. However, as can be seen from Table 1, the solubility of the developer of the polymer (R-3) is insufficient, and there is a concern that problems such as precipitation during the circulating use of the developer, which affects other partition openings in actual use, are concerned.

Industrial availability

The photosensitive composition of the present invention is an ink repellent component having no ethylenic double bond, and has good ink repellency in the upper part of the partition wall, developer resistance not eroded into the developer, and good wettability of ink against the partition openings. It is a photosensitive composition containing the ink repellent component which can be provided to the obtained partition. Such photosensitive composition of this invention is used suitably for formation of a partition for color filter manufacture using the inkjet recording technique, and organic electroluminescent display element manufacture, for example. Furthermore, it is used suitably as a material which forms a permanent film, such as the partition which divides each TFT of an organic TFT (Thin Film Transistor) array, the partition of the ITO electrode of a liquid crystal display element, the partition of a circuit wiring board, etc.

On the other hand, the whole content of the JP Patent application 2009-298959, a claim, drawing, and the abstract for which it applied on December 28, 2009 is referred here, and it takes in as an indication of the specification of this invention.

Claims (14)

Photosensitivity which has a side chain which has group represented by following General formula (1), and does not have a side chain which has ethylenic double bond, photocuring initiator (B), and binder resin (C) As a composition,
-CFXR ^f . (One)
(Wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents a fluoroalkyl group or a fluorine atom having 1 to 20 carbon atoms which may have an ether oxygen atom)
The mass average molecular weight (Mw (A)) of the said polymer (A) is 4.2 * 10 < ⁴ <Mw (A) <= 20 * 10 <^4> , The photosensitive composition characterized by the above-mentioned. The method of claim 1,
The photosensitive composition whose number average molecular weight (Mn (A)) of the said polymer (A) is 1.5 * 10 <^4><Mn (A) <= 6 * 10 <^4> . The method according to claim 1 or 2,
The photosensitive composition in which the said polymer (A) has an acidic group. The method according to any one of claims 1 to 3,
The fluorine atom content ratio in the polymer (A) is 20? 50 mass% photosensitive composition. The method according to any one of claims 1 to 4,
The ratio of the said polymer (A) in the total solid of the said photosensitive composition is 0.07? 1 mass% photosensitive composition. 6. The method according to any one of claims 1 to 5,
The photosensitive composition in which the said polymer (A) further has 1 or more types chosen from the group which consists of an epoxy group, a mercapto group, and a hydroxyl group. 7. The method according to any one of claims 1 to 6,
The photosensitive composition which has a side chain which the said polymer (A) further has group represented by following General formula (2).
[Formula 1]

(In formula, R <^1> and R <^2> is respectively independently the alkyl group, the cycloalkyl group, or the aryl group which may be substituted by the hydrogen atom or the fluorine atom, R <^3> is a hydrogen atom or the organic group which has 1-10 or more, n is 1 The integer of 200 or more is shown, respectively) The method according to any one of claims 1 to 7,
As a polymer (A) 'which does not have a side chain which has a group represented by the said General formula (1), has a side chain which has a group represented by following General formula (2), and does not have a side chain which has an ethylenic double bond, the weight average molecular weight (Mw (a) ') is ^{4.2 × 10 4 <Mw (a} )' ≤ 20 × 10 4 in the photosensitive composition further contains a polymer (a) '.
(2)

(In formula, R <^1> and R <^2> is respectively independently the alkyl group, the cycloalkyl group, or the aryl group which may be substituted by the hydrogen atom or the fluorine atom, R <^3> is a hydrogen atom or the organic group which has 1-10 or more, n is 1 The integer of 200 or more is shown, respectively) The method according to any one of claims 1 to 8,
The said photocuring initiator (B) is a photoinitiator, and the said binder resin (C) is a photosensitive resin which has an acidic group and ethylenic double bond. The method of claim 9,
Furthermore, the photosensitive composition containing the crosslinking agent (D) which has 2 or more of ethylenic double bonds. 11. The method according to any one of claims 1 to 10,
Furthermore, the photosensitive composition containing a black coloring agent (E). A partition wall formed in a form of dividing the substrate image into a plurality of sections for pixel formation, the partition wall including a cured film of the photosensitive composition according to any one of claims 1 to 11. A color filter having a partition located between a plurality of pixels and adjacent pixels on a substrate, wherein the partition is formed by the partition of claim 12, wherein the pixel is formed by an inkjet method. . An organic EL device having a partition located between a plurality of pixels and adjacent pixels on a substrate, wherein the partition is formed by the partition according to claim 12, wherein the pixel is formed by an inkjet method. EL element.

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