KR20120124392A - Photosensitive composition, partition wall, color filter and organic el element - Google Patents

Abstract

It 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 which does not erode in the developer, property of suppressing the occurrence of residual film, and good ink wetting diffusion property between the partition walls openings. It provides the photosensitive composition containing the ink repellent component which can be given to the partition obtained.
The mass average molecular weight (Mw) which has a side chain which has a side chain which has a group represented by following General formula (1), and a side chain which has a polyoxyalkylene group, and does not have a side chain which has ethylenic double bond is 2.6x10 < ⁴ A photosensitive composition containing a polymer having Mw ≦ 20 × 10 ⁴ , a photocuring initiator, and a binder resin.
-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 separating each TFT of organic TFT (Thin Film Transistor) arrays, and barrier ribs of ITO electrodes of liquid crystal display elements. The photosensitive composition attracts attention as a material which forms a permanent film, such as a partition of a circuit wiring board. For example, in forming 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 openings between the partition walls to form pixels. In forming the organic EL device, after forming the 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 the 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 the color filters and the adjacent pixels of the organic EL element, the upper surface of the partition wall needs to have ink splashing property or so-called liquid repellency. In addition, in order to prevent discoloration of the color filter and the organic EL element, the openings between the partition walls need to have a property of wet 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 a photosensitive resin composition comprising at least a repeating unit having a fluorine atom in the side chain and a repeating unit having a polyether structure in the side chain. The mass average molecular weight of the fluorine-containing compound described in the Example of patent document 1 is 26,000 at the maximum.

Patent Literature 2 discloses a photosensitive resin composition comprising a photopolymerizable compound, an ink repellent compound which is a copolymer obtained by copolymerizing at least a monomer containing an alkylene group having a fluorine-containing monomer and an ether oxygen atom, a photopolymerization initiator, and a colorant. It is described. The mass average molecular weight of the fluorine-containing copolymer described in the Example of patent document 2 is 10,900 at the maximum.

However, in the conventional ink repellent component, when using the fluorine-containing resin which has an ethylenic double bond, the said required performance in the partition obtained, ie, good ink repellency in the upper part of a partition, does not erode by a developing solution. Performances such as developer resistance and good ink wetting diffusion into the openings between partition walls are sufficiently obtained. However, when fluorine-containing resins having no ethylenic double bond are used, partition walls sufficiently satisfying all of these performances are not obtained. It was the present situation.

In addition, in the fluorine-containing resin having an ethylenic double bond having sufficient performance as the ink component, the number of steps is increased in order to introduce a group having an ethylenic double bond into the fluorine-containing resin. There was a disadvantage.

Japanese Laid-Open Patent Publication No. 2008-33229 Japanese Unexamined Patent Publication No. 2009-168948

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, which is an ink repellent component having no ethylenic double bond, good ink repellency in the upper part of a partition, developer resistance not to be eroded into a developer, and remain undeveloped. It is an object of the present invention to provide a photosensitive composition containing an ink repellent component capable of imparting a property of suppressing the occurrence of a residual film to be formed and good wettability of the ink into the openings between partition walls to the partitions to be obtained. The present invention also aims to provide a partition having good performance obtained from an economically advantageous material, a color filter having the partition and an organic EL element.

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

[1] A polymer (A) having a side chain having a group represented by the following General Formula (1) and a side chain having a polyoxyalkylene group, and not having a side chain having an ethylenic double bond, and a photocuring initiator ( B) and a photosensitive composition containing 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.)

The mass average molecular weight (Mw (A)) of the said polymer (A) is 2.6 * 10 < ⁴ <Mw (A) <= 20 * 10 <^4> , The photosensitive composition characterized by the above-mentioned.

[2] The content ratio of the polyoxyalkylene group in the polymer (A) is 5? The photosensitive composition as described in [1] which is 60 mass%.

[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 proportion 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 a hydrogen atom or the alkyl group, cycloalkyl group, or aryl group which may be substituted by 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 side chain having a side chain having a group represented by General Formula (2) and a side chain having a polyoxyalkylene group, and a side chain having a group represented by General Formula (1) and an ethylenic double bond Polymer (A) 'which does not have any, further contains polymer (A)' having a mass average molecular weight (Mw (A) ') of 2.6 × 10 ⁴ <Mw (A) ′ ≦ 20 × 10 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 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], and the pixel is 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).

In addition, in this specification, a polyoxyalkylene group is a bivalent group represented by-(RO) _{p <} -> (R is an alkylene group and p represents an integer of 2 or more.). One end of the polyoxyalkylene group is bonded to a terminal group, and the other end is a binding number that is bonded to the main chain side of the polymer.

According to the photosensitive composition of the present invention, an economically advantageous ink repellent ink component is used to suppress good ink repellency in the upper part of the partition, developer resistance not to be eroded into the developer, and development of residual film that is not developed. It is possible to impart the property and the wet spreading property of the ink to the openings between the partition walls. 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.

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 general 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 same is true of other prayers.

<1> photosensitive composition

The photosensitive composition of this invention has a side chain which has a side chain which has a group represented by following General formula (1), and a polyoxyalkylene group, and does not have a side chain which has ethylenic double bond, (Mw) (a)) is 2.6 × 10 ⁴ a photosensitive composition containing a <Mw (a) ≤ 20 × 10 4 a polymer (a), a photo-initiator (B) and a 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.)

The photosensitive composition of this invention is a photosensitive composition containing the said polymer (A), a photocuring initiator (B), and a binder resin (C), Comprising: A 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 curing type, according to the kind of hardening, for example, The photocuring initiator (B) and binder resin (C) to be used are according to the kind of hardening. Is selected. The photosensitive composition of the present invention can be applied to any curing type as long as it is a negative photosensitive composition, but is particularly suitable for a radical curable photosensitive composition. EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the photosensitive composition of this invention is described using a radical curable photosensitive composition and an acid curable photosensitive composition as an example.

(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 portion at the time of exposure in photolithography or the like to accelerate the curing 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)

A polymer (A) is a fluorine-containing polymer which has a side chain which has a group represented by the said General formula (1), has a polyoxyalkylene group and does not have a side chain which has ethylenic double bond, The mass mean molecular weight (Mw) (a)) is ^{2.6 × 10 4 <Mw (a} ) ≤ 20 × 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 is shown by 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 move 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 addition, in a polymer (A), developing solution solubility is also fully ensured by making mass mean molecular weight into the said range. As a result, in the partition formed by developing the coating film after exposure, it becomes possible to express liquid repellency on the upper surface, and to become lipophilic in the opening part between partitions. Moreover, even if heat (post-baking) process is performed after image development, a polymer (A) does not migrate to an opening part and it can maintain a lyophilic property in the opening part between partition walls.

Moreover, since a polymer (A) has a side chain which has a polyoxyalkylene group, even if the jet rinse process using the high pressure water after a image development process is performed, liquid repellency can be continued. The reason why the phenomenon is observed is not necessarily obvious, but is considered as follows.

By the interaction with a polyoxyalkylene group and another component, for example, binder resin (C), what is called an anchor effect, the effect that a polymer (A) does not detach | desorb easily from a coating film surface can be considered. In particular, when performing the jet rinse step using high pressure water after the developing step, the polymer (A) is likely to be detached from the surface layer. However, since the polymer (A) has a side chain having a polyoxyalkylene group, the polymer (A) tends to remain on the coating film surface by the anchor effect, and the coating film tends to exhibit liquid repellency. 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 discoloration of the openings can be suppressed. Moreover, a polymer (A) can suppress generation | occurrence | production of the residual film demonstrated below by having a side chain which has a polyoxyalkylene group.

That is, the phenomenon which a residual film generate | occur | produces is considered as follows. Since the alkali developer used when manufacturing a partition etc. by photolithography etc. generally contains surfactant, it is easy to generate | occur | produce foam in developing process. Moreover, when this bubble adheres to the liquid repellent surface, it is hard to remove. Therefore, by adhering bubbles to the portion that is to be dissolved and removed by the alkaline developing solution, ink repellent components contained in the photosensitive composition tend to remain in the form of a film. The polymer (A) which has a side chain which has a polyoxyalkylene group can suppress generation | occurrence | production of the residual film which arises in this way.

Although the mechanism by which the polyalkylene chain suppresses the formation of the residual film is not certain, even if the bubbles in the developer have adhered to the coating film, the polyalkylene chain is easily removed due to the presence of the polyalkylene chain on the surface, or at least at the same point. You can think of it as difficult to stay.

The weight average molecular weight (Mw (A)) of the polymer (A) used in the present invention is ^{2.6 × 10 4 <Mw (A} ) ≤ 20 × 10 4. More preferably 3.0 × 10 ⁴ <Mw (A) ≦ 12 × 10 ⁴ , still more preferably 3.5 × 10 ⁴ ≦ Mw (A) ≦ 12 × 10 ⁴ , particularly preferably 4.0 × 10 ⁴ ≦ Mw (A) ≤ 10 x 10 ⁴ .

If the mass average molecular weight of a polymer (A) is 2.6 * 10 <^4> or less, the lipophilic property of an opening part between partitions is inadequate, and when an ink is apply | coated using the inkjet method, ink will fully wet and it will not diffuse. Moreover, when mass average molecular weight exceeds 20 * 10 < ⁴ >, alkali solubility and developability will become inadequate.

If the weight average molecular weight (Mw (A)) is 3.0 × 10 ⁴ exceeds the range of 12 × 10 ⁴ or less, and without being influenced by the condition of the alkaline type and concentration, the jet rinsing, liquid repellency is liable to be kept high, the manufacture margin It is preferable to widen. Moreover, also in the ease of manufacture of a polymer (A), it is preferable.

The polymer (A) also preferably has a number average molecular weight (Mn (A)) of 1.0 × 10 ⁴ ≦ Mn (A) ≦ 15.0 × 10 ⁴ , with 1.5 × 10 ⁴ ≦ Mn (A) ≦ 12.0 × 10 ⁴ It is more preferable that it is 2.0 * 10 <^4> Mn (A) <= 10.0 * 10 <^4> . If the number average molecular weight of the polymer (A) is less than 1.0 × 10 ⁴ , the lipophilic properties of the openings between the partitions are insufficient, and when the ink is applied by using the inkjet method, the ink may sufficiently get wet in the openings and may not diffuse. When number average molecular weight exceeds 15.0 * 10 < 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 measured using polystyrene as a reference material 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 properties in the opening between the partition walls is not clear. Generally, the photosensitive composition, especially the photosensitive composition containing a black coloring agent, may not fully advance hardening reaction at the time of exposure, and the polymer (A) which is not immobilized at the time of exposure is normally after exposure and image development. At the time of heat processing called a post-baking (to be described later), it may shift to the side surface of a partition or flow out to the opening part between partitions. When the mass average molecular weight of the polymer (A) exceeds 2.6 × 10 ⁴ , and more preferably, the number average molecular weight is 1.0 × 10 ⁴ or more, the transition 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 1.2 or more and 8 or less, It is 1.3 or more 4 or less is 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 group (1), R ^f Carbon number which may have ether oxygen atom? In the case of the fluoroalkyl group which is 20, ^Rf may have a halogen atom except a fluorine atom. As such a halogen atom, a chlorine atom is preferable. Moreover, the structure of this fluoroalkyl group is not specifically limited, A linear structure, a branched structure, a ring structure, the structure which has a ring partially, etc. are mentioned, A linear structure is preferable. R ^f When 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.

In the group (1), R ^f When C is a fluoroalkyl group having from 1 to 20 carbon atoms which may have an ether oxygen atom, R ^f is not particularly limited as long as it has the configuration. Specifically, R ^f is -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 an integer from 1 to 8) ), -CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _q C ₆ F ₁₃ (q is an integer of 1 to 4), -CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _r C ₃ F ₇ (r is an integer of 1 to 5), and the like. .

R ^f When C is a fluoroalkyl group having 1 to 20 carbon atoms which may have an etheric oxygen atom, ^Rf is preferably a perfluoroalkyl group having no etheric oxygen atom and a perfluoroalkyl group having etheric oxygen atom, More preferred are perfluoroalkyl groups having no etheric oxygen atoms. 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 the same and may differ. 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.

In addition, the introduction position of the side chain which has group (1) in a polymer (A) is not restrict | limited, Preferably, it is regular with regularity, block-by-block, or random so that it may become the following fluorine atom content. 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 any form of an alternating copolymer, a block copolymer, and a random copolymer. As a polymer (A), it is preferable that it is a random copolymer from a viewpoint of manufacture efficiency, the intramolecular uniformity of a liquid repellent component, compatibility with components other than a liquid repellent component, etc. Moreover, it is preferable to introduce | transduce randomly by 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 the polymer (A) which has a side chain which mainly has a 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 a partition upper surface may become inadequate. Moreover, when content of the fluorine atom in a polymer (A) exceeds 50 mass%, there exists a tendency for a polymer (A) to self-aggregate, and as a result, the liquid repellency of a partition upper surface 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. However, 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 principal chain, the fluorine atom and group which the said group (1) has ( The content of the fluorine atom which combined the fluorine atom which a polymer (A) has other than 1) is said.

Moreover, in the polymer (A) used for this invention, it has a side chain which has a polyoxyalkylene group. This polyoxyalkylene group has C2-C? It is a polyoxyalkylene group which uses an oxyalkylene group of 4 as a repeating unit.

Content of the polyoxyalkylene group in the polymer (A) used by this invention is 5? 60 mass% is preferable. More preferably 10? 55 mass%, Especially preferably, it is 15? 50 mass%. When content of the polyoxyalkylene group in a polymer (A) is less than 5 mass%, when the jet rinse process using high pressure water is performed after the image development process, liquid repellency may fall remarkably. Moreover, there exists a possibility that it may be in the state which many residual films exist in the partition wall or partition opening part finally obtained. Moreover, when content of a polyoxyalkylene group exceeds 60 mass%, liquid repellency may fall.

In addition, the polyoxyalkylene group used for this invention is specifically, group represented by following General formula (11) (Hereinafter, it may be called group (11).).

-(R ¹¹ O) _m (R ¹² O) _j R ¹³ . (11)

(In formula (11), R <^11> is an ethylene group, R <^12> is a C3 or 4 alkylene group, R <^13> is a hydrogen atom or a C1-C10 alkyl group which may have a substituent, m is 4? 100 and j represent the integer of 0-100, respectively, and m + j is 4-100.

In the group (11), R ¹¹ represents an ethylene group (-CH ₂ CH _2- ), and R ¹² represents an alkylene group having 3 or 4 carbon atoms. The structure of a C3 or 4 alkylene group may be linear structure, or a branched structure may be sufficient as it. R ¹² is a propylene group (-CH ₂ CH (CH ₃ )-), trimethylene group (-CH ₂ CH ₂ CH _2- ), ethylethylene group (-CH ₂ CH (CH ₂ CH ₃ )-), 1, 2-dimethylethylene group (-CH (CH ₃ ) CH (CH ₃ )-), tetramethylene group (-(CH ₂ ) _4- ), and the like, and a propylene group or tetramethylene group is preferable.

In group (11), m is 4? 100, j is 0? Although the integer of 100 is shown respectively, it is preferable that it is 50 or less, respectively, and it is more preferable that it is 30 or less. Moreover, m / (m + j) which is the ratio of the number of R <^11> in a polyoxyalkylene group is 50? It is preferable that it is 100%, and is 80? It is more preferable that it is 100%, and it is especially preferable that it is substantially 100%.

M + j is 4? 100, preferably 6? 50, more preferably 8? 30 is. When m + j is 3 or less, when the jet rinse process using high pressure water is performed after the image development process, there exists a tendency for liquid repellency to fall. In addition, there is a tendency for a large amount of residual film to occur. When m + j is 101 or more, the polymer (A) migrates to the opening during post-baking, and the lipophilic properties of the inter-partition opening are insufficient, and when the ink is applied using the inkjet method, the ink is sufficiently wetted and diffused in the opening. There is no fear. In addition, in the said General formula (11), (R <^11> O) _m (R <^12> O) _j is what group 11 has m (R <^11> O) units and j (R <^12> O) units. as shown, (R ¹¹ O) is not particularly limited for the combination order of the units and the unit (R ¹² O). In other words, in the group 11, m (R ¹¹ O) units and j (R ¹² O) units may be combined alternately or randomly or in blocks, for example.

In the group (11), R ¹³ may have a substituent. In the case of the alkyl group of 10, the structure may be a linear structure, a branched structure, a ring structure, a structure having a ring partially, or the like. Moreover, as a substituent, a carboxyl group, a hydroxyl group, C1-C? 5 an alkoxy group etc. are mentioned. In this invention, it is C1-C as R <^13> in group (11). 5 linear and unsubstituted alkyl groups are preferable, and a methyl group and an ethyl group are more preferable.

In addition, polyoxyalkylene groups, such as the said group (11) which a polymer (A) has in a side chain, may be used individually by 1 type, and 2 or more types may be used together. In addition, introducing the side chain having the group (11) into the polymer (A), as described later, when producing the polymer (A) by polymerization of the raw material monomer, the raw material monomer of the monomer having the group (11) The compounding quantity with respect to the whole is adjusted suitably so that the compounding quantity which can give the effect of the said developability to a polymer (A) without impairing the effect of this invention.

The polymer (A) contained in the photosensitive composition of the present invention may have a side chain having a functional group according to various purposes, in addition to the side chain having the group (1) in a range that does not impair the effects of the present invention. Do. As an example of introduction of a functional group into such a polymer (A) side chain, for example, in order to improve ink decay and UV ozone resistance, a group having a siloxane bond represented by the following general formula (2) (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 a hydrogen atom or the alkyl group, cycloalkyl group, or aryl group which may be substituted by 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.)

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 These may be 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, and all It is especially preferable that R <^1> and R <^2> of a siloxane unit 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 the present invention, R ³ is a hydrogen atom, carbon number 1? 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 addition, 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, it becomes possible to give the said effect 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 aimed at the improvement of 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. The polymer (A) contained in a coating film unexposed part is removed with a developing solution. When the polymer (A) has the side chain which has an acidic group, since alkali solubility is favorable, it is very unlikely that a polymer (A) will again adhere to an opening part. Therefore, the lyophilic property of the opening part is good. In addition, the acidic group which a polymer (A) has in a side chain may be 1 type, or 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. Here, the introduction of acid groups into the side chains of the polymer (A) has terminal groups R ¹³ of the polyoxyalkylene group (11) It may be made by introducing into. 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 made 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 acid value is this range, the image development of an unexposed part can also be performed favorably, and liquid repellency in the upper part of the partition of an exposure part is also favorable. In addition, an acid value is the mass [mg] of potassium hydroxide required for neutralizing 1 g of samples, and describes a unit as mgKOH / g in this specification.

It is preferable that a polymer (A) further has a side chain which has a 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) can also be used individually by 1 type, and can also use 2 or more types together. In addition, introduction of these functional groups to the side chain of the polymer (A), the polyoxyalkylene group-end 11 has a short-term R ¹³ It may be made by introducing into. In addition, introduction of a hydroxyl group can also be performed by making R <^13> a hydrogen atom.

The photosensitive composition of this invention contains a photocuring initiator (B) and binder resin (C) other than a polymer (A). The binder resin (C) is cured by the action of the 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 by 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) and alkaline developing solution which have an acidic group is used normally.

When the polymer (A) has a functional group capable of thermally 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 and the acidic group together, in particular, the polymer (A) is thermally crosslinked with each other in a portion where the polymer (A) on the upper surface of the partition wall has a high density to polymerize more. It becomes a state fixed enough to a partition. Moreover, when a polymer (A) has a mercapto group, it carries out similarly to the above, and bridge | crosslinks with ethylenically unsaturated double bonds derived from binder resin (C) by a post-baking process, and it is fully fixed to a partition. Thereby, after that, it becomes possible to prevent the outflow and elution of the polymer (A) from the partition from the ink which are 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 and crosslinkable functional group which the partition matrix has to a polymer (A), when manufacturing a polymer (A) by superposition | polymerization of a raw material monomer, will have a partition matrix The effect of suppressing the outflow and elution of the polymer (A) at the time of injecting the said polymer into the polymer (A) at the said compounding quantity with respect to the whole raw material monomer of the monomer which has a functional group and a crosslinkable functional group is not impaired. It adjusts suitably so that the compounding quantity which can give | attach may be given.

(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 a side chain which has the said group (1), and polyoxyalkylene groups, such as the said group (11), and further optionally, the said group ( 2) side chains having these groups, the side chains having acidic groups, the side chains having acidic groups, the side chains having functional groups crosslinkable by heat or light, and the like. The method of forming or forming by chemical conversion after a polymerization reaction is mentioned.

To directly form the side chain having a polyoxyalkylene group, such as the group (11) and the side chain having the group (1) which the polymer (A) essentially has, and further optionally the side chain having each of the above-mentioned groups by a polymerization reaction. , A monomer having a group (1), a monomer having a side chain having a polyoxyalkylene group such as the group (11), a monomer having a group (2) if necessary, a monomer having an acidic group, and a functional group having a partition matrix. What is necessary is just to copolymerize by selecting conditions suitably the monomer which has a crosslinkable functional group, and / or another monomer.

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 a conventionally known method, respectively. In the present invention, the polymer (A) is obtained by copolymerization by random copolymerization. It is preferable that it is a random copolymer.

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 1? Carbon number which may have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, or an ethereal oxygen atom? 20 phosphorus fluoroalkyl group, cyano group, C1-C? 20 alkyl groups, carbon number 7? Alkyl group substituted by 20 aryl group, C6? 20 aryl group or 3? 20 cycloalkyl group. Y is a single bond or 1? It is a divalent organic group which does not have a 6-fluorine atom. -CFXR ^f Is a group corresponding to the group (1). That is, X is a hydrogen atom, a fluorine atom, or a trifluoromethyl group. R ^f has 1? Carbon number which may have ether oxygen atom? A 20-phosphorus fluoroalkyl group or a 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), -CFXR ^f Has 4 carbon atoms? It is a perfluoroalkyl group of 6, and Y is C2-C? (Meth) acrylate which is an alkylene group of 4 is especially preferable. Specifically, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, etc. are mentioned.

It is preferable that it is a compound represented by following General formula (12) or (13) as a monomer which has the said group (11) 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 ¹⁴ -COO- (WO) _q- (R ¹¹ O) _m (R ¹² O) _j R ¹³ . (12)

CH ₂ = CR ¹⁴ -O- (WO) _q- (R ¹¹ O) _m (R ¹² O) _j R ¹³ ... (13)

(In formulas (12) and (13), R ¹⁴ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkyl group substituted with a C7 to 20 aryl group, and carbon atoms 6 An aryl group having 20 or a cycloalkyl group having 3 to 20 carbon atoms, W is a divalent organic group having no fluorine atom having 1 to 10 carbon atoms, q is 0 or 1.-(R ¹¹ O) _m (R ¹² O) _j R ¹³ is a group corresponding to the group (11).)

Preferred embodiments _of- (R ¹¹ O) _m (R ¹² O) _j R ¹³ in the compounds (12) and (13) are the same as those described for the group (11).

-(WO) _q -in the compounds (12) and (13) represents a single bond when q is zero. When q is 1,-(WO) _q -is an organic group having an oxygen atom on the R ¹¹ side. When q is 1, W has 2? 10 divalent hydrocarbon groups are preferable and have 2 to 2 carbon atoms. 1 to 2 carbon atoms on both sides or one side of an alkylene group of 6, a cycloalkylene group of 5 or 6 carbon atoms, and a cycloalkylene group of 5 or 6 carbon atoms. Total carbon number having 2 alkylene group 6? It is preferable that it is a 10 cycloalkylene group containing alkylene group. However, when W is the same alkylene group as R ¹¹ (also, when q is not 0, even when it is the same alkylene group as R ¹² ), q is considered to be zero.

Moreover, as R <^14> in the said compounds (12) and (13), a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group is preferable, and a hydrogen atom or a methyl group is especially preferable.

In the formulas (12) and (13), when q is 1,-(WO)-is a structure having a linear structure, a branched structure, a ring structure, and a ring other than R ¹¹ O and R ¹² O Carbon number of 1? An oxygen atom terminal hydrocarbon group of 10 is preferred. More preferably, C3? It is an oxygen atom terminal hydrocarbon group of 8. The oxygen atom-terminal hydrocarbon group, specifically, _{CH 2 C 6 H 10 CH 2} O ( In the formula, C ₆ H ₁₀ is a cyclohexylene _{group.), CH 2 O, CH} (CH 3) O, CH 2 CH ₂ CH ₂ O, C (CH ₃ ) ₂ O, CH (CH ₂ CH ₃ ) O, CH ₂ CH ₂ CH ₂ CH ₂ O, CH (CH ₂ CH ₂ CH ₃ ) O, CH ₂ (CH ₂ ) ₃ CH ₂ O, CH (CH ₂ CH (CH ₃ ) ₂ ) O and the like. Among these, as W in the compounds (12) and (13), for ease of availability, an oxyalkylene group having 3 or 4 carbon atoms (but, when j is not 0, the same oxyalkylene group as R ¹² O) Other) is preferable.

In the compounds (12) and (13), among the groups represented by R ¹⁴ , a hydrogen atom, a chlorine atom, a methyl group, a phenyl group, a benzyl group, and the like are preferable, and a hydrogen atom, a chlorine atom, or a methyl group is more preferable.

As a compound represented by the said General formula (12) and General formula (13), the compound etc. which are shown below as a preferable compound are mentioned.

(Compound represented by General Formula (12)))

CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (CH ₂ CH ₂ O) _m R ¹³

CH ₂ = CHO (CH ₂ ) ₄ O (CH ₂ CH ₂ O) _m R ¹³

(Compound represented by General Formula (13))

CH ₂ = CHCOO (CH ₂ CH ₂ O) _m R ¹³ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _m R ¹³ ,

CH ₂ = CHCOO (CH ₂ CH ₂ O) _m (C ₃ H ₆ O) _j R ¹³ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _m (C ₃ H ₆ O) _j R ¹³ ,

CH ₂ = CHCOO (CH ₂ CH ₂ O) _m (C ₄ H ₈ O) _j R ¹³ ,

(In the formula, m and j are the same as above. C ₆ H ₁₀ is a cyclohexylene group, C ₃ H ₆ is a propylene group, C ₄ H ₈ is a tetramethylene group. R ^{13 in the} formula Silver 1 carbon number? 10 linear, unsubstituted alkyl groups, for example, methyl groups, hydrogen atoms and the like.)

In addition, in preparation of a polymer (A), it is possible to use a commercial item as said compound (12) and (13) which are used for the purpose of introduce | transducing group 11 into a side chain. As such a commercial item, the following are mentioned, for example.

Brenma PME-400 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula represents the mean value between molecules, and the value of k is about 9. Hereinafter, k, m, j in the molecular formula of each commercial item represent the average value between molecules.

NK ester M-230G :( trade name, manufactured by Shin-Nakamura Chemical Co. _{manufacture, CH 2 = C (CH 3} ) COO (CH 2 CH 2 O) k CH 3: Expression of k denotes the mean value between the molecules, the value of k is from about 23 to be.).

New Frontiers NF by Soma PEM6E (trade name, manufactured by Dai-ichi Kogyo _{Seiyaku, CH 2 = C (CH 3} ) COO (CH 2 CH 2 O) k H:., K is from about 6 in the formula).

Light ester 130A (trade name, manufactured Ischia Chemical Co. in _{Tokyo, CH 2 = CHCOO (CH 2} CH 2 O) k CH 3:., K is from about 9 in the formula).

Brenma AE-400 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = CHCOO (CH ₂ CH ₂ O) _k H: wherein k is about 10.).

Brenma PP-800 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (C ₃ H ₆ O) _k H: wherein k is about 13.),

Brenma AP-800 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = CHCOO (C ₃ H ₆ O) _k H: wherein k is about 13.).

Brenma 70PEP-350B (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (C ₂ H ₄ O) _m (C ₃ H ₆ O) _j H: In the formula, m is approximately 5, j is About 2.).

Brenma 55PET-800 (trade name, manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (C ₂ H ₄ O) _m (C ₄ H ₈ O) _j H: In the formula, m is approximately 10 and j is About 5.).

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. Moreover, the group which has a siloxane bond couple | bonded with Z is the said 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 represents a hydrogen atom or C 1-10. Is an organic group, and 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? Preferred divalent hydrocarbon groups are 6-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 _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. In particular, -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH ₂ -are preferable.

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, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, and one or more hydrogen atoms of these benzene rings, alkyl groups, such as a methyl group, an ethyl group, and n-butyl group, and methock Alkoxy groups, such as a time period, an ethoxy group, and n-butoxy group, a halogen atom, the haloalkyl group which has one or more halogen atoms, the compound substituted by the nitro group, the cyano group, the 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 the functional group which can be bridge | crosslinked by heat or light with the functional group which the said partition matrix used for manufacture of a polymer (A) has as needed, it may be called a "crosslinkable functional group" hereafter. If it has a functional group, it will not specifically limit. 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 a mercapto group illustrated above as a crosslinkable functional group, 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, the 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 in which the carboxyl group of thioacetic acid, thiopropionic acid, thiobutyric acid, and thiobenzoic acid is substituted by -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 the 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, 20? 50 mass%, More preferably, it is 25? 42 mass%, particularly preferably 25? It is preferable to set it as the ratio used as 35 mass%. As such a ratio, although depending on the kind of monomer which has group (1), it is specifically 20? It is preferable that it is 80 mass%, and it is 30? It is more preferable that it is 70 mass%, and 40? It is especially preferable that it is 60 mass%. When this ratio is too low, sufficient fluorine atom content cannot be secured and sufficient developing resistance tends not to be obtained, and polymer (A) transfers to the vicinity of the upper surface of the partition formed using the photosensitive composition of this invention. It becomes difficult to carry out, and as a result, the liquid repellency of the partition upper surface 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 is the said preferable range. What is necessary is just to adjust the ratio of each raw material monomer suitably so that it may become.

As for the ratio of the monomer mass which has group (11) with respect to the total mass of the monomer to copolymerize, content of the group (11) in a polymer (A) is 5? It is preferable to set it as the ratio used as 60 mass%. 10? It is more preferable to set it as the ratio used as 55 mass%, and it is 15? It is especially preferable to set it as the ratio used as 50 mass%. If it is this range, content of the group 11 in a polymer (A) will become the said preferable range generally, and liquid repellency can be maintained even when the jet rinse process using the high pressure water after a image development process is performed. In addition, it is possible to prevent the occurrence of residual film.

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), the ratio of the monomer mass which has an acidic group with respect to the total mass of the monomer to copolymerize has the acid value of a polymer (A) the said preferable range, specifically As 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. Since the ratio of the monomer which has an acidic group in all the monomers to copolymerize is this range, the phenomenon of an unexposed part can also be performed favorably, and the lyophilic property of an opening part can be improved, without impairing the effect of this invention. Good.

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, it will become possible to fix | immobilize the partition of a polymer (A) without impairing the effect of this invention, and developability will become favorable.

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% or less Is more preferable. When the ratio of this mass exceeds 70 mass%, alkali developability may fall.

The polymer (A) used for this invention has side chain which has a side chain which has the said group (1), and side chains which have polyoxyalkylene groups, such as the said group (11), as an essential structure, and further optionally the group (2) As a copolymer having a side chain having a side chain, a side chain having an acidic group, a side chain having a thermally crosslinkable functional group and the like, a monomer having a group (1) and a monomer having a polyoxyalkylene group such as the group (11); As needed, it can synthesize | combine by dissolving the monomer which has group (2), the monomer which has an acidic group, the monomer which has a thermal crosslinkable functional group, and / or other monomer in a solvent, 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 amount of polymerization initiators, and the addition amount of a chain transfer agent.

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.

Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds, and the like. 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 azo compounds 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 And 2,2'-azobis (2-amidinopropane) dihydrochloride.

Examples of the chain transfer agent include mercaptans such as n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, thioglycolic acid 2-ethylhexyl and 2-mercaptoethanol; chloroform and carbon tetrachloride And thiocarboxylic acid ester compounds exemplified in the introduction of a halogenated alkyl such as carbon tetrabromide and the mercapto group into the polymer (A).

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 thermal crosslinkable functional group, etc. can be formed also by the chemical conversion after a polymerization reaction. have. 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 partition upper surface 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, it is possible to contain the component which can provide a liquid repellent effect to a partition other than the said polymer (A). As such a component, the side chain which has a side chain which has a group represented by the said General formula (2), and a polyoxyalkylene group, and has a group represented by the said General formula (1), and ethylenic double A polymer (A) 'having none of the side chains having a bond, and the polymer (A)' whose mass mean molecular weight (Mw (A) ') is 2.6 × 10 ⁴ <Mw (A)' ≦ 20 × 10 ⁴ Can be mentioned.

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), although the structure was described about the polymer (A) which has a side chain which has group (2), polymer (A) 'is group Except not having the side chain which has (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, it becomes possible to give the photosensitive composition of this invention the effect of improving the liquid repellency of the partition surface obtained using this, without impairing the effect of this invention.

Polymer (A) 'is a side chain which has group (11) similarly to polymer (A), Preferably it is 5-content as group (11) with respect to polymer (A)'. It has it in the ratio which becomes 60 weight%. The polymer (A) 'may optionally have a side chain having an acidic group, a side chain having a functional group possessed by the partition matrix, and a side chain having a functional group that can be crosslinked by heat or light, and have a structure having such a side chain. Also about the polymerization reaction, it can be made similar to the said polymer (A) except not using the monomer which has group (1) as a raw material monomer, and using the monomer which has group (2) as an essential raw material monomer. .

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, it becomes possible to give the photosensitive composition of this invention the effect of improving the liquid repellency of the partition surface obtained using this, without impairing the effect of this invention. Moreover, when using a 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 with it, the effect similar to the above can be exhibited. .

(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 irradiation of light 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); and the like. You may use together.

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 C6-C20 unsubstituted or substituted by a hydrogen atom, a C1-C12 alkyl group, a C3-C8 cycloalkyl group, a C2-C5 alkenyl group, an alkyl group. C6-C20 phenoxy group unsubstituted or substituted by a phenyl group or an alkyl group, R ²² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or substituted or substituted by an alkyl group Substituted or unsubstituted by a phenyl group having 6 to 20 carbon atoms, alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, unsubstituted or substituted by an alkyl group, alkoxycarbonyl group having 2 to 12 carbon atoms or an alkyl group A phenoxycarbonyl group having 7 to 20 ring carbon atoms, R ²³ is an alkyl group having 1 to 12 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Substituted or unsubstituted by alkyl groups A cyclohexyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group, a benzo group having 7 to 20 carbon atoms substituted or unsubstituted with an alkyl group or a carbon group having 2 to 20 carbon atoms substituted or unsubstituted A C7-20 benzylcarbonyl group unsubstituted or substituted by a diary, an alkyl group, a C2-12 alkoxycarbonyl group, a C7-20 phenoxycarbonyl group unsubstituted or substituted by an alkyl group, or a C1-20 carbon atom. 20 phosphorus amide group or nitro group.)

In the compound represented by the general formula (5), R ²¹ is 1? 6 to 6 carbon atoms substituted or unsubstituted by 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), R ²² is 1? An alkyl group having 10 or 2? 5 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 7 to 7 carbon atoms substituted or unsubstituted with an alkyl group. 7 to 7 carbon atoms unsubstituted or substituted by a benzoyl group or an alkyl group. 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 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 benzoyl group; R ²¹ is methyl group, R ²² is butyl group, heptyl group or octyl group, R ²³ is ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, R ^A compound in which 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, and R ²⁵ is a 2-methylbenzoyl group; R ²¹ is a methyl group, R ^{A 22} -methyl group or an octyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁵ and R ²⁷ are hydrogen atoms, R ²⁵ is a 2-methylbenzoyl group; R ²¹ and R ²² are a methyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ is a hydrogen atom, R ²⁵ 2-methyl-5-tetrahydro-furanyl -dihydroxy-20 benzoyl group, 2-methyl-4-tetrahydropyranyl -dihydroxy-20 benzoyl group or a 2-methyl-5-Tet Dihydro-pyrazole, and the like due -dihydroxy-20-benzoyl compound.

As a photoinitiator (B1), it is possible to use a commercial item. 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- (O), for example. -Acetyl oxime): In the general formula (5), R ²¹ and R ²² are methyl groups, R ²³ is ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, R ²⁵ is 2-methylbenzoyl group) 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 15 mass%, and 2? 7 mass% is more preferable. One ? If it is 15 mass%, sclerosis | hardenability is favorable and a pattern and line | wire width | variety close to a mask pattern can be formed by exposure and image development.

Moreover, 2-mercapto benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1, 4- butanol bis (3-mercapto butyrate), and tris (with a photoinitiator (B1)) 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) generated is used. do.

Since the photosensitive resin (C1) has an ethylenic double bond that participates in the photopolymerization in one molecule and further has an acidic group, it is possible to selectively remove the unexposed portion of the photosensitive composition which is not cured using an alkaline developer. As a result, a partition can be formed. In addition, 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, You may use 2 or more types together. 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, Resin (C1-1) which has a side chain which has an acidic group, and a side chain which has ethylenic double bond, Ethylenic double bond and an acidic group in an epoxy resin Resin (C1-2) etc. which were introduce | transduced are mentioned. These may be used individually by 1 type and may use 2 or more types together.

The resin (C1-1) is, for example, a copolymer having a side chain having a reactive group and a side chain having an acidic group, obtained by copolymerizing a monomer having a reactive group such as a hydroxyl group, a carboxyl group, an epoxy group and a monomer having an acidic group, It can synthesize | combine by dissolving the compound which has an ethylenic double bond, and the functional group which can couple | bond with a reactive 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 by making polybasic carboxylic acid or its anhydride react, for example, after making an epoxy resin and the compound which has a carboxyl group and ethylenic double bond 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 into which ethylenic double bond was introduce | transduced.

Although it does not specifically limit as an epoxy resin, Bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, the trisphenol methane type epoxy resin, the epoxy resin which has a naphthalene skeleton, the following The epoxy resin which has a biphenyl skeleton represented by 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. Moreover, the hydrogen atom of a benzene ring is respectively independently a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent. May be substituted.)

[Formula 6]

In formula (7), R ³¹ , R ³² , R ³³ and R ³⁴ Each independently represents a hydrogen atom, a chlorine atom or a carbon number of 1? It is an alkyl group which is 5, t is 0? 10.)

[Formula 7]

(In formula (8), the hydrogen atom of a benzene ring may be respectively independently 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 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 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.

It is possible to use a commercial item as resin (C1-2) which introduce | transduced the acidic group and ethylenic double bond into epoxy resin. As such a commercial item, all are brand name 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 (above, manufactured by Nippon Kayaku Co., Ltd.) ) And EX1010 (manufactured by Nagase Chemtex Co., Ltd.).

As resin (C1-2) which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin, Resin which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin which has a biphenyl skeleton represented by Formula (6), Formula (7 Resin which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin represented by), or resin which introduce | transduced the acidic group and ethylenic double bond into the epoxy resin represented by Formula (8) is preferable. By using the said resin, a black coloring agent can be mix | blended more in a composition, and it becomes possible to raise light-shielding property and optical density. Moreover, peeling of the coating film at the time of image development is suppressed, and a high resolution pattern can be obtained. On the other hand, since the linearity of a line is favorable, it is preferable. Moreover, the external appearance after a post-baking process is maintained and a smooth coating film surface is easy to be obtained, and it is preferable.

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> ? 15 * 10 <^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 it becomes possible to form a fine pattern with a smaller exposure amount.

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? 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 acidic group and ethylenic double bond as said polymer (A), the photoinitiator (B1) as a photocuring initiator (B), and binder resin (C). ) As an essential component, but in the range that does not impair the effects of the present invention, it is possible to contain the optional components described below for the purpose of improving various functions.

(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.

Although it does not specifically limit as a crosslinking agent (D) which has two or more ethylenic double bonds, A (meth) acryloyloxy group has 2? Preference is given to compounds having ten. Specifically, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol Di (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, it is possible to use a commercial item 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.) Isocyanuric 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) , Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane), BANI-X (brand name, the Maruzen petrochemical company make) , N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)) and the like.

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. Can be mentioned.

A-9300, BANI-M, and BANI-X are preferable from the viewpoint of providing hardness to the coating film and suppressing thermal sag. A-9300-1CL is preferable from the viewpoint of providing flexibility to the coating film. Urethane acrylate is preferable because it can realize a suitable development time, and developability becomes favorable.

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 by 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 this specific surface area is too small, the partition shape may be deteriorated. If the specific surface area is too large, the dispersing aid described later will be excessively adsorbed to the black colorant (E), and it is necessary to add a large amount of the dispersing aid. It 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 diameter of 20? It is preferable that it is 50 nm. When this average primary particle diameter is too small, it will become difficult to disperse | distribute to high concentration, and the photosensitive composition with favorable stability over time may become difficult to be obtained, and when an average primary particle diameter is too large, it will cause deterioration of a partition shape. There is a case. Moreover, this carbon black has an average secondary particle size of 80? It is preferable that it is 200 nm. In addition, the particle diameter of carbon black can be measured using a transmission electron microscope.

In the radical curable photosensitive composition which concerns on this invention, content of the black coloring agent (E) at the time of mix | blending a black coloring agent (E) in order to provide the light-shielding property like a black matrix to this coating film hardened | cured material is required light shielding property. , Depending on the optical density, but for the total solids of the composition 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, 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 powder property, it is preferable to contain a polymeric dispersing agent. It does not specifically limit as a polymer dispersing agent, urethane type, polyimide type, alkyd type, epoxy type, polyester type, melamine type, phenol type, acryl type, polyether type, vinyl chloride type, vinyl chloride vinyl copolymer type copolymer, poly Amide system, polycarbonate system, etc. are mentioned. Especially, urethane type or polyester type is preferable. In addition, the polymer dispersant may have a polyoxyethylene group and / or a polyoxypropylene group.

When the polymer dispersant is used for dispersing the black colorant (E), it is preferable to use a polymer dispersant having a basic group in consideration of the affinity for the black colorant (E). Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.

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

The addition amount of the polymer dispersant is 5? To dispersible materials such as the 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 to adsorb | suck to dispersible materials, such as a black coloring agent (E), and a polymeric dispersing agent, and to improve dispersion stability.

(Fine particles)

The radical curable photosensitive composition which concerns on this invention may contain microparticles | fine-particles as needed. Thereby, the shape of a partition can be suppressed from changing 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, inorganic type microparticles | fine-particles are preferable in consideration of heat resistance, and silica or zirconia is preferable in consideration of the availability and dispersion stability. Moreover, when a 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) and h-line (405 nm), which are the main emission wavelengths of ultra-high pressure mercury lamps. It is particularly preferable not to absorb the g line (436 nm).

Since the surface smoothness of a partition becomes favorable, it is preferable that an average particle diameter is 1 micrometer or less, and, as for the particle size of microparticles | fine-particles, 200 nm or less is more preferable.

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 post-baking, 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 Dazolsilane, etc. are mentioned, You may use 2 or more types together.

(Thermal curing 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 thermal crosslinkable functional group, a 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 to 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 uniformly the various essential components demonstrated above and arbitrary components added as needed by a conventional method according to the said compounding quantity.

(2) acid-curable photosensitive composition

When the photosensitive composition of the present invention is an acid curable type, the photosensitive composition has a polymer (A), a photoacid 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) 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. In such an acid-curable photosensitive composition, an acid is generated from a photoacid generator (B2) in a light irradiation part during exposure in photolithography and the like, and an alkali-soluble resin (C21) having a carboxyl group and / or phenolic hydroxyl group, and a carboxyl group And / or crosslinking reaction of crosslinkable resin (C22) which is a compound which has two or more groups which can react with a phenolic hydroxyl group, 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, and also includes the preferable aspect, The polymer (A) demonstrated in the said radical curable photosensitive composition It can be applied in an 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) '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 hardening type, as a photocuring initiator (B), the photo-acid generator (B2) which is a compound which generate | occur | produces an acid by light is used. As a photo-acid 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 diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutane sulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate and tetrafluoroborate , Hexafluoroantimonate, (R ^f ) _k PF _(6-k) ^- (where k is an integer of 1 to 6), and the like. 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 is 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 is 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-furyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-furyl) 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) and 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 which crosslinks-polymerizes by the effect | action of the acid which the said photo-acid generator (B2) generated ( 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 a phenolic hydroxyl group. By having a carboxyl group and / or a phenolic hydroxyl group, it crosslinks with the crosslinkable resin (C22) which is a compound which is soluble in an alkaline solution and has 2 or more groups which can react with a carboxyl group and / or phenolic hydroxyl group, and hardens a coating film Can be formed. Alkali-soluble resin (C21) can be used without limitation as long as it is a resin which is soluble with respect to the alkaline solution which comprises the developing solution used for photolithography etc. of the photosensitive composition, For example, it has a carboxyl group and ethylenic double bond. Resin (C21-1) obtained by superposing | polymerizing a monomer which has a monomer and / or a phenolic hydroxyl group and ethylenic double bond as essential, a phenol resin, etc. are mentioned. It is preferable that these resins do not have group (1) and group (2) substantially.

Resin (C21-1) obtained by making the monomer which has a carboxyl group and ethylenic double bond and / or the monomer which has a phenolic hydroxyl group and ethylenic double bond essential, and polymerize is a monomer which has a carboxyl group and ethylenic double bond. And / or the monomer which has a phenolic 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 salts thereof. 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, are methyl, ethyl, n-butyl Alkoxy groups, such as an alkyl group, methoxy, ethoxy, and n-butoxy, a halogen atom, the compound by which the at least 1 hydrogen atom of the alkyl group was substituted by the halogen atom, the nitro group, the cyano group, and the amide group etc. are mentioned. Can be. 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, xylenol, resorcinol, hydroquinone and alkyl substituted or halogen substituted aromatic compounds thereof may be formed of formaldehyde, acetaldehyde, benzaldehyde, or the like. It is obtained by polycondensation with an aldehyde compound, and examples thereof include a phenol formaldehyde resin, a cresol formaldehyde resin, a phenol cresol formaldehyde cocondensation resin, and the like.

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, mass average molecular weight is 1.5 * 10 <^3> ? It is preferable that it is 30 * 10 <^3> , and it is 2.0 * 10 <^3> ? 15 * 10 <^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 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 cured coating film. 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 part or all of the hydroxyl groups of a compound in which some or all of the amino groups, such as melamine compound, guanamine compound and urea compound, are hydroxymethylated, or the hydroxymethylated compound is partially converted into 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 novolac type epoxy resins, cresol novolac type epoxy resins, trisphenol methane type epoxy resins, and brominated epoxy resins. Alicyclic epoxy resins such as 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexanecarboxylate and bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, diglycidyl Complexes such as glycidyl esters such as tetrahydrophthalate and diglycidyl phthalate, glycidylamines such as tetraglycidyl diaminodiphenylmethane and triglycidyl paraaminophenol, and triglycidyl isocyanurate Cyclic epoxy resin etc. are mentioned.

The oxazoline compounds include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline And copolymers of polymerizable monomers such as 2-isopropenyl-4-methyl-2-oxazoline.

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 a phenolic hydroxyl group, is 1? To the total solids of the composition. 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

An 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), a photoacid generator (B2) as a photocuring initiator (B), and a binder resin (C) ( C21) and a crosslinkable resin (C22), which is a compound having two or more groups capable of reacting with a carboxyl group and / or phenolic hydroxyl group, in the range of not impairing the effects of the present invention, and improving various functions. It is possible to contain various arbitrary components for the purpose of this.

As such an optional component, all components other than the crosslinking agent (D) which has 2 or more of ethylenic double bond among the arbitrary components demonstrated by the said radical curable photosensitive composition are the same as the case of a radical curable photosensitive composition, and acid-curable photosensitive It is possible to use in the composition.

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 curable photosensitive composition and acid-curable photosensitive composition mentioned above, after forming a coating film (wet film) using the dilution liquid which diluted the photosensitive composition with a solvent, It is preferable to volatilize and to form the coating film of the photosensitive composition.

The solvent for diluting the photosensitive composition is not particularly limited. 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 , Cellosolves such as 2-butoxyethanol and 2-propoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxye) Carbitols such as methoxy) ethanol; 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, propyl Lenglycol diacetate, ethyl 3-ethoxypropionate, cyclohexanol acetate, ethyl lactate, n-butyl lactate, γ-butyrolactone, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, glycerin Esters such as triacetate; 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, Ethers, such as dibutyl ether and diethylene glycol methyl ethyl ether, cyclohexanone, 4-butyrolactone, etc. are mentioned, You may use 2 or more types together.

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. It does not specifically limit as a board | substrate, Various glass plates; Inorganic substrates, such as a SiC substrate and silicon; Inorganic oxide substrates, such as ITO; Polyester (polyethylene terephthalate etc.), polyolefin (polyethylene, polypropylene etc.), polycarbonate, polymethyl Thermoplastic resin sheets such as methacrylate, polysulfone, polyimide and poly (meth) acrylic resin; 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. In addition, since the exposure from the surface where the partition wall of the board | substrate is not formed is possible, it is preferable that a board | substrate is transparent. In addition, the substrate may be formed on a transparent substrate such as a glass substrate, a substrate on which an organic 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 coat 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. It is preferable to use vacuum drying and heat drying together in order to dry efficiently, without generating the nonuniformity of a coating film external appearance. Although drying conditions differ according to the kind, composition, etc. of components contained in the photosensitive composition, 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 laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser such as an excimer laser , X-rays, electron beams, and the like. 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. In addition, 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, alkanolamine, 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, A liquid mounting method, a dipping method, a shower method, etc. are mentioned.

Jet Rinse Process

In addition, jet rinsing is preferable. Jet rinsing is a process of compressing water or spraying water and air by compressing water on a substrate on which partition walls are formed. Pressure is 2? It is preferable that it is 20 Mpa. By performing jet rinsing, it is possible to remove the residue which melt | dissolved in the image development process, and the part which the component of the photosensitive composition melt | dissolved during image development reattached to the board | substrate.

After jet rinsing, the water on the substrate can be removed by air drying with compressed air or compressed nitrogen.

(Post exposure process)

Next, you may perform post exposure with respect to the developed partition. At this time, you may expose to either side of the surface 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. These light sources generally emit light with a wavelength of 600 nm or less, which contributes to the hardening of the partition wall, and emit light with a wavelength of 200 nm or less that causes oxidative decomposition of the partition wall. Moreover, it is preferable that the quartz tube glass used for the light source has a function of the optical filter which blocks the light whose wavelength is 200 nm or less.

An exposure amount 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 condition is 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 an ink is apply | coated to a partition, a partition may swell or ink may leak out.

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 value) of 0.05? It is preferable that it is 50 micrometers, and is 0.2? 10 micrometers is more preferable.

Generally as water-repellent property (ink repellency) of the partition which consists of a coating film hardened | cured material of the photosensitive composition, water repellency and oil-repellency are mentioned, and water and PGMEA (propylene glycol monomethyl ether acetate: a lot of solvents of 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 an adjacent pixel 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 is characterized by. 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 the intermittent spraying using the foaming is carried out. The method etc. are mentioned.

The arrangement of the pixels is not particularly limited, and known arrangements 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, it is preferable to remove the liquid repellency of the partition upper surface before forming the protective film. Thereby, it can suppress that the upper surface of a partition jumps off the coating liquid for protective films. Although it does not specifically limit as a method of removing the liquid repellency of an 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 photo spacer on a partition, for example, a black matrix, as needed.

<4> organic EL element

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

The organic EL element of this invention can be manufactured as follows. First, transparent electrodes, such as ITO, are formed in transparent substrates, such as a glass substrate, using a sputtering method etc., and a transparent electrode is etched in a desired pattern as needed. 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 the 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. In addition, an organic EL device is obtained by forming electrodes by forming electrodes such as aluminum 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 , R ³ Each methyl group and n is 24 as an average value between molecules)

MAA: Methacrylic acid

2-HEMA: 2-hydroxyethyl methacrylate

PME400: Brenma PME-400 (manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula represents the mean value between molecules, and the value of k is about 9. .)

PME1000: Brenma PME-1000 (manufactured by Nippon Oil Industries, Ltd., CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula represents the mean value between molecules, and the value of k is about 23. .)

GMA: glycidyl methacrylate

MMA: Methyl methacrylate

(Polymerization initiator)

V-65: V-65 (made 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): Photoinitiator (B1))

OXE02: OXE02 (made by Chiba Specialty Chemicals, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl oxime) (General formula A compound according to (5), wherein 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)

(Binder resin (C): photosensitive resin (C1))

EX1010: EX-1010 (The solution of resin which introduce | transduced ethylenic double bond and acidic group into the epoxy resin represented by Nagase ChemteX Corporation, General formula (7), solid content 70 mass%, mass average molecular weight: 3,020).

ZCR1569H: ZCR-1569H (The solution of resin which introduce | transduced ethylenic double bond and acidic group into the epoxy resin which has 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 Nippon Kayaku Co., Ltd., dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

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 diameter 120nm, dispersion medium: PGMEA, carbon black 20 mass%, polyurethane-based 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)

Into a 1 liter autoclave with a stirrer was charged MEK (420.0 g), C6FMA (90.0 g), MAA (9.0 g), PME1000 (81.0 g), and polymerization initiator V-65 (0.5 g), The crude copolymer was synthesized by polymerization at 50 ° C. for 24 hours while stirring in a nitrogen atmosphere. Hexane was added to the obtained crude copolymer solution, and it refine | purified by reprecipitation, and it vacuum-dried and obtained the polymer (A-1) (162.4g) corresponded to a polymer (A).

The polymer (A-1) had a number average molecular weight of 37,800 and a mass average molecular weight of 58,730.

[Synthesis example 2 of polymer (A)? 4]

In the synthesis of the polymer (A-1), the polymer (A-2) to correspond to the polymer (A) by the same reaction, except that the compounding of the raw material is changed as shown in Table 1. (A-4) was obtained.

[Comparative Synthesis Examples 1 and 2]: Synthesis of Comparative Example Polymer (R) Not Suitable for Polymer (A)

In the synthesis of the polymer (A-1), the polymer (R-1), which is not suitable for the polymer (A) in the present invention by the same reaction, except that the compounding of the raw materials is changed as shown in Table 1 R-2) 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, The content rate of a polyoxyalkylene group, 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 using gel permeation chromatography as polystyrene as a standard substance. As the gel permeation chromatography, HPLC-8220GPC (manufactured by Tosoh Corporation) was used. The column which 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 material. In addition, when measuring a number average molecular weight and a mass average molecular weight, the column is hold | maintained at 37 degreeC, tetrahydrofuran is used as an eluent, the flow rate is 0.2 ml / min, 0.5 mass% tetrahydrofuran of a measurement sample. 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.

<Content rate of polyoxyalkylene group>

The content rate of the polyoxyalkylene group 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 is 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, is calculated | required, and the solubility with respect to the aqueous alkali solution of a polymer is obtained. It was taken as an index.

Example 1

Polymer (A-1) (0.03 parts) obtained in the above Synthesis Example, CB (31.6 parts) as dispersion of black colorant (E), OXE02 (0.76 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 (34.4 parts) as a solvent, and cyclohexanone (25.0 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 0.20 mass%.

After using the spinner, after apply | coating the dilution liquid of the photosensitive composition on a glass substrate, it dried on 100 degreeC on a hotplate for 2 minutes, 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 100 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 exposed. The mask is a lattice pattern having a light shielding portion of 150 μm × 400 μm and a light transmitting portion of 20 μm, and has a volume of 120 pL. Moreover, the area of the pattern was 10 cm <2>. Next, image development was performed using the developing machine. As the developing solution, a 10-fold diluted aqueous solution of semi-clean DL-A4 (trade name, manufactured by Yokohama Oil and Fat Industry Co., Ltd.) was used. Using the nozzle whose irradiation angle with respect to the board | substrate was narrowed to 8 degrees or less, the developing solution was discharged to the board | substrate by applying the pressure of 0.15 Mpa, and foaming was performed and spin development was performed. Thereafter, 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 (post-baking) a glass plate for 30 minutes at 220 degreeC in oven.

Except having exposed without using a mask, it carried out similarly to the above, and obtained the glass substrate sample (2) of Example 1 in which the hardened | cured material of the coating film of the photosensitive composition was formed. Furthermore, the glass substrate sample (3) of Example 1 which performed the jet rinse with 4.0 MPa high-pressure jet water for 10 second was obtained.

Example 2 5]

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 which formed the partition which consists of coating film hardened | cured material of the photosensitive composition containing (A-5), respectively? Example 2 which the hardened | cured material of the glass substrate sample 1 of 5 and the coating film of this photosensitive composition was formed? The glass substrate sample (3) which carried out 5 glass substrate samples (2) and jet rinse was obtained.

[Comparative Examples 1 and 2]

Application of the photosensitive composition containing the polymer (R-1) and (R-2) which were obtained by the said comparative synthesis example similarly to Example 1 except having changed the compounding of each component as shown in Table 2, The glass substrate samples (1) of the comparative examples 1 and 2 with which the partition which consists of a film hardened | cured material were formed, and the glass substrate samples (2) and jet rinse of the comparative examples 1 and 2 in which the hardened | cured material of the coating film of this photosensitive composition were formed further The performed glass substrate sample (3) was obtained.

[Evaluation Method and Evaluation Result]

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

In a table, (double-circle) is the best, (circle) is good, (triangle | delta) is possible and x represents impossibility. It is preferable that all the evaluations of this invention are (double-circle) or (circle).

<Liquid repellency>

Liquid repellency was evaluated by measuring the contact angle of PGMEA of the coating film hardened | cured material surface of the glass substrate sample (2). Moreover, the liquid repellency tolerance by jet rinse was evaluated by measuring the contact angle of PGMEA of the coating film hardened | cured material surface of the glass substrate sample (3).

The contact angle is an angle formed by the tangent to the liquid surface and the solid surface at the point of contact between the solid and the liquid, and is defined as the angle of the side containing the liquid. For this reason, it means that the liquid repellency of a coating film hardened | cured material is excellent, so that a contact angle is large. The contact angles of PGMEA were determined to be?, 35 ° or more, and 40 ° or less,?, 35 ° or less, and?

<State of residual film generation>

In the glass substrate sample 1, the state of residual film generation was evaluated by visually measuring the number of image development defects. (Circle) and the thing of 100 or more and less than 200 things (triangle | delta) and the thing of 200 or more were determined as x with the thing with less than 100 developing defects per area.

<Wet diffusion of ink in the openings between partition walls>

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 ink was prepared by stirring and mixing for 1 hour using a stirrer.

Using the inkjet method, about 10 pL or 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 it image | photographed using the super depth shape measuring microscope VK-8500 (made by Keyence Corporation). By observing the photograph, the wet diffusion property of the ink in the opening between the partition walls was evaluated.

In the obtained photograph, the portion where the ink bounced was 0 points with respect to 10 points between the partition openings. ○, 3? △, 5? Ten points were determined as x.

As can be seen from Table 3, even when jet rinsing is performed, the mass average molecular weight (Mw (A)) is in the range of 2.6 × 10 ⁴ <Mw (A) ≦ 20 × 10 ⁴ , and the polyoxyalkylene group Polymer (A-1) equivalent to the polymer (A) to contain? Having a partition obtained using the photosensitive composition of this invention each containing (A-5) (The content rate of the polyoxyalkylene group in a polymer is all in the range of 5-60 mass% preferable in this invention.) Example 1 In the glass substrate sample 3 of 5, liquid repellency was favorable. This is Example 1? In the partition obtained by using the photosensitive composition of 5, even if it carries out high pressure water washing | cleaning, such as jet rinse, it shows that the liquid repellency was maintained without peeling off a polymer (A) from the surface layer.

Polymer (A-1) equivalent to polymer (A)? Example 1 which has a partition obtained by using the photosensitive composition of this invention containing (A-5), respectively. In the glass substrate sample 1 of 5, generation | occurrence | production of a residual film was few. This is Example 1? Since sufficient amount of polyoxyalkylene group existed on the surface of the partition obtained using the 5 photosensitive composition, it shows that generation | occurrence | production of a residual film was suppressed.

Polymer (A-1) equivalent to the polymer (A) even when about 20 pL of ink is applied to the opening of the partition wall having a volume of 120 pL, that is, when the application amount of the ink is small relative to the volume of the opening. Example 1 which has a partition obtained by using the photosensitive composition of this invention containing (A-5), respectively. In the glass substrate sample 1 of 5, ink wetted and spread | diffused in the opening part between partitions, and there was no discoloration. This is Example 1? In the coating film obtained from the photosensitive composition of 5, developability is favorable and it shows that there was no movement of the polymer (A) component from the partition surface to the opening part between partition walls.

In addition, even when less ink of about 10 pL is applied, the mass average molecular weight of the polymer (A) is 40000 or more. 4, the ink wetted and diffused into the openings between the partition walls, and there was no discoloration.

On the other hand, the photosensitive composition containing polymer (R-1) outside the mass mean molecular weight Mw (A) of the polymer (A) which concerns on this invention, specifically the mass mean molecular weight Mw is less than 2.6 * 10 <^4> is used. The liquid-repellency after jet rinse of the glass substrate sample 3 of the comparative example 1 which has the partition which was obtained by remarkably fell. Moreover, when about 20 pL of ink was apply | coated to the opening part between partitions with a volume of 120 pL, ie, when the application amount of ink is small with respect to the volume of the opening, there existed a part which ink does not diffuse into the opening and does not diffuse. This shows that at the time of post-baking, the polymer (R-1) migrates into the openings, and the lyophilic properties of the openings are reduced.

In the glass substrate sample (1) of the comparative example 2 which has a partition obtained using the photosensitive composition containing the polymer (R-2) which does not have a polyoxyalkylene group, many residual films were generated.

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 that does not erode into the developer, property of suppressing the development of the residual film remaining undeveloped, And the ink repellent component which can provide the wettightness | diffusion property of the favorable ink to the opening part between partition walls to the partition which is obtained.

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. Moreover, it is used suitably as a material which forms permanent films, such as the partition which isolate | separates each TFT of an organic TFT (Thin Film Transistor: thin film transistor) array, the partition of the ITO electrode of a liquid crystal display element, the partition of a circuit wiring board, etc.

In addition, the JP Patent application 2009-298961, the claim, and all the content of the abstract for which it applied on December 28, 2009 are referred here, and it takes in as an indication of the specification of this invention.

Claims (14)

A polymer having a side chain having a group represented by the following General Formula (1) and a side chain having a polyoxyalkylene group, and not having a side chain having an ethylenic double bond, a photocuring initiator (B), , As a photosensitive composition containing 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.)
The mass average molecular weight (Mw (A)) of the said polymer (A) is 2.6 * 10 < ⁴ <Mw (A) <= 20 * 10 <^4> , The photosensitive composition characterized by the above-mentioned. The method of claim 1,
The content rate of the polyoxyalkylene group in the said polymer (A) is 5? It is 60 mass%, The photosensitive composition. 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 said 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 a hydrogen atom or the alkyl group, cycloalkyl group, or aryl group which may be substituted by 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.) The method according to any one of claims 1 to 7,
It has a side chain which has a group represented by the following general formula (2), and a side chain which has a polyoxyalkylene group, and has neither the side chain which has a group represented by the said General formula (1), and the side chain which has ethylenic double bond. The photosensitive composition which further contains polymer (A) 'whose mass mean molecular weight (Mw (A)') is 2.6 * 10 < ⁴ <Mw (A) '<= 20 * 10 <^{4> as a non} -polymer (A)'.
(2)

(In formula, R <^1> and R <^2> is respectively independently a hydrogen atom or the alkyl group, cycloalkyl group, or aryl group which may be substituted by 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.) The method according to any one of claims 1 to 8,
The said photocuring initiator (B) is a photoinitiator, The said photosensitive resin 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 an adjacent pixel on a substrate, wherein the partition is formed by the partition according to 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 an adjacent pixel 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.