JP6620743B2 - Resin, photosensitive resin composition, cured product, color filter, and image display device - Google Patents

Description

  The present invention relates to a resin, a photosensitive resin composition, a cured product, a color filter, and an image display device. In particular, when used as a resin of a photosensitive resin composition, a resin having good sensitivity and resolution, a photosensitive resin composition containing the resin, a cured product obtained by curing the resin, and a color having the cured product The present invention relates to a filter and an image display device including the color filter.

  A color filter usually forms a black black matrix (hereinafter sometimes abbreviated as “BM”) on the surface of a transparent substrate such as glass or plastic, and then three types such as red, green, and blue. The above different pixels are sequentially formed in a striped pattern or a mosaic pattern.

  A pigment dispersion method is currently used as a representative method for producing a color filter. In this method, first, a photosensitive resin composition containing a black pigment is applied on a transparent substrate, dried, further exposed to an image, developed, and then cured by high-temperature treatment at 200 ° C. or higher to form a BM. A color filter is formed by repeating this for each color such as red, green, and blue.

  The BM is generally arranged in a grid, stripe, or mosaic between pixels such as red, green, and blue, and has a role of preventing contrast improvement or light leakage by suppressing color mixture between pixels. Yes. For this reason, the BM is required to have high light shielding properties.

  Further, since the edge portions of the red, green, and blue pixels formed after the BM overlap with the BM, a step is formed at the overlapping portion due to the influence of the BM film thickness. In this overlapping portion, the flatness of the pixel is impaired, and the liquid crystal cell gap becomes nonuniform or the alignment of the liquid crystal is disturbed, resulting in a decrease in display capability.

  Therefore, in recent years, particularly BM thinning has been demanded, and the pigment content in the photosensitive resin composition tends to be higher in order to exhibit sufficient light shielding properties when thinned.

  In recent years, when the manufactured color filter is assembled on a panel, a frame portion has been separately formed, and a sealing agent has been applied to the panel to attach it to an array substrate. A method of forming a part at the same time and applying a sealant to the part has been performed. For this reason, a strong adhesion between the substrate of the color filter and the BM has been increasingly required.

  On the other hand, in order to obtain a photosensitive resin composition by the pigment dispersion method, first, a composition containing a colorant, a dispersant, a solvent, and the like is dispersed with glass beads or the like to prepare a dispersion. Then, it stirs and mixes with binder resin, a photoinitiator, etc., and produces the photosensitive resin composition.

  As a binder resin in the photosensitive resin composition for color filters, an uncured portion is subjected to alkali development after being cured by UV exposure through a mask so that pixels such as BM, red, green and blue can be formed. A removable alkali-soluble resin having a carboxyl group or the like is used. Conventionally, an acrylic copolymer resin obtained by copolymerizing acrylic acid has been used as an alkali-soluble resin having a carboxyl group.

  However, due to recent demands for high color characteristics and demands for thinning BM as described above, the pigment content in the photosensitive resin composition is increasing, and it may be difficult to cure depending on the conditions. Therefore, a resin having high curing characteristics has been desired.

  Under such circumstances, so-called epoxy acrylate resins have recently been used. For example, Patent Document 1 describes examples of epoxy acrylate resins having various bisphenoxy skeletons. Patent Document 2 describes an example of an epoxy acrylate resin having an adamantyl group.

  On the other hand, Patent Document 3 has a bisphenoxy skeleton and a specific alkylidene group as an epoxy resin used in applications such as light emitting devices such as LEDs or light receiving devices such as solar cells, which are excellent in heat resistance and moisture absorption. Epoxy resins are described.

Japanese Unexamined Patent Publication No. 2005-126684 Japanese Unexamined Patent Publication No. 2008-287246 Japanese Unexamined Patent Publication No. 2013-253153

  When the present inventors examined, when using the epoxy acrylate resin described in Patent Documents 1 and 2, depending on the color material content ratio in the photosensitive resin composition, the sensitivity or resolving power deteriorates, It has been found that good BM or pixels cannot be formed. In particular, when trying to form a fine line pattern under conditions where the color material content ratio is high, sufficient curing cannot be performed due to a decrease in sensitivity, and the pattern is excessively removed during development, resulting in the width of the opening of the mask. It was found that only a pattern having a narrow width was obtained, and control of the pattern shape was difficult. Further, Patent Document 3 does not describe any photosensitive resin composition for a color filter, and characteristics when used as a resin for the photosensitive resin composition were unknown.

  Therefore, the present invention is a resin that is excellent in sensitivity and resolution and can form a good color filter regardless of the pigment content in the photosensitive resin composition when applied as a resin in the photosensitive resin composition. It is an object of the present invention to provide a photosensitive resin composition containing the resin, a cured product obtained by curing the photosensitive resin composition, a color filter having the cured product, and an image display device including the color filter.

  As a result of intensive studies by the present inventors to solve the above problems, a partial structure having a specific bisphenoxy skeleton and a specific alkylidene group and a partial structure having a specific ethylenically unsaturated group and a carboxyl group residue are obtained. It has been found that a resin having a solution to the above problems. That is, the gist of the present invention is as follows.

[1] A resin including at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (II).

[In said formula (I), R < ¹² > is a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, or a C7-C20 aralkyl group.
In the above formula (II), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. , R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, k is an integer of 1 to 5, and l is an integer of 0 to 13. is there.
Each * is a bond independently. ]
[2] The resin according to [1], wherein the partial structure represented by the formula (II) is a partial structure represented by the following formula (III).

[In the formula ^(III), R 1 ~R ⁴ are as defined in the formula (II).
Each * is a bond independently. ]
[3] The resin according to [1], wherein the resin including a partial structure represented by the formulas (I) and (II) is a resin including a partial structure represented by the following formula (IV).

[In said formula (IV), R < ¹¹ > is respectively independently a C1-C5 alkylene group, and m is an integer of 0-5.
Moreover, R < ¹ > -R < ⁵ >, k and l are synonymous with said Formula (II). R ¹² is independently synonymous with the formula (I).
Each * is a bond independently. ]
[4] The resin according to [3], wherein the partial structure represented by the formula (IV) is a partial structure represented by the following formula (V).

[In said formula (V), R < ¹ > -R < ⁴ >, R < ¹¹ >, R < ¹² > and m are respectively synonymous with said Formula (IV) independently.
Each * is a bond independently. ]
[5] The resin according to any one of [1] to [4], further including at least one of a partial structure represented by the following formula (VI) and a partial structure represented by the following formula (VII).

[In the above formula (VI), X is a divalent carboxylic acid residue. In the above formula (VII), Y is a tetravalent carboxylic acid residue.
Each * is a bond independently. ]
[6] The resin according to [5], further having a partial structure represented by the following formula (VIII).

[In the above formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2-8.
* Is a bond. ]
[7] The resin according to [5], further having a partial structure represented by the following formula (IX).

[In the above formula (IX), Z ′ represents a polyvalent methylol residue. n 'is an integer of 2-6.
* Is a bond. ]
[8] A resin obtained by reacting at least (A-1) an epoxy group-containing compound represented by the following formula (X) with (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.

[In the formula (X), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Yes, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is an alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5. ]
[9] The resin according to [8], wherein the (A-1) epoxy group-containing compound is a compound represented by the following formula (XI).

[In said formula (XI), R < ¹ > -R < ⁴ >, R < ¹¹ > and m are respectively independently synonymous with said Formula (X). ]
[10] A resin obtained by reacting the resin according to [8] or [9] with (A-3) a polybasic acid anhydride.
[11] The resin according to [10], which is obtained by further reacting with (A-4) a polybasic acid anhydride and (A-4) a polyhydric alcohol.
[12] (A-4) The polyhydric alcohol is at least one selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. The resin according to [11], which is a polyhydric alcohol.
[13] The resin according to any one of [1] to [12], which is a color filter resin.

[14] A photosensitive resin composition comprising at least the resin (resin (a-1)) of any one of [1] to [13] and a photopolymerization initiator (b).
[15] The photosensitive resin composition according to [14], further containing a color material (d).
[16] The photosensitive resin composition according to [15], wherein the color material (d) is a pigment and further contains a dispersant (e).
[17] The photosensitive resin composition according to [16], wherein the color material (d) is a black pigment and the dispersant (e) is a polymer compound having a basic functional group.
[18] The photosensitive resin composition according to [17], wherein the content ratio of the black pigment is 45% by mass or more based on the total solid content.
[19] The photosensitive resin composition according to any one of [14] to [18], which contains at least an oxime ester compound as the photopolymerization initiator (b).

[20] A cured product obtained by curing the photosensitive resin composition according to any one of [14] to [19].
[21] A color filter including at least one of a pixel and a black matrix made of the cured product according to [20].
[22] An image display device comprising the color filter according to [21].

  According to the present invention, when applied as a resin in a photosensitive resin composition, a good color filter can be formed with excellent sensitivity and resolution regardless of the pigment content in the photosensitive resin composition. A resin, a photosensitive resin composition containing the resin, a cured product obtained by curing the resin, a color filter having the cured product, and an image display device including the color filter can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device provided with the color filter of the present invention.

  Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

  In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”. The terms “acid (anhydride)” and “(anhydrous)... Acid” mean that both an acid and its anhydride are included.

  In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive resin composition or in the ink described later.

  In the present invention, the number average molecular weight and the weight average molecular weight mean a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).

Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
In the present invention, the “carboxylic acid residue” means a group remaining after removing all carboxyl groups from the carboxylic acid compound. For example, the carboxylic acid residue in the carboxylic acid compound represented by A-COOH means a monovalent group represented by A. Similarly, the “polyhydric alcohol residue” means a group remaining after removing all hydroxyl groups from the polyhydric alcohol compound. The “multivalent methylol residue” means a group remaining after removing all methylol groups (—CH ₂ —OH groups) from the polyvalent methylol compound.

  In the present specification, a bond may be indicated using “*”. In addition, in this specification, a numerical range may be indicated using “to”, which means a numerical range including an upper limit value and a lower limit value.

<Resin (a-1)>
The resin of the present invention (hereinafter sometimes referred to as “resin (a-1)”) includes at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (II). It is characterized by that.

  Resin (a-1) has a bulky structure such as the following formula (II), and also has a structure of an ethylenically unsaturated group such as the following formula (I). Or there exists a tendency which is excellent in hardened | cured material characteristics, such as moisture absorption resistance.

In said formula (I), R < ¹² > is a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, or a C7-C20 aralkyl group.

In the above formula (II), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, k is an integer of 1 to 5, and l is an integer of 0 to 13. is there.
Each * is a bond independently.

[Partial structure represented by formula (I)]
R ¹² in the partial structure represented by the formula (I) is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

The carbon number of the alkyl group represented by R ¹² in formula (I) is usually 1 or more, preferably 6 or less, more preferably 3 or less, and still more preferably 2 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is good. Tend to be.

  Specifically, for example, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, cyclopentyl group 1-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, octyl group, nonan-1-yl group and decan-1-yl group. Among these, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1-hexyl group, 2 -A hexyl group, a 3-hexyl group, or a cyclohexyl group is preferable, a methyl group, an ethyl group, a 1-propyl group, or a 2-propyl group is more preferable, and a methyl group is further preferable.

In addition, the carbon number of the aryl group represented by R ¹² in formula (I) is usually 6 or more, usually 20 or less, preferably 15 or less, and more preferably 10 or less.

  When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is good. Tend to be. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

The carbon number of the aralkyl group of R ¹² in formula (I) is usually 7 or more, and usually 20 or less, preferably 15 or less, more preferably 11 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is good. Tend to be. Specifically, a benzyl group or a methylene naphthyl group is preferable, and a phenyl group is more preferable.

Among these, R ¹² in the formula (I) is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or a methyl group is the most manifested characteristic of the present invention. It is particularly preferable because it tends to be generated.

  In the resin (a-1), the content ratio of the partial structure represented by the formula (I) is not particularly limited, but is preferably 1% by mass or more based on the total mass of the resin (a-1). It is more preferably 5% by mass or more, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

  When it is within the above range, the curing characteristics such as chemical resistance tend to be good, and when used as a resin in the photosensitive resin composition, the compatibility with other components tends to be good. There is.

[Partial structure represented by formula (II)]
K in the cycloalkylidene group in the partial structure represented by the formula (II) is an integer of 1 to 5, preferably an integer of 2 or more, preferably an integer of 4 or less, more preferably 3.

  When it is within the above range, curing characteristics such as chemical resistance tend to be good. In addition, when used as a resin in the photosensitive resin composition, if it is equal to or higher than the lower limit value, the effect due to its bulk tends to be expressed well, and if it is equal to or lower than the upper limit value, There is a tendency for the compatibility with the components to be good.

  As specific examples of the cycloalkylidene group, a cycloundecylidene group, a cyclododecylidene group, or a cyclotridecylidene group is preferable, and a cyclododecylidene group is particularly preferable.

R ⁵ which is a substituent that the cycloalkylidene group in the partial structure represented by the formula (II) may have is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or It is an aralkyl group having 7 to 20 carbon atoms.

The carbon number of the alkyl group of R ⁵ is usually 1 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 5 or less, still more preferably 3 or less, and more preferably 2 or less. Particularly preferred. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is good. Tend to be.

  Specifically, for example, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, cyclopentyl group 1-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, octyl group, nonan-1-yl group, decan-1-yl group, undecan-1-yl group, dodecan-1-yl group, Tridecan-1-yl group, tetradecan-1-yl group, pentadecan-1-yl group, hexadecan-1-yl group, heptadecan-1-yl group, octadecan-1-yl group, nonadecan-1-yl group, icosane A -1-yl group is mentioned.

  Among these, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1-hexyl group, 2 -A hexyl group, a 3-hexyl group, or a cyclohexyl group is preferable, a methyl group, an ethyl group, a 1-propyl group, or a 2-propyl group is more preferable, and a methyl group is further preferable.

The carbon number of the aryl group of R ⁵ is usually 6 or more, usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is high. There is a tendency to improve. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

The carbon number of the aralkyl group of R ⁵ is usually 7 or more, usually 20 or less, preferably 15 or less, more preferably 11 or less, and further preferably 9 or less. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is high. There is a tendency to improve. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a benzyl group is more preferable.

Among them, R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably from the viewpoint of properties of the resin are most expressed a methyl group.

In the formula (II), l, which is the number of substituents R ⁵ that the cycloalkylidene group may have, is an integer of 0 to 13, preferably an integer of 4 or less, more Preferably it is an integer of 2 or less. In particular, the case where l is 0, that is, the case where there is no substituent is particularly preferable. By being within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in the photosensitive resin composition, compatibility with other components is good. Tend.

When l is an integer of 2 or more, R ⁵ may be the same or different, and the substitution positions may be the same or different.

In the formula (II), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. It is.

In the formula (II), the carbon number of the alkyl group in R ^{1 to} R ⁴ is usually 1 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. It is further preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is high. There is a tendency to improve.

  Specifically, for example, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, cyclopentyl group 1-hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, octyl group, nonan-1-yl group, decan-1-yl group, undecan-1-yl group, dodecan-1-yl group, Tridecan-1-yl group, tetradecan-1-yl group, pentadecan-1-yl group, hexadecan-1-yl group, heptadecan-1-yl group, octadecan-1-yl group, nonadecan-1-yl group and icosane A -1-yl group is mentioned.

  Among these, methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1-hexyl group, A 2-hexyl group, a 3-hexyl group, or a cyclohexyl group is preferable, a methyl group, an ethyl group, a 1-propyl group, or a 2-propyl group is more preferable, and a methyl group is particularly preferable.

In the formula (II), the number of carbon atoms of the aryl group in R ^{1 to} R ⁴ is usually 6 or more, usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less. . When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is high. There is a tendency to improve. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

In the formula (II), the carbon number of the aralkyl group in R ^{1 to} R ⁴ is usually 7 or more, usually 20 or less, preferably 15 or less, more preferably 11 or less, and further preferably 9 or less. . When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when used as a resin in a photosensitive resin composition, compatibility with other components is high. There is a tendency to improve. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a benzyl group is more preferable.

In the formula (II), R ^{1 to} R ⁴ may be the same or different.
Among these, it is preferable that R ¹ to R ⁴ is a hydrogen atom from the viewpoint of heat resistance, also, it is preferable from the viewpoint of chemical resistance is a methyl group.

Although the substitution positions of R ^{1 to} R ⁴ in the formula (II) are not particularly limited, for example, any of the positions b to f in the following formula (II ′) can be mentioned, and R ^{1 to} R ⁴ are each independently carbon. In the case of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, the substitution position is any one of b, c, e, and f. It is preferably a position, and more preferably a position b or f.

  In the formula (II), the substitution position of the cycloalkylidene group may be any of positions b to f in the following formula (II ′), but when heat resistance based on the cycloalkylidene group is efficiently obtained, From the point of view, the position d is preferred.

In said formula (II '), R < ¹ > -R < ⁵ >, k and l are synonymous with the definition in said Formula (II).

  Specific examples of the partial structure of the formula (II) include the following, but are not limited to the following. In addition, the numerical value described in the cycloalkylidene group in the following chemical formula indicates the carbon number of the cycloalkylidene group.

  Among these, as the partial structure of the formula (II), any one selected from (A-1-9) to (A-1-12) and (A-1-33) to (A-1-40) Are more preferable, any one selected from (A-1-9) to (A-1-12) is more preferable, and any one selected from (A-1-9) to (A-1-11) is further (A-1-9) is particularly preferable.

  When the partial structure of the formula (II) is any of these structures, curing characteristics such as chemical resistance tend to be good, and when used as a resin in the photosensitive resin composition, The compatibility with the components tends to be good, and the properties of the resin tend to be expressed well.

  Resin (a-1) includes any structure selected from the following (A-1-29) to (A-1-32) as a structure including the partial structure of (A-1-1). You may go out.

  In the present invention, as the partial structure of the general formula (II), as long as the general formula (II) is satisfied, one type may be used alone, or two or more types may be used in combination.

  In the resin (a-1), the content of the partial structure represented by the formula (II) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, The content is preferably 95% by mass or less, and more preferably 90% by mass or less. When it is within the above range, the curing characteristics such as chemical resistance tend to be good, and when used as a resin in the photosensitive resin composition, the compatibility with other components tends to be good. There is.

[Partial structure represented by formula (III)]
In the resin (a-1), the partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (III).

In the formula ^(III), R 1 ~R ⁴ are as defined in the formula (II). Each * is a bond independently.

  The reason why the partial structure represented by the formula (II) is preferably the partial structure represented by the formula (III) is that curing properties such as chemical resistance tend to be good, When used as a resin in a photosensitive resin composition, the balance between good compatibility with other components and the effect resulting from the bulkiness of the cycloalkylidene group tends to be excellent, and the handleability is good There is a tendency.

  The partial structure represented by the formula (III) contained in the resin (a-1) may be one type or two or more types. The resin (a-1) may contain a partial structure that does not satisfy the formula (III) and satisfies the formula (II).

  In the resin (a-1), the content ratio of the partial structure represented by the formula (III) in the partial structure represented by the formula (II) is such that the characteristics of the resin are easily expressed well. From the viewpoint, 5% by mass or more is preferable, 10% by mass or more is more preferable, 20% by mass or more is more preferable, 50% by mass or more is more preferable, 80% by mass or more is particularly preferable, and usually 100% by mass. It is as follows.

(Partial structure represented by formula (IV))
The resin (a-1) preferably includes a partial structure represented by the following formula (IV) as the partial structure represented by the formula (I) and the partial structure represented by the formula (II). That is, it is preferable that the resin including the partial structure represented by the formulas (I) and (II) is a resin including the partial structure represented by the following formula (IV).

In said formula (IV), R < ¹¹ > is a C1-C5 alkylene group each independently, and m is an integer of 0-5. Moreover, R < ¹ > -R < ⁵ >, k and l are synonymous with said Formula (II). R ¹² is independently synonymous with the formula (I). Each * is a bond independently.

  The reason why it is preferable to include the partial structure represented by the formula (IV) is that the partial structure has a bulky cycloalkylidene group, and the chemical resistance tends to be good. When the partial structure represented by the formula (I) exists away from the bulky cycloalkylidene group, the influence of the steric hindrance is small, and it is easy to crosslink by ultraviolet irradiation or high heat. Tends to be even larger. Moreover, when it uses as resin in the photosensitive resin composition, a sensitivity becomes favorable with the improvement of a crosslinking reaction, and there exists a tendency for the tolerance with an alkali developing solution to become favorable.

The carbon number in the alkylene group of R ^{11 in} the above formula (IV) is usually 1 or more, preferably 2 or more, and usually 5 or less. By being in the said range, there exists a tendency for hardening characteristics, such as chemical resistance, to become favorable, and there exists a tendency for the effect of resin of this invention to express favorably. Further, when used as a resin in the photosensitive resin composition, when the amount is not less than the lower limit value, the influence of steric hindrance due to the cycloalkylidene group tends to be small, and when the amount is not more than the upper limit value. Tends to have good compatibility with other components.

The alkylene group for R ¹¹ may be linear or branched. Specifically, methylene group, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, 1,2-butylene group, 1,5-pentylene group, 1,2- A pentylene group, a 1,3-pentylene group or a cyclopentylene group is preferable, and an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,2-butylene group, 1 , 5-pentylene group, 1,2-pentylene group, or 1,3-pentylene group is more preferable.

Moreover, in said formula (IV), m is an integer of 0-5, Preferably it is an integer of 2 or less, More preferably, it is 0 or 1, More preferably, it is 0. In the said range, there exists a tendency for hardening characteristics, such as chemical resistance, to become favorable, and there exists a tendency for the effect of resin (a-1) to express favorably. Further, when the resin (a-1) is used as a resin in the photosensitive resin composition, the influence of the steric hindrance of the cycloalkylidene group tends to be small, and the compatibility with other components is good. Tend to be. Further, when m is an integer of 2 or more, R ¹¹ may be the same or different.

  Moreover, * in the said formula (IV) is a bond independently. For example, the bond can be bonded to a hydrogen atom, or can be bonded to a bond of formula (VI) and / or formula (VII) described later.

  The partial structure represented by the formula (IV) contained in the resin (a-1) may be one type alone or two or more types.

  The content ratio of the partial structure represented by the formula (IV) in the resin (a-1) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, The content is preferably 95% by mass or less, and more preferably 90% by mass or less. When it is within the above range, the curing characteristics such as chemical resistance tend to be good, and when used as a resin in the photosensitive resin composition, the resistance to an alkaline developer tends to be good. .

[Partial structure represented by formula (V)]
In the resin (a-1), the partial structure of the formula (IV) is preferably a partial structure represented by the following formula (V).

In said formula (V), R < ¹ > -R < ⁴ >, R < ¹¹ >, R < ¹² > and m are respectively synonymous with said Formula (IV) independently. Each * is a bond independently.

  The reason why the partial structure represented by the formula (V) is preferable is that the cycloalkylidene group is a cyclododecylidene group, and thus the curing characteristics such as chemical resistance tend to be improved. It is mentioned that there is a tendency that the effect of can be expressed best. Further, when the resin (a-1) is used as the resin in the photosensitive resin composition, the resistance to the alkali developer tends to be good due to the bulk of the cyclododecylidene group. The influence of steric hindrance on the partial structure represented by (I) is also reduced, and the sensitivity or resistance to an alkaline developer tends to be improved.

  The partial structure represented by the formula (V) contained in the resin (a-1) may be one type alone or two or more types. The resin (a-1) may include a partial structure that does not satisfy the formula (V) and satisfies the formula (IV).

  The content ratio of the partial structure represented by the formula (V) in the partial structure represented by the formula (IV) contained in the resin (a-1) is such that the characteristics of the present invention are easily expressed. From this point of view, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, still more preferably 50% by mass or more, and 80% by mass or more. Is particularly preferred. Moreover, it is 100 mass% or less normally.

  Moreover, * in the said Formula (V) is a bond independently. For example, the bond can be bonded to a hydrogen atom, or can be bonded to a bond of formula (VI) and / or formula (VII) described later.

[Partial Structures Represented by Formula (VI) and Formula (VII)]
The resin (a-1) preferably further includes a partial structure represented by the following formula (VI) and / or a partial structure represented by the following formula (VII).

  In the above formula (VI), X is a divalent carboxylic acid residue. In the above formula (VII), Y is a tetravalent carboxylic acid residue. Each * is a bond independently.

  The resin (a-1) contains the partial structure represented by the formula (VI), that is, the resin (a-1) has at least one carboxyl group, whereby the resin (a-1) is added to the substrate. When coated, there is a tendency that the adhesion to the substrate due to the carboxyl group of the polar group can be improved. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, the adjustment of the solubility at the time of alkali development becomes easy, and the adhesion to the substrate tends to be improved.

  X in the formula (VI) is not particularly limited as long as it is a divalent carboxylic acid residue, but as described later in the synthesis, from the viewpoint of ease of synthesis, a dibasic acid anhydride ( It is preferably a divalent carboxylic acid residue of dicarboxylic acid anhydride).

  Examples of the divalent carboxylic acid residue include a divalent hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. What connected the aliphatic hydrocarbon and the aromatic hydrocarbon may be used. Further, it may be a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of improving substrate adhesion and chemical resistance. More preferably, it is 10 or less, More preferably, it is 8 or less. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, a carbonyl group, and the like, but unsubstituted is preferable.

  Specifically, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride The divalent carboxylic acid residues such as tetrahydrophthalic anhydride or succinic anhydride are more preferable. These dibasic acid anhydride divalent carboxylic acid residues may be used alone or in combination of two or more.

  By making X as described above, the substrate adhesion and chemical resistance tend to be improved. Further, when used as a resin in the photosensitive resin composition, it becomes easy to adjust the solubility during alkali development, and the adhesion to the substrate tends to be improved.

  Specific examples of the partial structure represented by the formula (VI) include the following, but the structure is not limited to the following as long as it has the structure of the formula (VI), and is applied to the present invention. Is done.

  Further, the resin (a-1) contains a partial structure represented by the formula (VII), that is, the resin (a-1) has at least two carboxyl groups. Tend to improve. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, the adjustment of the solubility at the time of alkali development becomes easy, and the adhesion to the substrate tends to be improved.

  Moreover, since the partial structure represented by the formula (VII) has two bonds, two partial structures represented by the formula (IV) or (V) having an ethylenically unsaturated group are included. When it is contained above, the molecular weight can be increased, and at the same time, the content of ethylenically unsaturated groups can be increased, the crosslinking reaction can be increased during curing, and the substrate adhesion and chemical resistance can be improved. Seem.

  Y in the formula (VII) is not particularly limited as long as it is a tetravalent carboxylic acid residue, but from the viewpoint of ease of synthesis as described later, 4-basic acid anhydride (tetracarboxylic acid anhydride) It is preferable that it is a tetravalent carboxylic acid residue.

  Examples of the tetravalent carboxylic acid residue include a tetravalent hydrocarbon group which may have a substituent. The hydrocarbon group may have a hetero atom such as an oxygen atom or a sulfur atom.

  Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. What connected the aliphatic hydrocarbon and the aromatic hydrocarbon may be used. Further, it may be a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 5 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of improving substrate adhesion and chemical resistance. It is. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, a carbonyl group, and the like, but unsubstituted is preferable.

  Specifically, for example, tetravalent carboxylic acid such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, bicarboxylic ether tetracarboxylic dianhydride, etc. An acid residue is preferable, and a tetravalent carboxylic acid residue of biphenyltetracarboxylic anhydride is more preferable. These tetravalent acid anhydride tetravalent carboxylic acid residues may be used alone or in combination of two or more.

  By setting Y to the above, curing characteristics such as substrate adhesion and chemical resistance tend to be improved. Further, when the resin (a-1) is used as a resin in the photosensitive resin composition, it becomes easy to adjust the solubility at the time of alkali development, the alkali resistance of the image portion becomes good, and the adhesion to the substrate. Tend to improve.

  Specific examples of the partial structure represented by the formula (VII) include the following, but the invention is not particularly limited as long as it has the structure of the formula (VII) and is applied to the present invention.

  Resin (a-1) is similar to the partial structure represented by formula (VI) and / or the partial structure represented by formula (VII) derived from polybasic acid anhydrides in addition to the partial structure described above. A partial structure may be included. Among these, the case where it contains a partial structure represented by the following formula (VI ′) derived from a tribasic acid anhydride is preferable.

  In the above formula (VI ′), X ′ is a trivalent carboxylic acid residue. * Represents a bond.

  The resin (a-1) contains a partial structure represented by the formula (VI ′), that is, the resin (a-1) has at least two carboxyl groups, so that the substrate adhesion, chemical resistance, etc. There is a tendency to improve the curing characteristics of. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, it is easy to adjust the solubility during alkali development, and the adhesion to the substrate tends to be good. .

  X ′ in the formula (VI ′) is not particularly limited as long as it is a trivalent carboxylic acid residue, but from the viewpoint of ease of synthesis as described later, a tribasic acid anhydride (tricarboxylic acid anhydride) is used. It is preferable that it is a trivalent carboxylic acid residue.

  Examples of the trivalent carboxylic acid residue include a trivalent hydrocarbon group which may have a substituent. The hydrocarbon group may have a hetero atom such as an oxygen atom or a sulfur atom.

  Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. What connected the aliphatic hydrocarbon and the aromatic hydrocarbon may be used. Further, it may be a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 5 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of improving substrate adhesion and chemical resistance. It is. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, a carbonyl group, and the like, but unsubstituted is preferable.

  Specifically, for example, a trivalent carboxylic acid residue such as trimellitic anhydride or hexahydrotrimellitic anhydride is preferable, and a trivalent carboxylic acid residue of trimellitic anhydride is more preferable. The trivalent carboxylic acid residues of these tribasic acid anhydrides may be used alone or in combination of two or more.

  By setting X ′ as described above, curing characteristics such as substrate adhesion and chemical resistance tend to be improved. Further, when used as a resin in the photosensitive resin composition, it becomes easy to adjust the solubility during alkali development, and the adhesion to the substrate tends to be improved.

  The bond * in the partial structure represented by the formula (VI), the partial structure represented by the formula (VI ′), or the partial structure represented by the formula (VII) is, for example, independently It can be combined with a bond * in the partial structure represented by the formula (IV) or (V).

  Moreover, the bond * in the partial structure represented by the formula (IV) or the partial structure represented by the formula (V) is, for example, a hydrogen atom or a moiety represented by the formula (VI). The structure and / or the bond may be combined with a bond * in the partial structure represented by the formula (VII).

  The partial structure represented by the formula (VI), the partial structure represented by the formula (VI ′), or the partial structure represented by the formula (VII) is represented by the formula (VII). A partial structure is preferred. Among these, when the partial structure represented by the formula (VII) is contained alone, the bond between the partial structure represented by the formula (VII) and the partial structure represented by the formula (IV) The ratio of bonding with the hands is usually 10 to 90%, preferably 20 to 85%, more preferably 30 to 80%, where the total number of bonding hands * in the formula (IV) is 100%. The bond in the formula (IV) that is not bonded to the bond in the formula (VII) can be bonded to, for example, a hydrogen atom.

  Curing characteristics such as substrate adhesion and chemical resistance are improved by setting the proportion of bonds in the formula (IV) bonded to the bonds in the formula (VII) within the above range. Moreover, when used as a resin in the photosensitive resin composition, the solubility in an alkali developer and the adhesion to a substrate tend to be good.

  In addition, from the viewpoint of curing properties such as substrate adhesion and chemical resistance, the resin of the present invention includes a partial structure represented by the formula (VI) in addition to the partial structure represented by the formula (VII). It is preferable.

  When the resin (a-1) contains both the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII), the content ratio (molar ratio) is 70:30. It is preferably ˜1: 99, more preferably 60:40 to 1:99.

  The content of the partial structure represented by the formula (VI) is 1 mol% with respect to the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII). Preferably, it is 70 mol% or less, and more preferably 60 mol% or less.

  The content of the partial structure represented by the formula (VII) with respect to the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII) is 30 mol%. Preferably, the amount is 40 mol% or more, more preferably 99 mol% or less.

  By setting the partial structure content ratio represented by the formula (VII) to be equal to or higher than the lower limit value, there is a tendency that a decrease in film properties of the obtained coating film can be suppressed, and the formula (VI) is used. By making the content rate of a partial structure more than the said lower limit, there exists a tendency for the increase in the viscosity of the resin solution obtained to be suppressed and for handleability to become favorable.

  In the case where both the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII) and the partial structure represented by the formula (VI ′) are contained, the formula (VI ′ The content of the partial structure represented by) is not particularly limited, but from the viewpoint of curing properties such as substrate adhesion and chemical resistance, the bond of the partial structure represented by the formula (VI ′) and the formula ( The ratio of bonds to the bonds of the partial structure represented by IV) is usually 5 to 70%, preferably 10 to 40%, where the total number of bonds * in the formula (IV) is 100%. is there.

  When the partial structure represented by the formula (VII) and the partial structure represented by the formula (VI) are contained, or the partial structure represented by the formula (VI) and the formula (VII) And a partial structure represented by the formula (VI ′), the total number of bonds * in the formula (IV) is defined as 100%, of which the formula (VI), (VI ′) And the ratio which has couple | bonded with the bond of (VII) is 10 to 90% normally, Preferably it is 20 to 85%, More preferably, it is 30 to 80%.

  Of the bond * in the formula (IV), the bond * not bonded to the bond * in the formulas (VI), (VI ′) and (VII) is, for example, bonded to a hydrogen atom. can do. By setting it within the above range, curing characteristics such as substrate adhesion and chemical resistance tend to be good.

  * Which is a bond in the formula (VI) and the formula (VII) can be independently bonded to * which is a bond in the formula (IV) or (V). Moreover, * which is a bond in the formula (IV) or (V) is independently a hydrogen atom, a bond * in the formula (VI), or a bond in the formula (VII). Can be combined with *. As described above, the resin of the present invention includes various embodiments.

  A portion when a bond * in the formula (V) is bonded to a hydrogen atom, a bond * in the formula (VI), or a bond * in the formula (VII) The main specific examples of the structure are given below. Similar examples can be given when the formula (IV) is used instead of the formula (V).

  In the above (A-2-6), the bond * may be further bonded to the bond * in the formula (V). That is, a plurality of partial structures represented by the formula (V) may be linked using the partial structure represented by the formula (VII) as a linking group.

  As described above, the resin (a-1) may contain a partial structure represented by the formula (VI ′) in addition to the partial structure represented by the formula (VI) and / or the formula (VII). preferable. * Which is a bond in the formula (VI ′) can also be bonded to * which is a bond in the formula (IV) and / or the formula (V).

  Principal specific examples of the partial structure in the case where the bond * in the formula (V) and the bond * in the formula (VI ′) are bonded are given below. Similar examples can be given when the formula (IV) is used instead of the formula (V).

  Among these specific examples, the (A-2-3), (A-2-5), (A-2-6), or (A-2) having the partial structure represented by the formula (VII). The structure containing the partial structure of -9) is preferable. In particular, the partial structure of (A-2-6) having two partial structures represented by the formula (VII), or the partial structure represented by the formula (VII) and the part represented by the formula (VI) The partial structure (A-2-5) having a structure is preferable.

  The reason for this is that by containing the partial structure represented by the formula (VII), the bond * in the formula (VII) is further replaced by the partial structure represented by the formula (IV) or ( V) increases the molecular weight by combining with the partial structure represented by V), increases the content of the ethylenically unsaturated group structure, and further increases the content of the carboxyl group. It can be mentioned that there is a tendency to improve the curing properties such as chemical resistance.

  In addition, * which is a bond in the formula (IV) or (V) is independently a hydrogen atom, a bond in the formula (VI) *, or a bond in the formula (VI ′). *, Or a bond in a partial structure derived from other polybasic acid anhydrides, in addition to * or a bond in the formula (VII), as long as the effect of the present invention is not adversely affected. May be combined.

[Partial structure represented by formula (VIII)]
The resin (a-1) preferably has a partial structure represented by the following formula (VIII) in addition to the partial structures of the above formulas (I) to (VII).

  In the above formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2-8. * Represents a bond.

  When the resin (a-1) contains the partial structure represented by the formula (VIII), the molecular weight of the resin (a-1) can be increased, and the carboxyl group and the ethylenically unsaturated group can be increased. There is a tendency that the amount of introduction can be increased, and curing characteristics such as substrate adhesion or chemical resistance can be further improved.

  In the formula (VIII), n is an integer of 2 to 8, and is preferably an integer of 4 or less. When n is within the above range, curing characteristics such as substrate adhesion or chemical resistance tend to be further improved.

  Z in the formula (VIII) is a polyhydric alcohol residue. Specifically, an alcohol residue such as 1,2,3-propanetriol or a polyhydric alcohol residue such as a sugar alcohol described later can be used. Any compound can be used as long as it satisfies the above formula (VIII).

  Examples of the polyhydric alcohol residue include an n-valent hydrocarbon group which may have a substituent. The hydrocarbon group may have a hetero atom such as an oxygen atom or a sulfur atom.

  Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. What connected the aliphatic hydrocarbon and the aromatic hydrocarbon may be used. Further, it may be a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 20 from the viewpoint of improving substrate adhesion and chemical resistance. Or less, preferably 15 or less, and more preferably 10 or less. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, a carbonyl group, and the like, but unsubstituted is preferable.

  Specific examples of the partial structure represented by the formula (VIII) include partial structures of the following formulas (A-3-1) to (A-3-4) or a formula (IX) described later. Among these, the case of having a partial structure represented by the following formula (A-3-1) or formula (IX) described below is more preferable from the viewpoint of curing characteristics such as substrate adhesion or chemical resistance.

[Partial structure represented by formula (IX)]
The resin of the present invention may contain a partial structure represented by the following formula (IX) as the partial structure represented by the formula (VIII).

  In the above formula (IX), Z 'is a polyvalent methylol residue. n 'is an integer of 2-6. * Represents a bond.

  In the formula (IX), n ′ is an integer of 2 to 6, and is preferably an integer of 2 to 4 from the viewpoint of curing characteristics such as substrate adhesion or chemical resistance.

  Z ′ in the formula (IX) is a multivalent methylol residue, preferably trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, or trimethylolethane multivalent methylol residue, Others may be used as long as the formula (IX) is satisfied. Specific examples of the partial structure represented by the formula (IX) are given below.

  Among the partial structure represented by the formula (VIII) and / or the partial structure represented by the formula (IX), from the viewpoint of curing characteristics such as substrate adhesion or chemical resistance, (A-3-1) And at least one selected from (A-3-5) to (A-3-8).

  In addition, examples of the polymethylol residue include an n′-valent hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. What connected the aliphatic hydrocarbon and the aromatic hydrocarbon may be used. Further, it may be a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of improving substrate adhesion and chemical resistance. More preferably, it is 10 or less, and particularly preferably 5 or less. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, a carbonyl group, and the like, but unsubstituted is preferable.

  As the partial structure represented by the formula (VIII) and / or the partial structure represented by the formula (IX), one type may be used alone, or two or more types may be used in combination.

  * Which is a bond in the formula (VIII) and the formula (IX) is independently a hydrogen atom, a bond in the formula (VI) *, or a bond in the formula (VII). It can be combined with a certain * or * which is a bond in the formula (VI ′). Various embodiments may be mentioned depending on the combination of bonds.

  When * which is a bond in the formula (VIII) and the formula (IX) is bonded to * which is a bond in the formula (VI), the resin (a-1) of the present invention is a carboxyl group. It can have at least one group.

  Moreover, when * which is a bond in the formula (VIII) and the formula (IX) is bonded to * which is a bond in the formula (VI ′), the resin (a-1) of the present invention. May have at least two carboxyl groups.

  As an embodiment in which * which is a bond in the formulas (VIII) and (IX) is combined with * which is a bond in the formula (VII), there are two bonds in the formula (VII). A mode in which both are bonded together and a mode in which only one bond is bonded are exemplified.

  In the case of binding to two bonds in the formula (VII), the resin (a-1) of the present invention can have at least two carboxyl groups and further increase the branched structure. Can be used.

  Further, when binding to only one bond in the formula (VII), for example, the formulas (A-2-3) and (A-2) having a partial structure represented by the formula (VII). -5), (A-2-6), and (A-2-9). Thereby, while increasing the molecular weight of resin (a-1) of this invention, many carboxyl groups or ethylenically unsaturated groups can be contained.

  Moreover, * which is a bond in the formulas (VIII) and (IX) may be bonded to a hydrogen atom. As will be described later, the partial structures represented by the formulas (VIII) and (IX) can be introduced from a polyhydric alcohol, and when the hydroxyl group of the polyhydric alcohol is unreacted during the synthesis process, It is because it may become a combined structure.

  Among these, from the viewpoint of curing properties such as substrate adhesion or chemical resistance, * which is a bond in the formulas (VIII) and (IX) is the formula (A-2-3), (A -2-5), (A-2-6), or (A-2-9) is preferably bonded to * which is a bond.

  In the resin (a-1), the content ratio of the partial structure represented by the formula (VIII) or the partial structure represented by the formula (IX) is not particularly limited, but in the formula (IV) or (V) When the content ratio of the represented partial structure is 100 parts by mass, it is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 6 parts by mass or less. The amount is more preferably 5 parts by mass or less, and further preferably 4 parts by mass or less. When it is within the above range, curing characteristics such as substrate adhesion or chemical resistance tend to be good.

[Physical properties of resin (a-1)]
The acid value of the resin (a-1) is usually 10 mg-KOH / g or more, preferably 50 mg-KOH / g or more, and the acid value is preferably 200 mg-KOH / g or less, 150 mg-KOH / g. The following is more preferable. When it is within the above range, curing characteristics such as substrate adhesion or chemical resistance tend to be well expressed.

  The weight average molecular weight of the resin (a-1) is preferably 1,500 or more, more preferably 2,000 or more, further preferably 3,000 or more, and 4,000 or more. More preferably, it is more preferably 5,000 or more. Moreover, it is preferable that it is 40,000 or less, and it is more preferable that it is 30,000 or less. When it is within the above range, curing characteristics such as substrate adhesion or chemical resistance tend to be well expressed.

[Synthesis of Resin (a-1)]
The resin (a-1) is obtained by reacting at least (A-1) an epoxy group-containing compound represented by the following formula (X) with (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. A resin is preferred.

  Further, from the viewpoint of adjusting the adhesion to the substrate or the solubility during alkali development, the resin obtained by the reaction of (A-1) and (A-2) is further converted into (A-3) a polybasic acid. A resin obtained by reacting with an anhydride is more preferable.

In the above formula (X), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. , R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is an alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5.

  To synthesize the resin (a-1), for example, first, (A-1) an epoxy group-containing compound represented by the formula (X) and (A-2) an unsaturated carboxylic acid or unsaturated carboxylic acid ester To obtain a reaction product (hereinafter referred to as “epoxy acrylate resin”).

  At this time, the partial structure represented by the formula (II) can be obtained from the epoxy group-containing compound represented by the formula (X) of (A-1), and the defect of (A-2) can be obtained. From the saturated carboxylic acid or unsaturated carboxylic acid ester, the partial structure represented by the formula (I) can be obtained. Moreover, as the epoxy acrylate resin, a resin containing a partial structure represented by the formula (IV) can be obtained.

  Next, the epoxy acrylate resin is reacted with (A-3) polybasic acid anhydride to obtain a resin. At this time, partial structures represented by the above formulas (VI), (VI ′), and (VII) can be obtained from the (A-3) polybasic acid anhydride.

[(A-1): Epoxy group-containing compound]
R ^{1 to} R ⁴ , R ⁵ , R ^11, and k, l, and m in the formula (X) have the same meanings as the formulas (I) to (IV), and the formulas (I) to (V) Those mentioned above are preferred.

  Specific examples of the epoxy group-containing compound represented by the formula (X) include (A-1-1) to (A-1-20) and (A-1-29) to (A-1-40). ), The following (A-1-1 ′) to (A-1-20 ′) and (A-1-29 ′) to (A-1-40 ′) are exemplified. However, any epoxy group-containing compound that satisfies the formula (X) can be applied to the present invention without being limited thereto. In addition, the numerical value described in the cycloalkylidene group in the following chemical formula indicates the carbon number of the cycloalkylidene group.

  Examples of the epoxy group-containing compound represented by the formula (X) include (A-1-9 ′) to (A-1-12 ′), (A-1-29 ′) to (A-1-40). ') Is preferable, any of (A-1-9') to (A-1-12 ') is more preferable, and (A-1-9') to (A-1- 11 ′) is more preferable, and (A-1-9 ′) is particularly preferable.

  When the epoxy group-containing compound is as described above, the resin (a-1) tends to have good curing characteristics such as chemical resistance, and the characteristics of the resin (a-1) tend to be exhibited most. .

  In the present invention, the epoxy-containing compound represented by the formula (X) may be used alone or in combination of two or more.

  The epoxy group-containing compound represented by the formula (X) is preferably an epoxy group-containing compound represented by the following formula (XI).

In said formula (XI), R < ¹ > -R < ⁴ >, R < ¹¹ > and m are respectively synonymous with said Formula (X) independently.

  The reason why the compound represented by the formula (XI) is preferable is that, as described above, curing properties such as chemical resistance tend to be good, and the effect of the resin (a-1) can be favorably expressed. In addition, the epoxy group-containing compound of the formula (XI) is easy to handle and tends to be produced.

  In addition, as a method for synthesizing the compounds of the formula (X) and the formula (XI), a known method can be used, for example, a method described in Japanese Patent Application Laid-Open No. 2013-253153 can be used. .

[(A-2): unsaturated carboxylic acid or unsaturated carboxylic acid ester]
As unsaturated carboxylic acid used for the synthetic reaction of resin (a-1) of this invention, unsaturated carboxylic acid which has an ethylenically unsaturated group is mentioned, for example. Specific examples include (meth) acrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, cinnamic acid, α-position is haloalkyl group, alkoxyl group, halogen atom, nitro group Or a monocarboxylic acid such as (meth) acrylic acid substituted with a cyano group; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyl Roxyethylphthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyl Loxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypro Ruphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalate Acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutylmaleic acid and other (meth) acryloyloxyalkyl esters of dibasic acids; (meth) acrylic acid with ε-caprolactone , Β-propiolactone, γ-butyrolactone, δ-valerolactone and other lactones added to the monomer; (meth) acrylic acid dimer and the like.

  Also, for example, hydroxyl-containing unsaturated compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, glycidyl methacrylate acrylic acid adduct, glycidyl methacrylate methacrylic acid adduct Also included are compounds obtained by adding acid anhydrides such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride.

  Particularly preferred is (meth) acrylic acid. These may be used alone or in combination of two or more.

  In the synthetic reaction of the resin (a-1), an unsaturated carboxylic acid ester can be used instead of the unsaturated carboxylic acid. For example, α, β-unsaturated monocarboxylic acid ester can be used. Specific examples thereof include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid. -2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthaloyloxyethyl, crotonic acid-2-succinoyloxyethyl, etc. Can be mentioned. Preferably, it is acrylate-2-malenoyloxyethyl acrylate or -2-phthaloyloxyethyl acrylate, and acrylate-2-malenoyloxyethyl acrylate is particularly preferable.

  As a method of reacting the epoxy group in the epoxy group-containing compound with the unsaturated carboxylic acid, a known method can be used. For example, the epoxy group-containing compound and an unsaturated carboxylic acid are converted into a tertiary amine such as triethylamine or benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, or benzyltriethylammonium chloride. Carboxylic acid can be added to the epoxy group-containing compound by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using pyridine, triphenylphosphine or the like as a catalyst.

  The amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.3 to 5% by mass, based on the reaction raw material mixture (total of epoxy group-containing compound and unsaturated carboxylic acid). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). The amount is preferably 0.01 to 10% by mass, particularly preferably 0.03 to 0.5% by mass, based on the reaction raw material mixture.

  The proportion of the unsaturated carboxylic acid added to the epoxy group of the epoxy group-containing compound is usually preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol% with respect to the epoxy group. preferable. Since the remaining epoxy group adversely affects the storage stability, the unsaturated carboxylic acid is usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1, with respect to 1 equivalent of the epoxy group of the epoxy group-containing compound. It is preferable to carry out the reaction at a ratio of 1 equivalent.

  As described above, by the addition reaction of the epoxy group-containing compound represented by the formula (X) of (A-1) and the unsaturated carboxylic acid or unsaturated carboxylic acid ester of (A-2), the formula (IV) An epoxy acrylate resin having the following partial structure (hereinafter sometimes referred to as “(A-5) epoxy acrylate resin”) is obtained.

  By an addition reaction between the epoxy group-containing compound and the unsaturated carboxylic acid, an ethylenically unsaturated group can be introduced into the epoxy group-containing compound, thereby imparting ultraviolet reactivity, that is, photocurability.

  Further, the hydroxyl group produced by the addition reaction between the epoxy group-containing compound and the unsaturated carboxylic acid is further subjected to an addition reaction with a polybasic acid anhydride (A-3) described later, whereby a carboxyl group is converted as described later. It can be introduced or increased in molecular weight.

[(A-3): Polybasic acid anhydride]
As the polybasic acid anhydride used for the synthesis reaction of the resin (a-1), dibasic acid anhydride, tribasic acid anhydride, tetrabasic acid anhydride and the like can be preferably used.

  A partial structure represented by the formula (VI) is obtained from the dibasic acid anhydride, and a partial structure represented by the formula (VI ′) is obtained from the tribasic acid anhydride. A partial structure represented by the formula (VII) is obtained from the acid anhydride.

  Known tetrabasic acid anhydrides (tetracarboxylic dianhydrides) can be used, such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and biphenyl ether tetracarboxylic acid. And tetracarboxylic dianhydrides such as dianhydrides. These may be used individually by 1 type and may be used in combination of 2 or more type.

  As the 4-basic acid anhydride, among the above exemplified compounds, biphenyltetracarboxylic dianhydride is particularly preferable. When 4-basic acid anhydride is used as the polybasic acid anhydride, when the resin of the present invention is used as the resin in the photosensitive resin composition, the molecular weight increases due to the crosslinking reaction, and the resulting adhesion to the substrate. There is a tendency that effects such as improvement in solubility, adjustment of solubility, improvement in sensitivity or alkali resistance are obtained.

  Examples of the dibasic acid anhydride (dicarboxylic acid anhydride) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Examples thereof include chlorendic anhydride and methyltetrahydrophthalic anhydride. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These dibasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

  When a dibasic acid anhydride is used as the polybasic acid anhydride, the solubility can be easily adjusted when the resin of the present invention is used as the resin in the photosensitive resin composition. There is a tendency for adhesion to improve.

  Examples of the tribasic acid anhydride (tricarboxylic acid anhydride) include trimellitic anhydride and hexahydrotrimellitic anhydride, and trimellitic anhydride is particularly preferable. These tribasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

  When a tribasic acid anhydride is used as the polybasic acid anhydride, the amount of acid groups introduced into the resin molecule can be increased. When used as a resin in a photosensitive resin composition, the sensitivity is increased. , There is a tendency to easily balance the adhesion and developability.

  Among the polybasic acid anhydrides, it is particularly preferable to use a 4-basic acid anhydride. When the 4-basic acid anhydride is used alone, the addition rate of the 4-basic acid anhydride to the hydroxyl group of the (A-5) epoxy acrylate resin is usually 10 to 90 mol%, preferably 20 to 85 mol%, more preferably. 30 to 80 mol%.

  (A-5) Of the hydroxyl groups of the epoxy acrylate resin, the portion where the 4-basic acid anhydride does not undergo addition reaction may remain as hydroxyl groups. By setting the addition rate of the 4-basic acid anhydride (d) within the above range, curing characteristics such as substrate adhesion and chemical resistance tend to be improved.

  In addition, when using it as resin in the photosensitive resin composition, it is preferable to use a dibasic acid anhydride together with the 4-basic acid anhydride mentioned above from the point of viscosity adjustment or solubility adjustment.

  When using together 4 basic acid anhydride and 2 basic acid anhydride, it is preferable that the molar ratio is 2 basic acid anhydride: 4 basic acid anhydride = 70: 30-1: 99, 60: 40- More preferably, it is 1:99. By setting the ratio of the 4-basic acid anhydride to be equal to or higher than the lower limit value, there is a tendency to suppress a decrease in film properties of the obtained coating film, and by setting the ratio of the 2-basic acid anhydride to be equal to or higher than the lower limit value, There exists a tendency which can suppress the handleability fall by the increase in the viscosity of the resin solution obtained.

  Moreover, when using together 4 base acid anhydride and 2 base acid anhydride, and 3 base acid anhydride, from the viewpoint of hardening characteristics, such as board | substrate adhesion and chemical resistance by use of 3 base acid anhydride, 3 bases The usage-amount of an acid anhydride is 5-70 mol% normally with respect to the hydroxyl group of (A-5) epoxy acrylate resin, Preferably it is 10-40 mol%.

  When two types of polybasic acid anhydrides are used, that is, four basic acid anhydrides and two basic acid anhydrides, or three types of four basic acid anhydrides, two basic acid anhydrides, and three basic acid anhydrides are used. In this case, the addition rate of all polybasic acid anhydrides is usually 10 to 90 mol%, preferably 20 to 85 mol%, more preferably 30 to 80 mol%, based on the hydroxyl group of (A-5) epoxy acrylate resin. It is. (A-5) Of the hydroxyl groups of the epoxy acrylate resin, the portion where the polybasic acid does not undergo addition reaction may remain as hydroxyl groups. By setting the addition rate of the polybasic acid anhydride to the lower limit value or more, curing characteristics such as substrate adhesion and chemical resistance tend to be improved.

[(A-4): Polyhydric alcohol]
(A-5) When adding a polybasic acid anhydride to an epoxy acrylate resin, it can be added to the polybasic acid anhydride together with the polybasic acid anhydride (A-4) a polyhydric alcohol and / or polyhydric acid. The reaction is preferably carried out using a valent methylol (hereinafter abbreviated as “polyhydric alcohol”). By reacting polyhydric alcohols together, there is a tendency that polyhydric alcohols can be added to polybasic acid anhydrides to increase the acid value or increase the molecular weight.

From the polyhydric alcohols used in the synthesis reaction of the resin (a-1), partial structures of the above formulas (VIII) and (IX) can be obtained.
The polyhydric alcohol used in the synthesis reaction of the resin (a-1) is not particularly limited as long as it is a compound having two or more hydroxyl groups. From the viewpoint of easiness, specifically, at least one kind selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably, it is a monohydric alcohol.

  By using a polyhydric alcohol, the molecular weight of the resin (a-1) can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced. In addition, the rate of introduction of acid groups into the molecule can be increased, and the substrate adhesion and chemical resistance curing characteristics tend to be good. The use amount of the polyhydric alcohol is usually about 0.5 to 6% by mass, preferably about 1 to 4% by mass with respect to the (A-5) epoxy acrylate resin, from the viewpoint of the effect by use and handling properties. is there.

[Reaction of epoxy acrylate resin with polybasic acid anhydride and polyhydric alcohol]
As described above, after obtaining the (A-5) epoxy acrylate resin, a method of adding a polybasic acid anhydride to the epoxy acrylate resin, or adding a polybasic acid anhydride and a polyhydric alcohol, A known method can be used.

  The reaction temperature is usually 80 to 130 ° C., preferably 80 to 110 ° C., and the reaction is continued for 4 to 15 hours until a predetermined acid value, molecular weight, viscosity and the like are reached. By setting it to the upper limit or less, there is a tendency that a sudden increase in molecular weight due to polymerization of unsaturated groups tends to be suppressed, and if it is too low, the reaction does not proceed smoothly and polybasic acid anhydride may remain. is there.

<Photosensitive resin composition>
The resin (a-1) is preferably used as a resin for a photosensitive resin composition for forming a color filter, a spacer, a coloring spacer, and a member for an image display device such as a liquid crystal display or an organic EL. In particular, it can be preferably used as a color filter resin.

  In addition to resin (a-1), it is preferable that a photosensitive resin composition contains a photoinitiator (b). Preferably, it further contains a photopolymerizable monomer (c), a colorant (d), and a dispersant (e), and if necessary, thiols, a dispersion aid (pigment derivative), an adhesion improver, and coating properties. It contains other compounding components such as an improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant and the like, and each compounding component is usually used in a state dissolved or dispersed in a solvent.

  The photosensitive resin composition of the present invention is characterized by containing a resin (a-1) as the resin (a). In particular, when the resin (a-1) has a partial structure represented by the above formulas (VI) to (VII), the cured film obtained by applying and drying the photosensitive resin composition is exposed after exposure. It can function as a so-called alkali-soluble resin in which the solubility changes during alkali development with respect to parts and non-exposed parts.

  By containing the resin (a-1), the photosensitive resin composition of the present invention tends to be excellent in sensitivity, development adhesion, development stability, substrate adhesion, and the like as described below. In addition, in the photosensitive resin composition of this invention, in addition to resin (a-1), other resin (a-2) may be included.

  The photosensitive resin composition of the present invention contains at least the aforementioned resin (a-1), and the resin contains at least a partial structure represented by the formula (I) and a partial structure represented by (II). To do.

  The photosensitive colored resin composition containing the resin (a-1) tends to be excellent in sensitivity, development adhesion, substrate adhesion and the like. The reason for this is that the resin (a-1) has a bulky cycloalkylidene group in the partial structure of the formula (II), so that the resistance to an alkali developer tends to increase, Because of the bisphenol structure in the partial structure of (II) and the ethylenically unsaturated group structure in the formula (I), the steric hindrance structure around the ethylenically unsaturated group is small and a crosslinking reaction tends to occur. it is conceivable that.

  Furthermore, it is considered that the overall bulkiness tends to be further increased by crosslinking by ultraviolet irradiation. As a result, the line width is increased, the resistance to an alkaline developer is increased, and the mechanical strength of the cured film tends to increase, and the sensitivity, development adhesion, substrate adhesion, etc. tend to improve. Conceivable.

[Other resins (a-2)]
Although it does not specifically limit as other resin (a-2) which can be used together with resin (a-1), after exposing the cured film obtained by apply | coating and drying the photosensitive resin composition, an exposure part and a non-exposure part It is preferably an alkali-soluble resin whose solubility in alkali development changes, more preferably an alkali-soluble resin having a carboxyl group, and still more preferably an alkali-soluble resin having an ethylenically unsaturated bond and a carboxyl group.

  Specific examples include epoxy (meth) acrylate resins having a carboxyl group and acrylic copolymer resins. More specifically, as described below, it is described as (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4) described later. These may be used, and these may be used alone or in combination of two or more. Among the above, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly preferable.

  When the color filter is prepared, a resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group is applied to dissolve the non-exposed portion in the alkali developer. Among these, a resin having a carboxyl group is preferable. When the resin has a carboxyl group, it tends to be more soluble in an alkali developer than a hydroxyl group.

  Moreover, although the phosphoric acid group or the sulfonic acid group has higher acidity than the carboxylic acid group, it reacts with a basic initiator, monomer or dispersant, or other additive in the photosensitive resin composition. It tends to be easy and storage stability is poor.

  As described above, as other resins, epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group and an ethylenically unsaturated group are particularly preferable. The reason for this is that (A1-1) and (A1-2) resins, like the resin (a-1), add a lot of unsaturated groups or carboxyl groups, contain a lot of aromatic ring structures, It can contain a bulky alicyclic structure, has good compatibility with the resin (a-1), and developability or pattern shape without reducing the effect of the resin (a-1). This is because it is considered that the characteristics such as can be improved.

  Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (A1-1) and / or epoxy (meth) acrylate resin (A1-2).

<Epoxy (meth) acrylate resin (A1-1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.

<Epoxy (meth) acrylate resin (A1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  As the epoxy (meth) acrylate resin (A1-1) and the epoxy (meth) acrylate resin (A1-2), an alkali-soluble resin (c1) and an alkali-soluble resin described in Japanese Patent Application Laid-Open No. 2013-195681, respectively. (C2) can be used.

<Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)>
Examples of the acrylic copolymer resin include Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259987, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-14144, Japanese Patent Laid-Open No. 11 Various polymer compounds described in various publications such as JP-A-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and JP-A No. 2007-270147 can be used. . Preferably, the following resins (A2-1) to (A2-4) are exemplified, and among them, (A2-1) resin is particularly preferable.

  (A2-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. A resin obtained by addition or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction (hereinafter sometimes referred to as “(A2-1) resin”).

  (A2-2): Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as “(A2-2) resin”)

  (A2-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the (A2-2) resin (hereinafter may be referred to as “(A2-3) resin”).

  (A2-4): (Meth) acrylic resin (hereinafter sometimes referred to as “(A2-4) resin”)

  The resin (A2-1) is also included in the concept of epoxy (meth) acrylate resin.

  Among these, as the (A2-1) resin, [2-1-1] resin described in JP-A-2009-052010 can be used. Similarly, as the (A2-2) resin to (A2-4) resin, [2-1-2] resin to [2-1-4] resin described in Japanese Unexamined Patent Publication No. 2009-052010 is used. be able to.

  Among these, the photosensitive resin composition of the present invention includes (A1-1), (A1-2), (A2-1), and (A2-2) as other resins used in combination with the resin (a-1). , (A2-3), and (A2-4) preferably include at least one of them.

  In particular, the other resin is at least one of (A1-1), (A1-2), (A2-1), and (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group. More preferably it includes a seed.

  Moreover, it is especially preferable that other resin contains at least any 1 type among (A1-1) and (A1-2) which is an epoxy acrylate resin as alkali-soluble resin containing an ethylenically unsaturated group. .

  As other resins of the present invention, alkali-soluble resins other than those described above may be used. Although there is no restriction | limiting in particular, What is necessary is just to select from resin normally used for the photosensitive resin composition for color filters. Examples thereof include alkali-soluble resins described in JP-A No. 2007-271727, JP-A No. 2007-316620, JP-A No. 2007-334290, and the like.

<Photopolymerization initiator (b)>
The photosensitive resin composition of this invention contains a photoinitiator (b) with resin (a). The photopolymerization initiator is a component having a function of directly absorbing light and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

  By containing the photopolymerization initiator (b), the photosensitive resin composition of the present invention has good crosslinkability due to ultraviolet irradiation or the like, and the effect of the resin (a-1) is further improved. In particular, when an oxime ester compound is contained as the photopolymerization initiator (b), the effect tends to be further improved.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A No. 2000-56118. N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in JP-A-10-39503 , N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters and α-aminoalkylphenone derivatives; Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 2006-36750 The oxime ester derivative etc. which are described in the gazette etc. are mentioned.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyl titanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.

  Examples of the biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl). ) Imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer and (4′- And methoxyphenyl) -4,5-diphenylimidazole dimer.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 '-Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole And 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Methyl) -s-triazine and the like.

  Examples of the α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylamino Isoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3 -(4-Diethylaminobenzoyl) coumarin and 4- (diethylamino) Rukon, and the like.

  As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity, and are disadvantageous in terms of sensitivity when using an alkali-soluble resin containing a phenolic hydroxyl group. In some cases, oxime derivatives (oxime-based and ketoxime-based compounds) excellent in such sensitivity are particularly useful. Among oxime derivatives, oxime esters are preferred from the viewpoint of increasing sensitivity under high pigment concentrations.

  The photopolymerization initiator of oxime ester has both a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals. Therefore, it is possible to design a photosensitive resin composition that is stable and sensitive in a small amount.

  In particular, in the case of an oxime ester compound having a carbazole ring, this structural property is well expressed and is more preferable. Currently, the market demands a high degree of shading, a thin BM (black matrix), and the pigment concentration is also increasing. In such a situation, it is particularly effective.

  The resin (a-1) contained in the photosensitive resin composition of the present invention has a structure in which a biphenyl structure and a greatly expanded alicyclic structure having 10 or more carbon atoms are largely twisted at the joint. In addition, since it has a structure having an ethylenically unsaturated group via a biphenyl structure, a cross-linked structure that is twisted and spreads three-dimensionally by ultraviolet irradiation is formed. For this reason, it is considered that the sensitivity is increased, the line width is increased, the resistance to alkali developer is increased, and the stability to the alkali developer tends to be increased. In particular, it is considered that these effects are further improved when combined with a photopolymerization initiator of an oxime ester that exhibits high sensitivity even in a small amount.

  Examples of the oxime compound include a compound including a structural moiety represented by the following general formula (22), and preferably include an oxime ester compound represented by the following general formula (23).

In said formula (22), R < ²² > may be respectively substituted C2-C12 alkanoyl group, C1-C20 heteroaryl alkanoyl group, C3-C25 alkenoyl group, Carbon number 3 to 8 cycloalkanoyl group, 3 to 20 alkoxycarbonylalkanoyl group, 8 to 20 phenoxycarbonylalkanoyl group, 3 to 20 heteroaryloxycarbonylalkanoyl group, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms;

In the above formula (23), R ^21a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon A heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or a heteroarylthioalkyl group An aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, and a carbon number 1-20 heteroarylloyl group, C2-C10 alkoxycarbonyl group, C7-20 aryloxy group A rubonyl group or a cycloalkylalkyl group having 1 to 10 carbon atoms; R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

R ^21a may form a ring together with R ^21b , and the linking group thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3). R ^22a represents the same group as R ²² in the above formula (22).

Among these, from the viewpoint of sensitivity, R ²² in the general formula (22) and R ^22a in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms and a heteroaryl having 1 to 20 carbon atoms. An alkanoyl group and a C3-C8 cycloalkanoyl group are mentioned, More preferably, a C2-C10 alkanoyl group is mentioned, More preferably, a C2-C5 alkanoyl group is mentioned.

Moreover, as R ^<21a> in the said General formula (23), from the viewpoint of the solubility to a solvent and a sensitivity, Preferably, it is the C1-C20 alkyl group which may be substituted, The carbon number which may be substituted Examples thereof include 1 to 10 cycloalkylalkyl groups and optionally substituted aryl groups having 6 to 20 carbon atoms. More preferably, propyl substituted with a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group or an N-acetyl-N-acetoxyamino group Groups.

In addition, R ^21b in the general formula (23) is preferably an optionally substituted carbazole group, an optionally substituted thioxanthonyl group, or an optionally substituted phenyl sulfide group. The case where a carbazole group is contained as R ^21b is more preferable for the reason described above. An oxime ester initiator having a carbazole group having a nitro group is also effective.

As the oxime ester initiator, those containing a carbazole group as R ^21b are preferred for the reasons described above. Furthermore, an aryl group having 6 to 25 carbon atoms which may be substituted, an arylcarbonyl group having 7 to 25 carbon atoms which may be substituted, a heteroaryl group having 5 to 25 carbon atoms which may be substituted, and substitution A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group which may be used is preferable. In particular, from the viewpoint of sensitivity, a carbazole group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. These groups are preferably bonded to the 3-position of the carbazole group. Similarly, the C atom in the formula (23) is preferably bonded to the 6-position of the carbazole group.

  In addition, the H atom bonded to the N atom of the carbazole group may be substituted with any substituent, and the optional substituent is an alkyl having 1 to 20 carbon atoms from the viewpoint of solubility in a solvent. Group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.

An oxime ester is useful as the initiator used in the present invention. Oxime ester initiators having a carbazole group are preferred. The oxime ester initiator in which R ^{21a of} the general formula (23) has a linear alkyl part and a cycloalkyl part or an oxime ester initiator having a carbazole group having a nitro group is more preferably used. Examples of such commercially available initiators include OXE-02 manufactured by BASF, TR-PBG-304, and TR-PBG-314 manufactured by Changzhou Power Electronics.

  Specific examples of preferred oxime ester compounds in the present invention include the compounds exemplified below, but the oxime ester compounds are not limited to these compounds.

  Examples of the ketoxime compound include a compound containing a structural moiety represented by the following general formula (24), and preferably an oxime ester compound represented by the following general formula (25).

In the general formula ^{(24), R 24} has the same meaning as ^{R 22} in the general formula (22).

In the general formula (25), each R ^23a may be a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl having 1 to 20 carbon atoms. Group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or a heteroarylthio group An alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, C1-C20 heteroarylloyl group, C2-C10 alkoxycarbonyl group, C7-C7 20 aryloxycarbonyl group or a C1-C10 cycloalkylalkyl group is shown.

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring. Note that R ^23a may form a ring together with R ^23b , and the linking group thereof may have a substituent, an alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) _r. -), A polyethynylene group (-(C≡C) _r- ) or a group formed by a combination thereof (where r is an integer of 0 to 3).

R ^24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group.

R ²⁴ in the general formula (24) and R ^24a in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.

R ^23a in the general formula (25) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.

Moreover, as R ^<23b> in the said General formula (25), Preferably the carbazoyl group which may be substituted and the phenyl sulfide group which may be substituted are mentioned. The case where a carbazole group is contained as R ^23b is more preferable for the above reason.

  Specific examples of preferred ketoxime ester compounds in the present invention include compounds exemplified below, but the compounds are not limited to these compounds.

  These oxime and ketoxime ester compounds are known compounds per se, for example, a kind of a series of compounds described in Japanese Unexamined Patent Publication No. 2000-80068 or Japanese Unexamined Patent Publication No. 2006-36750. It is. The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  In addition, for example, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydride Xyl-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) ) -2-morpholino-1-propanone and acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2 Thioxanthone derivatives such as 1,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenyl Examples also include acridine derivatives such as acridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone. Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the reasons described above.

  The photosensitive resin composition of the present invention can be used in combination with a photopolymerization initiator and an additive such as the following accelerator and sensitizing dye as required.

<Accelerator>
As the accelerator, for example, a mercapto compound having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used. Accelerators may be used alone or in combination of two or more.

<Sensitizing dye>
If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and heterocyclic rings described in JP-A-3-239703 and JP-A-5-289335. , A 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, a pyromethene dye described in JP-A-6-19240, and other JP JP 47-2528, JP 54-155292, JP 45-37377, JP-A 48-84183, JP 52-112681, 58-15503, JP 60-88005, 59-56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Home Hei 5-107761 and JP Japanese Hei 5-210240 discloses, can be mentioned dyes having a dialkyl aminobenzene skeleton described in JP Japanese Patent Laid-Open No. 4-288818.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

<Photopolymerizable monomer (c)>
It is preferable that the photosensitive resin composition of this invention contains a photopolymerizable monomer (c) from points, such as a sensitivity. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. It is done.

  In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylate esters of aliphatic polyhydroxy compounds such as acrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Acid esters, as well as itaconates instead of itaconates, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to Roneto the like.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Acid ester etc. are mentioned.

  The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and ethylene. Examples include a condensate of glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol, and glycerin.

  In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate And vinyl group-containing compounds such as divinyl phthalate. These may be used alone or in combination of two or more.

<Coloring material (d)>
The photosensitive resin composition of the present invention preferably contains a coloring material (d) when used for forming a pixel of a color filter or a black matrix. By containing the color material (d), the light shielding property or color characteristic of the color filter can be imparted. A coloring material means what colors the photosensitive resin composition of this invention. As the coloring material, dyes and pigments can be used. From the viewpoints of heat resistance, light resistance, etc., and from the viewpoint of light shielding properties or color characteristics, pigments are preferable. It is preferable to contain.

  Examples of the pigment include pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment. The structure includes, for example, various inorganic pigments in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Is also available.

  Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275 and 276.

  Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. And CI Pigment Red 177, 209, 224 and 254.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 and 79.

  Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 and 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Of these, C.I. I. CI pigment green 7, 36 and 58.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207 and 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185, more preferably C.I. I. And CI pigment yellow 83, 138, 139, 150 and 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. Of these, C.I. I. Pigment violet 19 and 23, more preferably C.I. I. And CI Pigment Violet 23.

  Moreover, when the photosensitive resin composition of this invention is the photosensitive resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material (d). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.

  Examples of color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B ( 45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. [The numbers in parentheses above indicate color indexes (CI)].

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154 and 166, C.I. I. Orange pigments 36, 43, 51, 55, 59 and 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228 and 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60 and 64, C.I. I. Green pigment 7 and C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Further, as a black color material that can be used alone, a black pigment is preferable in order to obtain a high light-shielding property. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these color materials (d), when a black color material is used as the photosensitive resin composition, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of the carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B

  Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Wol, Black Bol, Col Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 manufactured by Cabot Inc .: 80, Mon (registered trademark). , Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark; the same shall apply hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, RE AL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark. Hereinafter the same.) XC72R and ELFTEX (registered trademark) -8 Koronbiyan

  Made by Colombian Carbon: RAVEN (registered trademark; the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RA101000RA, VENT20H , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750 and RAVEN7000

  As other black pigments, for example, titanium black, aniline black and iron oxide black pigments, and organic pigments of three colors of red, green and blue can be mixed and used as black pigments.

  Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As the carbon black coated with resin, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 is preferable.

  As carbon black to be coated, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is composed of raw material oil or combustion oil (or gas) at the time of normal production, reaction stop water or granulated water, or Na, Ca, K, Mg, Al or Fe mixed from the furnace material of the reaction furnace. Ashes are contained in the order of percent. Of these, Na or Ca is generally contained in several hundred ppm or more, but if they are present in large quantities, they penetrate into the transparent electrode (ITO) or other electrodes, causing electrical shorts. This is because there is a case.

  As a method for reducing the content of ash containing Na or Ca, carefully select those with as little content as possible as raw oil or fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from a furnace is washed with water or hydrochloric acid to dissolve and remove Na or Ca.

  The surface of these black pigments is often acidic. Therefore, in order to disperse the black pigment satisfactorily, the dispersant to be combined is preferably a polymer compound having a basic functional group.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can be used as the pigment. These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

<Particle particle size>
In the photosensitive resin composition of the present invention, the average primary particle size of the pigment that can be used as the colorant (d) is any pigment that can produce a desired color when used as a colored layer of a color filter. It is not particularly limited, and it varies depending on the type of pigment used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 10 to 70 nm.

  When the average primary particle size of the pigment is within the above range, the color characteristics of the image display device manufactured using the negative resist composition for color filter of the present invention tend to be of high quality. There is.

  Further, when the pigment is carbon black, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 60 nm or less, and further preferably 50 nm or less. Further, when the pigment is carbon black, the average primary particle diameter of the pigment is preferably 20 nm or more. When the pigment becomes too large, scattering increases and color characteristics such as light shielding properties or contrast deteriorate. On the other hand, if the pigment particle size is too small, a large amount of dispersant is required, and the dispersibility is lowered.

  The average primary particle size of the pigment can be determined by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle is obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size is obtained and used as the average primary particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

  Moreover, although it is preferable that the photosensitive resin composition of this invention contains a pigment at least, you may use together a dye in the range which does not affect the effect of this invention besides. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5 and C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56 and C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic blue 9 etc. are mentioned.

  Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<Dispersant (e)>
In the photosensitive resin composition of the present invention, when the color material (d) is used, it is important to ensure the quality stability that the color material is finely dispersed and the dispersion state is stabilized. Therefore, it is preferable to include a dispersant.

  As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine, is preferable.

  Among these, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is particularly preferable. Dispersibility can be improved by using a polymer dispersant having these basic functional groups, and particularly when a black pigment is used as a coloring material, there is a tendency that high light shielding properties can be achieved.

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

  Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (registered trademark, manufactured by BYK Chemie), and Disparon (registered trademark, Enomoto Kasei). ), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow, Florene (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Finetech Co., Ltd.) Can be mentioned. These polymer dispersants may be used alone or in combination of two or more.

  Among these, it is particularly preferable that the dispersant (e) contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a basic functional group in terms of adhesion and linearity. In particular, a urethane-based polymer dispersant is preferable in terms of adhesion. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or polyether bond is preferred.

  The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and particularly preferably 30,000 or less. When the weight average molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is high.

  Examples of the urethane-based and acrylic-based polymer dispersants include Disperbyk 160 to 167 and 182 series (both are urethane-based), Disperbyk 2000 and 2001 (all are acrylic-based) (all manufactured by Big Chemie). Disperbyk 167, 182 and the like are particularly preferred urethane polymer dispersants having a basic functional group and having a polyester and / or polyether bond and having a weight average molecular weight of 30,000 or less.

(Urethane polymer dispersant)
If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanates, hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates and dimer acid diisocyanates and other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate) and ω, ω Alicyclic diisocyanates such as' -diisocyanate dimethylcyclohexane, xylylene diisocyanate and α, α aliphatic diisocyanates having an aromatic ring such as α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1, Triisocyanates such as 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof Is mentioned.

  Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include, for example, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc. Examples thereof include those alkoxylated with an alkyl group of 1 to 25 and a mixture of two or more of these.

  Examples of polyether glycols include polyether diols and polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homo- or copolymerization of alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and The mixture of 2 or more types of those is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.

  Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Examples of the polyester glycol include dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and phthalic acid) or anhydrides thereof and glycols (for example, ethylene glycol, diethylene glycol, triglyceride). Ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5- Pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 5-pentanediol, 1,6-hexanedi 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5- Hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, and the like And an aromatic glycol such as bishydroxyethoxybenzene and an N-alkyl dialkanolamine such as N-methyldiethanolamine). Specific examples include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate.

  Moreover, for example, polylactone diol or polylactone monool obtained by using the diol or the monohydric alcohol having 1 to 25 carbon atoms as an initiator may be mentioned. Specific examples include polycaprolactone glycol and polymethylvalerolactone, and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

  Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of a primary amino group is preferred.

  The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of the compound having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N- Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1, 4-butanediamine and the like can be mentioned.

  In addition, when the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and a benzimidazole ring. N-containing hetero 5-membered rings such as benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring A 6-membered ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

  Examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole and 1- (2-aminoethyl) imidazole.

  Examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1,2,4. -Triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl -1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable. These may be used alone or in combination of two or more.

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3. -24 parts by mass.

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a class amine system, are mentioned.

<Method of measuring amine value>
The tertiary amine value of a dispersant such as a block copolymer is represented by the amount of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and can be measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO ₄ (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.

  The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. In particular, 30,000 or less is preferable. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility tends to be low and the dispersibility is poor, and at the same time, the reaction tends to be difficult to control. When the molecular weight is 30,000 or less, alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferred commercially available urethane dispersant include Disperbyk 167 and 182 (Bic Chemie).

(Acrylic polymer dispersant)
As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random polymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) ) Tertiary amino such as unsaturated monomers having a carboxyl group such as acryloyloxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof And unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N- N-substituted maleimides such as cyclohexyl maleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene Examples thereof include macromonomers such as glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used alone or in combination of two or more.

(Acrylic block copolymer)
In the photosensitive resin composition of the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant in order to improve the dispersibility of the colorant and improve the dispersion stability. The acrylic block copolymer containing such nitrogen atoms has a nitrogen atom contained therein having an affinity for the colorant surface, and a portion other than the nitrogen atom increases the affinity for the medium, It is estimated that it contributes to the improvement of dispersion stability. The performance of a dispersant is its adsorption behavior on the solid surface. The reason why the block copolymer is excellent in adsorption behavior is not clear in detail, but the following is presumed.

  That is, in the case of a normal random copolymer, it is highly likely that the monomer constituting the copolymer is stably arranged in the copolymer sterically and / or electrically during the copolymerization. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may be an obstacle when adsorbing to the colorant.

  On the other hand, in a resin whose molecular arrangement is controlled, such as a block copolymer, a portion that prevents adsorption of the dispersant can be disposed at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorbing portion between the colorant and the dispersing agent, and a portion suitable for it can be arranged in a portion requiring solvent affinity. In particular, the dispersion of a coloring material containing a colorant having a small crystallite size is presumed that this molecular arrangement affects the good dispersibility.

  An acrylic block copolymer containing a nitrogen atom is preferable in that the colorant used in the present invention can be dispersed very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed to the colorant.

  As an acrylic block copolymer, an AB block copolymer comprising an A block having a quaternary ammonium base and / or amino group in a side chain and a B block having no quaternary ammonium base and amino group. And / or B-A-B block copolymers are preferred.

When the A block has a quaternary ammonium base, the quaternary ammonium base is preferably —N ⁺ R ⁵¹ R ⁵² R ⁵³ · M ⁻ (where R ⁵¹ , R ⁵² and R ⁵³ are each independently hydrogen Represents an atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R ⁵¹ , R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure; M ⁻ represents a counter anion. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

As the cyclic structure formed by combining two or more of R ⁵¹ , R ^52, and R ⁵³ with each other in —N ⁺ R ⁵¹ R ⁵² R ⁵³ , for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle Or the condensed ring formed by condensing two of these is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

In the above formula, R represents any one of R ^{51 to} R ⁵³ . As ^R 51 ^{to R 53} in ^{-N + R 51 R 52 R 53} , more preferably it may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.

  As the A block having a quaternary ammonium base, those containing a partial structure represented by the following general formula (e1) are particularly preferable.

In the formula (e1), R ⁵¹ , R ⁵² , and R ⁵³ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R ⁵¹ , R ⁵² and R ⁵³ may be bonded to each other to form a cyclic structure. R ⁵⁴ represents a hydrogen atom or a methyl group. X represents a divalent linking group, and M ⁻ represents a counter anion.

In the general formula (e1), the hydrocarbon groups of R ⁵¹ , R ⁵² and R ⁵³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.

In the general formula (e1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁶ — (provided that R ⁵⁵ and R ⁵⁶ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R ⁵⁷ —O—R ⁵⁸ —: R ⁵⁷ and R ⁵⁸ are each independently an alkylene group). And the like, and preferably —COO—R ⁵⁶ —.

Examples of M ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ and PF ₆ ⁻ .

  Two or more kinds of partial structures containing the specific quaternary ammonium base as described above may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.

The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.
In addition, the A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that is not quaternized.

  When the A block has an amino group, the amino group may be any of primary to tertiary. The content ratio of the monomer having the primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol% or more in the monomer composition constituting the acrylic block copolymer. It is. This amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

The primary to tertiary amino group is preferably —NR ⁶¹ R ⁶² (wherein R ⁶¹ and R ⁴² each independently represents a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure including this (repeating unit), preferred examples include the following: A structure represented by the general formula can be given.

^{However, R 61} and ^{R 62} are synonymous with ^{R 61} and ^{R 62 above, R 63} is 1 or more alkylene groups having a carbon ^{number, R 64} represents a hydrogen atom or a methyl group. Among them, R ⁶¹ and R ⁶² are preferably methyl groups, R ⁶³ is preferably a methylene group and an ethylene group, and R ⁶⁴ is preferably a hydrogen atom or a methyl group.

  As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.

In the above general formula, R ⁶⁴ has the same meaning as described above.

  Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one A block. In that case, two or more types of amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.

  A partial structure not containing an amino group may be partially contained in the A block. Examples of such a partial structure include a partial structure derived from a (meth) acrylic acid ester monomer. The content in the A block of the partial structure not containing such an amino group is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, but such an amino group-free partial structure is present in the A block. Most preferably it is not included.

  The A block may have either one of a quaternary ammonium base or an amino group, or may have both.

  On the other hand, the B block constituting the acrylic block copolymer has no quaternary ammonium base and amino group as described above, and is composed of a monomer that can be copolymerized with the monomer constituting the A block as described above. There is no particular limitation. The B block is a solvophilic site that does not have a nitrogen atom-containing functional group serving as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .

  Examples of the B block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic. Acid butyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate and N, N-dimethylaminoethyl (Meth) acrylate monomers such as (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide and N, N-dimethylaminoethyl acrylamide (meth) acrylamide monomer; vinyl acetate; acrylonitrile; allyl glycidyl ether and crotonic acid glycidyl ether; N- methacryloyl polymer structure obtained by copolymerizing comonomers including morpholine.

  As the B block, one containing a partial structure derived from a (meth) acrylic acid ester monomer represented by the following formula (e2) is particularly preferable.

In the above formula ^{(e2), R 61} represents a hydrogen atom or a methyl group. ^R62 represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent.

  Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.

  When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 99 mass%, more preferably 0 to 85 mass%.

  The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by a living polymerization method.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. For example, the method described in Japanese Patent Application Laid-Open No. 2007-270147 can be mentioned.

  The amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the A block has a quaternary ammonium base and when it does not. It is different. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of acid necessary for neutralizing the amino group in 1 g of the copolymer.

  That is, in the AB block copolymer and the B-A-B block copolymer according to the present invention, when the A block has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is Usually, it is preferably 0.1 to 10 mmol, and outside this range, it may not be possible to combine good heat resistance and dispersibility.

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 80 mgKOH / g. . More preferably, it is 1-50 mgKOH / g.

  When the quaternary ammonium base is not included in the A block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH / g. Hereinafter, it is more preferably 90 to 150 mgKOH / g.

  The acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g. g or less, more preferably 40 mgKOH / g or less.

  The molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC. When the molecular weight of the acrylic block copolymer is too small, the dispersion stability decreases, and when it is too large, the developability and resolution tend to decrease.

  In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.

  In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by mass or more and 90% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably based on the pigment. It is 5 mass% or more and 40 mass% or less. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too much, the proportion of other components will decrease and the voltage holding ratio will decrease. On the other hand, the shape of the colored spacer and the formation of the step may not be possible.

  In the present invention, a dispersant other than an acrylic block copolymer containing a nitrogen atom may be used in combination. The dispersant used in combination is preferably a polymer dispersant, and is preferably a polymer having a completely different structure from the colorant.

  Examples of the dispersant used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene diester-based dispersant, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

(Graft copolymer containing nitrogen atoms)
As the graft copolymer containing a nitrogen atom, those having a repeating unit containing a nitrogen atom in the main chain are preferred. Especially, it is preferable to have a repeating unit represented by the following general formula (i) or / and a repeating unit represented by the following general formula (ii).

In formulas (i) and (ii), R ⁹¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably an alkylene group having 2 to 3 carbon atoms. And more preferably an ethylene group. A represents a hydrogen atom or any one of the following general formulas (iii) to (v), preferably the following general formula (iii).

  In general formula (iii), W1 represents a linear or branched alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is particularly preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In General Formula (iv), G ¹ represents a divalent linking group, and in particular, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy. preferable. W ² represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.

G ² represents a hydrogen atom or —CO—R ⁹² (R ⁹² represents an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, hexyl, etc., among which carbon number 2 such as ethyl, propyl, butyl, pentyl, etc. ~ 5 alkyl groups are preferred). q represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the general formula (v), W ³ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and among them, an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.

  The content of the repeating unit represented by the general formula (i) or (ii) in the graft copolymer containing a nitrogen atom is preferably higher, and is usually 50 mol% or more in total, preferably 70 mol%. That's it.

  The repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) may both be present, and the content ratio is not particularly limited, but is preferably the general formula ( It is preferable that the repeating unit i) is contained in a larger amount.

  The total number of repeating units represented by general formula (i) or general formula (ii) in the graft copolymer is 1 or more, preferably 10 or more, more preferably 20 or more, and usually 100 or less, preferably 70. Hereinafter, it is more preferably 50 or less.

Further, the graft copolymer may contain a repeating unit other than the general formula (i) and the general formula (ii), and examples of the other repeating unit include an alkylene group and an alkyleneoxy group. Graft copolymer in the present invention, the terminal -NH ₂ and ^-R 91 _-NH 2 ^{(R 91} has the general formula (i), definitive when synonymous to (ii)) is one of the preferred.

  In the case of the graft copolymer as described above, the main chain may be linear or branched.

  The weight average molecular weight of the graft copolymer measured by GPC is preferably 3,000 or more, particularly 5,000 or more, and preferably 100,000 or less, particularly 50,000 or less. If the mass average molecular weight is less than 3,000, the color material cannot be aggregated, and may increase in viscosity or gel. If it exceeds 100,000, the viscosity itself increases. This is not preferable because the solubility in an organic solvent is insufficient.

  As a method for synthesizing the dispersant, a known method can be employed, and for example, a method described in Japanese Patent Publication No. 63-30057 can be used.

<Thiols>
It is preferable to add thiols to the photosensitive resin composition of the present invention in order to increase sensitivity and improve adhesion to the substrate. Examples of the thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhiol. Glycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropioate Nate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (PGM for short) ), Butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane; [trade name; Karenz (registered trademark, the same applies hereinafter) MT BD1, manufactured by Showa Denko KK ], Butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, manufactured by Showa Denko KK), pentaerythritol tris (3-mercapto) Butyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate) Rate); (TPMB for short) Limethylolpropane tris (2-mercaptoisobutyrate); (TPMIB for short), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione (trade name; Karenz MT NR1, manufactured by Showa Denko KK). Various types of these can be used alone or in combination of two or more. Preferred are polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MT PE1 is preferable. Particularly preferred.

<Solvent>
The photosensitive resin composition of the present invention usually has a resin (a), a photopolymerization initiator (b), a photopolymerizable monomer (c), a colorant (d), a dispersant (e), and as necessary. Various materials used are used in a state of being dissolved or dispersed in an organic solvent.

  As an organic solvent, it is preferable to select an organic solvent having a boiling point (under a pressure of 101.25 [hPa], hereinafter the same for boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

  Examples of such organic solvents include the following. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

  Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

  Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, Ethers such as dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone , Methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone, etc. Ketones: monovalent or polyvalent such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic groups such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl Hydrocarbons;

  Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, Propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxy carboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid Emissions acids;

  Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; # 2, Apco # 18 Solvent, Apco Thinner, Soak Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve" is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).

  These organic solvents may be used alone or in combination of two or more.

  When forming a pixel or black matrix of a color filter by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

  Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance in coating properties, surface tension, and the like, and relatively high solubility of constituent components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.

  Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive resin composition obtained later increases. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent together, the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying.

  That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, further preferably 5% by mass to 30% by mass, and further 5% by mass to 10% by mass. % Is particularly preferred. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that it may cause problems such as a tact defect in the vacuum drying process or a pin mark of prebaking in the filter manufacturing process.

  The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.

  Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol among the various solvents described above. Examples include diacetate and triacetin.

<Other ingredients of the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition of the present invention includes an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, a surfactant, a pigment derivative, and the like. Can be appropriately blended.

(Adhesion improver)
In order to improve the adhesion to the substrate, an adhesion improver may be included in the photosensitive resin composition of the present invention. For example, a silane coupling agent, a phosphoric acid adhesion improver, other adhesion improvers, etc. Can be mentioned.

  As a kind of silane coupling agent, various types, such as an epoxy type, a (meth) acrylic type, and an amino type, can be used singly or in combination of two or more.

  Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy silanes such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane Isocyanate silanes such as 3-isocyanatopropyltriethoxysilane are preferable, and epoxy silane silane coupling agents are particularly preferable.

  As the phosphate-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2), and (g3) are particularly preferable.

In the general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.

Examples of other adhesion improvers include TEGO ^* Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds or other adhesives may be used alone or in combination of two or more.

(Surfactant)
The photosensitive resin composition of the present invention may contain a surfactant in order to improve applicability. As the surfactant, for example, anionic, cationic, nonionic and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.

  Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar) and FC4430 (Sumitomo 3M). In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(Other ingredients)
In addition to the above components, the photosensitive resin composition of the present invention further includes a polymerization accelerator, a photoacid generator, a crosslinking agent, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, and an organic carboxylic acid anhydride. Product, development improver, thermal polymerization inhibitor and the like.

(Pigment derivative)
The photosensitive coloring composition of the present invention may contain a pigment derivative for improving dispersibility and storage stability. Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole. And derivatives of dioxazine and the like. Of these, phthalocyanine and quinophthalone are preferable.

  Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group, an aryl group. Examples thereof include those bonded via a group and a heterocyclic group, and a sulfonic acid group is preferred. Further, a plurality of these substituents may be substituted on one pigment skeleton.

  Examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.

<Component blending ratio in photosensitive resin composition>
The content ratio of the resin (a) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 20% by mass or more, particularly preferably 25% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, Preferably it is 40 mass% or less, Most preferably, it is 30 mass% or less.

  When the content ratio of the resin (a) is remarkably small, the solubility of the unexposed portion in the developing solution tends to be lowered, and development failure tends to be induced. On the other hand, when the content ratio of the resin (a) is too large, the permeability of the developer into the exposed portion tends to be high, and the sharpness or adhesion of the pixel may be lowered.

  As described above, in the photosensitive resin composition of the present invention, the resin (a) can contain another resin (a-2) together with the resin (a-1). When it is necessary to particularly improve the performance such as sensitivity and adhesion, the content ratio of the resin (a-1) is preferably 10% by mass or more based on the total mass of the resin (a). More preferably, it is more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and more preferably 90% by mass or more. Most preferably, it is usually 100% by mass or less.

  The resin (a) may contain other resin (a-2) in addition to the resin (a-1). In this case, the mass ratio of the resin (a-1) and the other resin (a-2) is not particularly limited. However, the sensitivity, adhesion, and other resin characteristics of the resin (a-1) of the present invention are not limited. From the viewpoint of taking a balance, 1:99 to 99: 1 is preferable, 5:95 to 95: 5 is more preferable, and 10:90 to 90:10 is more preferable.

  Moreover, when it is mainly desired to obtain the performance of the other resin (a-2), the content ratio of the resin (a-1) to the resin (a) is preferably 1% by mass or more, and 90% by mass. % Or less, more preferably 50% by mass or less, and further preferably 60% by mass or less.

  The content rate of a photoinitiator (b) is 0.1 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 0.00. 7% or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass. Or less, more preferably 10% by mass or less. If the content of the photopolymerization initiator (b) is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure is likely to be induced.

  In particular, the proportion of the oxime ester compound in the photopolymerization initiator (b) is usually 10% by mass or more, preferably 50% by mass or more, more preferably 90% by mass or more, and usually 100% by mass or less. is there. By setting it to the lower limit value or more, there is a tendency that after ultraviolet irradiation, the development stability can be improved by increasing the line width by improving the sensitivity and by improving the resistance to alkali developer.

  When using an accelerator with a photoinitiator (b), the content rate of an accelerator is 0.01 mass% or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.02. It is 10% by mass or less, preferably 5% by mass or less.

  The accelerator is preferably used in a proportion of 0.1 to 50% by mass, particularly 0.1 to 10% by mass with respect to the photopolymerization initiator (b). By using the photopolymerization initiator (b) and the accelerator above the lower limit value, the sensitivity to exposure light tends to be sufficient, and by using the photopolymerization initiator below the upper limit value, the solubility of the unexposed part in the developer is good. Tend to be.

  Moreover, when using a sensitizing dye, the compounding ratio of the sensitizing dye in the photosensitive resin composition of this invention is 0-20 mass% normally in the total solid in the photosensitive resin composition, Preferably it is 0-0. It is 15 mass%, More preferably, it is 0-10 mass%.

  The content of the photopolymerizable monomer (c) is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30%, based on the total solid content of the photosensitive resin composition. It is 10% by mass or less, particularly preferably 10% by mass or less. When the content ratio of the photopolymerizable monomer is not more than the above upper limit, the penetrability of the developer into the exposed area becomes appropriate and a good image tends to be obtained.

  The minimum of the content rate of a photopolymerizable monomer (c) is 1 mass% or more normally, Preferably it is 5 mass% or more. By being more than the said minimum, it exists in the tendency for the photocuring by ultraviolet irradiation to improve, and for alkali developability to also become favorable.

  The content rate of a coloring material (d) can be normally selected in 1-70 mass% with respect to the total amount of solids in the photosensitive resin composition. In this range, 20 to 70% by mass is more preferable.

  The photosensitive resin composition of the present invention can be used for various applications as described above, but excellent image forming properties are particularly effective when used for forming a black matrix for a color filter. . When using it for forming a black matrix, use the black color material such as carbon black or titanium black described above as the color material (d), or mix several types of color materials other than black and adjust to black. That's fine. Among these, it is particularly preferable to use carbon black.

  The present invention is particularly effective in the region where the pigment concentration of the black pigment increases. Particularly in recent years, it is necessary to increase the black pigment concentration in order to increase the degree of light shielding. Thus, the content of the black pigment exhibiting a great effect is preferably 40% by mass or more, more preferably more than 40% by mass, further preferably 45% by mass or more, based on the total solid content of the photosensitive resin composition. Especially preferably, it is 50 mass% or more, and is 70 mass% or less normally.

  In the photosensitive resin composition, by setting the content of the black pigment within the above range, a photosensitive resin composition having high light shielding properties (optical density, OD value) can be obtained. Specifically, for example, by setting the content of the black pigment to 45% by mass or more, the optical density when the black matrix having a thickness of 1 μm is formed using the colored photosensitive resin composition of the present invention is 4. The value can be 0 or more.

  The optical density is more preferably 4.2 or more. In regions with high light shielding properties, ultraviolet rays are difficult to penetrate deeper, and crosslinking by photopolymerization is weak particularly in the area where the substrate and the fine wire are in close contact, but particularly when the photosensitive resin composition of the present invention is used, the pigment concentration When the value is large, the effect of the present invention can be confirmed well.

  When used for the purpose of forming a pixel of a color filter or the like, a pigment concentration of 40 to 65% by mass with respect to the total solid content is particularly effective. By setting the content of the color material to the lower limit value or more, the film thickness with respect to the color density does not become too large, and there is a tendency that adverse effects on gap control and the like during the liquid crystal cell formation can be prevented. Moreover, there exists a tendency for sufficient image formation property to be acquired by setting it as the said upper limit or less.

  In the photosensitive resin composition, when a color material is used, the amount of the resin (a) with respect to 100 parts by mass of the color material (d) is usually 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass. In addition, it is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less.

  By setting the content of the resin (a) with respect to the color material (d) to be equal to or higher than the lower limit value, the solubility of the unexposed portion in the developer tends to be sufficient, and it is desired to be equal to or lower than the upper limit value. It tends to be easy to obtain the pixel film thickness.

  When using a thiol compound, the content ratio of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0% with respect to the total solid content of the photosensitive resin composition of the present invention. 0.5 mass% or more, usually 10 mass% or less, preferably 5 mass% or less. There exists a tendency which can make sensitivity sufficient by making content of a thiol compound more than the said lower limit, and there exists a tendency for storage stability to become favorable by making it below the said upper limit.

  The content of the dispersant (e) is usually 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less, in the solid content of the photosensitive resin composition. 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more.

  The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less, with respect to 100 parts by mass of the coloring material (d). Preferably it is 80 mass parts or less, More preferably, it is 50 mass parts or less. By making the content of the dispersant more than the above lower limit value, there is a tendency that sufficient dispersibility tends to be obtained, and by making the content below the upper limit value, the ratio of other components is relatively sufficient. The color density, sensitivity, film formability, etc. tend to be good.

  In particular, it is preferable to use a polymer dispersant and a pigment derivative in combination as the dispersant. In this case, the blending ratio of the pigment derivative is usually 0 with respect to the total solid content of the photosensitive resin composition of the present invention. .1% by mass or more, preferably 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less.

  When using a surfactant, the content thereof is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass with respect to the total solid content in the photosensitive resin composition. Or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, more preferably It is 0.3 mass% or less.

  There is a tendency that the smoothness and uniformity of the coating film can be improved by setting the content of the surfactant to the lower limit value or more, and the smoothness of the coating film by setting the upper limit value or less, In addition to improving the uniformity, there is a tendency that deterioration of other characteristics can be suppressed.

  The photosensitive resin composition of the present invention has the solid content concentration of usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30 by using the organic solvent described above. The liquid is prepared so as to be not more than mass%, more preferably not more than 20 mass%.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.

  Usually, it is preferable to disperse the color material (d) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the color material (d) is finely divided by the dispersion treatment, the resist coating characteristics are improved. Further, when a black color material is used as the color material (d), it contributes to an improvement in light shielding ability.

  The dispersion treatment is usually preferably carried out in a system in which a coloring material (d), a dispersant (e), an organic solvent, and, if necessary, a part or all of the resin (a) are used together (hereinafter referred to as dispersion treatment). And the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”). In particular, it is preferable to use a polymer dispersant as the dispersant because thickening of the obtained ink and resist with time is suppressed (excellent dispersion stability).

  In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

  When the color material (d) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.

  The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss [JIS Z8741 (1997)] of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered with a filter or the like.

<Hardened product>
A cured product can be obtained by curing the photosensitive resin composition of the present invention. A cured product obtained by curing the photosensitive resin composition can be preferably used as a black matrix or a colored spacer.

<Black Matrix>
Next, the black matrix using the photosensitive resin composition of the present invention will be described in accordance with its production method.

(1) Support The support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

The support may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as a silane coupling agent or a urethane-based resin, if necessary, in order to improve surface properties such as adhesiveness.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix In order to form the black matrix of the present invention by the above-described photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied on a transparent substrate and dried, and then the sample is formed. A black mask is formed by placing a photomask on the substrate and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.

(3) Formation of black matrix (3-1) Application of photosensitive resin composition Application of the photosensitive resin composition for a black matrix onto a transparent substrate is, for example, a spinner method, a wire bar method, a flow coating method, It can be performed by a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible.

  The thickness of the coating is usually preferably in the range of 0.2 to 10 μm as the film thickness after drying, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm. is there.

(3-2) Drying of coating film The drying of the coating film after applying the photosensitive resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.

  The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the alkali-soluble resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive resin composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.

  The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a lamp light source such as a carbon arc and a fluorescent lamp, and an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The black matrix according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive resin composition with the above light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, and mono-di- or triethanolamine, mono-di- Or trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH) And organic alkaline compounds, such as choline. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.

  The black matrix formed as described above has a bottom width of usually 3 to 50 μm, preferably 4 to 30 μm, particularly 4 to 8 μm in the case of a high fine wire, and a height of usually 0.5 to 5 μm, preferably Is 1 to 4 μm.

Further, the low volume efficiency is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, and the relative dielectric constant is 6 or less, preferably 5 or less. Furthermore, the optical density (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.2 or more.

[Formation of other color filter pixels]
On a transparent substrate provided with a black matrix, a photosensitive colored resin composition containing a color material of one color of red, green, and blue is applied in the same process as the above (3-1) to (3-5), After drying, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and heat curing or photocuring as necessary through this photomask to form a colored layer. By performing this operation for the photosensitive colored resin compositions of three colors of red, green, and blue, pixels of the color filter can be formed. The order of these is not limited to the above.

[Coloring spacer]
The colored photosensitive composition of the present embodiment can be used as a resist for a colored spacer other than the black matrix. When the spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and the colored spacer is used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 describes that a spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.

(3-6) Formation of transparent electrode In this state, the color filter forms a transparent electrode such as ITO on the image and is used as a part of components such as a color display and a liquid crystal display device. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Image display device]
The image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display described later.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described black matrix of the present invention, and is not particularly limited in terms of formation order and formation position of color pixels and black matrix.

  A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is preferable.

  For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa.

  Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.

[Organic EL display]
The organic EL display of the present invention is produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is produced using the photosensitive colored resin composition of the present invention.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used.

  A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

  Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

<Preparation of carbon black dispersion ink>
A pigment, a dispersant, a dispersion aid, and a solvent were prepared with the following composition, and a carbon black dispersion ink was prepared by the following method.
First, the solid content and the solvent of the pigment, the dispersant, and the dispersion aid were prepared as follows.
・ Pigment:
R1060 (carbon black produced by Colombia); 100 parts by mass / dispersant:
BYK167 (basic urethane dispersant manufactured by Big Chemie); 20 parts by mass (in terms of solid content)
・ Dispersing aid (pigment derivative):
S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group); 2 parts by mass / solvent; propylene glycol methyl ether acetate: 226.6 parts by mass

The above was sufficiently stirred and mixed.
Next, the dispersion process was performed for 6 hours in the range of 25-45 degreeC with the paint shaker, and the dispersion liquid was obtained. As the beads, zirconia beads having a diameter of 0.5 mm were used, and 60 parts by mass of the dispersion and 180 parts by mass of the beads were added. After the dispersion was completed, the beads were separated by a filter to prepare a carbon black dispersion ink having a solid content of 35% by mass.

<Examples 1-4: Synthesis of alkali-soluble resins (1) to (4)>

  7.3 g of epoxy compound having the above chemical structure (epoxy equivalent 240), 2.2 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.007 g of p-methoxyphenol were thermometer and stirrer. The mixture was placed in a flask equipped with a condenser and allowed to react at 100 ° C. with stirring until the acid value was 5 mg-KOH / g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.

  The obtained epoxy acrylate solution, trimethylolpropane (TMP), biphenyltetracarboxylic dianhydride (BPDA), tetrahydrophthalic anhydride (THPA), and propylene glycol monomethyl ether acetate (PGMEA) are listed in Table 1 below. Prepare the amount, put them in a flask equipped with a thermometer, stirrer, and cooling tube, slowly raise the temperature to 105 ° C. while stirring, and react with the acid value and weight average molecular weight of Table 1 below, solid content of 40 mass % Alkali-soluble resins (1) to (4) were obtained. Moreover, the content rate of the partial structure contained in alkali-soluble resin (1)-(4) is shown in Table 2.

<Comparative Example 1: Synthesis of alkali-soluble resin (5)>

  50 g of an epoxy compound having the above chemical structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were added to a thermometer, a stirrer, and a cooling tube. Was stirred and stirred at 90 ° C. until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

  25 parts by mass of the above epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 4.0 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.

  When the resin solution becomes transparent, it is diluted with methoxybutyl acetate and prepared to have a solid content of 40% by mass. 5) was obtained.

<Comparative Example 2: Synthesis of alkali-soluble resin (6)>

  An epoxy compound having the above structure (epoxy equivalent 217), 2.4 g of acrylic acid, 6.4 g of propylene glycol monomethyl ether acetate, 0.18 g of tetraethylammonium chloride, and 0.008 g of p-methoxyphenol were thermometer, stirrer, It put into the flask which attached the cooling tube, and it was made to react at 100 degreeC, stirring until an acid value became 5 mg-KOH / g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.

  16 parts by mass of the resulting epoxy acrylate solution, 0.42 parts by mass of trimethylolpropane (TMP), 3.7 g of biphenyltetracarboxylic dianhydride (BPDA), 0.076 parts by mass of tetrahydrophthalic anhydride (THPA) , And 15 parts by mass of propylene glycol monomethyl ether acetate are placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the reaction is performed by slowly raising the temperature to 105 ° C. while stirring. An alkali-soluble resin (6) having a weight-average molecular weight of 9300 in terms of polystyrene measured and a solid content of 40% by mass was obtained.

<Synthesis Example 1: Synthesis of photopolymerization initiator (1)>
(Diketone body)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then added with AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 Stir for minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

(Oxime ester)
The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator (1). Obtained. The chemical shift of ¹ H-NMR of the photopolymerization initiator (1) is shown below.

¹ H-NMR (CDCl ₃ ): σ 1.17 (d, 3H), 1.48 (t, 3H), 1.53 (s, 3H), 1.81 (s, 3H), 2.16 (s 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7. 45-7.59 (m, 5H), 7.65 (dd, 1H), 7.95 (m, 2H), 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 (D, 1H), 8.64 (d, 1H)

  The structure of the photopolymerization initiator (1) is as follows.

<Example 5>
(Preparation of black resist 1)
Using the carbon black dispersion ink prepared in <Preparation of carbon black dispersion ink>, the components shown in Table 3 were mixed in the proportions shown in Table 3, and stirred and dissolved with a stirrer to prepare black resist 1. .

  In Table 3, the amount of each component used in the carbon black dispersed ink and others is a solid content value. Moreover, the usage-amount in a solvent is the total usage-amount of a solvent also including the solvent contained in carbon black dispersion | distribution ink and each other component.

Moreover, the detail of each component in a table | surface is as follows.
Alkali-soluble resin (1): Resin synthesized in Example 1.
Photopolymerization initiator (1): Photopolymerization initiator synthesized in Synthesis Example 1.
Photopolymerizable monomer (1): Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
-Surfactant: F559 (manufactured by DIC)

<Example 6>
(Preparation of black resist 2)
A black resist 2 was prepared in the same manner as in Example 5 except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (2) synthesized in Example 2.

<Example 7>
(Preparation of black resist 3)
A black resist 3 was prepared in the same manner as in Example 5 except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (3) synthesized in Example 3.

<Example 8>
(Preparation of black resist 4)
A black resist 4 was prepared in the same manner as in Example 5 except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (4) synthesized in Example 4.

<Example 9>
(Preparation of black resist 5)
A black resist 5 was prepared in the same manner as in Example 5 except that the photopolymerization initiator was changed to photopolymerization initiator (2) (TR-PBG-304, manufactured by Changzhou Strong Electronics Co., Ltd.).

<Example 10>
(Preparation of black resist 6)
A black resist 6 was prepared in the same manner as in Example 5 except that the photopolymerization initiator was changed to photopolymerization initiator (3) (NCI-831, manufactured by ADEKA).

<Example 11>
(Preparation of black resist 7)
A black resist 7 was prepared in the same manner as in Example 5 except that the photopolymerization initiator was changed to photopolymerization initiator (4) (OX02, manufactured by BASF).

<Example 12>
(Preparation of black resist 8)
A black resist 8 was prepared in the same manner as in Example 5 except that the content ratio of each component was changed to that shown in Table 4 so that the content ratio of carbon black with respect to the total solid content was 45% by mass.

<Example 13>
(Preparation of black resist 9)
A black resist 9 was prepared in the same manner as in Example 5 except that the content ratio of each component was changed to that shown in Table 4 so that the content ratio of carbon black with respect to the total solid content was 40% by mass.

<Comparative Example 3>
(Preparation of comparative black resist 10)
A comparative black resist 10 was prepared in the same manner as in Example 5 except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (5) synthesized in Comparative Example 1.

<Comparative Example 4>
(Preparation of comparative black resist 11)
A comparative black resist 11 was prepared in the same manner as in Example 5 except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (6) synthesized in Comparative Example 2.

(Evaluation of resist)
(I) Formation line width evaluation / development adhesion evaluation (1) Preparation method of black matrix (BM) resist pattern The prepared black resists 1 to 9 and comparative black resists 10 and 11 were applied to a glass substrate with a spin coater, and the pressure was reduced. After drying, it was dried on a hot plate at 100 ° C. for 120 seconds to obtain a dried coating film. Subsequently, KOH adjusted to 0.04 mass% with ultrapure water at room temperature (23 ° C.) after pattern exposure was performed through an exposure mask described later at 40 mJ with a high-pressure mercury lamp on the obtained dried coating film. Various BM resist patterns were obtained by spray development using an aqueous solution as an alkaline developer for 80 seconds, 100 seconds, or 120 seconds. With respect to the formed BM resist pattern, the formation line width (sensitivity) and resolving power (development adhesion) were evaluated according to the criteria described in (2) and (3) below, and the results are shown in Table 5.

(2) Formation line width evaluation method (sensitivity)
Using an exposure mask with an opening of 10 μm (a striped opening with a width of 10 μm), the formation line width of the BM resist pattern obtained by the method (1) above is observed with a microscope at a magnification of 200 times, and the formation line width is measured. did. When evaluated with the same exposure amount and the same development time, the larger the formation line width, the higher the sensitivity.

(3) Development adhesion evaluation method (resolution)
A BM resist pattern was formed by the method (1) above using an exposure mask having openings of 1 μm to 10 μm (stripe-shaped openings with a width of 1 to 10 μm in 1 μm increments). The BM resist pattern was observed visually or using an optical microscope. Among the BM resist patterns remaining on the glass substrate with no chipping or surface roughness, the value of the opening width of the exposure mask corresponding to the pattern having the narrowest line width was defined as the development adhesion value. A smaller development adhesion value means better adhesion to the substrate and higher resolution.

(II) Evaluation of light shielding degree Using the prepared black resists 1 to 9 (Examples 5 to 13) and comparative black resists 10 (Comparative Example 3) and 11 (Comparative Example 4), The produced various BM resist patterns were post-baked in an oven at 230 degrees for 30 minutes to produce BM. The film thickness was measured with a level difference measuring device Alpha-Step-500 (KLA-Tencor), and the OD value was measured with a transmission density measuring device GretagMacbeth D200-II (GretagMacbeth). From this, the OD value per 1 μm (unit OD value) was determined. As a result, all BMs had an OD value of 4.0 / μm.

(III) Evaluation of Adhesion of Substrate Adhesion of Substrate of BM produced as follows using prepared Black Resist 1 (Example 5), Comparative Black Resist 10 (Comparative Example 3) and 11 (Comparative Example 4) evaluated. Substrate adhesion was determined as follows.

  A substrate having a thickness of 1.20 μm and a 2.5 cm square BM was prepared by the same process as in (II) (however, the entire surface was exposed without using an exposure mask). A thermosetting sealant Structbond XN-21-S (Mitsui Chemicals) was used and aluminum stud pins (P / N: 901106U, diameter 2.7 mm) (Quad Group) were joined. A tensile test was performed on the prepared sample at a rate of 2.0 kg / s using a thin film adhesion strength measuring device Romulus (manufactured by Quad Group), and the breaking strength and bonding area when the black matrix and the glass substrate broke. Thus, the substrate adhesion stress was determined by the following equation.

Substrate adhesion stress (kg / cm ² ) = breaking strength (kg) / bonding area (cm ² )

The results are shown in Table 6. The substrate adhesion force (%) in Table 6 is a relative value (%) when the value of substrate adhesion stress (kg / cm ² ) in Example 5 is 100%.

  As shown in Tables 5 and 6, the resin of the present invention has excellent sensitivity (formation line width) and resolution (development adhesion) when applied to a photosensitive resin composition, and also has excellent substrate adhesion. It turns out that.

  As shown in Table 5, the photosensitive resin compositions of Examples 5 to 13 of the present invention have good development adhesion and a large and large formation line width when the development time is as long as 80 to 120 seconds. Sensitivity was obtained. This is because the resins in the photosensitive resin compositions of Examples 5 to 13 of the present invention have a bulky ring structure in which the alkylidene group at the bisphenoxy site is greatly expanded in a planar shape as in the formula (II). Therefore, the hydrophobicity is high, the resistance to an alkaline developer is large, and since it has a bisphenoxy structure, the steric hindrance around the acrylic group is small and the crosslinking reaction is likely to occur as described above. . Further, comparison between Example 5 and Example 12 and Example 13 confirmed that both the formation line width and the development adhesion were good regardless of the pigment content.

  On the other hand, in the photosensitive resin composition of Comparative Example 4, no pattern remained in the range of 1 to 10 μm when the development adhesion was 120 seconds, and the development stability was poor.

  This is because the resin in the photosensitive resin composition of Comparative Example 4 has an alkylidene group ring structure at the bisphenoxy site, but the number of carbon atoms forming the ring is 6, and Examples 5 to 13 This is considered to be because the hydrophobicity is low and the bulkiness is small as compared with the above resin.

  In addition, as shown in Table 4, the photosensitive resin composition of Comparative Example 3 had a smaller formation line width and lower sensitivity than Examples 1 to 4, and the development adhesion was also worse than that of Examples 5 to 13. Also, in the substrate adhesion evaluation of Table 4, it decreased to about three-quarters of Example 1.

  This is because the resin in the photosensitive resin composition of Comparative Example 3 has two adamantyl group structures and has a large number of carbons, but does not have a bulky structure spread in a plane. Since it does not have a phenoxy structure, it is considered that resistance to an alkali developer and high sensitivity could not be obtained.

Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2014-138870) for which it applied on July 4, 2014, The whole is used by reference.

Claims (16)

Look containing a partial structure represented by at least partial structure and the following formula represented by the following formula (I) (III),
Furthermore, resin containing at least one of the partial structure represented by the following formula (VI) and the partial structure represented by the following formula (VII), and the partial structure represented by the following formula (VIII).

[In said formula (I), R < ¹² > is a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, or a C7-C20 aralkyl group.
In the above formula (III), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. .
Each * is a bond independently. ]

[In the above formula (VI), X is a divalent carboxylic acid residue. In the above formula (VII), Y is a tetravalent carboxylic acid residue.
Each * is a bond independently. ]

[In the above formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2-8.
* Is a bond. ] Including at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (III),
Further, a resin comprising at least one of a partial structure represented by the following formula (VI) and a partial structure represented by the following formula (VII), and a partial structure represented by the following formula (IX).

[In the above formula (I), R ¹² Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
In the above formula (III), R ¹ ~ R ⁴ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
Each * is a bond independently. ]

[In the above formula (VI), X is a divalent carboxylic acid residue. In the above formula (VII), Y is a tetravalent carboxylic acid residue.
Each * is a bond independently. ]

[In the above formula (IX), Z 'is a polyvalent methylol residue. n 'is an integer of 2-6.
* Is a bond. ] The resin according to claim 1 or 2 , wherein the resin containing a partial structure represented by the formulas (I) and (III) is a resin containing a partial structure represented by the following formula (V).

[In the formula (V), R ^{1 to} R ⁴ have the same meanings as the formula (III), each R ¹¹ is independently an alkylene group having 1 to 5 carbon atoms, and each R ¹² is independently the above formula ( It is synonymous with I), m is an integer of 0-5 each independently.
Each * is a bond independently. ] A resin obtained by reacting at least (A-1) an epoxy group-containing compound represented by the following formula (XI) and (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester ,
(A-3) A resin obtained by further reacting with a polybasic acid anhydride and (A-4) a polyhydric alcohol.

[In the above formula (XI), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ¹¹ is an alkylene group having 1 to 5 carbon atoms.
m is an integer of 0-5. ] (A-4) The polyhydric alcohol is at least one polyvalent selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. The resin according to claim 4 which is alcohol. Resin according to any one of claims 1 to 5 which is a resin for a color filter. At least claims 1 to according to any one of 6 resin, and a photosensitive resin composition containing a photopolymerization initiator (b). Furthermore, the photosensitive resin composition of Claim 7 containing a coloring material (d). The photosensitive resin composition according to claim 8 , wherein the color material (d) is a pigment and further contains a dispersant (e). The photosensitive resin composition according to claim 9 , wherein the color material (d) is a black pigment and the dispersant (e) is a polymer compound having a basic functional group. A resin containing at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (III), and a photopolymerization initiator (b);
Furthermore, it contains a coloring material (d) and a dispersant (e),
The color material (d) is a black pigment, and the dispersant (e) is a polymer compound having a basic functional group,
The photosensitive resin composition whose content rate of a black pigment is 45 mass% or more in a total solid.

[In the above formula (I), R ¹² Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
In the above formula (III), R ¹ ~ R ⁴ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
Each * is a bond independently. ] at least
(A-1) an epoxy group-containing compound represented by the following formula (XI)
(A-2) Unsaturated carboxylic acid or unsaturated carboxylic acid ester
Containing a resin obtained by reacting a photopolymerization initiator (b),
Furthermore, it contains a coloring material (d) and a dispersant (e),
The color material (d) is a black pigment, and the dispersant (e) is a polymer compound having a basic functional group,
The photosensitive resin composition whose content rate of a black pigment is 45 mass% or more in a total solid.

[In the above formula (XI), R ¹ ~ R ⁴ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ Is an alkylene group having 1 to 5 carbon atoms.
m is an integer of 0-5. ] The photosensitive resin composition of any one of Claims 7 thru | or 12 which contains an oxime ester compound at least as a photoinitiator (b). Cured product obtained by curing the photosensitive resin composition according to any one of claims 7 to 13. The color filter containing at least one of the pixel which consists of hardened | cured material of Claim 14 , and a black matrix. An image display device comprising the color filter according to claim 15 .

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