KR102305058B1 - Resin, photosensitive resin composition, cured product, color filter, and image display device - Google Patents

Abstract

When this invention is applied as resin in the photosensitive resin composition, irrespective of the color material content rate in the photosensitive resin composition, it is excellent in a sensitivity and resolving power, resin which can form a favorable color filter, and the photosensitive resin containing this resin A composition, a cured product obtained by curing the same, a color filter having the cured product, and an image display device provided with the color filter are provided. The present invention relates to a resin comprising at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (II).

Description

Resin, photosensitive resin composition, cured product, color filter, and image display device {RESIN, PHOTOSENSITIVE RESIN COMPOSITION, CURED PRODUCT, COLOR FILTER, AND IMAGE DISPLAY DEVICE}

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 the 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, a color filter having the cured product, and a color filter comprising the same It relates to an image display device that

A color filter normally forms a black black matrix (it may abbreviate as "BM" hereafter) on the surface of transparent substrates, such as glass and plastic, and then forms three types, such as red, green, and blue. The above different pixels are sequentially formed in a pattern such as a stripe shape or a mosaic shape.

As a representative manufacturing method of a color filter, the pigment dispersion method is currently used. In this method, first, after apply|coating the photosensitive resin composition containing a black pigment on a transparent substrate, drying, and also image exposure and development, BM is formed by hardening by high temperature treatment at 200 degreeC or more. A color filter is formed by repeating this for every color, such as red, green, and blue.

BM is generally arranged in a grid shape, stripe shape, or mosaic shape between pixels such as red, green, and blue, and has a role of improving contrast or preventing light leakage by suppressing mixed colors between pixels. For this reason, high light-shielding property is calculated|required by BM.

Moreover, since the edge part of pixels, such as red, green, blue, formed behind BM overlaps with this BM, it receives the influence of the film thickness of BM, and a level|step difference is formed in the overlapping part. In this overlapping part, the flatness of a pixel is impaired, the non-uniformity of a liquid crystal cell gap, or disorder of a liquid-crystal orientation arises, and the fall of a display ability is caused.

Therefore, in recent years, especially thin film formation of BM is calculated|required, and when it thins, in order to express sufficient light-shielding property, the pigment content rate in the photosensitive resin composition exists in the direction which becomes higher.

In addition, in recent years, when stacking the manufactured color filters on a panel, conventionally, a frame portion is separately formed, and a sealing agent is applied thereto and bonded to the array substrate. A method of forming a frame portion at the same time and applying a sealing agent thereto and bonding it together has come to be implemented. Therefore, the strong adhesiveness of the board|substrate of a color filter, and BM has come to be calculated|required more.

On the other hand, in order to obtain the photosensitive resin composition in the pigment dispersion method, first, the composition containing a color material, a dispersing agent, a solvent, etc. is disperse|distributed with glass beads etc., and a dispersion liquid is manufactured. Thereafter, the photosensitive resin composition is prepared by stirring and mixing the binder resin and the photopolymerization initiator.

As the binder resin in the photosensitive resin composition for color filters, the uncured portion can be removed by alkali development after curing by UV exposure through a mask so as to form pixels such as BM, red, green and blue, carboxyl group, etc. Alkali-soluble resin having a Conventionally, as alkali-soluble resin which has a carboxyl group, the acrylic copolymer resin which copolymerized acrylic acid was used.

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

Under such circumstances, recently, so-called epoxy acrylate resins have come to be used. For example, Patent Document 1 describes examples of epoxy acrylate resins having various bisphenoxy skeletons. Moreover, in patent document 2, the example of the epoxy acrylate resin which has an adamantyl group is described.

On the other hand, in Patent Document 3, an epoxy resin having a bisphenoxy skeleton and a specific alkylidene group is described as an epoxy resin used for a light-emitting device such as an LED excellent in heat resistance and moisture absorption resistance, or a light-receiving device such as a solar cell. has been

Japanese Laid-Open Patent Publication No. 2005-126674 Japanese Patent Laid-Open No. 2008-287246 Japanese Patent Application Laid-Open No. 2013-253153

As a result of the present inventors' examination, when the epoxy acrylate resin described in patent documents 1 and 2 is used, the sensitivity or resolution deteriorates depending on the color material content rate in the photosensitive resin composition, and favorable BM or pixel It was found that it cannot be formed. In particular, if a thin line pattern is to be formed under a condition in which the content of the color material is high, sufficient curing cannot be performed due to a decrease in sensitivity, and the pattern is excessively removed during development, and the width is narrow compared to the width of the opening of the mask. It was discovered that only a pattern was obtained, and control of the pattern shape was difficult. Moreover, in patent document 3, it did not describe at all about the photosensitive resin composition for color filters, but the characteristic at the time of using as resin for photosensitive resin compositions was unclear.

Therefore, when the present invention is applied as a resin in the photosensitive resin composition, regardless of the pigment content in the photosensitive resin composition, it is excellent in sensitivity and resolution, and a resin capable of forming a good color filter, including the resin It makes it a subject to provide the image display apparatus provided with the photosensitive resin composition, the hardened|cured material obtained by hardening|curing it, the color filter which has this hardened|cured material, and this color filter.

As a result of the present inventors earnestly examining in order to solve the said subject, resin which has a partial structure which has a specific bisphenoxy backbone and a specific alkylidene group, and has a specific ethylenically unsaturated group and a carboxyl group residue can solve the said subject found out to solve it. That is, the summary of this invention is as follows.

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

[Formula 1]

[In the 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 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, and 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.

In addition, * is each independently a bond.]

[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).

[Formula 2]

[In the formula (III), R ¹ to R ⁴ have the same meaning as in the formula (II).

In addition, * is each independently a bond.]

[3] The resin according to [1], wherein 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).

[Formula 3]

[In the formula (IV), R ¹¹ is each independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 0 to 5;

In addition, R<^1>-R<^5> , k and 1 have the same meaning as said Formula (II). In addition, R ¹² has the same meaning as each independently of the said Formula (I).

In addition, * is each independently a bond.]

[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).

[Formula 4]

[In the formula (V), R ¹ to R ⁴ , R ¹¹ , R ¹² and m each independently have the same meaning as in the formula (IV).

In addition, * is each independently a bond.]

[5] The resin according to any one of [1] to [4], further comprising at least one of a partial structure represented by the following formula (VI) and a partial structure represented by the following formula (VII).

[Formula 5]

[Formula 6]

[In the formula (VI), X is a divalent carboxylic acid residue. Moreover, in said Formula (VII), Y is a tetravalent carboxylic acid residue.

In addition, * is each independently a bond.]

[6] The resin according to [5], further having a partial structure represented by the following formula (VIII).

[Formula 7]

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

Also, * is a bonding hand.]

[7] The resin according to [5], further having a partial structure represented by the following formula (IX).

[Formula 8]

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

Also, * is a bonding hand.]

[8] at least

(A-1) an epoxy group-containing compound represented by the following formula (X);

(A-2) Unsaturated carboxylic acid or unsaturated carboxylic acid ester

A resin obtained by reacting

[Formula 9]

[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, 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 from 1 to 5, l is an integer from 0 to 13, and m is an integer from 0 to 5]

[9] (A-1) The resin according to [8], wherein the epoxy group-containing compound is a compound represented by the following formula (XI).

[Formula 10]

[In Formula (XI), R ¹ to R ⁴ , R ¹¹ , and m each independently have the same meaning as in 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], obtained by reacting with (A-3) polybasic acid anhydride and (A-4) polyhydric alcohol.

[12] (A-4) the polyhydric alcohol is selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol The resin according to [11], which is at least one type of polyhydric alcohol.

[13] The resin according to any one of [1] to [12], which is a resin for color filters.

[14] A photosensitive resin composition comprising at least the resin according to any one of [1] to [13] (resin (a-1)) and a photoinitiator (b).

[15] The photosensitive resin composition according to [14], further comprising 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 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], wherein the photopolymerization initiator (b) contains at least an oxime ester compound.

[20] A cured product obtained by curing the photosensitive resin composition according to any one of [14] to [19].

[21] A color filter comprising at least one of a pixel made of the cured product according to [20] and a black matrix.

[22] An image display device comprising the color filter according to [21].

According to the present invention, when applied as a resin in the photosensitive resin composition, regardless of the pigment content in the photosensitive resin composition, it is excellent in sensitivity and resolution, including a resin capable of forming a good color filter, and the resin The photosensitive resin composition to do, the hardened|cured material obtained by hardening|curing it, the color filter which has this hardened|cured material, and the image display apparatus provided with this color filter can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic which shows an example of the organic electroluminescent element provided with the color filter of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to the following embodiment, It can implement with various changes within the scope of the summary.

In addition, in this invention, "(meth)acryl" means "acryl and/or methacryl", and it is the same also about "(meth)acrylate" and "(meth)acryloyl." In addition, "acid (anhydride)", "(anhydride) ... Acid" means containing both an acid and its anhydride.

In addition, in this invention, "total solid content" shall mean all components other than a solvent contained in the photosensitive resin composition or the ink mentioned later.

In addition, in this invention, a number average molecular weight and a weight average molecular weight point out the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In addition, in the present invention, unless otherwise specified, the term "amine value" refers to an amine value in terms of effective solid content, and is a value expressed by the weight of the amount of base and equivalent KOH per 1 g of solid content of the dispersant. In addition, a measurement method is mentioned later. In addition, unless otherwise indicated, an "acid value" shows an acid value in terms of effective solid content, and is computed by neutralization titration.

In addition, in this invention, a "carboxylic acid residue" means the group which remains after removing all the carboxyl groups from a carboxylic acid compound. For example, the carboxylic acid residue in the carboxylic acid compound represented by A-COOH means the monovalent group represented by A. Similarly, a "polyhydric alcohol residue" means the group which remains after all hydroxyl groups are removed from a polyhydric alcohol compound. In addition, the "polyhydric methylol moieties" refers to means a group remaining after removing from a methylol compound polyvalent all methylol group (-CH ₂ -OH groups).

In addition, in this specification, a bond may be represented using "*". In addition, in this specification, although a numerical range is shown using "-", it means the numerical range including an upper limit and a lower limit.

<Resin (a-1)>

The resin of the present invention (hereinafter sometimes referred to as “resin (a-1)”) contains at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (II), do.

Since the resin (a-1) has a bulky structure as shown in the following formula (II) and has a structure of an ethylenically unsaturated group as shown in the following formula (I), the resin (a-1) has the same chemical resistance or moisture absorption resistance. It tends to have good cargo properties.

[Formula 11]

[Formula 12]

In said formula (I), R<^12> is a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, or a C7-20 aralkyl group.

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, and 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.

In addition, each * independently represents a bond.

[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.

^{Carbon number of the alkyl group of R<12>} in Formula (I) is 1 or more normally, and it is preferable that it is 6 or less, It is more preferable that it is 3 or less, It is still more preferable that it is 2 or less. When carbon number exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable.

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-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 still more preferable.

^{Moreover, carbon number of the aryl group of R<12>} in Formula (I) is 6 or more normally, and it is 20 or less normally, It is preferable that it is 15 or less, It is more preferable that it is 10 or less.

When carbon number exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

^{Moreover, carbon number of the aralkyl group of R<12>} in Formula (I) is 7 or more normally, and is 20 or less normally, 15 or less are preferable and 11 or less are more preferable. When carbon number exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a phenyl group is more preferable.

^{Among these, R 12} in 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 tends to exhibit the characteristics of the present invention most. desirable.

In resin (a-1), although the content rate of the partial structure represented by said Formula (I) is not specifically limited, It is preferable that it is 1 mass % or more with respect to the total mass of resin (a-1), and 5 mass % It is more preferable that it is more than it, and it is preferable that it is 50 mass % or less, and it is more preferable that it is 40 mass % or less.

When it exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable.

[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, and more preferably 3 .

When it exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable. Moreover, when it uses as resin in the photosensitive resin composition, when it is more than the said lower limit, there exists a tendency which the effect by the large volume can express favorably, Moreover, when it is below the said upper limit, compatibility with other components is favorable. tends to break

As a specific example of a cycloalkylidene group, a cycloundecylidene group, a cyclododecylidene group, or a cyclotridecylidene group is preferable, and a cyclododecylidene group is especially preferable.

^{R 5 which} is a substituent which the cycloalkylidene group in the partial structure represented by the said formula (II) may have is a C1-C20 alkyl group, a C6-C20 aryl group, or a C7-20 aralkyl group.

The number of carbon atoms 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, still more preferably 5 or less, even more preferably 3 or less, and 2 The following are particularly preferred. When carbon number exists in the said range, hardening characteristics, such as chemical-resistance, tend to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable.

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, tri Decan-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, icosan -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-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 still more preferable.

Carbon number of the aryl group of R<^5> is 6 or more normally, and it is normally 20 or less, It is preferable that it is 15 or less, It is more preferable that it is 10 or less, It is still more preferable that it is 8 or less. When carbon number exists in the said range, it exists in the tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, compatibility with another component tends to become favorable. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

Carbon number of the aralkyl group of R<^5> is 7 or more normally, and it is normally 20 or less, It is preferable that it is 15 or less, It is more preferable that it is 11 or less, It is still more preferable that it is 9 or less. When carbon number exists in the said range, it exists in the tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, compatibility with another component tends to become favorable. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a benzyl group is more preferable.

Among these ^{, it is preferable that R<5>} is a C1-C10 alkyl group, and it is more preferable that it is a methyl group from a viewpoint which the characteristic of resin most expresses.

Further, the formula (II) in, l which is the number of substituent R ⁵ are groups cycloalkylidene may have is, an integer from 0 to 13, preferably an integer of less than 4, more preferably 2 an integer of not less. In particular, it is particularly preferred when l is 0, that is, there is no substituent. When it exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable.

In addition, when l is an integer of 2 or more, R<^5> may be the same or different, and the substitution position may also be same or different.

In the formula (II), R ¹ to R ⁴ each independently represent 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.

In the formula (II), ^{the number of carbon atoms in the alkyl group in R 1} to R ⁴ is usually 1 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and 5 or less. It is still more preferable, it is still more preferable that it is 3 or less, It is especially preferable that it is 2 or less. When carbon number exists in the said range, it exists in the tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, compatibility with another component tends to become favorable.

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, tri Decan-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 1- diary.

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-hexyl group A sil group, 3-hexyl group, or cyclohexyl group is preferable, a methyl group, an ethyl group, 1-propyl group, or 2-propyl group is more preferable, and a methyl group is especially preferable.

The formula (II) of, R ¹ ~ R and the carbon atoms of the aryl group in the ^4, typically six or more, and, typically is no more than 20, 15 or less is preferable, and 10 or less is more preferred, and less than or equal to 8 is more preferable. When carbon number exists in the said range, it exists in the tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, compatibility with another component tends to become favorable. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

The formula (II) of, R ¹ ~ R ⁴ of the aralkyl group having a carbon number in the can, and usually not less than 7, and typically is less than 20, 15 or less is preferable, and 11 or less is more preferable, and 9 or less is more preferable. When carbon number exists in the said range, it exists in the tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, compatibility with another component tends to become favorable. 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.

Of these, methyl group is preferred in the point of view of heat resistance R ¹ ~ R ⁴ is preferably a hydrogen atom, and further, the chemical resistance viewpoint.

The substitution position of R ¹ ~ R ⁴ in the formula (II) may be not particularly limited, and examples thereof include the following formula (II ') which of the positions of the b ~ f in, R ¹ ~ R ^{When 4} is each independently 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 each independently one of b, c, e, and f. It is preferable that it is any position, and it is more preferable that it is the position of b or f.

Further, in the formula (II), the substitution position of the cycloalkylidene group may be any of the positions b to f in the following formula (II'), but the heat resistance based on the cycloalkylidene group is efficiently obtained. From a viewpoint, it is preferably the position of d.

[Formula 13]

In the formula (II'), R ¹ to R ⁵ , k and 1 have the same meanings as defined in the formula (II).

Although the following are mentioned as a specific example of the partial structure of said Formula (II), It is not limited to the following at all. In addition, the numerical value described in the cycloalkylidene group in the following formula represents the carbon number of the cycloalkylidene group.

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

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

When the partial structure of the said Formula (II) is these structures, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, the tendency for compatibility with another component to become favorable. There exists a tendency for the characteristic of resin to be expressed favorably.

Further, the resin (a-1) is a structure containing the partial structure of (A-1-1), and includes any structure selected from the following (A-1-29) to (A-1-32). you may be doing

[Formula 18]

[Formula 19]

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

In the resin (a-1), the content rate of the partial structure represented by the formula (II) is not particularly limited, but is preferably 10 mass% or more, more preferably 20 mass% or more, and 95 mass% or less. It is preferable, and it is more preferable that it is 90 mass % or less. When it exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for compatibility with another component to become favorable.

[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).

[Formula 20]

In the formula (III), R ¹ to R ⁴ have the same meaning as in the formula (II). In addition, each * independently represents a bond.

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

The number of partial structures represented by the said Formula (III) contained in resin (a-1) may be one, and two or more types may be sufficient as them. Moreover, in resin (a-1), the partial structure which does not satisfy the said Formula (III), and also satisfy|fills the said Formula (II) may be contained.

In the resin (a-1), the content ratio of the partial structure represented by the formula (III) to the partial structure represented by the formula (II) is 5 mass from the viewpoint that the characteristics of the resin are easily expressed favorably. % or more is preferable, 10 mass % or more is more preferable, 20 mass % or more is still more preferable, 50 mass % or more is still more preferable, 80 mass % or more is especially preferable, and usually 100 mass % is below.

(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 containing the partial structure represented by said formula (I) and (II) is resin containing the partial structure represented by following formula (IV).

[Formula 21]

In said formula (IV), R<^11> is a C1-C5 alkylene group each independently, and m is an integer of 0-5. In addition, R<^1>-R<^5> , k and 1 have the same meaning as said Formula (II). In addition, R ¹² has the same meaning as each independently of the said Formula (I). In addition, each * independently represents a bond.

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 tends to have good chemical resistance, and furthermore, the partial structure represented by the formula (I) When the partial structure exists apart from the bulky cycloalkylidene group, the effect of the resulting steric hindrance is small, and crosslinking is facilitated by ultraviolet irradiation or high heat, and the curing properties tend to be further increased. have. Moreover, when it uses as resin in the photosensitive resin composition, a sensitivity becomes favorable with the improvement of a crosslinking reaction, and the thing in the tendency for tolerance by an alkali developing solution to become favorable is mentioned.

^{Carbon number in the alkylene group of R<11>} in said Formula (IV) is 1 or more normally, It is preferable that it is 2 or more, And it is 5 or less normally. When it exists 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 be able to express favorably. Moreover, when used as resin in the photosensitive resin composition, when it is more than the said lower limit, the influence of the steric hindrance by a cycloalkylidene group tends to become small, Moreover, when it is below the said upper limit, compatibility with other components becomes favorable. tends to

The ^{alkylene group of R 11} may be linear or may be 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-pentyl group Rene group, 1,3-pentylene group, or cyclopentylene group is preferable, ethylene group, 1,3-propylene group, 1,2-propylene group, 1,4-butylene group, 1,2-butylene group, 1, A 5-pentylene group, a 1,2-pentylene group, or a 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. When it exists 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 be able to express favorably. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, there exists a tendency for the influence of the steric hindrance of a cycloalkylidene group to become small, and there exists a tendency for compatibility with another component to become favorable. Moreover, when m is an integer of 2 or more, R ¹¹ may be same or different.

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

One type of partial structure represented by the said Formula (IV) contained in resin (a-1) may be sufficient, and two or more types may be sufficient as it.

Although the content rate of the partial structure represented by said Formula (IV) in resin (a-1) is not specifically limited, It is preferable that it is 10 mass % or more, It is more preferable that it is 20 mass % or more, and 95 mass % It is preferable that it is less than, and it is more preferable that it is 90 mass % or less. When it exists in the said range, there exists a tendency for hardening characteristics, such as chemical-resistance, to become favorable, and when it uses as resin in the photosensitive resin composition, there exists a tendency for tolerance with respect to an alkali developing solution to become favorable.

[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).

[Formula 22]

In the formula (V), R ¹ to R ⁴ , R ¹¹ , R ¹² and m each independently have the same meaning as in the formula (IV). In addition, each * independently represents a bond.

The reason why the partial structure represented by the formula (V) is preferable is that, when the cycloalkylidene group is a cyclododecylidene group, curing properties such as chemical resistance tend to be good, and the effect of the resin of the present invention is best expressed. There are things that tend to be possible. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, the tolerance with respect to an alkali developing solution tends to become favorable by the bulk of a cyclododecylidene group, and the partial structure represented by said formula (I) The influence of the steric hindrance to , tends to be small, and the sensitivity or resistance to an alkali developer tends to be good.

One type of partial structure represented by the said Formula (V) contained in resin (a-1) may be sufficient, and two or more types may be sufficient as it. Moreover, resin (a-1) may contain the partial structure which does not satisfy said Formula (V), and also satisfy|fills said Formula (IV).

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

In addition, * in said formula (V) is a bond each independently. For example, the bond may be bonded to a hydrogen atom or may be bonded to a bond of formulas (VI) and/or formulas (VII) described later.

[Partial structure represented by formula (VI), formula (VII)]

The resin (a-1) preferably further contains a partial structure represented by the following formula (VI) and/or a partial structure represented by the following formula (VII).

[Formula 23]

[Formula 24]

In the formula (VI), X is a divalent carboxylic acid residue. Moreover, in said Formula (VII), Y is a tetravalent carboxylic acid residue. In addition, each * independently represents a bond.

When 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, so that the substrate is coated with the resin (a-1), There exists a tendency which can improve the adhesiveness with the board|substrate by the carboxyl group of a polar group. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, it exists in the tendency for solubility adjustment at the time of alkali image development to become easy, and to improve the adhesiveness to a board|substrate.

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 section, from the viewpoint of easiness of synthesis, dibasic acid anhydride (dicarboxylic acid anhydride) It is preferably a divalent carboxylic acid residue of

As a divalent carboxylic acid residue, the divalent hydrocarbon group which may have a substituent is mentioned, for example. Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. Moreover, a linear or branched chain hydrocarbon group may be sufficient, and a cyclic hydrocarbon group may be sufficient. Although carbon number of a hydrocarbon group is not specifically limited, From a viewpoint of board|substrate adhesiveness and chemical-resistance improvement, it is 1 or more normally, Preferably it is 2 or more, And it is 20 or less normally, Preferably it is 15 or less, More preferably is 10 or less, more preferably 8 or less. Although a halogen atom, a hydroxyl group, an ether group, a carbonyl group etc. are mentioned as a substituent, Unsubstituted thing is preferable.

Specifically, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride A divalent carboxylic acid residue, such as these, is preferable, and the divalent carboxylic acid residue of tetrahydrophthalic anhydride or succinic anhydride is more preferable. The divalent carboxylic acid residue of these dibasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

By making X into said thing, there exists a tendency for board|substrate adhesiveness and chemical-resistance to improve. Moreover, when it uses as resin in the photosensitive resin composition, adjustment of the solubility at the time of alkali image development becomes easy, and there exists a tendency for the adhesiveness to a board|substrate to improve.

Although the following are mentioned as a specific example of the partial structure represented by the said Formula (VI), As long as it has a structure of the said Formula (VI), it will not be limited to the following, It will apply to this invention.

[Formula 25]

Further, when the resin (a-1) contains the partial structure represented by the formula (VII), that is, the resin (a-1) has at least two carboxyl groups, substrate adhesion and chemical resistance tend to improve. . Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, it exists in the tendency for solubility adjustment at the time of alkali image development to become easy, and to improve the adhesiveness to a board|substrate.

Further, since the partial structure represented by the formula (VII) has two bonds, when it contains two or more partial structures represented by the formula (IV) or (V) having an ethylenically unsaturated group, the molecular weight is It can increase, and with it, content of an ethylenically unsaturated group can be increased, and when hardening|curing, a crosslinking reaction can also increase, and it is thought that board|substrate adhesiveness and chemical-resistance can be improved.

Y in the formula (VII) is not particularly limited as long as it is a tetravalent carboxylic acid residue, but as will be described later, from the viewpoint of easiness of synthesis, tetravalent carboxyl of tetrabasic acid anhydride (tetracarboxylic acid anhydride) It is preferably an acid residue.

As a tetravalent carboxylic acid residue, the tetravalent hydrocarbon group which may have a substituent is mentioned, for example. The hydrocarbon group may have a hetero atom, such as an oxygen atom and a sulfur atom.

Moreover, as a hydrocarbon group, an aliphatic or aromatic hydrocarbon is mentioned. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. Moreover, a linear or branched chain hydrocarbon group may be sufficient, and a cyclic hydrocarbon group may be sufficient. Although carbon number of a hydrocarbon group is not specifically limited, From a viewpoint of board|substrate adhesiveness and chemical-resistance improvement, it is 1 or more normally, Preferably it is 5 or more, Moreover, it is 20 or less normally, Preferably it is 15 or less. Although a halogen atom, a hydroxyl group, an ether group, a carbonyl group etc. are mentioned as a substituent, Unsubstituted thing is preferable.

Specifically, for example, tetracarboxylic dianhydride, such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. A tetravalent carboxylic acid residue is preferable, and a tetravalent carboxylic acid residue of biphenyltetracarboxylic acid anhydride is more preferable. The tetravalent carboxylic acid residues of these tetrabasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

By making Y into said thing, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness and chemical-resistance, to improve. Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, it exists in the tendency for adjustment of the solubility at the time of alkali development to become easy, alkali resistance of an image part becomes favorable, and the adhesiveness to a board|substrate tends to improve.

Although the following are mentioned as a specific example of the partial structure represented by said Formula (VII), As long as it has a structure of said Formula (VII), it will not specifically limit, It will apply to this invention.

[Formula 26]

Resin (a-1) may contain a partial structure similar to the partial structure represented by Formula (VI) derived from a polybasic acid anhydride, and/or a partial structure represented by Formula (VII) other than the partial structure mentioned above. Especially, the case where it contains the partial structure represented by the following formula (VI') derived from tribasic acid anhydride is preferable.

[Formula 27]

In the formula (VI'), X' is a trivalent carboxylic acid residue. In addition, * represents a bond.

When the resin (a-1) contains the partial structure represented by the formula (VI'), that is, the resin (a-1) has at least two carboxyl groups, curing properties such as substrate adhesion and chemical resistance are improved tends to Moreover, when resin (a-1) is used as resin in the photosensitive resin composition, it exists in the tendency for solubility adjustment at the time of alkali image development to become easy and the adhesiveness to a board|substrate becomes favorable.

X' in the formula (VI') is not particularly limited as long as it is a trivalent carboxylic acid residue, but as will be described later, from the viewpoint of easiness of synthesis, a trivalent carboxylic acid of tribasic acid anhydride (tricarboxylic acid anhydride) It is preferably an acid residue.

As a trivalent carboxylic acid residue, the trivalent hydrocarbon group which may have a substituent is mentioned, for example. The hydrocarbon group may have a hetero atom, such as an oxygen atom and a sulfur atom.

Moreover, as a hydrocarbon group, an aliphatic or aromatic hydrocarbon is mentioned. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. Moreover, a linear or branched chain hydrocarbon group may be sufficient, and a cyclic hydrocarbon group may be sufficient. Although carbon number of a hydrocarbon group is not specifically limited, From a viewpoint of board|substrate adhesiveness and chemical-resistance improvement, it is 1 or more normally, Preferably it is 5 or more, Moreover, it is 20 or less normally, Preferably it is 15 or less. Although a halogen atom, a hydroxyl group, an ether group, a carbonyl group etc. are mentioned as a substituent, Unsubstituted thing is preferable.

Specifically, for example, it is preferable that they are trivalent carboxylic acid residues, such as trimellitic anhydride and hexahydro trimellitic anhydride, and the trivalent carboxylic acid residue of trimellitic anhydride is more preferable. The trivalent carboxylic acid residue of these tribasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

By making X' into said thing, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness and chemical-resistance, to improve. Moreover, when it uses as resin in the photosensitive resin composition, adjustment of the solubility at the time of alkali image development becomes easy, and there exists a tendency for the adhesiveness to a board|substrate to improve.

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, each independently the formula (IV) or It can be set as the thing couple|bonded with the bond * in the partial structure represented by (V).

Further, a bond * in the partial structure represented by the formula (IV) or the partial structure represented by the formula (V) is, for example, each independently a hydrogen atom or a partial structure represented by the formula (VI) and/or the above It can be set as what couple|bonded with the bond * in the partial structure represented by Formula (VII).

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

Among the bonds in the formula (IV), by setting the ratio of bonds to the bonds in the formula (VII) within the above range, curing properties such as substrate adhesion and chemical resistance are improved, and as a resin in the photosensitive resin composition When used, there exists a tendency for the solubility to an alkali developing solution and the adhesiveness to a board|substrate to become favorable.

In addition, in addition to the partial structure represented by the said Formula (VII), it is preferable that the resin of this invention contains the partial structure represented by the said Formula (VI) from a viewpoint of hardening characteristics, such as board|substrate adhesiveness and chemical-resistance.

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) thereof is 70:30 to 1:99 It is preferable, and it is more preferable that it is 60:40-1:99.

Further, the content of the partial structure represented by the formula (VI) relative to the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII) is preferably 1 mol% or more, It is preferable that it is 70 mol% or less, and it is more preferable that it is 60 mol% or less.

Further, the content of the partial structure represented by the formula (VII) relative to the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII) is preferably 30 mol% or more, and 40 mol% % or more is more preferable, and it is preferable that it is 99 mol% or less.

By setting the partial structure content ratio represented by the formula (VII) to the lower limit or more, it tends to be possible to suppress a decrease in the film physical properties of the obtained coating film, and the content ratio of the partial structure represented by the formula (VI) is set as above. By using more than a lower limit, increase in the viscosity of the resin solution obtained is suppressed, and there exists a tendency for handleability to become favorable.

In addition, when 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 together, the partial structure represented by the formula (VI') The content 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 bond of the partial structure represented by the formula (IV) are bonded A ratio makes the total number of bonds * in said formula (IV) 100 %, and is 5 to 70 % normally, Preferably it is 10 to 40 %.

In the case of containing the partial structure represented by the formula (VII) and the partial structure represented by the formula (VI), or the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII), and the formula ( In the case of containing a partial structure represented by VI'), the total number of bonds * in the formula (IV) is 100%, among them, the bonds represented by the formulas (VI), (VI') and (VII) The couple|bonding ratio is 10-90 % normally, Preferably it is 20 to 85 %, More preferably, it is 30 to 80 %.

Among the bonds * in the formula (IV), the bonds * not bonded to the bonds * in the formulas (VI), (VI') and (VII) can be bonded to, for example, a hydrogen atom. . By setting it as the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness and chemical-resistance, to become favorable.

Each of * as a bond in formulas (VI) and (VII) can independently bond with * as a bond in formulas (IV) or (V). Moreover, * which is a bond in said formula (IV) or (V) can bond with a hydrogen atom, * which is a bond in said formula (VI), or * which is a bond in said formula (VII), respectively independently. Thus, various aspects are mentioned to resin of this invention.

The main specific examples of the partial structure in the case where * in the formula (V) is bonded to a hydrogen atom, * in the formula (VI), or * in the formula (VII) is shown below. . Also in the case where the said Formula (IV) is used instead of the said Formula (V), the same example is given.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

Moreover, in said (A-2-6), the * which is the bond may couple|bond with the * which is a bond in the said formula (V). That is, you may make the partial structure represented by the said Formula (VII) into a coupling group, and you may connect two or more partial structures represented by the said Formula (V).

As described above, the resin (a-1) preferably also contains a partial structure represented by the formula (VI') in addition to the partial structure represented by the formula (VI) and/or the formula (VII). * which is a bond in said formula (VI') can also couple|bond with * which is a bond in said formula (IV) and/or said formula (V).

The main specific example of the partial structure in the case where * which is a bond in said Formula (V), and * which is a bond in said Formula (VI') couple|bonds is given below. Also in the case where the said Formula (IV) is used instead of the said Formula (V), the same example is given.

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

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

The reason for this is that by containing the partial structure represented by the formula (VII), * as a bond in the formula (VII) is further bonded to the partial structure represented by the formula (IV) or the partial structure represented by (V), resulting in molecular weight When this increases, and the content of the ethylenically unsaturated group structure also increases, and the content of the carboxyl group also increases, there is a tendency for improvement of curing properties such as substrate adhesion and chemical resistance to be improved.

In addition, * which is a bond in said formula (IV) or (V) is each independently a hydrogen atom, * which is a bond in said formula (VI), * which is a bond in said formula (VI'), or said formula (VII) ) in addition to *, a bond in a partial structure derived from another polybasic acid anhydride may also be bonded to a bond in a range that does not adversely affect the effects of the present invention.

[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 formulas (I) to (VII).

[Formula 38]

In the formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2-8. In addition, * 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 introduction amount of a carboxyl group and an ethylenically unsaturated group can be increased, There exists a tendency which can further improve hardening characteristics, such as board|substrate adhesiveness or chemical-resistance.

n in the said formula (VIII) is an integer of 2-8, and it is preferable that it is an integer of 4 or less. When n is in the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness or chemical-resistance, to improve further.

Z in the formula (VIII) is a polyhydric alcohol residue, and specific examples thereof include alcohol residues such as 1,2,3-propanetriol and polyhydric alcohol residues such as sugar alcohols described later. VIII) can be used without particular limitation as long as it satisfies.

As a polyhydric alcohol residue, the n-valent hydrocarbon group which may have a substituent is mentioned, for example. The hydrocarbon group may have a hetero atom, such as an oxygen atom and a sulfur atom.

Moreover, as a hydrocarbon group, an aliphatic or aromatic hydrocarbon is mentioned. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. Moreover, a linear or branched chain hydrocarbon group may be sufficient, and a cyclic hydrocarbon group may be sufficient. Although carbon number of a hydrocarbon group is not specifically limited, From a viewpoint of board|substrate adhesiveness and chemical-resistance improvement, it is 1 or more normally, Preferably it is 2 or more, More preferably, it is 3 or more, And it is usually 20 or less, Preferably Preferably it is 15 or less, More preferably, it is 10 or less. Although a halogen atom, a hydroxyl group, an ether group, a carbonyl group etc. are mentioned as a substituent, Unsubstituted thing is preferable.

Specific examples of the partial structure represented by the formula (VIII) include the partial structures of the following formulas (A-3-1) to (A-3-4) or the following-mentioned formula (IX). Among these, the case which has a partial structure of a following formula (A-3-1) or a formula (IX) mentioned later is more preferable from a viewpoint of hardening characteristics, such as board|substrate adhesiveness or chemical-resistance.

[Formula 39]

[Formula 40]

[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).

[Formula 41]

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

Although n' in said Formula (IX) is an integer of 2-6, it is preferable that it is an integer of 2-4 from a viewpoint of hardening characteristics, such as board|substrate adhesiveness or chemical-resistance.

Z' in the formula (IX) is a polyvalent methylol residue, preferably a polyvalent methylol residue of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, or trimethylolethane, IX), another one may be used. Specific examples of the partial structure represented by the formula (IX) are given below.

[Formula 42]

[Formula 43]

[Formula 44]

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

Moreover, as a polyvalent methylol residue, the hydrocarbon group of n' valence which may have a substituent is mentioned, for example. Examples of the hydrocarbon group include aliphatic or aromatic hydrocarbons. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. Moreover, a linear or branched chain hydrocarbon group may be sufficient, and a cyclic hydrocarbon group may be sufficient. Although carbon number of a hydrocarbon group is not specifically limited, From a viewpoint of board|substrate adhesiveness and chemical-resistance improvement, it is 1 or more normally, Preferably it is 2 or more, And it is 20 or less normally, Preferably it is 15 or less, More preferably Preferably it is 10 or less, Especially preferably, it is 5 or less. Although a halogen atom, a hydroxyl group, an ether group, a carbonyl group etc. are mentioned as a substituent, Unsubstituted thing is preferable.

As a partial structure represented by the said Formula (VIII) and/or a partial structure represented by the said Formula (IX), 1 type may be used individually, and 2 or more types may be used together and may be used.

Each of the bonds in the formulas (VIII) and (IX) is independently a hydrogen atom, * in the formula (VI), * in the formula (VII), or the formula (VI'). ), which is a bond in *. Depending on the combination of bonds, various aspects can be mentioned.

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

Moreover, when * which is a bond in said formula (VIII) and said formula (IX) bonds with * which is a bond in said formula (VI'), the resin (a-1) of this invention has at least 2 carboxyl groups It can be done by having a dog.

As an embodiment in which * as a bond in the formulas (VIII) and (IX) binds to * as a bond in the formula (VII), an embodiment in which two bonds in the formula (VII) are bonded together, and one An aspect of binding only to the binding hand is exemplified.

In the case of bonding together to two bonds in the formula (VII), the resin (a-1) of the present invention can have at least two carboxyl groups and can also have an increased branched structure. have.

Further, when bonding to only one bond in the above formula (VII), for example, the above formulas (A-2-3) and (A-2-5) having a partial structure represented by the above formula (VII) , (A-2-6), (A-2-9) can be bonded to the bond of the partial structure. 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 said formula (VIII) and (IX) may couple|bond with the 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 in the synthesis process, it becomes a structure bonded to a hydrogen atom because there is

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), ( It is preferable to combine with * which is a bond in A-2-6) or (A-2-9).

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 the partial structure represented by the formula (IV) or (V) When the content ratio of is 100 parts by mass, it is preferably 0.5 parts by mass or more, more preferably 1 parts by mass or more, more preferably 6 parts by mass or less, more preferably 5 parts by mass or less, and 4 parts by mass or less. more preferably. When it exists in the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness or chemical-resistance, to become favorable.

[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, and 150 mg-KOH/g or more. g or less is more preferable. When it exists in the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness or chemical-resistance, to express favorably.

Moreover, it is preferable that it is 1,500 or more, and, as for the weight average molecular weight of resin (a-1), it is more preferable that it is 2,000 or more, It is still more preferable that it is 3,000 or more, It is still more preferable that it is 4,000 or more, It is especially preferable that it is 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 exists in the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness or chemical-resistance, to express favorably.

[Synthesis of Resin (a-1)]

Resin (a-1) is at least

(A-1) an epoxy group-containing compound represented by the following formula (X);

(A-2) Unsaturated carboxylic acid or unsaturated carboxylic acid ester

It is preferable that it is resin obtained by making it react.

Moreover, it is obtained by making resin obtained by reaction of said (A-1) and (A-2) further react with (A-3) polybasic acid anhydride from a viewpoint of adhesiveness with a board|substrate, or adjustment of the solubility at the time of alkali development It is more preferable that it is resin.

[Formula 45]

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, and 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 1-5, l is an integer of 0-13, and m is an integer of 0-5.

In order to synthesize|combine resin (a-1), for example, first, (A-1) the epoxy group-containing compound represented by said Formula (X), and (A-2) unsaturated carboxylic acid or unsaturated carboxylic acid ester are reacted, , a reaction product (hereinafter referred to as "epoxy acrylate resin") is obtained.

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

Next, the said epoxy acrylate resin and (A-3) polybasic acid anhydride are made to react, and resin is obtained. At this time, the partial structure represented by said formula (VI), (VI'), (VII) can be obtained from (A-3) polybasic acid anhydride.

[(A-1): Epoxy group-containing compound]

^{R 1} to R ⁴ , R ⁵ , R ¹¹ , and k, 1, m in the formula (X) have the same meaning as in the formulas (I) to (IV), and in the formulas (I) to (V) It is preferable to exemplify.

Specific examples of the epoxy group-containing compound represented by the formula (X) correspond to the above (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 mentioned. However, as long as it is an epoxy-group containing compound which satisfy|fills said Formula (X), it is not limited to these, It can apply to this invention. In addition, the numerical value described in the cycloalkylidene group in the following formula represents the carbon number of the cycloalkylidene group.

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

[Formula 50]

[Formula 51]

[Formula 52]

[Formula 53]

As an epoxy group-containing compound represented by said formula (X), in said (A-1-9') - (A-1-12'), (A-1-29') - (A-1-40') Any one selected is preferable, any one selected from (A-1-9') to (A-1-12') is more preferable, (A-1-9') to (A-1-11') Any one selected from is more preferable, and (A-1-9') is particularly preferable.

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

In the present invention, the epoxy group-containing compound represented by the formula (X) may be used individually by 1 type, or may use 2 or more types together.

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

[Formula 54]

In the formula (XI), R ¹ to R ⁴ , R ¹¹ , and m each independently have the same meaning as in the formula (X).

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) tends to be expressed favorably. and the like, and the epoxy group-containing compound of the formula (XI) is easy to handle and tends to be easy to manufacture.

In addition, as a method for synthesizing the compounds of the formulas (X) and (XI), a known method can be used, for example, the method described in JP 2013-253153 A can be used.

[(A-2): Unsaturated carboxylic acid or unsaturated carboxylic acid ester]

As an unsaturated carboxylic acid used for the synthesis reaction of resin (a-1) of this invention, the unsaturated carboxylic acid which has an ethylenically unsaturated group is mentioned, for example. Specific examples include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group Monocarboxylic acids such as substituted (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid , 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl Adipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acrylo Iloxybutyl succinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth)acryl (meth)acryloyloxyalkyl esters of dibasic acids such as royloxybutylmaleic acid; ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to (meth)acrylic acid Monomers to which lactones, such as these, were added; (meth)acrylic acid dimer, etc. are mentioned.

Moreover, for example, acrylic acid adduct of pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylol propane diacrylate, glycidyl methacrylate, glycidyl methacrylic The compound which added acid anhydrides, such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, to a hydroxyl-containing unsaturated compound like the methacrylic acid adduct of a rate, is also mentioned.

Particularly preferred is (meth)acrylic acid. These may be used individually by 1 type, and may mix and use 2 or more types.

An unsaturated carboxylic acid ester can be used for the synthesis reaction of resin (a-1) instead of an unsaturated carboxylic acid. For example, α,β-unsaturated monocarboxylic acid ester may be used. Specific examples thereof include acrylic acid-2-succiinoyloxyethyl, acrylic acid-2-maleinoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid -2-succiinoyloxyethyl, methacrylic acid-2-maleinoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthaloyloxyethyl, crotonic acid-2 - succiinoyloxyethyl, etc. are mentioned. Preferably, it is acrylic acid-2-maleinoyloxyethyl or acrylic acid-2-phthaloyloxyethyl, and acrylic acid-2-maleinoyloxyethyl is particularly preferable.

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

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

The ratio of adding the unsaturated carboxylic acid to the epoxy group of the epoxy group-containing compound is usually preferably from 90 to 100 mol%, more preferably from 95 to 100 mol%, particularly preferably from 100 mol% with respect to the epoxy group. . Since the residual epoxy group adversely affects storage stability, the unsaturated carboxylic acid is preferably reacted in a ratio of 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents, with respect to 1 equivalent of the epoxy group of the epoxy group-containing compound.

By the addition reaction of the epoxy group-containing compound represented by the said formula (X) of (A-1), and the unsaturated carboxylic acid or unsaturated carboxylic acid ester of (A-2) by the above, the part of the said formula (IV) An epoxy acrylate resin having a structure (hereinafter, sometimes referred to as "(A-5) epoxy acrylate resin") is obtained.

By addition reaction of an epoxy group-containing compound and an unsaturated carboxylic acid, an ethylenically unsaturated group can be introduce|transduced into an epoxy-group containing compound, and ultraviolet-ray reactivity, ie, photocurability, can be provided by it.

In addition, with respect to the hydroxyl group generated by the addition reaction of the epoxy group-containing compound and the unsaturated carboxylic acid, further addition reaction of (A-3) polybasic acid anhydride described later to introduce a carboxyl group or to increase the molecular weight as described later I think it can be done.

[(A-3): polybasic acid anhydride]

As polybasic acid anhydride used for the synthesis reaction of resin (a-1), dibasic acid anhydride, tribasic acid anhydride, tetrabasic acid anhydride, etc. can be used preferably.

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

As the tetrabasic acid anhydride (tetracarboxylic dianhydride), a known one can be used, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether. Tetracarboxylic dianhydride, such as tetracarboxylic dianhydride, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a tetrabasic acid anhydride, especially among the said exemplary compounds, biphenyltetracarboxylic dianhydride is preferable. When a tetrabasic acid anhydride is used as the polybasic acid anhydride, when the resin of the present invention is used as a resin in the photosensitive resin composition, an increase in molecular weight due to a crosslinking reaction, an accompanying improvement in adhesion to a substrate, adjustment of solubility, sensitivity Or there exists a tendency for effects, such as an improvement of alkali resistance, to be acquired.

Examples of the dibasic acid anhydride (dicarboxylic anhydride) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and phthalic anhydride. Chlorendic acid, methyltetrahydrophthalic anhydride, etc. are mentioned. Especially, 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 a polybasic acid anhydride, when the resin of this invention is used as resin in the photosensitive resin composition, it exists in the tendency for solubility control to become easy and the adhesiveness to a board|substrate improves.

As tribasic acid anhydride (tricarboxylic acid anhydride), trimellitic anhydride, hexahydro trimellitic anhydride, etc. are mentioned, Especially trimellitic anhydride is preferable. These tribasic acid anhydrides may be used individually by 1 type, and may be used in combination of 2 or more type.

When tribasic acid anhydride is used as the polybasic acid anhydride, the amount of acid group introduced into the resin molecule can be increased, and when used as a resin in the photosensitive resin composition, it tends to be easy to balance sensitivity, adhesion, developability, etc. .

It is especially preferable to use a tetrabasic acid anhydride among polybasic acid anhydrides. When using a tetrabasic acid anhydride independently, the addition rate with respect to the hydroxyl group of (A-5) epoxy acrylate resin of a tetrabasic acid anhydride is 10-90 mol% normally, Preferably it is 20-85 mol%, more Preferably it is 30-80 mol%.

(A-5) Among the hydroxyl groups of epoxy acrylate resin, the part to which a tetrabasic acid anhydride does not addition-react may remain as a hydroxyl group. By making the addition rate of a tetrabasic acid anhydride (d) into the said range, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness and chemical-resistance, to become favorable.

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

When using tetrabasic acid anhydride and dibasic acid anhydride together, it is preferable that the molar ratio is dibasic acid anhydride:tetrabasic acid anhydride =70:30-1:99, and it is more preferable that it is 60:40-1:99 desirable. By making the ratio of tetrabasic acid anhydride more than the said lower limit, there exists a tendency that the fall of the film|membrane physical property of the coating film obtained can be suppressed, and by making the ratio of dibasic acid anhydride more than the said lower limit, to increase in the viscosity of the resin solution obtained It exists in the tendency which can suppress the handleability fall by this.

Moreover, when using a tetrabasic acid anhydride, a dibasic acid anhydride, and a tribasic acid anhydride together, from a viewpoint of hardening characteristics, such as board|substrate adhesiveness and chemical resistance by use of a tribasic acid anhydride, the usage-amount of tribasic acid anhydride is , (A-5) With respect to the hydroxyl group of an epoxy acrylate resin, it is 5-70 mol% normally, Preferably it is 10-40 mol%.

As polybasic acid anhydride, even when using 2 types of tetrabasic acid anhydride and dibasic acid anhydride, or when using 3 types of tetrabasic acid anhydride, dibasic acid anhydride, and tribasic acid anhydride, all polybasic acid anhydrides The addition rate of (A-5) is 10-90 mol% normally with respect to the hydroxyl group of epoxy acrylate resin, Preferably it is 20-85 mol%, More preferably, it is 30-80 mol%. (A-5) Among the hydroxyl groups of epoxy acrylate resin, the part to which polybasic acid anhydride does not addition-react may remain as a hydroxyl group. By making the addition rate of a polybasic acid anhydride more than the said lower limit, there exists a tendency for hardening characteristics, such as board|substrate adhesiveness and chemical-resistance, to become favorable.

[(A-4): polyhydric alcohols]

(A-5) When adding a polybasic acid anhydride to an epoxy acrylate resin, together with the polybasic acid anhydride, (A-4) polyhydric alcohol and/or polyhydric methylol which can be added to the polybasic acid anhydride (hereinafter "polyhydric alcohols") It is preferable to react using By making polyhydric alcohols react together, polyhydric alcohols are added to a polybasic acid anhydride, and there exists a tendency which an acid value can be increased or high molecular weight can be made.

From the polyhydric alcohols used for the synthesis reaction of the resin (a-1), the partial structures of the formulas (VIII) and (IX) are 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, but from the viewpoint of substrate adhesion and chemical resistance curing characteristics, and from the viewpoint of ease of handling Specifically, it is at least one polyhydric alcohol selected from the group consisting of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. desirable.

By using polyhydric alcohols, the molecular weight of resin (a-1) can be increased, a branch can be introduce|transduced in a molecule|numerator, and there exists a tendency which can balance molecular weight and a viscosity. Moreover, the introduction rate of an acidic radical into a molecule|numerator can be increased, and there exists a tendency for the hardening characteristic of board|substrate adhesiveness and chemical-resistance to become favorable. The usage-amount of polyhydric alcohol is about 0.5-6 mass % normally with respect to (A-5) epoxy acrylate resin from the viewpoint of the effect by use, and a handleability, Preferably it is about 1-4 mass %.

[Reaction of epoxy acrylate resin, polybasic acid anhydride and polyhydric alcohol]

After obtaining the epoxy acrylate resin (A-5) as described above, a known method can be used as a method of adding a polybasic acid anhydride to the epoxy acrylate resin or adding a polybasic acid anhydride and polyhydric alcohols.

The reaction temperature is usually 80 to 130°C, preferably 80 to 110°C, and reacts for 4 to 15 hours until a predetermined acid value, molecular weight, viscosity, etc. are reached. By setting it below the said upper limit, there exists a tendency which can suppress the rapid increase of molecular weight by polymerization of an unsaturated group, and when it is too low, reaction does not advance smoothly, and a polybasic acid anhydride may remain.

<Photosensitive resin composition>

Resin (a-1) is preferably used as resin of the photosensitive resin composition for forming the member for image display apparatuses, such as a color filter, a spacer, a color spacer, and a liquid crystal display or organic EL. In particular, it can be used suitably as resin for color filters.

It is preferable that a photoinitiator (b) is included in the photosensitive resin composition in addition to resin (a-1). Preferably, it further contains a photopolymerizable monomer (c), a colorant (d), and a dispersing agent (e), and if necessary, thiols, dispersing aids (pigment derivatives), adhesion improvers, coating properties improving agents, and development improving agents , ultraviolet absorber, antioxidant, surfactant, etc. are included, and each compounding component is normally used in the state melt|dissolved or disperse|distributed in a solvent.

The photosensitive resin composition of this invention contains resin (a-1) as resin (a), It is characterized by the above-mentioned. In particular, when the resin (a-1) has a partial structure represented by the formulas (VI) to (VII), the cured film obtained by applying and drying the photosensitive resin composition is exposed, followed by alkali development for the exposed portion and the non-exposed portion. It can function as so-called alkali-soluble resin whose solubility changes at the time of time.

When the photosensitive resin composition of the present invention contains the resin (a-1), it tends to be excellent in sensitivity, development adhesion, stability during development, substrate adhesion, and the like, as will be described later. Moreover, in addition to resin (a-1), other resin (a-2) may be included in the photosensitive resin composition of this invention.

The photosensitive resin composition of this invention contains resin (a-1) mentioned above at least, and this resin contains the partial structure represented by said Formula (I), and partial structure represented by (II) at least.

The photosensitive colored resin composition containing resin (a-1) exists in the tendency which is excellent in a sensitivity, image development adhesion, board|substrate adhesiveness, etc. The reason for this is that since the resin (a-1) has a bulky cycloalkylidene group in the partial structure of the formula (II), the resistance to alkali developer tends to increase, but the part of the formula (II) According to the bisphenol structure in the structure and the ethylenically unsaturated group structure in the formula (I), the steric hindered structure around the ethylenically unsaturated group is small, and it is considered that the crosslinking reaction tends to occur easily.

Moreover, it is thought that it is because there exists a tendency for the whole bulk to become still larger by crosslinking by ultraviolet irradiation. As a result, the line width is also increased, the resistance to alkali developer is also increased, and it is considered that the mechanical strength of the cured film tends to increase, and it is considered that the sensitivity, development adhesion, substrate adhesion, etc. tend to be improved.

[Other resin (a-2)]

Although it does not specifically limit as other resin (a-2) which can be used together with resin (a-1), After exposure of the cured film obtained by apply|coating and drying the photosensitive resin composition, the solubility with respect to alkali development of an exposed part and a non-exposed part It is preferable that it is alkali-soluble resin which changes, It is more preferable that it is alkali-soluble resin which has a carboxyl group, It is more preferable that it is alkali-soluble resin which has an ethylenically unsaturated bond and a carboxyl group.

Specifically, the epoxy (meth)acrylate resin and acrylic copolymer resin which have a carboxyl group are mentioned, for example. Preferred examples include those described as (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4), which will be more specifically described later. and these may use 1 type or 2 or more types may be used for them. Among the above, the epoxy (meth)acrylate resins (A1-1) and (A1-2) which have a carboxyl group are especially preferable.

In order to dissolve an unexposed part in an alkali developing solution at the time of manufacture of a color filter, resin which has acidic functional groups, such as a hydroxyl group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group, is applied. Among these, resin which has a carboxyl group is preferable. When resin has a carboxyl group, there exists a tendency for it to become easy to melt|dissolve in an alkali developing solution rather than a hydroxyl group.

Moreover, although a phosphoric acid group or a sulfonic acid group has higher acidity than a carboxylic acid group, it reacts easily with the basic initiator, a monomer or a dispersing agent, or other additives in the photosensitive resin composition, and storage stability tends to be bad.

As mentioned above, as other resin, the epoxy (meth)acrylate resin (A1-1) and (A1-2) which have a carboxyl group and an ethylenically unsaturated group are especially preferable. The reason for this is that the resin (A1-1) and (A1-2) also adds a large amount of unsaturated groups or carboxyl groups, contains a large amount of aromatic ring structure, or is sterically bulky, similarly to the resin (a-1). A large alicyclic structure can be included, and compatibility with resin (a-1) is good, and properties such as developability or pattern shape can be improved without reducing the effect of resin (a-1). because it is thought to be possible.

As epoxy (meth)acrylate resin which has a carboxyl group, the following epoxy (meth)acrylate resin (A1-1) and/or epoxy (meth)acrylate resin (A1-2) is mentioned, for example. .

<Epoxy (meth)acrylate resin (A1-1)>

Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or anhydride thereof.

<Epoxy (meth)acrylate resin (A1-2)>

Alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and reacting it with a polyhydric alcohol and a polybasic acid and/or anhydride thereof.

As the epoxy (meth)acrylate resin (A1-1) and the epoxy (meth)acrylate resin (A1-2), respectively, alkali-soluble resin (c1) and alkali-soluble resin (c1) described in JP 2013-195681 A ( c2) can be used.

<Acrylic copolymer resin (A2-1) (A2-2) (A2-3) (A2-4)>

As an acrylic copolymer resin, For example, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10-300922, Unexamined-Japanese-Patent No. 11-140144, Various high molecular compounds described in Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 2000-56118, Japanese Patent Application Laid-Open No. 2003-233179, and Japanese Patent Application Laid-Open No. 2007-270147 can be used. Preferably, resin etc. of the following (A2-1) - (A2-4) are mentioned, Especially, (A2-1) resin is especially preferable.

(A2-1): With respect to a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, a resin formed by adding an unsaturated monobasic acid to at least a part of the epoxy groups of the copolymer, or the addition reaction Resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by

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

(A2-3): Resin which added an epoxy group-containing unsaturated compound to the carboxyl group part of said (A2-2) resin (Hereinafter, it may call "(A2-3) resin".)

(A2-4): (meth)acrylic resin (Hereinafter, "(A2-4) resin" may be called.)

In addition, the resin of the above (A2-1) is also included in the concept of the epoxy (meth)acrylate resin.

Among these, as (A2-1) resin, [2-1-1] resin of Unexamined-Japanese-Patent No. 2009-052010 can be used. Similarly, as (A2-2) resin - (A2-4) resin, [2-1-2] resin - [2-1-4] resin of Unexamined-Japanese-Patent No. 2009-052010 can be used.

Among these, the photosensitive resin composition of this invention is other resin used together with resin (a-1), Comprising: (A1-1), (A1-2), (A2-1), (A2-2), (A2-) It is preferable to include at least any 1 type among 3) and (A2-4).

In particular, the other resin is an alkali-soluble resin containing an ethylenically unsaturated group, and contains at least any one of (A1-1), (A1-2), (A2-1), and (A2-3). more preferably.

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

As other resin of this invention, you may use alkali-soluble resin other than the above. 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. For example, alkali-soluble resin of Unexamined-Japanese-Patent No. 2007-271727, Unexamined-Japanese-Patent No. 2007-316620, Unexamined-Japanese-Patent No. 2007-334290, etc. are mentioned.

<Photoinitiator (b)>

The photosensitive resin composition of this invention contains a photoinitiator (b) with resin (a). A photoinitiator is a component which has a function which absorbs light directly, raise|generates a decomposition reaction or a hydrogen extraction reaction, and generate|occur|produces a polymerization active radical.

When the photosensitive resin composition of this invention contains a photoinitiator (b), crosslinkability becomes favorable by ultraviolet irradiation etc., and the effect by resin (a-1) becomes more favorable. In particular, when an oxime ester compound is contained as a photoinitiator (b), there exists a tendency for the effect to improve further.

As a photoinitiator, For example, the metallocene compound containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197 each; Unexamined-Japanese-Patent No. 2000- The hexaarylbiimidazole derivatives described in No. 56118; the halomethylated oxadiazole derivatives described in Japanese Patent Application Laid-Open No. 10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine radical activators and α-aminoalkylphenone derivatives, such as N-aryl-α-amino acid salts and N-aryl-α-amino acid esters; Japanese Patent Laid-Open Nos. 2000-80068 and 2006-36750, etc. The described oxime ester derivative etc. are mentioned.

Specifically, for example, as the titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6) -Pentafluorophen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6 -trifluorophen-1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophene- 1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophen-1-yl), di(methylcyclopentadienyl)titaniumbis(2,6 -difluorophen-1-yl) and dicyclopentadienyl titanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl], and the like.

In addition, as biimidazole derivatives, for example, 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'-methoxyphenyl)-4,5-diphenylimidazole dimer etc. are mentioned.

In addition, as halomethylated oxadiazole derivatives, for example, 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; and the like.

In addition, as halomethyl-s-triazine derivatives, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methyl Toxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2- (4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine etc. are mentioned.

In addition, as α-aminoalkylphenone derivatives, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate , 4-Dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethyl aminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone; and the like.

Especially as a photoinitiator, oxime derivatives (oxime type and ketooxime type compound) are effective from a point of sensitivity, and when alkali-soluble resin containing a phenolic hydroxyl group is used, it becomes disadvantageous from a point of sensitivity. Since there are cases, especially the oxime derivatives (oxime type and ketooxime type compound) excellent in such a sensitivity are useful. Among the oxime derivatives, oxime ester is particularly preferred from the viewpoint of sensitization under high chemical concentration.

Since 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 in its structure, it is highly sensitive to a small amount, and is stable to a thermal reaction, and a small amount It is possible to design a highly sensitive photosensitive resin composition.

Especially in the case of the oxime ester compound which has a carbazole ring, this structural characteristic is expressed favorably and it is more preferable. Currently, in the market, BM (black matrix) which is a thin film with high light-shielding degree is calculated|required, and the pigment concentration is also increasing gradually. In such a situation, it is especially effective.

The resin (a-1) contained in the photosensitive resin composition of the present invention has a structure in which the biphenyl structure and the greatly expanded alicyclic structure having 10 or more carbon atoms are greatly twisted at the bonding portion, and the biphenyl structure is Since it has a structure having an ethylenically unsaturated group therebetween, the crosslinked structure is twisted three-dimensionally and expanded by ultraviolet irradiation. Therefore, it is thought that there exists a tendency for a sensitivity to rise, a line|wire width to become thick, and alkali-resistant developing solution also to rise, and to also increase stability with respect to an alkali developing solution. When it combines with the photoinitiator of the oxime ester which shows high sensitivity especially even in a small amount, it is thought that these effects improve further.

As an oxime type compound, the compound containing the structural moiety represented by the following general formula (22) is mentioned, Preferably, the oxime ester type compound represented with the following general formula (23) is mentioned.

[Formula 55]

In the formula (22), R ²² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or an alkanoyl group having 3 to 8 carbon atoms. Cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxycarbonylalkanoyl group, C2-C10 aminoalkyl A carbonyl group, a C7-C20 arylloyl group, a C1-C20 hetero aryl group, a C2-C10 alkoxycarbonyl group, or a C7-20 aryloxycarbonyl group is represented.

[Formula 56]

In the 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, or heteroaryl having 1 to 20 carbon atoms. Alkyl group, C3-C20 alkoxycarbonylalkyl group, C8-C20 phenoxycarbonylalkyl group, C1-C20 heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, C1-C20 aminoalkyl group, C2 to 12 alkanoyl group, C3 to C25 alkenoyl group, C3 to C8 cycloalkanoyl group, C7 to C20 aryloyl group, C1 to C20 heteroaryloyl group, C2 to C10 alkoxy A carbonyl group, a C7-C20 aryloxycarbonyl group, or a C1-C10 cycloalkylalkyl group is represented. R ^21b represents an optional substituent including an aromatic ring or a heteroaromatic ring.

In addition, R ^21a may ^{form a ring together with R 21b,} and the linking group is an alkylene group having 1 to 10 carbon atoms which may each have a substituent, a polyethylene group (-(CH=CH) _r- ), and a polyethynylene group. (-(C≡C) _r- ) or a group formed by combining them (in addition, r is an integer of 0 to 3). R ^22a represents the same group ^{as R 22} in the formula (22).

Among them, 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 an alkanoyl group having 1 to 20 carbon atoms. A heteroaryl 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. can be heard

^{Moreover, as R 21a} in the said General formula (23), From a viewpoint of solubility with respect to a solvent, and a sensitivity, Preferably, a C1-C20 alkyl group which may be substituted, C1-C10 cycloalkyl which may be substituted is preferable. An alkyl group or an optionally substituted C6-C20 aryl group is mentioned. More preferably, a propyl group 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 can be heard

^{Moreover, as R 21b} in the said General formula (23), Preferably, the optionally substituted carbazole group, the optionally substituted thioxanthonyl group, and the optionally substituted phenyl sulfide group are mentioned. The ^{case containing a carbazole group as R 21b} is more preferable for the above reason. Moreover, the oxime ester initiator which has a carbazole group which has a nitro group is also effective.

Oxime ester initiator, as R ^21b are preferable for the reason described above to contain a carbazole group. Further, an optionally substituted aryl group having 6 to 25 carbon atoms, an optionally substituted arylcarbonyl group having 7 to 25 carbon atoms, an optionally substituted heteroaryl group having 5 to 25 carbon atoms, or heteroaryl having 6 to 25 carbon atoms which may be substituted A carbazole group having at least one group selected from the group consisting of a carbonyl group and a nitro group 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 toluyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. Moreover, it is preferable that these groups are couple|bonded at the 3-position of a carbazole group. Similarly, the C atom in the formula (23) is preferably bonded to the 6-position of the carbazole group.

Moreover, the H atom couple|bonded with the N atom of a carbazole group may be substituted by arbitrary substituents, and a C1-C20 alkyl group is preferable from a solubility viewpoint with respect to a solvent as an arbitrary substituent, and it is C1. A -10 alkyl group is more preferable, and a C1-C5 alkyl group is still more preferable.

An oxime ester is useful as an initiator used in the present invention. An oxime ester initiator having a carbazole group is preferred. ^{An oxime ester initiator in which R 21a} in the general formula (23) has a linear alkyl moiety and a cycloalkyl moiety or an oxime ester initiator having a nitro group in the carbazole group is more preferably used. As such a commercially available initiator, OXE-02 by the BASF company, TR-PBG-304 and TR-PBG-314 by the Sangju strong electronics company are mentioned, for example.

Although the compound which is specifically illustrated below is mentioned as a preferable oxime ester type compound in this invention, It is not limited to these compounds at all.

[Formula 57]

[Formula 58]

[Formula 59]

[Formula 60]

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

As a ketoxime type compound, the compound containing the structural moiety represented by the following general formula (24) is mentioned, Preferably, the oxime ester type compound represented by the following general formula (25) is mentioned.

[Formula 65]

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

[Formula 66]

In the general formula (25), R ^23a is each optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, or a heteroarylalkyl group having 3 to 20 carbon atoms. An alkoxycarbonylalkyl group, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, 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, a heteroaryloyl group having 1 to 20 carbon atoms, 2 to 10 carbon atoms an alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

R ^23b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring. In addition, R ^23a may ^{form a ring together with R 23b,} and the coupling group is a C1-C10 alkylene group which may each have a substituent, a polyethylene group (-(CH=CH) _r- ), a polyethynylene group. (-(C≡C) _r- ) or a group formed by combining them (in addition, r is an integer of 0 to 3).

R ^24a is each optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, benzoyl group having 7 to 20 carbon atoms, or benzoyl group having 3 to 20 carbon atoms. A heteroaryl group, a C2-C10 alkoxycarbonyl group, a C7-20 aryloxycarbonyl group, a C2-C20 heteroaryl group, or a C2-C20 alkylamino carbonyl group is represented.

^{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 a heteroaryl alkanoyl group having 1 to 20 carbon atoms. A 3-8 cycloalkanoyl group and a C7-20 arylloyl group are mentioned.

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

^{Moreover, as R 23b} in the said General formula (25), Preferably, the optionally substituted carbazolyl group and the optionally substituted phenyl sulfide group are mentioned. The ^{case containing a carbazolyl group as R 23b} is more preferable for the above reason.

Although the compounds which are specifically illustrated below are mentioned as a preferable ketooxime ester type compound in this invention, It is not limited to these compounds at all.

[Formula 67]

[Formula 68]

[Formula 69]

[Formula 70]

These oximes and ketooxime ester compounds are known compounds per se, and are, for example, a kind of a series of compounds described in JP-A-2000-80068 or JP-A-2006-36750. 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- Anthraquinone derivatives such as t-butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4 -benzophenone derivatives such as bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α -Hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-( Acetophenone derivatives such as 4'-methylthiophenyl)-2-morpholino-1-propanone and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; thioxanthone, 2-ethylthio thioxanthone derivatives such as xanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; p- Benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; 9,10- Phenazine derivatives, such as dimethylbenzphenazine; Anthrone derivatives, such as a benzanthrone, etc. are mentioned. Among these photoinitiators, the oxime ester derivatives are especially preferable for the above-mentioned reason.

The photosensitive resin composition of this invention can use together additives, such as the following accelerators and a sensitizing dye, with a photoinitiator as needed.

<Accelerator>

As the accelerator, for example, a mercapto compound or an aliphatic polyfunctional mercapto compound having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, and 2-mercaptobenzoimidazole is used. do. An accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

<sensitizing dye>

A photoinitiator can be made to use together the sensitizing dye according to the wavelength of an image exposure light source for the purpose of raising a sensitivity sensitivity as needed. As these sensitizing dyes, the xanthene dye described in Japanese Patent Application Laid-Open Nos. 4-221958 and 4-219756, and heterocyclic rings described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335 Coumarin dye, 3-ketocoumarin compound described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, pyromethene dye described in Japanese Patent Application Laid-Open No. 6-19240, and others, Japanese Patent Application Laid-Open No. No. 47-2528, No. 54-155292, No. 45-37377, No. 48-84183, No. 52-112681, No. 58-15503, No. 60-88005, No. 59 -56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Japanese Unexamined Patent Publication No. Hei 5-107761, Japanese Unexamined Patent Publication No. 5-210240, Japanese Unexamined Patent Publication No. Hei 4 - The pigment|dye etc. which have dialkylamino benzene frame|skeleton of 288818 are mentioned.

Among these sensitizing dyes, an amino group-containing sensitizing dye is preferable, and more preferable is a compound 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'-diaminobenzo Benzophenone compounds such as phenone, 3,3'-diaminobenzophenone, and 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-diethylaminophenyl)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 and (p-diethylaminophenyl)pyrimidine, etc. of p-dialkylaminophenyl group-containing compounds. Among these, 4,4'-dialkylaminobenzophenone is the most preferable. 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. As a photopolymerizable monomer used for this invention, the compound (Hereinafter, it may call an "ethylenic monomer") which has at least 1 ethylenically unsaturated group in a molecule|numerator is mentioned. Specific examples include (meth)acrylic acid, (meth)acrylic acid alkylester, acrylonitrile, styrene, and monoester of carboxylic acid having one ethylenically unsaturated bond and polyhydric or monohydric alcohol. have.

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more of ethylenically unsaturated groups in 1 molecule. As such a polyfunctional ethylenic monomer, For example, Ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; Ester of an aromatic polyhydroxy compound and unsaturated carboxylic acid; An aliphatic polyhydroxy compound, an aromatic polyhydroxy compound Ester obtained by esterification of polyhydric hydroxy compounds, such as these, and unsaturated carboxylic acid and polybasic carboxylic acid, etc. are mentioned.

As ester of the said aliphatic polyhydroxy compound and unsaturated carboxylic acid, For example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylolethane triacrylate, pentaerythritol Aliphatic polyhydrides such as diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acrylic acid esters of hydroxy compounds, methacrylic acid esters in which acrylates of these exemplary compounds are replaced with methacrylates, itaconic acid esters similarly replaced with itaconate, crotonic acid esters or maleate replaced with crotonate Maleic acid ester etc. are mentioned.

As ester of an aromatic polyhydroxy compound and unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, for example Acrylic acid ester of aromatic polyhydroxy compounds, such as methacrylic acid ester, etc. are mentioned.

The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyhydric hydroxy compound is not necessarily a single substance, but representative specific examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, and a condensate of maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, and 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)acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth)acrylic acid ester are reacted with a urethane obtained (meth)acrylates; Epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate and a vinyl group-containing compound such as divinyl phthalate. These may be used individually by 1 type, and may use 2 or more types together.

<Color material (d)>

When the photosensitive resin composition of this invention is used for formation of the pixel of a color filter, formation of a black matrix, etc., it is preferable to contain a color material (d). By containing a color material (d), the light-shielding property or color characteristic of a color filter can be provided. A color material means coloring the photosensitive resin composition of this invention. As the color material, a dye pigment can be used, but from the viewpoint of heat resistance, light resistance, and the like, and from the viewpoint of light blocking properties or color characteristics, a pigment is preferable, and it contains a dispersing agent described later in order to disperse the pigment well. desirable.

As a pigment, the pigment 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, is mentioned, for example. In addition, as the structure, for example, organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based organic pigments, as well as various inorganic pigments, etc. Available.

Below, the specific example of the pigment which can be used for this invention is shown by a pigment number. In addition, "C. Terms such as "I. Pigment Red 2" mean a color index (C.I.).

As a red pigment, it is CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, for example. , 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, 179, 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.

Among these, preferably CI pigment red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably CI pigment red 177, 209, 224 and 254 can be heard

As a blue pigment, it is CI pigment blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, for example. , 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 are mentioned.

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

As a green pigment, For example, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Among these, Preferably, C.I. Pigment Green 7, 36 and 58 are mentioned.

As a yellow pigment, it is CI pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, for example. , 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, 173, 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. Among these, Preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185, More preferably, CI Pigment Yellow 83, 138, 139, 150 and 180 are mentioned. have.

As an orange pigment, it is CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, for example. , 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among these, Preferably, C.I. pigment orange 38 and 71 are mentioned.

As a purple pigment, it is CI pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, for example. , 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. Among these, preferably C. I. Pigment Violet 19 and 23, More preferably, C. I. Pigment Violet 23 is mentioned.

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

As a colorant that can be mixed to prepare a black colorant, for example, Victoria Pure Blue (42595), Oramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70:100 (50240), Erioglaucine X (42080), No. 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Simultaneous First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simulative First Red 4015 (12355), Lionol Red 7B4401 (15850) ), FirstGen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lyonogen Red GD (Pigment Red 168) and Lionol Green 2YS (Pigment) Figure 36) etc. are mentioned [In addition, the number in said () means the color index (CI)].

In addition, when expressed by CI number for another mixed useable pigment, for example, CI yellow pigment 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154 and 166, CI orange pigment 36, 43, 51, 55, 59 and 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228 and 240, CI violet pigment 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15:1, 15:4, 22, 60 and 64, CI green pigment 7 and CI brown pigments 23, 25 and 26; and the like.

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

In these color materials (d), when the photosensitive resin composition uses a black color material, carbon black is preferable from a light-shielding rate and a viewpoint of an image characteristic. As carbon black, the following carbon black is mentioned, for example.

Made by 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, #1 #12400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B

Manufactured by Degusa: Printex (registered trademark, hereinafter the same.) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160 , Color Black S170 Manufactured by Cabot Corporation: Monarch (registered trademark, hereinafter the same.) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, hereinafter the same.) 99 , REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark. hereinafter referred to as Golli.) XC72R and ELFTEX (registered trademark)-8 Colombia

Product made by Colombian Carbon: RAVEN (registered trademark, hereinafter the same.) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN78010, RAVEN850, RAVEN1060U, RAVEN1020, RAVEN1000, RAVEN1020, RAVEN890H, RAVEN1020 , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750 and RAVEN7000

As another black pigment, titanium black, aniline black, and iron oxide type black pigment, and red, green, and blue tricolor organic pigments can be mixed and used as a black pigment, for example.

As carbon black, you may use what was coat|covered with resin. When carbon black coated with resin is used, there is an effect of improving the adhesion to the glass substrate and the volume resistance value. As carbon black coated with resin, the carbon black etc. which are described in Unexamined-Japanese-Patent No. 09-71733, etc. are preferable, for example.

As carbon black to be coated, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black is usually Na, Ca, K, Mg mixed from raw material oil or combustion oil (or gas), reaction stop water or granulated water, or furnace material of a reactor at the time of manufacture. , Al or Fe, etc., are contained in percent order. Of these, Na or Ca is generally contained in each of several hundred ppm or more, but when there are many of them, they may penetrate into the transparent electrode (ITO) or other electrodes and cause an electrical short circuit.

As a method of reducing the content of the ash content containing Na or Ca, as raw material oil or fuel oil (or gas) when producing carbon black, and reaction stop water, those with as little these content as possible are carefully selected and the structure It is possible by minimizing the amount of alkali material added to adjust the As another method, there may be mentioned a method in which the carbon black produced from the furnace is washed with water or hydrochloric acid to dissolve and remove Na or Ca.

The surface of these black pigments is acidic in many cases, Therefore, in order to disperse|distribute a black pigment favorably, it is preferable that the dispersing agent to combine is a high molecular compound which has a basic functional group.

Moreover, as a pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengala, chromium oxide, etc. can also be used. These various pigments can also use multiple types together. For example, for adjustment of chromaticity, a green pigment and a yellow pigment can be used together, or a blue pigment and a purple pigment can be used together.

<Pigment particle size>

In the photosensitive resin composition of the present invention, the average primary particle diameter of the pigment that can be used as the color material (d) is as long as it can develop a desired color when it is used as a colored layer of a color filter, and is not particularly limited. Although it changes with the kind of pigment, it is preferable to exist in the range of 10-100 nm, and it is more preferable to exist in the range which is 10-70 nm.

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

Moreover, 100 nm or less is preferable, as for the pigment average primary particle diameter in case a pigment is carbon black, 60 nm or less is more preferable, and its 50 nm or less is still more preferable. Moreover, as for the pigment average primary particle diameter in case a pigment is carbon black, 20 nm or more is preferable. When a pigment becomes large too much, scattering will become large and color characteristics, such as light-shielding property or contrast, will fall. Moreover, when a pigment particle diameter is too small, much quantity of a dispersing agent will be required, and dispersibility will fall.

In addition, the average primary particle diameter of the said pigment can be calculated|required by the method of directly measuring the size of a primary particle from an electron micrograph. Specifically, the minor axis 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 a rectangular parallelepiped of the obtained particle size, the volume average particle size is obtained, and this is taken as the average primary particle size. In addition, the electron microscope can obtain the same result even if it uses either 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, in addition, it may use dye together in the range which does not affect the effect of this invention. The dyes that can be used in combination include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like. have.

Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5 and CI Mordant Black 7 etc. are mentioned.

Examples of the anthraquinone dye include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue. 56 and CI Disperse Blue 60; and the like.

In addition, examples of the phthalocyanine dye include C. I. Pad Blue 5 and the like, and examples of the quinone imine dye include C. I. Basic Blue 3 and C. I. Basic Blue 9.

As a quinoline type dye, CI solvent yellow 33, CI acid yellow 3, CI dispers yellow 64 etc. are a nitro type dye, For example, CI acid yellow 1, CI acid orange 3, CI Disperse Yellow 42 etc. are mentioned.

<Dispersant (e)>

In the photosensitive resin composition of the present invention, in the case of using the color material (d), it is important to finely disperse the color material and to stabilize the dispersed state, since it is important to ensure quality stability, it is preferable to include a dispersing agent. do.

As the dispersant, a polymeric dispersing agent having a functional group is preferable, and further, in terms 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 dispersing agent having a functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyrimidine or pyrazine is preferable.

Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; Dispersibility can be made favorable by using the polymer dispersing agent which has these basic functional groups, and especially when a black pigment is used as a color material, there exists a tendency which high light-shielding property can be achieved.

Further, as the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, polyoxyethylene di and ester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersing agent include EFKA (registered trademark, manufactured by EFKA), Disperbyk (registered trademark, manufactured by Vick Chemie), and Disparon (registered trademark, kus) as trade names. Moto Chemical Co., Ltd.), SOLSPERSE (registered trademark, Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow, Florene (Kyoeisha Chemical Co., Ltd.) and Ajiper (registered trademark, manufactured by Ajinomoto Finetech) .) and the like. These polymeric dispersants may be used individually by 1 type, or may use 2 or more types together.

Among these, it is especially preferable that the dispersing agent (e) contains the urethane-type polymer dispersing agent and/or the acrylic polymer dispersing agent which have a basic functional group from the point of adhesiveness and linearity. In particular, a urethane-based polymer dispersant is preferable from the viewpoint of adhesiveness. Moreover, the polymer dispersing agent which has a basic functional group and has a polyester and/or polyether bond is preferable from the point of dispersibility and storage property.

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 a weight average molecular weight is 30,000 or less, even when a pigment density|concentration is high, there exists a tendency for alkali developability to become favorable.

Examples of the urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167 and 182 series (all of which are urethane-based), and Disperbyk 2000 and 2001 (all are acrylic-based) (all of which are manufactured by Vick Chemie). It is a urethane-type polymer dispersing agent which has the said basic functional group and has a polyester and/or polyether bond, and Disperbyk167, 182 etc. are mentioned as a especially preferable thing with a weight average molecular weight of 30,000 or less.

(Urethane-based polymer dispersant)

If a chemical structure preferable as a urethane-based polymer dispersant is specifically illustrated, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and active hydrogen and tertiary in the same molecule and dispersion resins having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an amino group, and the like.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5- Aromatic diisocyanates, such as diisocyanate and tolidine diisocyanate; Alicyclic diisocyanates such as 4,4'-methylenebis(cyclohexylisocyanate) and ω,ω'-diisocyanatedimethylcyclohexane, xylylenediisocyanate, and α,α,α',α'-tetramethylxylyl Aliphatic diisocyanate having an aromatic ring such as rendiisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylenetri and triisocyanates such as isocyanate, bicycloheptane triisocyanate, tris(isocyanatephenylmethane) and tris(isocyanatephenyl)thiophosphate, trimers thereof, water adducts, and polyol adducts thereof.

As the polyisocyanate, preferred is a trimer of organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the polyisocyanate is partially formed by using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc. After performing trimerization and stopping trimerization by addition of a catalyst poison, solvent extraction and thin film distillation remove unreacted polyisocyanate, The method of obtaining the target isocyanurate group containing polyisocyanate is mentioned can

As a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule, for example, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, one terminal hydroxyl group of these compounds has carbon atoms What was alkoxylated with the alkyl group of 1-25, and a mixture of these 2 or more types are mentioned.

As polyether glycol, polyether diol and polyether ester diol, and these 2 or more types of mixture are mentioned, for example. Examples of the polyetherdiol include those obtained by copolymerizing alkylene oxide alone or by copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol. and mixtures of two or more thereof.

As the polyether ester diol, one obtained by reacting a mixture with an ether group-containing diol or other glycol with dicarboxylic acid or anhydride thereof, or reacting an alkylene oxide with polyester glycol, for example, poly (poly oxytetramethylene) adipate and the like.

The most preferable 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.

As the polyester glycol, for example, dicarboxylic acids (eg, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid and phthalic acid, etc.) or anhydrides thereof and glycols (eg, , Ethylene glycol, diethylene glycol, triethylene 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-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3 -aliphatic glycols such as hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, bishydes those obtained by polycondensing alicyclic glycols such as hydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and N-alkyl dialkanolamines such as N-methyldiethanolamine) . Specifically, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene/propylene adipate etc. are mentioned, for example.

Moreover, for example, polylactonediol or polylactone monool obtained by using the said diol or a C1-C25 monohydric alcohol as an initiator is mentioned. Specifically, for example, polycaprolactone glycol and polymethyl valerolactone, and mixtures of two or more thereof are mentioned. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of polycarbonate glycol include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate. As polyolefin glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. are mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together.

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000 normally, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom, or a sulfur atom includes, for example, a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group, and among them, an amino group, particularly a primary A hydrogen atom of the 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-dipropylethylene Diamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butane Diamine, N,N-dibutyl-1,4-butanediamine, etc. are mentioned.

Moreover, as the nitrogen-containing heterocyclic ring in case a tertiary amino group has a nitrogen-containing heterocyclic structure, for example, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, and inda N-containing hetero 5-membered rings such as azole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine and nitrogen-containing hetero 6-membered rings such as a ring, a quinoline ring, an acridine ring and an isoquinoline ring. Preferred among these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

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

Further, as the compound having a triazole ring and an amino group, for example, 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- and 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 is preferred. These may be used individually by 1 type, and may use 2 or more types together.

A preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 parts by mass of a compound 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, preferably Preferably it is 20-190 mass parts, More preferably, it is 30-180 mass parts, 0.2-25 mass parts of compounds which have active hydrogen and a tertiary amino group in the same molecule, Preferably it is 0.3-24 mass parts.

The production of the urethane-based polymer dispersant is carried out according to a known method for producing a polyurethane resin. As a solvent at the time of manufacture, usually, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, Esters, such as ethyl acetate, butyl acetate, and cellosolve acetate , hydrocarbons such as benzene, toluene, xylene, and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol, and tertiary butanol, chlorides such as methylene chloride and chloroform, tetrahydrofuran, diethyl ether, etc. Aprotic polar solvents, such as ethers, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. are used. These may be used individually by 1 type, and may use 2 or more types together.

In the above preparation, a urethanation reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltindilaurate, dioctyltindilaurate, dibutyltindioctoate, and stanasoctoate; iron-based compounds such as iron acetylacetonate and ferric chloride; 1 type, or 2 or more types, such as tertiary amine types, such as ethylamine and triethylenediamine, are mentioned.

<Method for measuring amine titer>

The tertiary amine titer of a dispersing agent such as a block copolymer is expressed by the amount of the base per 1 g of solid content excluding the solvent in the dispersant sample and the mass of the equivalent KOH, and can be measured by the following method. In a 100 ml beaker, 0.5 to 1.5 g of the dispersant sample is precisely weighed and dissolved with 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this _{solution is neutralized and titrated with a 0.1 mol/L HClO 4} (perchloric acid) acetic acid solution. Using the inflection point of the titration pH curve as the titration end point, the amine number is calculated by the following formula.

Amine number [mgKOH/g] = (561 × V) / (W × S)

[However, W: the dispersant sample balance [g], V: the titration amount [ml] at the titration end point, S: the solid content concentration [mass %] of the dispersant sample.]

The introduction amount of the compound having active hydrogen and a 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 expressed by the number of mg of KOH by titration by neutralizing a basic amino group with an acid and corresponding to the acid value. When the amine value is lower than the above range, the dispersibility tends to decrease, and when the amine value exceeds the above range, developability tends to decrease.

In addition, when an isocyanate group remains in the polymer dispersing agent due to the above reaction, it is preferable to break the isocyanate group with an alcohol or an amino compound, since the stability of the product over 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, and more preferably 3,000 to 50,000. In particular, 30,000 or less is preferable. When this molecular weight is less than 1,000, dispersibility and dispersion stability are inferior, and when this molecular weight exceeds 200,000, solubility falls and dispersibility tends to be inferior and control of reaction tends to become difficult. When the molecular weight is 30,000 or less, especially when the pigment concentration is high, alkali developability tends to be good. Disperbyk 167, 182 (Bick Chemie), etc. are mentioned as an example of such a especially preferable commercially available urethane dispersing agent.

(Acrylic polymer dispersant)

Examples of the acrylic polymer dispersant include a random polymer of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the aforementioned functional group as a functional group contained in the polymer dispersing agent) and an unsaturated group-containing monomer having no functional group, a graft copolymer, Preference is given to using block copolymers. These copolymers can be prepared by a known method.

As an unsaturated group containing monomer which has a functional group, For example, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acrylo Unsaturated monomers having a carboxyl group such as yloxyethylhexahydrophthalic acid and acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternary products thereof, quaternary ammonium and unsaturated monomers having a base. These may be used individually by 1 type, and may use 2 or more types together.

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- N-substituted maleimides such as vinylpyrrolidone, styrene and derivatives thereof, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl macromonomers such as (meth)acrylate macromonomer, polystyrene macromonomer, poly2-hydroxyethyl(meth)acrylate macromonomer, polyethyleneglycol macromonomer, polypropyleneglycol macromonomer, and polycaprolactone macromonomer have. These may be used individually by 1 type, and may use 2 or more types together.

(Acrylic block copolymer)

As for the photosensitive resin composition of this invention, for the improvement of the dispersibility of a coloring agent, and the improvement of dispersion stability, the acrylic block copolymer containing a nitrogen atom as a dispersing agent is used. In the acrylic block copolymer containing such nitrogen atoms, nitrogen atoms contained therein have affinity for the colorant surface, and portions other than nitrogen atoms increase affinity for the medium, thereby contributing to the improvement of overall dispersion stability. It is presumed to do The performance of the dispersant is its adsorption behavior on its solid surface. Although the detailed mechanism is not clear why the block copolymer is excellent in the adsorption|suction behavior, the following is guessed.

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

On the other hand, in a resin with a controlled molecular arrangement, 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, a portion suitable for adsorption can be disposed in the adsorption portion of the colorant and dispersant, and a portion suitable therefor can be disposed in a portion requiring solvent affinity. In particular, it is presumed that the dispersion of the color material containing the colorant having a small crystallite size affects the good dispersibility of this molecular arrangement.

The acrylic block copolymer containing a nitrogen atom is preferable at the point which can disperse|distribute the coloring agent used for this invention very efficiently. Although the reason is not clear, it is presumed to be because there are few structures which become an obstacle when a dispersing agent adsorb|sucks to a coloring agent because molecular arrangement is controlled.

The acrylic block copolymer is preferably an AB block copolymer and/or a BAB block copolymer comprising an A block having a quaternary ammonium base and/or an amino group in the side chain and a B block having no quaternary ammonium base and an amino group. do.

When the A block has a quaternary ammonium base, the quaternary ammonium base is preferably -N ⁺ R ⁵¹ R ⁵² R ⁵³ ·M ^- (provided that R ⁵¹ , R ⁵² and R ⁵³ are each independently, . represents a hydrogen atom, or cyclic or a hydrocarbon chain that may be substituted, or, R ^51, and are bonded to each other at least two of R ⁵² and R ^53, may form a cyclic structure M ^-., the counter anion). Although this quaternary ammonium base may be couple|bonded with the principal chain directly, it may couple|bond with the principal chain through a divalent coupling group.

In -N ⁺ R ⁵¹ R ⁵² R ⁵³ , ^{the cyclic structure formed by bonding at least two of R 51} , R ⁵² and R ⁵³ to each other is, for example, a 5- to 7-membered nitrogen-containing heterocyclic ring. A monocyclic ring or a condensed ring formed by condensing two of these is mentioned. It is preferable that this nitrogen-containing heterocyclic ring does not have aromaticity, and if it is a saturated ring, it is more preferable. Specifically, the following are mentioned, for example. These cyclic structures may further have a substituent.

[Formula 71]

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

Moreover, it is preferable to contain the partial structure especially represented by the following general formula (e1) as A block which has a quaternary ammonium base.

[Formula 72]

In the formula (e1), R ⁵¹ , R ⁵² , and R ⁵³ each independently represents 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 group of R 51} , R ⁵² , and R ⁵³ is each independently preferably an alkyl group having 1 to 10 carbon atoms or a substituent having an aromatic group having 6 to 20 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, a phenyl group, etc. are mentioned, for example. Among them, a methyl group, an ethyl group, a propyl group and a benzyl group are preferable.

In the general formula (e1), the divalent linking group X is, 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 -OR ⁵⁸ -: R ⁵⁷ and R ⁵⁸ are each independently an alkylene group). and, preferably -COO-R ⁵⁶ -.

^{Further, examples of M −} of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ and PF ₆ ⁻ .

Two or more types of partial structures containing the above specific quaternary ammonium bases may be contained in one A block. In that case, two or more types of quaternary ammonium base containing partial structures may be contained in the A block by any aspect of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in A block, The partial structure etc. derived from the (meth)acrylic acid ester type monomer mentioned later are mentioned as an example of the partial structure.

The content in the A block of the partial structure not containing such a quaternary ammonium base is preferably 0 to 50 mass%, more preferably 0 to 20 mass%, but this partial structure not containing a quaternary ammonium base is A It is most preferable not to be included in the block.

In addition, the A block of the acrylic block copolymer mentioned above may have the unreacted tertiary amino group which is not quaternized.

When the A block has an amino group, any of 1-3 may be sufficient as an amino group. The content ratio of the monomer having a 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. Although this amino group may be couple|bonded with the main chain directly, it may couple|bond with the main chain through a bivalent linking group.

Moreover, as said 1-3 tertiary amino group, Preferably -NR ⁶¹ R ⁶² (provided that R ⁶¹ and R ⁶² are each independently a cyclic or chain alkyl group which may have a substituent, even if it has a substituent It represents an aryl group or an aralkyl group which may have a substituent.), and preferable as a partial structure (repeating unit) containing this is a structure represented by the following general formula, for example. .

[Formula 73]

However, R ⁶¹ and R ⁶² have the same meanings ^{as R 61} and R ^{62 above, R 63} represents an alkylene group having 1 or more carbon atoms, and R ⁶⁴ represents a hydrogen atom or a methyl group. Among them, R ⁶¹ and R ⁶² are preferably a methyl group, R ⁶³ is preferably a methylene group or 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.

[Formula 74]

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

In addition, 2 or more types of partial structures containing the said amino group may be contained 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 either aspect of random copolymerization or block copolymerization.

Moreover, a partial structure which does not contain an amino group may be contained in A block. Examples of such a partial structure include a partial structure derived from a (meth)acrylic acid ester-based monomer. The content in the A block of the partial structure not containing such an amino group is preferably 0 to 50 mass%, more preferably 0 to 20 mass%, but such a partial structure not containing an amino group is not contained in the A block. Most preferred.

You may have either one of a quaternary ammonium base or an amino group in A block, and you may have both.

On the other hand, the B block constituting the acrylic block copolymer does not have the above-described quaternary ammonium base and amino group, and is not particularly limited as long as it is composed of a monomer that can be copolymerized with the above-mentioned monomer constituting the A block. B block is a solvent-philic site|part which does not have a nitrogen atom containing functional group used as a pigment adsorption group, and since it has affinity to a solvent, it has a function of stabilizing the pigment adsorbed to a dispersing agent in a solvent.

Examples of the B block include styrene-based monomers such as styrene and α-methylstyrene; (meth)methyl acrylate, ethyl (meth)acrylate propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate , (meth) octyl acrylate, (meth) acrylate 2-ethylhexyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethyl acrylate glycidyl and N,N -(meth)acrylic acid ester-based monomers such as dimethylaminoethyl (meth)acrylate; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N-methylolacrylamide, N,N -(meth)acrylamide-based monomers such as dimethylacrylamide and N,N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and crotonic acid glycidyl ether; N-methacryloyl The polymer structure which copolymerized comonomers, such as morpholine, is mentioned.

As B block, it is preferable to contain the partial structure derived from a (meth)acrylic acid ester type monomer especially represented by a following formula (e2).

[Formula 75]

In the formula (e2), R ⁶¹ represents a hydrogen atom or a methyl group. R ⁶² 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 types of partial structures derived from the said (meth)acrylic acid ester type monomer may be contained in one B block. Of course, the B block may further contain partial structures other than these. When the partial structure derived from 2 or more types of monomer exists in the B block which does not contain a quaternary ammonium base, each partial structure may be contained in the B block in either aspect of random copolymerization or block copolymerization.

When the B block contains a partial structure other than the partial structure derived from the (meth)acrylic acid ester-based monomer, the content in the B block of the partial structure other than the (meth)acrylic acid ester-based monomer is preferably 0 to 99. It is mass %, More preferably, it is 0-85 mass %.

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

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method. For example, the method of Unexamined-Japanese-Patent No. 2007-270147 is mentioned.

In addition, the amine titer of the acrylic block copolymer is usually about 1 to 300 mgKOH/g in terms of effective solid content, but the preferable range is different from the case where the A block has a quaternary ammonium base and the case where it does not. Incidentally, the amine titer is a value expressed by the number of mg of KOH corresponding to the molar equivalent of an acid required to neutralize the amino group in 1 g of the copolymer.

That is, in the AB block copolymer and BAB 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 0.1 to 10 mmol. It is preferable, and it may not be possible to have favorable heat resistance and dispersibility outside this range.

In addition, such a block copolymer usually contains an amino group generated during the production process, but the amine value is usually about 1 to 100 mgKOH/g, preferably 1 to 80 mgKOH/g, more preferably is 1 to 50 mgKOH/g.

Moreover, when the A block does not contain a quaternary ammonium base, the amine titer of the said copolymer is about 50-300 mgKOH/g normally, Preferably it is 50-200 mgKOH/g, More preferably, it is 80 mgKOH/g. More than 150 mgKOH/g or less, More preferably, it is 90-150 mgKOH/g.

Although the acid value of such an acrylic block copolymer varies depending on the presence or absence and type of an acidic group that is the source of the acid value, the lower one is generally preferable, and the acid value is usually 100 mgKOH/g or less, and preferably 50 mgKOH. /g or less, more preferably 40 mgKOH/g or less.

Moreover, the molecular weight of an acryl-type block copolymer is the range of 1000 or more and 100,000 or less normally as a weight average molecular weight (Mw) of polystyrene conversion measured by GPC. When the molecular weight of the acrylic block copolymer is too small, dispersion stability will fall, and when too large, there exists a tendency for developability and resolution to fall.

In the present invention, a commercially available acrylic block copolymer having the same structure as that 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 with respect to the pigment, preferably 5% by mass or more and 60% by mass or less, more preferably 5 They are mass % or more and 40 mass % or less. When the content of the acrylic block copolymer containing nitrogen atoms is too small, sufficient dispersibility may not be obtained. In some cases, it may not be possible to form a level difference.

In this invention, you may use together dispersing agents other than the acrylic block copolymer containing a nitrogen atom. It is preferable that the dispersing agent used together is a polymer dispersing agent, and it is preferable that it is a polymer from which a structure completely differs from a coloring agent.

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

(Graft copolymer containing nitrogen atom)

The graft copolymer containing a nitrogen atom preferably has a repeating unit containing a nitrogen atom in its main chain. Among them, it is preferable to have a repeating unit represented by the following general formula (i) and/or a repeating unit represented by the following general formula (ii).

[Formula 76]

In the general 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. , more preferably an ethylene group. A represents a hydrogen atom or any of the following general formulas (iii) to (v), but preferably is the following general formula (iii).

[Formula 77]

In the general formula (iii), W ¹ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among these, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene and hexylene is preferable. p represents the integer of 1-20, Preferably it is an integer of 5-10.

[Formula 78]

In the general formula (iv), G ¹ represents a divalent linking group, and among them, 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, are 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 and propylene is preferable.

G ² is a hydrogen atom or —CO-R ⁹² (R ⁹² is an alkyl group having 1 to 10 carbon atoms such as ethyl, propyl, butyl, pentyl, and hexyl, and among them, 2 to 5 carbon atoms such as ethyl, propyl, butyl and pentyl) of preferably an alkyl group). q represents the integer of 1-20, Preferably it is an integer of 5-10.

[Formula 79]

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, monohydric A C10-20 hydroxyalkyl group which has 1-2 hydroxyl groups, such as hydroxystearyl, is preferable.

The content rate of the repeating unit represented by general formula (i) or (ii) in the graft copolymer containing a nitrogen atom is preferably high, and is usually 50 mol% or more in total, Preferably it is 70 mol%. More than that.

Both the repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) may be co-existed, and the content ratio is not particularly limited, but preferably the repeating unit represented by the general formula (i) The one containing a lot of indigo plant is preferable.

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

Moreover, repeating units other than general formula (i) and general formula (ii) may be included in the graft copolymer, and an alkylene group, an alkyleneoxy group, etc. can be illustrated as another repeating unit, for example. The graft copolymer in the present invention preferably has the terminals -NH ₂ and -R ⁹¹ -NH ₂ (R ⁹¹ has the same meaning as in the general formulas (i) and (ii)).

Moreover, if it is a graft copolymer as mentioned above, the main chain may be linear or may be branched.

As a mass average molecular weight measured by GPC of this graft copolymer, 3,000 or more, especially 5,000 or more are preferable, and 100,000 or less, especially 50,000 or less are preferable. If the mass average molecular weight is less than 3,000, aggregation of the color material cannot be prevented, and viscosity or gelation may occur. don't

A well-known method can be employ|adopted for the synthesis|combining method of the said dispersing agent, For example, the method of Unexamined-Japanese-Patent No. 63-30057 can be used.

<thiols>

It is preferable that the photosensitive resin composition of this invention adds thiol for high sensitivity-ization and the improvement of the adhesiveness to a board|substrate. As the kind of thiols, for example, hexanedithiol, decanedithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylol Propane tristhioglycolate, butanediolbisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakistioglycolate, tris Hydroxyethyl tristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate); (abbreviated PGMB), butanediol bis (3-mercaptobutyrate), 1,4 -Bis(3-mercaptobutyryloxy)butane; [Brand name; Karenz (registered trademark, hereinafter the same.) MT BD1, manufactured by Showa Denko Co., Ltd.], butanediol trimethylol propane tris (3-mercaptobutyrate) , pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT PE1, manufactured by Showa Denko Co., Ltd.), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mer) captoisobutyrate), butanediolbis(3-mercaptoisobutyrate), trimethylolpropanetris(3-mercaptoisobutyrate), trimethylolpropanetris(3-mercaptobutyrate); (abbreviated as TPMB) trimethyl Allpropane tris(2-mercaptoisobutyrate); (abbreviated as TPMIB), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion; (brand name; Karenz MT NR1, Showa Denko Co., Ltd. product) etc. are mentioned. These can use various things individually by 1 type or in mixture of 2 or more types. Preferably, polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferable, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 is more preferred, and Karenz MT PE1 is particularly preferred.

<solvent>

The photosensitive resin composition of this invention is normally resin (a), a photoinitiator (b), a photopolymerizable monomer (c), a color material (d), a dispersing agent (e), and various materials used as needed, etc. It is used in a state in which it is dissolved or dispersed in an organic solvent.

As the organic solvent, it is preferable to select a solvent having a boiling point (under a pressure of 1013.25 [hPa]. Hereinafter, the boiling point is all the same.) in the range of 100 to 300°C. More preferably, it is a solvent which has a boiling point of 120-280 degreeC.

As such an organic solvent, the following are mentioned, for example. 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 Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and 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, and 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 mono glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

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

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propioate Nate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methyl Chain or cyclic esters such as ethyl oxypropionate, 3-methoxypropyl propionate, 3-methoxybutyl propionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid ;

Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile No. 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #1150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cellosolve” is a registered trademark; the same hereinafter), ethyl cellosolve, ethyl cellosolve acetate , methyl cellosolve acetate, diglyme (all are brand names), and the like.

These organic solvents may be used independently and may use 2 or more types together.

When forming the pixel or black matrix of a color filter by the photolithography method, it is preferable to select the thing with a boiling point of 100-200 degreeC as an organic solvent. More preferably, it has a boiling point of 120-170 degreeC.

Among the said organic solvents, the balance of applicability|paintability, surface tension, etc. is good, and the point of the solubility of the structural component in a composition is comparatively high, glycol alkyl ether acetates are preferable.

Moreover, although glycol alkyl ether acetate may be used independently, they may use another organic solvent together. As an organic solvent to be used together, glycol monoalkyl ethers are particularly preferable. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of the constituents in the composition.

In addition, glycol monoalkyl ethers have high polarity, and when there are too many addition amounts, pigments tend to aggregate, and storage stability, such as increasing the viscosity of the photosensitive resin composition obtained later, tends to decrease. Therefore, glycol monoalkyl ethers in the solvent 5 mass % - 30 mass % are preferable, and, as for the ratio, 5 mass % - 20 mass % are more preferable.

Moreover, it is also preferable to use together the organic solvent (Hereinafter, it may call a "high boiling point solvent".) which has a boiling point of 150 degreeC or more. By using such a high boiling point solvent together, although the photosensitive resin composition becomes difficult to dry, it is effective in preventing that the uniform dispersion state of the pigment in a composition is destroyed by rapid drying.

That is, for example, there is an effect of preventing the occurrence of a foreign material defect due to precipitation and solidification of the color material at the tip of the slit nozzle. Among the various solvents mentioned above, especially diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are preferable at the point with such a high effect.

3 mass % - 50 mass % are preferable, as for the content rate of the high boiling point solvent in an organic solvent, 5 mass % - 40 mass % are more preferable, 5 mass % - 30 mass % are still more preferable, 5 mass % - 10 mass % is especially preferable. If the amount of the high boiling point solvent is too small, for example, a colorant or the like may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects. In this, we are concerned about causing problems such as tact failure of the reduced pressure drying process or the fin marks of prebaking.

Moreover, glycol alkyl ether acetates may be sufficient as the high boiling point solvent with a boiling point of 150 degreeC or more, and glycol alkyl ethers may be sufficient as it, In this case, it is not cared about without containing the high boiling point solvent of 150 degreeC or more separately.

As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butylene glycol di Acetate, 1,6-hexanediol diacetate, triacetin, etc. are mentioned.

<Other compounding components of the photosensitive resin composition>

The photosensitive resin composition of this invention can mix|blend suitably a close_contact|adherence improver, an applicability|paintability improver, a developing agent, a ultraviolet absorber, antioxidant, a silane coupling agent, surfactant, a pigment derivative, etc. other than the component mentioned above.

(adhesion enhancer)

In order to improve adhesiveness with a board|substrate, you may contain a close_contact|adherence improver in the photosensitive resin composition of this invention, For example, a silane coupling agent, a phosphoric acid type_adhesion improver, other adhesion|adhesion improvers, etc. are mentioned.

As a kind of a silane coupling agent, various things, such as an epoxy type, a (meth)acrylic type, and an amino type, can be used individually by 1 type or in mixture of 2 or more types.

Preferred silane coupling agents include, for example, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxy). Epoxysilanes such as cyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, 3-woo Although urea silanes, such as laid propyl triethoxy silane, and isocyanate silanes, such as 3-isocyanate propyl triethoxy silane, are mentioned, Especially preferable are the silane coupling agents of epoxy silanes.

As the phosphoric acid-based adhesion improving agent, (meth)acryloyloxy group-containing phosphates are preferable, and among these, those represented by the following general formulas (g1), (g2) and (g3) are preferable.

[Formula 80]

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

As another adhesion improving agent, TEGO ^* Add Bond LTH (made by Evonik) etc. are mentioned, for example. These phosphoric acid group containing compounds or other adhesive agents may be used individually by 1 type, and may be used in combination of 2 or more type.

(Surfactants)

You may make the photosensitive resin composition of this invention contain surfactant for an applicability|paintability improvement. As surfactant, various things, such as an anionic, cationic, nonionic, and amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant from the viewpoint of a low possibility of adversely affecting various properties, and among them, a fluorine-based or silicone-based surfactant is effective in terms of applicability.

Examples of such surfactants include TSF4460 (manufactured by Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Corporation), BYK-300, BYK-325, BYK-330 (manufactured by Bick Chemie Corporation), KP340 ( Shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-559 (Dainippon Ink Chemical Co., Ltd.), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 (made by Nippon Unika) and FC4430 (made by Sumitomo 3M), etc. are mentioned. In addition, surfactant may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Other Ingredients)

In the photosensitive resin composition of the present invention, in addition to the above components, a polymerization accelerator, a photoacid generator, a crosslinking agent, a plasticizer, a storage stabilizer, a surface protecting agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improving agent, a thermal polymerization inhibitor, etc. may contain

(pigment derivative)

You may make the photosensitive coloring composition of this invention contain a pigment derivative for a dispersibility and a storage improvement improvement. As the pigment derivative, for example, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perylene Derivatives, such as a non-type, a diketopyrrolopyrrole type, and a dioxazine type, are mentioned. Especially, a phthalocyanine type and a quinophthalone type are preferable.

As a substituent of the pigment derivative, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group and an amide group are directly attached to the pigment skeleton or an alkyl group, an aryl group, etc. And what couple|bonded through the heterocyclic group etc. are mentioned, Preferably it is a sulfonic acid group. Moreover, two or more of these substituents may be substituted by one pigment frame|skeleton.

Examples of the pigment derivative 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. can These may be used individually by 1 type, and may use 2 or more types together.

<Ingredient blending ratio in photosensitive resin composition>

The content rate of resin (a) is 5 mass % or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 10 mass % or more, More preferably, it is 15 mass % or more, More preferably is 20 mass% or more, particularly preferably 25 mass% or more, and is usually 90 mass% or less, preferably 70 mass% or less, more preferably 50 mass% or less, still more preferably It is 40 mass % or less, Especially preferably, it is 30 mass % or less.

When the content rate of resin (a) is remarkably small, the solubility with respect to the developing solution of an unexposed part will fall, and there exists a tendency which becomes easy to cause poor image development. Conversely, when there is too much content rate of resin (a), there exists a tendency for the permeability of the developing solution to an exposure part to become high, and the sharpness or adhesiveness of a pixel may fall.

In addition, as mentioned above, in the photosensitive resin composition of this invention, although resin (a) can contain other resin (a-2) with resin (a-1), resin (a-1) When it is necessary to especially improve performance, such as a sensitivity and adhesiveness, it is preferable that the content rate of resin (a-1) is 10 mass % or more with respect to the total mass of resin (a), It is 50 mass % or more More preferably, it is more preferably 60 mass% or more, still more preferably 70 mass% or more, particularly preferably 80 mass% or more, most preferably 90 mass% or more, and usually 100 mass% or less.

Moreover, in resin (a), you may contain other resin (a-2) other than resin (a-1). In this case, the mass ratio of the resin (a-1) to the other resins (a-2) is not particularly limited, but the resin (a-1) of the present invention balances the sensitivity, adhesion, and other properties of the resin. From the viewpoint of

Moreover, when it is desired to mainly obtain the performance by other resin (a-2), it is preferable that the content rate of resin (a-1) with respect to resin (a) is 1 mass % or more, and it is 90 mass % or less. It is preferable that it is 50 mass % or less, More preferably, it is 60 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 0.7 mass or more, More preferably is 1 mass % or more, more preferably 3 mass % or more, still more preferably 5 mass % or more, and is usually 30 mass % or less, preferably 20 mass % or less, more preferably 10 mass% or less. When there is too little content rate of a photoinitiator (b), a sensitivity fall may be caused, and when there is too much conversely, the solubility with respect to the developing solution of an unexposed part falls, and it is easy to cause poor image development.

In particular, the ratio for which the oxime ester compound in a photoinitiator (b) occupies is 10 mass % or more normally, Preferably it is 50 mass % or more, More preferably, it is 90 mass % or more, and is usually 100 mass % or less. . By setting it as more than the said lower limit, there exists a tendency which can improve the development stability by the increase of the line|wire width by a sensitivity improvement and alkali-resistance improvement after ultraviolet irradiation.

When using an accelerator together 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 mass % or more, Usually, it is 10 mass % or less, Preferably it is 5 mass % or less.

It is preferable to use an accelerator in the ratio of 0.1-50 mass %, especially 0.1-10 mass % with respect to a photoinitiator (b). When the photopolymerization initiator (b) and the accelerator are used above the lower limit, the sensitivity to the exposure light tends to be sufficient, and by using the photopolymerization initiator (b) and the accelerator below the upper limit, the solubility of the unexposed portion in the developer tends to be good.

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

The content rate of a photopolymerizable monomer (c) is 90 mass % or less normally with respect to the total solid of the photosensitive resin composition, Preferably it is 70 mass % or less, More preferably, 50 mass % or less, More preferably, 30 It is mass % or less, Especially preferably, it is 10 mass % or less. When the content rate of a photopolymerizable monomer is below the said upper limit, the permeability of the developing solution with respect to an exposed part becomes moderate, and there exists a tendency for a favorable image 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. When it is more than the said lower limit, while improving photocuring by ultraviolet irradiation, there exists a tendency for alkali developability also to become favorable.

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

Although the photosensitive resin composition of this invention can be used for various uses as mentioned above, when the outstanding image formation property is used for formation of the black matrix for color filters, it is especially effective. When used for black matrix formation, as the color material (d), a black color material such as carbon black or titanium black described above may be used, or a plurality of types of color materials other than black may be mixed and used after adjusting to black. Especially, it is especially preferable to use carbon black.

The present invention is particularly effective in a region where the pigment concentration of the black pigment becomes large. In particular, in recent years, it is necessary to increase the concentration of the black pigment in order to increase the degree of shading. As for content of the black pigment which the effect is largely expressed in this way, with respect to the total solid of the photosensitive resin composition, Preferably it is 40 mass % or more, More preferably, it is more than 40 mass %, More preferably, it is 45 mass % or more, Especially preferably is 50 mass% or more, and is usually 70 mass% or less.

Photosensitive resin composition WHEREIN: The photosensitive resin composition with high light-shielding property (optical density, OD value) can be obtained by carrying out content of a black pigment in the said range. Specifically, for example, by making content of a black pigment 45 mass % or more, the optical density in the case of forming a 1 micrometer-thick black matrix using the coloring photosensitive resin composition of this invention is a value of 4.0 or more. can do.

The optical density is more preferably 4.2 or more. In a region with high light-shielding properties, ultraviolet rays are difficult to penetrate into the deep part, and crosslinking by photopolymerization is weak, particularly in the portion where the substrate and the fine wire are in close contact. In this case, the effect of the present invention can be well confirmed.

When using for the use which forms the pixel of a color filter etc., 40-65 mass % is especially effective as a pigment density|concentration with respect to total solid. By making content of a color material more than the said lower limit, the film thickness with respect to color density does not become large too much, and there exists a tendency which can prevent the adverse effect on the gap control etc. at the time of forming into a liquid crystal cell. Moreover, there exists a tendency for sufficient image formability to be obtained by setting it as below the said upper limit.

Moreover, in the photosensitive resin composition, when using a color material, the quantity of resin (a) with respect to 100 mass parts of color material (d) is 20 mass parts or more normally, Preferably it is 30 mass parts or more, More preferably, 40 mass parts. part or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less.

When the content of the resin (a) in the color material (d) is equal to or more than the lower limit, the solubility of the unexposed portion in the developer tends to be sufficient, and when the content of the color material (d) is equal to or less than the upper limit, the desired pixel film thickness tends to be easily obtained. There is this.

When using a thiol compound, the content rate of a thiol compound is 0.1 mass % or more normally with respect to the total solid of the photosensitive resin composition of this invention, Preferably it is 0.3 mass % or more, More preferably, it is 0.5 mass % or more. , is usually 10 mass% or less, preferably 5 mass% or less. When content of a thiol compound shall be more than the said lower limit, there exists a tendency for a sensitivity to be sufficient, and there exists a tendency for storage stability to become favorable by using below the said upper limit.

The content rate of a dispersing agent (e) is 50 mass % or less normally in solid content of the photosensitive resin composition, Preferably it is 30 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less, Usually 1 mass % or more, Preferably it is 3 mass % or more, More preferably, it is 5 mass % or more.

Moreover, content of a dispersing agent is 5 mass parts or more normally with respect to 100 mass parts of color material (d), Preferably it is 10 mass parts or more, More preferably, it is 15 mass parts or more, Usually 200 mass parts or less, Preferably Preferably it is 80 mass parts or less, More preferably, it is 50 mass parts or less. When the content of the dispersant is greater than or equal to the lower limit, sufficient dispersibility tends to be easily obtained, and when the content of the dispersant is less than or equal to the upper limit, the ratio of other components can be relatively made sufficient, color density, sensitivity, film formability, etc. This tends to be good.

In particular, as the dispersant, it is preferable to use a polymer dispersing agent and a pigment derivative in combination, but in this case, the blending ratio of the pigment derivative is usually 0.1 mass% or more, preferably 0.5% by mass or more with respect to the total solid content of the photosensitive resin composition of the present invention. Mass % or more, usually 10 mass % or less, Preferably it is 5 mass % or less, It is preferable to set it as 3 mass % or less more preferably.

When using surfactant, the content is 0.001 mass % or more normally with respect to the total solid in the photosensitive resin composition, Preferably it is 0.005 mass % or more, More preferably, it is 0.01 mass % or more, More preferably, it is 0.03 mass %. or more, particularly preferably 0.05 mass% or more, and usually 10 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, still more preferably 0.3 mass% or less.

When the content of the surfactant is greater than or equal to the lower limit, the smoothness and uniformity of the coating film tend to be good, and when the content of the surfactant is equal to or less than the upper limit, the smoothness and uniformity of the coating film can be improved, and other characteristics. tend to be able to suppress the deterioration of

Moreover, the photosensitive resin composition of this invention uses the organic solvent mentioned above, and the solid content concentration is 5 mass % or more normally, Preferably it is 10 mass % or more, Moreover, 50 mass % or less normally, Preferably 30 mass % or more. It is made into a crude liquid so that it may become mass % or less, More preferably, it may become 20 mass % or less.

<The manufacturing method of the photosensitive resin composition>

The photosensitive resin composition of this invention (henceforth "resist" may be called.) is manufactured according to a conventional method.

Usually, the color material (d) is preferably dispersed 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 properties are improved. Moreover, when a black color material is used as a color material (d), it contributes to the improvement of light-shielding ability.

The dispersion treatment is usually preferably carried out in a system in which a color material (d), a dispersing agent (e), an organic solvent, and, if necessary, some or all of the resin (a) are used in combination (hereinafter referred to as dispersion treatment) The mixture and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, use of a polymer dispersing agent as the dispersing agent is preferable because the time-dependent thickening of the obtained ink and resist is suppressed (excellent in dispersion stability).

Moreover, when a dispersion process is performed with respect to the liquid containing all the components mix|blended with the photosensitive resin composition, a highly reactive component may be modified|denatured because of the heat_generation|fever generated at the time of a dispersion process. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersing agent.

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. The dispersion treatment condition is that the temperature is usually 0°C to 100°C, preferably in the range of room temperature to 80°C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, and the like.

The dispersion standard is to control the gloss of the ink so that the 20 degree specular gloss of the resist [JIS Z8741 (1997)] is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient and coarse pigment (colorant) particles remain in many cases, which may result in insufficient developability, adhesiveness, resolution, and the like. In addition, if dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed to generate a large number of ultrafine particles, and thus dispersion stability tends to be impaired on the contrary.

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, since fine dust is often mixed in a liquid, it is preferable to filter the obtained resist with a filter etc.

<Cured product>

By hardening the photosensitive resin composition of this invention, hardened|cured material can be obtained. The hardened|cured material formed by hardening|curing the photosensitive resin composition can be used suitably as a black matrix and a colored spacer.

<Black Matrix>

Next, the black matrix using the photosensitive resin composition of this invention is demonstrated according to the manufacturing method.

(1) support

As a support body for forming a black matrix, if there exists moderate intensity|strength, the material will not be specifically limited. Although a transparent substrate is mainly used, as a material, For example, polyester resins, such as polyethylene terephthalate, polyolefin resins, such as polypropylene and polyethylene, thermoplastic resins, such as polycarbonate, polymethyl methacrylate, polysulfone sheet, an epoxy resin, an unsaturated polyester resin, a thermosetting resin sheet, such as a poly(meth)acrylic resin, or various glass etc. are mentioned. Among these, from a heat resistant viewpoint, glass and heat resistant resin are preferable. Moreover, transparent electrodes, such as ITO and IZO, may be formed into a film on the surface of a board|substrate. It is also possible to form on a TFT array other than a transparent substrate.

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 urethane resin, etc. as necessary for improvement of surface properties such as adhesiveness.

The thickness of a transparent substrate is 0.05-10 mm normally, Preferably it becomes the range of 0.1-7 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 this invention with the photosensitive resin composition of this invention mentioned above, after apply|coating and drying the photosensitive resin composition of this invention on a transparent substrate, a photomask is put on the sample, and the photomask A black matrix is formed by image exposure, development, and thermal curing or photocuring if necessary.

(3) formation of black matrix

(3-1) Application of photosensitive resin composition

Application|coating to the transparent substrate of the photosensitive resin composition for black matrices can be performed by the spinner method, the wire bar method, the flow coat method, the die coat method, the roll coat method, or the spray coat method, for example. Especially, according to the die coating method, the amount of coating liquid used is significantly reduced, and there is no effect of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed, which is preferable from a general viewpoint.

When the thickness of the coating film is too thick, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation process may become difficult, and when too thin, it becomes difficult to increase the pigment concentration, and desired color expression becomes impossible there is

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

(3-2) Drying of the coating film

It is preferable that drying of the coating film after apply|coating the photosensitive resin composition to a board|substrate is based on the drying method using a hot plate, IR oven, or a convection oven. Drying conditions can be suitably selected according to the kind of the said solvent component, the performance of the dryer to be used, etc.

Drying time is usually selected from the range of 15 seconds - 5 minutes at a temperature of 40-200 degreeC according to the kind of solvent component, performance of the dryer to be used, etc., Preferably it is 30 at the temperature of 50-130 degreeC. It is selected from the range of seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but when it is too high, the alkali-soluble resin is decomposed, thermal polymerization is induced, and poor development may occur. In addition, the reduced-pressure drying method may be sufficient as the drying process of this coating film, which dries in a pressure reduction chamber, without raising a temperature.

(3-3) Exposure

Image exposure overlaps a negative mask pattern on the coating film of the photosensitive resin composition, and irradiates and performs the light source of an ultraviolet-ray or visible light through this mask pattern. In this case, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer by oxygen, exposure may be performed after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film.

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

(3-4) phenomenon

The black matrix which concerns on this invention image-exposes the coating film by the photosensitive resin composition with the said light source, Then, by image development using the aqueous solution containing an organic solvent or surfactant and an alkaline compound, on a board|substrate It can be produced by forming an image. The aqueous solution may also contain organic solvents, buffers, complexing agents, dyes or pigments.

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, potassium phosphate, sodium hydrogen phosphate. , inorganic alkaline compounds such as potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, and mono-di- or triethanolamine, mono-di- or trimethylamine, mono-di- or triethyl organic alkaline compounds such as amine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH) and choline can A mixture of 2 or more types may be sufficient as these alkaline compounds.

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 anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfate salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts, 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. An organic solvent may be used independently and may be used together with aqueous solution.

The conditions of the developing treatment are not particularly limited, and the developing temperature is usually in the range of 10 to 50°C, particularly 15 to 45°C, particularly preferably 20 to 40°C, and the developing method is an immersion developing method or spray development. Any method, such as a method, a brush developing method, an ultrasonic developing method, can be followed.

(3-5) heat curing treatment

The substrate after image development is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment conditions at this time are the temperature in the range of 100-280 degreeC, Preferably it is selected in the range of 150-250 degreeC, and the time is selected in the range of 5 to 60 minutes.

As for the black matrix formed as mentioned above, the width of a bottom part is 3-50 micrometers normally, Preferably 4-30 micrometers, 4-8 micrometers especially in the case of a fine wire are preferable, and the height is usually 0.5-5 micrometers, Preferably It is preferably 1 to 4 µm.

Further, the volume resistivity is 1×10 ¹³ Ω·cm or more, preferably 1×10 ¹⁴ Ω·cm or more, and the relative permittivity is 6 or less, preferably 5 or less. Moreover, the optical density (OD) per 1 micrometer of thickness is 3.0 or more, Preferably it is 3.5 or more, More preferably, it is 4.0 or more, Especially preferably, it is 4.2 or more.

[Formation of other color filter pixels]

On the transparent substrate on which the black matrix was formed, the photosensitive colored resin composition containing the color material of one color among red, green, and blue was apply|coated by the same process as said (3-1)-(3-5), and after drying , a photomask is overlaid on the coating film, and a pixel image is formed through the photomask by image exposure, development, and optionally thermal curing or photocuring to prepare a colored layer. The pixel of a color filter can be formed by performing this operation with respect to the photosensitive colored resin composition of three colors of red, green, and blue, respectively. These sequence numbers are not limited to the above.

[Colored spacer]

It is also possible to use the coloring photosensitive composition of this embodiment as a resist for coloring spacers other than a black matrix. When a spacer is used for a TFT-type LCD, the TFT as a switching element may malfunction by the light incident on the TFT in some cases, and a colored spacer is used in order to prevent this. For example, it is described in Unexamined-Japanese-Patent No. 8-234212 that making a spacer light-shielding property. The colored spacer can be formed in the same manner as the black matrix described above except for using a mask for the colored spacer.

(3-6) Formation of transparent electrode

A color filter forms transparent electrodes, such as ITO, on an image in the state as it is, and is used as a part of components, such as a color display and a liquid crystal display device, In order to improve surface smoothness and durability, as needed, it is on an image. It is also possible to form a top coat layer of polyamide, polyimide, or the like. Moreover, in some uses, such as a planar alignment type drive system (IPS mode), a 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 or an organic EL display, which will be described later.

[Liquid crystal display device]

The liquid crystal display device of this invention is manufactured using the black matrix of this invention mentioned above, and a restriction|limiting in particular, such as the formation order and formation position of a color pixel and a black matrix, is not received.

A liquid crystal display device forms an orientation film on a color filter normally, after disperse|distributing a spacer on this orientation film, it bonds with a counter board|substrate, forms a liquid crystal cell, injects a liquid crystal into the formed liquid crystal cell, and a counter electrode Connect to and complete. As an orientation film, resin films, such as a polyimide, are preferable.

Usually, the gravure printing method and/or the flexographic printing method are employ|adopted for formation of an alignment film, and the thickness of an alignment film will be several 10 nm. After hardening of an alignment film by thermal baking, it surface-treats by irradiation of an ultraviolet-ray or treatment with a rubbing cloth, and is processed to the surface state which can adjust the inclination of a liquid crystal.

As the spacer, a spacer having a size corresponding to the gap (gap) with the opposing substrate is used, and the spacer is usually preferably 2 to 8 m. On a color filter substrate, the photo-spacer PS of a transparent resin film is formed by the photolithographic method, and this can also be utilized instead of a spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

Although the gap of bonding with a counter board|substrate changes with the use of a liquid crystal display device, it is normally selected in the range of 2-8 micrometers. After bonding with a counter board|substrate, parts other than a liquid crystal injection port are sealed with sealing materials, such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.

After the liquid crystal cell in which the periphery was sealed is cut|disconnected in panel unit, it is made into pressure reduction in a vacuum chamber, and after immersing the said liquid crystal injection port in a liquid crystal, the inside of a chamber is leaked, and a liquid crystal is inject|poured into a liquid crystal cell. Although the pressure reduction degree in a liquid crystal cell is 1x10 ^-2 - 1x10 ^-7 Pa normally, Preferably it is 1x10 ^-3 - 1x10 ^-6 Pa.

Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and a heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The heating and maintenance at the time of reduced pressure is normally in the range for 10 to 60 minutes, and is immersed in the liquid crystal after that. A liquid crystal display device (panel) is completed by the liquid crystal cell which inject|poured a liquid crystal hardening UV curing resin and sealing a liquid crystal injection port.

There is no restriction|limiting in particular in the kind of liquid crystal, As a conventionally known liquid crystal, such as an aromatic type, an aliphatic type, and a polycyclic compound, any of a lyotropic liquid crystal, a thermotropic liquid crystal, etc. may be sufficient. As a thermotropic liquid crystal, although a nematic liquid crystal, a smetic liquid crystal, a cholesteric liquid crystal, etc. are known, any may be sufficient.

[Organic EL Display]

The organic electroluminescent display of this invention is manufactured using the color filter of this invention.

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

As a lamination method of the organic light emitting body 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 on the upper surface of the color filter. ), the method of bonding the organic light-emitting body 500 formed on the other board|substrate on the inorganic oxide film 40, etc. are mentioned sequentially.

Using the organic EL element 100 produced in this way, for example, the method described in "Organic EL Display" (Oum Corporation, published on August 20, 2004, by Shizuo Tokito, Chihaya Adachi, Hideyuki Murata), etc. Thus, an organic EL display can be manufactured.

Moreover, the color filter of this invention is applicable also to the organic electroluminescent display of a passive driving system, and an organic electroluminescent display of an active driving system.

Example

Next, although the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, the present invention is not limited to the following Examples unless the gist thereof is exceeded.

<Preparation of carbon black dispersion ink>

A pigment, a dispersing agent, a dispersing aid, and a solvent were combined with the following composition, and carbon black dispersion ink was prepared by the following method.

First, it prepared so that the solid content and solvent of a pigment, a dispersing agent, and a dispersing auxiliary agent might become the following.

・Pigment:

R1060 (carbon black manufactured by Colombia); 100 parts by mass

・Dispersant:

BYK167 (Basic urethane dispersant manufactured by Bick Chemie); 20 parts by mass (in terms of solid content)

・Dispersion aid (pigment derivative):

S12000 (manufactured by Lubrizol, a 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, with a paint shaker, dispersion processing was performed in the range of 25-45 degreeC for 6 hours, 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 with a filter to prepare a carbon black dispersion ink having a solid content of 35 mass%.

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

[Formula 81]

7.3 g of the epoxy compound (epoxy equivalent 240) of the above chemical structure, 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 mixed with a thermometer, a stirrer, and a cooling tube. It was put into the attached flask, and it was made to react at 100 degreeC with stirring until the acid value became 5 mg-KOH/g or less. 9 hours were required for reaction, and the epoxy acrylate solution was obtained.

The obtained epoxy acrylate solution, trimethylolpropane (TMP), biphenyltetracarboxylic dianhydride (BPDA), tetrahydrophthalic anhydride (THPA), and propylene glycol monomethyl ether acetate (PGMEA) were added in amounts shown in Table 1 below. Prepared, put them in a flask equipped with a thermometer, a stirrer, and a cooling tube, and react by slowly raising the temperature to 105 ° C. while stirring, and an alkali-soluble resin having an acid value and weight average molecular weight shown in Table 1 below and a solid content of 40 mass% ) 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)>

[Formula 82]

50 g of an epoxy compound of 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, equipped with a thermometer, stirrer, and cooling tube It was put in one flask, and reacted at 90°C with stirring until the acid value became 5 mgKOH/g or less. 12 hours were required for reaction, and the epoxy acrylate solution was obtained.

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

When the resin solution became transparent, it was diluted with methoxybutyl acetate, prepared so as to have a solid content of 40% by mass, and an acid value of 110 mg-KOH/g, alkali-soluble resin having a weight average molecular weight of 4000 in terms of polystyrene measured by GPC (5 ) was obtained.

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

[Formula 83]

7.1 g of 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 equipped with a thermometer, a stirrer, and a cooling tube. It was put in one flask, and reacted at 100°C with stirring until the acid value became 5 mg-KOH/g or less. 9 hours were required for reaction, and the epoxy acrylate solution was obtained.

16 parts by mass of the obtained 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 propylene glycol monomethyl 15 parts by mass of ether acetate was placed in 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, acid value 114 mg-KOH/g, polystyrene conversion weight average molecular weight 9300 measured by GPC, Alkali-soluble resin (6) having a solid content of 40 mass% was obtained.

<Synthesis Example 1: Synthesis of photoinitiator (1)>

(diketone body)

Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoylchloride (5.13 g, 26.89 mmol) were dissolved in 30 mL of dichloromethane, cooled to 2° C. in an ice-water bath and stirred, and 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, AlCl ₃ (4.1 g, 30.73 mmol) was added, and further 1 hour 30 stirred 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 recovered organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a white solid (10 g) of a diketone.

(oxime)

A diketone body (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 in 30 ml of isopropanol, and refluxed for 3 hours.

After completion of the reaction, the reaction solution was concentrated, and 30 ml of ethyl acetate was added to the obtained residue, washed with 30 ml of a saturated aqueous sodium hydrogencarbonate 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 refine|purified by column chromatography, and the oxime body of 2.22g of pale yellow solids was obtained.

(Oxime ester)

The oxime body (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, cooled on ice, and triethylamine (1.77 g, 17.5 mmol) was added dropwise, as it is for 1 hour. reacted. After confirming the 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 hydrogencarbonate 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 obtained residue was purified by column chromatography (ethyl acetate/hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator (1). ^{The chemical shift of 1} H-NMR of the photoinitiator (1) is shown below.

The structure of the photoinitiator (1) is as follows.

[Formula 84]

<Example 5>

(Preparation of black resist 1)

Using the carbon black dispersion ink prepared in <Preparation of a carbon black dispersion ink>, each component of Table 3 was mixed in the ratio shown in Table 3, it stirred and melt|dissolved with a stirrer, and the black resist 1 was prepared.

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

In addition, the detailed content of each component in a table|surface is as follows.

- Alkali-soluble resin (1): The resin synthesize|combined in Example 1.

- Photoinitiator (1): The photoinitiator synthesize|combined by Synthesis Example 1.

・Photopolymerizable monomer (1): dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

・Surfactant: F559 (manufactured by DIC)

<Example 6>

(Preparation of black resist 2)

Black resist 2 was prepared similarly to Example 5 except having changed alkali-soluble resin (1) into alkali-soluble resin (2) synthesize|combined in Example 2.

<Example 7>

(Preparation of black resist 3)

Black resist 3 was prepared similarly to Example 5 except having changed alkali-soluble resin (1) into alkali-soluble resin (3) synthesize|combined in Example 3.

<Example 8>

(Preparation of black resist 4)

Black resist 4 was prepared similarly to Example 5 except having changed alkali-soluble resin (1) into alkali-soluble resin (4) synthesize|combined in Example 4.

<Example 9>

(Preparation of black resist 5)

Black resist 5 was prepared similarly to Example 5 except having changed the photoinitiator into the photoinitiator (2) (TR-PBG-304, Sangju strong electronics company make).

<Example 10>

(Preparation of black resist 6)

Black resist 6 was prepared similarly to Example 5 except having changed the photoinitiator into the photoinitiator (3) (NCI-831, ADEKA company make).

<Example 11>

(Preparation of black resist 7)

Black resist 7 was prepared similarly to Example 5 except having changed the photoinitiator into the photoinitiator (4) (OXE02, BASF company make).

<Example 12>

(Preparation of black resist 8)

Black resist 8 was prepared similarly to Example 5 except having changed the content rate of each component into what is shown in Table 4 so that the content rate of carbon black with respect to total solid might be 45 mass %.

<Example 13>

(Preparation of black resist 9)

Black resist 9 was prepared similarly to Example 5 except having changed the content rate of each component into what is shown in Table 4 so that the content rate of carbon black with respect to total solid might be set to 40 mass %.

<Comparative example 3>

(Preparation of comparative black resist 10)

Comparative black resist 10 was prepared similarly to Example 5 except having changed alkali-soluble resin (1) into alkali-soluble resin (5) synthesize|combined in the comparative example 1.

<Comparative Example 4>

(Preparation of comparative black resist 11)

Comparative black resist 11 was prepared similarly to Example 5 except having changed alkali-soluble resin (1) into alkali-soluble resin (6) synthesize|combined by the comparative example 2.

(Evaluation of the resist)

(I) Formation line width evaluation and development adhesion evaluation

(1) Method for producing black matrix (BM) resist pattern

The prepared black resists 1-9 and the comparative black resists 10 and 11 were apply|coated to the glass substrate with the spin coater, it dried under reduced pressure and dried at 100 degreeC for 120 second with a hotplate, and obtained the dry coating film. Subsequently, the obtained dry coating film was subjected to pattern exposure using a high-pressure mercury lamp at 40 mJ through an exposure mask described later, and then at room temperature (23° C.), an aqueous KOH solution adjusted to 0.04 mass % with ultrapure water was used as an alkali developer. Various BM resist patterns were obtained by spray-developing for 80 sec, 100 sec, or 120 sec. About the formed BM resist pattern, the formation line width (sensitivity) and resolution (development adhesion) were evaluated by the criteria described in (2) and (3) mentioned later, and the result is shown in Table 5.

(2) Formation line width evaluation method (sensitivity)

Using an exposure mask with a 10 µm opening (a stripe-shaped opening with a width of 10 µm), the formation line width of the BM resist pattern obtained by the method (1) above was observed under a microscope at a magnification of 200 times, and the formation line width was measured. did. When evaluated with the same exposure dose and the same development time, it means that a sensitivity is so high that a formation line width is large.

(3) Development adhesion evaluation method (resolution)

The BM resist pattern was created by the method of said (1) using the exposure mask of 1 micrometer - 10 micrometers opening (1 micrometer at a time in the range of 1-10 micrometers in width|variety, stripe-shaped opening). The BM resist pattern was observed with the naked eye or using an optical microscope. Among the BM resist patterns that were free from defects and surface roughness, the value of the opening width of the exposure mask corresponding to the pattern was defined as the value of developing adhesion for the pattern with the thinnest line width among the BM resist patterns remaining on the glass substrate. It means that adhesiveness with a board|substrate is so good that the value of image development adhesion is small, and resolution is high.

(II) Light-shielding degree evaluation

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), various BM resist patterns prepared in (1) of (I) above were obtained. Post-baking was performed for 30 minutes by 230 degreeC oven, and BM was manufactured. The film thickness was measured with a level difference measuring device Alpha-Step-500 (KLA-Tencor), and the OD value was measured with a permeation density measuring device GretagMacbeth D200-II (GretagMacbeth). From this, an OD value per µm (unit OD value) was obtained. As a result, both BMs had an OD value of 4.0/μm.

(III) Substrate adhesion evaluation

Using the prepared black resist 1 (Example 5) and comparative black resists 10 (Comparative Example 3) and 11 (Comparative Example 4), the adhesion to the substrate of BM produced as follows was evaluated. The board|substrate adhesive force was calculated|required as follows.

By the same process as (II) above (however, the entire surface was exposed without using an exposure mask), a substrate having a BM having a thickness of 1.20 µm and a width of 2.5 cm was manufactured. The aluminum stud pin (P/N:901106U, diameter 2.7mm) (made by Quad Group) was joined using thermosetting type sealing compound struct bond XN-21-S (made by Mitsui Chemicals). The prepared sample was subjected to a tensile test at a rate of 2.0 kg/s using a thin film adhesion strength measuring instrument Romulus (manufactured by Quad Group), and from the breaking strength and adhesion area when the black matrix and the glass substrate were broken, The substrate adhesion stress was calculated|required by the following formula|equation.

Substrate adhesion stress (kg/cm2) = breaking strength (kg)/adhesive area (cm2)

A result is shown in Table 6. In addition, the board|substrate adhesive force (%) in Table 6 is a relative value (%) when the value of the board|substrate adhesive stress (kg/cm<2>) in Example 5 is 100 %.

As shown in Tables 5 and 6, it was found that the resin of the present invention, when applied to the photosensitive resin composition, was excellent in sensitivity (formation line width) and resolving power (development adhesion), and also excellent in substrate adhesion. .

As shown in Table 5, the photosensitive resin composition of Examples 5-13 of this invention WHEREIN: Development time is 80 to 120 second, and long time. . This is because the resin in the photosensitive resin composition of Examples 5 to 13 of the present invention has a bulky ring structure in which the alkylidene group of the bisphenoxy moiety is greatly expanded in a planar shape as in Formula (II). , hydrophobicity is high, resistance to alkali developer is large, and since it has a bisphenoxy structure, as described above, the steric hindrance of the portion surrounding the acryl group is small, and it is considered that the crosslinking reaction is easy to occur. Moreover, from the comparison of Example 5, Example 12, and Example 13, it was confirmed that both the formation line width and image development close_contact|adherence were favorable irrespective of the pigment content ratio.

On the other hand, in the photosensitive resin composition of the comparative example 4, the pattern did not remain in the range of 1-10 micrometers in developing adhesion for 120 second of developing time, and the image development stability was also unsatisfactory.

Although this resin in the photosensitive resin composition of Comparative Example 4 has a ring structure of an alkylidene group at the bisphenoxy moiety, the number of carbon atoms forming the ring is 6, and compared with the resins of Examples 5 to 13, hydrophobicity is It is low, and it is thought that it is because a bulk is also small.

Moreover, like Table 4, the photosensitive resin composition of the comparative example 3 also had a small formation line width compared with Examples 1-4, and a sensitivity was low, and image development was also worse than Examples 5-13. Moreover, also in the board|substrate adhesion evaluation of Table 4, it fell to about three-quarters with respect to Example 1.

This is because the resin in the photosensitive resin composition of Comparative Example 3 has two adamantyl group structures, and thus has a large number of carbon atoms, but does not have a bulky structure expanded planarly, and has a bisphenoxy structure, Since it does not exist, it is thought that the tolerance with respect to an alkali developing solution and high sensitivity were not acquired.

Although this invention was demonstrated in detail using the specific aspect, it is clear for those skilled in the art that various changes and deformation|transformation are possible without deviating from the intent and scope of this invention. In addition, this application is based on the JP Patent application (Japanese Patent Application No. 2014-138870) for which it applied on July 4, 2014, The whole is used by reference.

Claims (22)

A resin comprising at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (III).

[In the 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 formula (III), each of R ¹ to R ⁴ independently represents 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.
In addition, * is each independently a bond.] delete The method of claim 1,
The resin including the partial structure represented by the formulas (I) and (III) is a resin including the partial structure represented by the following formula (V).

[In the formula (V), R ¹¹ is each independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 0 to 5.
In addition, R ¹ ~ R ⁴ is the same meaning as the formula (III). In addition, R ¹² has the same meaning as each independently of the said Formula (I).
In addition, * is each independently a bond.] delete The method of claim 1,
A resin further comprising 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 formula (VI), X is a divalent carboxylic acid residue. Moreover, in said Formula (VII), Y is a tetravalent carboxylic acid residue.
In addition, * is each independently a bond.] 6. The method of claim 5,
A resin further having a partial structure represented by the following formula (VIII).

[In the formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2-8.
Also, * is a bonding hand.] 6. The method of claim 5,
A resin having a partial structure further represented by the following formula (IX).

[In the formula (IX), Z' is a polyvalent methylol residue. n' is an integer of 2-6.
Also, * is a bonding hand.] At least
(A-1) an epoxy group-containing compound represented by the following formula (XI);
(A-2) Resin obtained by making unsaturated carboxylic acid or unsaturated carboxylic acid ester react.

[In the 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 a C1-C5 alkylene group.
m is an integer from 0 to 5.] delete Resin obtained by making resin of Claim 8 react with (A-3) polybasic acid anhydride. 11. The method of claim 10,
(A-3) Resin obtained by making it react with polybasic acid anhydride further (A-4) polyhydric alcohol. 12. The method of claim 11,
(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 resin, which is a polyhydric alcohol of The method of claim 1,
A resin that is a resin for color filters. The photosensitive resin composition containing at least the resin of any one of Claims 1, 3, 5-8, and 10-13, and a photoinitiator (b). 15. The method of claim 14,
The photosensitive resin composition further containing a color material (d). 16. The method of claim 15,
The photosensitive resin composition in which a color material (d) is a pigment, and contains a dispersing agent (e) further. 17. The method of claim 16,
The photosensitive resin composition in which a color material (d) is a black pigment, and the dispersing agent (e) is a high molecular compound which has a basic functional group. 18. The method of claim 17,
The photosensitive resin composition in which the content rate of the said black pigment is 45 mass % or more in total solid. 15. The method of claim 14,
The photosensitive resin composition containing an oxime ester compound at least as a photoinitiator (b). Hardened|cured material obtained by hardening|curing the photosensitive resin composition of Claim 14. The color filter containing at least one of the pixel which consists of hardened|cured material of Claim 20, and a black matrix. The image display apparatus provided with the color filter of Claim 21.

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