CN106488941B

CN106488941B - Resin, photosensitive resin composition, cured product, color filter, and image display device

Info

Publication number: CN106488941B
Application number: CN201580035552.9A
Authority: CN
Inventors: 宫崎贵裕; 中谷和裕
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-07-04
Filing date: 2015-07-02
Publication date: 2019-12-10
Anticipated expiration: 2035-07-02
Also published as: JPWO2016002911A1; TW201602210A; TWI647270B; KR20170026449A; JP6620743B2; KR102305058B1; WO2016002911A1; CN106488941A

Abstract

the present invention relates to a resin capable of forming a color filter having excellent sensitivity and resolution regardless of the content ratio of a color material in a photosensitive resin composition when used as a resin in the photosensitive resin composition, a photosensitive resin composition containing the resin, a cured product obtained by curing the composition, a color filter having the cured product, and an image display device provided with the color filter, and relates to a resin containing 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

Technical Field

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

Background

The color filter is generally formed by forming a black matrix (hereinafter also simply referred to as "BM") on the surface of a transparent substrate such as glass or plastic, and then sequentially forming 3 or more different pixels such as red, green, and blue in a pattern such as a stripe pattern or a mosaic pattern.

As a representative manufacturing method of a color filter, a pigment dispersion method is currently used. In this method, first, a photosensitive resin composition containing a black pigment is applied onto a transparent substrate and then dried, and then, after image exposure and development, the BM is formed by curing the photosensitive resin composition by a high-temperature treatment at 200 ℃. By repeating this operation for each color such as red, green, or blue, a color filter is formed.

The BM is usually arranged in a lattice, stripe, or mosaic pattern between pixels of red, green, or blue, and has an effect of improving contrast or preventing light leakage by suppressing color mixing between pixels. Therefore, the BM is required to have high light-shielding properties.

Further, since the edge portions of the pixels of red, green, blue, etc. formed after the BM overlap with the BM, a level difference is formed in the overlapping portion due to the film thickness of the BM. In the overlapping portion, the flatness of the pixel is deteriorated, and non-uniformity of the liquid crystal cell gap or disorder of the liquid crystal orientation occurs, thereby causing a reduction in display capability.

Therefore, in recent years, thinning of BM in particular has been required, and in order to exhibit sufficient light-shielding properties when thinning, the pigment content in the photosensitive resin composition has been increased.

In recent years, when a manufactured color filter is stacked on a panel, conventionally, a frame portion is separately formed and a sealant is applied to the frame portion to be bonded to an array substrate. Therefore, a strong adhesion between the substrate of the color filter and the BM is required more.

On the other hand, in the pigment dispersion method, in order to obtain a photosensitive resin composition, first, a composition containing a color material, a dispersant, a solvent, and the like is dispersed with glass beads or the like to prepare a dispersion liquid. Then, the mixture is stirred and mixed with a binder resin, a photopolymerization initiator, and the like to prepare a photosensitive resin composition.

As the binder resin in the photosensitive resin composition for color filters, an alkali-soluble resin having a carboxyl group or the like which is cured by ultraviolet exposure through a mask and then removed in an alkali development to form pixels such as BM, red, green, and blue is used. Conventionally, as an alkali-soluble resin having a carboxyl group, an acrylic copolymer resin obtained by copolymerizing acrylic acid has been used.

However, in recent years, due to the demand for high color characteristics and the demand for thin films of BM as described above, the content ratio of the pigment in the photosensitive resin composition is increasing, and curing may become difficult depending on the conditions, and therefore, a resin having high curing characteristics is required.

Under such a background, so-called epoxy acrylate resins have come to be used in recent years. For example, patent document 1 describes examples of various epoxy acrylate resins having a biphenyloxy skeleton. Patent document 2 describes an example of an epoxy acrylate resin having an adamantyl group.

On the other hand, patent document 3 describes an epoxy resin having a biphenyl oxygen-based skeleton and a specific alkylidene group as an epoxy resin having excellent heat resistance and moisture absorption resistance and being useful for applications such as light-emitting devices such as LEDs and light-receiving devices such as solar cells.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-126674

Patent document 2: japanese patent laid-open No. 2008-287246

patent document 3: japanese patent laid-open publication No. 2013-253153

disclosure of Invention

Problems to be solved by the invention

The present inventors have found through studies that when the epoxy acrylate resins described in patent documents 1 and 2 are used, sensitivity and resolution are deteriorated depending on the content ratio of the color material in the photosensitive resin composition, and thus good BM or pixels cannot be formed. In particular, if a thin line pattern is formed under a condition where the color material content ratio is high, sufficient curing cannot be achieved due to a decrease in sensitivity, the pattern is excessively removed during development, and only a pattern having a width smaller than the width of the mask opening can be obtained, and it is difficult to control the pattern shape. Patent document 3 does not describe any photosensitive resin composition for color filters at all, and the properties of the composition when used as a resin for a photosensitive resin composition are not clear.

Accordingly, an object of the present invention is to provide a resin capable of forming a color filter having excellent sensitivity and resolution regardless of the pigment content in a photosensitive resin composition when used as a resin in the photosensitive resin composition, a photosensitive resin composition containing the resin, a cured product obtained by curing the composition, a color filter having the cured product, and an image display device including the color filter.

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, they have found that a resin containing a partial structure having a specific biphenyloxy skeleton and a specific alkylidene group and a partial structure having a specific ethylenically unsaturated group and a carboxyl residue can solve the above problems. That is, the gist of the present 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).

[ chemical formula 1]

[ in the above formula (I), R¹²The alkyl group is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

In the above formula (II), R¹～R⁴Each 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, R⁵Is 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.

And each is independently a bonding site. ]

[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).

[ chemical formula 2]

[ in the above formula (III), R¹～R⁴The same meaning as in the above formula (II).

And each is independently a bonding site. ]

[3] The resin according to [1], wherein the resin having a partial structure represented by the above formulae (I) and (II) is a resin having a partial structure represented by the following formula (IV).

[ chemical formula 3]

[ in the above formula (IV), R¹¹Each independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 0 to 5.

In addition, R¹～R⁵K and l are the same as those of the above formula (II). In addition, R¹²Each independently is synonymous with the above formula (I).

And each is independently a bonding site. ]

[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).

[ chemical formula 4]

[ in the above formula (V), R¹～R⁴、R¹¹、R¹²And m are each independently synonymous with formula (IV) above.

And each is independently a bonding site. ]

[5] The resin according to any one of the above [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).

[ chemical formula 5]

[ chemical formula 6]

[ in the formula (VI), X represents a 2-valent carboxylic acid residue. In the formula (VII), Y is a 4-valent carboxylic acid residue.

And each is independently a bonding site. ]

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

[ chemical formula 7]

[ in the formula (VIII), Z is a polyol residue. n is an integer of 2 to 8.

In addition, is a bonding site. ]

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

[ chemical formula 8]

[ in the above formula (IX), Z' is a polyhydric hydroxymethyl residue. n' is an integer of 2 to 6.

In addition, is a bonding site. ]

[8] a resin obtained by reacting at least the following (A-1) and the following (A-2),

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

(A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.

[ chemical formula 9]

[ in the above formula (X), R¹～R⁴Each 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, R⁵Is alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms or aralkyl of 7 to 20 carbon atoms, R¹¹Is an alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5.]

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

[ chemical formula 10]

[ in the above formula (XI), R¹～R⁴、R¹¹And m are each independently synonymous with the above 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] above, which is obtained by reacting the resin with (A-3) a polybasic acid anhydride and further reacting the resin with (A-4) a polyhydric alcohol.

[12] the resin according to [11] above, wherein the (A-4) polyol is at least one polyol selected from the group consisting of: trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol.

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

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

[15] The photosensitive resin composition according to [14], further comprising a coloring material (d).

[16] The photosensitive resin composition according to [15], wherein the coloring material (d) is a pigment, and the photosensitive resin composition further comprises a dispersant (e).

[17] The photosensitive resin composition according to [16], wherein the coloring 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 a content ratio of the black pigment is 45% by mass or more of the total solid content.

[19] The photosensitive resin composition according to any one of the above [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 and a black matrix formed from the cured product according to [20 ].

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

ADVANTAGEOUS EFFECTS OF INVENTION

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

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element including a color filter according to the present invention.

Detailed Description

The present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.

In the present invention, the "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and the "(meth) acrylate" and the "(meth) acryloyl group" are also the same. The meaning of "acid (anhydride)", "… acid (anhydride)" includes both acid and anhydride thereof.

In the present invention, the "total solid content" refers to all components other than the solvent contained in the photosensitive resin composition or the ink described later.

In the present invention, the number average molecular weight and the weight average molecular weight refer to a number average molecular weight (Mn) and a weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography) and converted into polystyrene.

In the present invention, unless otherwise specified, the "amine number" represents an amine number in terms of an effective solid content, and is a value represented by the weight of KOH equivalent to the amount of base per 1g of solid content of the dispersant. The measurement method is as described below. On the other hand, unless otherwise specified, the "acid value" represents an acid value converted into an effective solid content, and can be calculated by neutralization titration.

in the present invention, the "carboxylic acid residue" refers to a group remaining after removing all the carboxylic groups from the carboxylic acid compound. For example, the carboxylic acid residue in the carboxylic acid compound represented by A-COOH is a 1-valent group represented by A. Likewise, the "polyol residue" refers to the group remaining after all hydroxyl groups have been removed from the polyol compound. In addition, the "polyhydric hydroxymethyl group residue" means that all hydroxymethyl groups (-CH) are removed from the polyhydric hydroxymethyl compound₂-OH groups).

In the present specification, the bonding position may be indicated by an "+" symbol. In the present specification, a numerical range may be represented by "to" which indicates a numerical range including an upper limit and a lower limit.

< resin (a-1) >

The resin of the present invention (hereinafter also referred to as "resin (a-1)") is characterized by comprising at least a partial structure represented by the following formula (I) and a partial structure represented by the following formula (II).

Since the resin (a-1) has a bulky structure represented by the following formula (II) and an ethylenically unsaturated group structure represented by the following formula (I), cured product characteristics such as chemical resistance and moisture absorption resistance tend to be excellent.

[ chemical formula 11]

[ chemical formula 12]

In the above formula (I), R¹²The alkyl group 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.

And each is independently a bonding site.

[ partial Structure represented by the formula (I) ]

R in the partial structure represented by the formula (I)¹²Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atomsA C7-20 aralkyl group.

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

Specific examples thereof include: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, 1-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, octyl, nonan-1-yl and decan-1-yl. Among these groups, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, a 2-pentyl group, a 3-pentyl group, a 1-hexyl group, a 2-hexyl group, a 3-hexyl group, or a cyclohexyl group is preferable, a methyl group, an ethyl group, a 1-propyl group, or a 2-propyl group is more preferable, and a methyl group is further preferable.

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

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

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

As R in formula (I)¹²Among these groups, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and hydrogen is particularly preferableAtoms or methyl groups as they are most intended to exhibit the characteristics of the present invention.

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

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

[ partial Structure represented by the formula (II) ]

In the cycloalkylene group in the partial structure represented by the formula (II), k 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 the amount is within the above range, curing properties such as chemical resistance tend to be good. When the resin is used as a resin in a photosensitive resin composition, the effect of the large volume can be exhibited favorably at the lower limit or more, and the compatibility with other components tends to be favorable at the upper limit or less.

Specific examples of the cycloalkylidene group are preferably a cycloundecylidene group, a cyclododecylidene group, or a cyclotridecylidene group, and a cyclododecylidene group is particularly preferable.

R⁵(the partial structure of the formula (II) in the cycloalkylidene optionally has a substituent) is a carbon atom number of 1-20 alkyl, a carbon atom number of 6-20 aryl, or a carbon atom number of 7-20 aralkyl.

R⁵The alkyl group (b) has usually 1 or more carbon atoms, and usually 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 5 or less, further preferably 3 or less, and particularly preferably 2 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when the resin is used as a resin in a photosensitive resin composition, the resin may be mixed with other componentsThe compatibility of the components tends to be good.

Specific examples thereof include: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, 1-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, octyl, nonan-1-yl, decan-1-yl, undecan-1-yl, dodecane-1-yl, tridecan-1-yl, tetradecan-1-yl, pentadecan-1-yl, hexadecan-1-yl, heptadecan-1-yl, octadecan-1-yl, nonadecane-1-yl, eicosan-1-yl.

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

R⁵The number of carbon atoms of the aryl group (b) is usually 6 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when the resin is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

R⁵The number of carbon atoms of the aralkyl group (b) is usually 7 or more, and usually 20 or less, preferably 15 or less, more preferably 11 or less, and still more preferably 9 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when the resin composition is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a benzyl group is more preferable.

In these groups, R⁵Preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group from the viewpoint of exhibiting the most characteristic properties of the resin.

Further, l (substituent R optionally having a cycloalkylidene group in the above formula (II))⁵The number of (b) is an integer of 0 to 13, preferably an integer of 4 or less, more preferablyPreferably an integer of 2 or less. Particularly, the case where l is 0, that is, the case where there is no substituent is preferable. When l is within the above range, curing properties such as chemical resistance tend to be good, and when the resin is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good.

When l is an integer of 2 or more, R⁵They may be the same or different from each other, and the substitution positions may be the same or different from each other.

In the above formula (II), R¹～R⁴Each 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 the above formula (II), R¹～R⁴the alkyl group in (b) has usually 1 or more carbon atoms, and usually 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 5 or less, further preferably 3 or less, and particularly preferably 2 or less. When the number of carbon atoms is within the above range, curing properties such as chemical resistance tend to be good, and when the resin composition is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good.

Specific examples thereof include: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, 1-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, octyl, nonan-1-yl, decan-1-yl, undecan-1-yl, dodecane-1-yl, tridecan-1-yl, tetradecan-1-yl, pentadecan-1-yl, hexadecan-1-yl, heptadecan-1-yl, octadecan-1-yl, nonadecane-1-yl and eicosan-1-yl.

Of these, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, or cyclohexyl is preferred, methyl, ethyl, 1-propyl, or 2-propyl is more preferred, and methyl is particularly preferred.

In the above formula (II), R¹～R⁴The number of carbon atoms of the aryl group in (1)Usually 6 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when the resin is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good. Specifically, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

In the above formula (II), R¹～R⁴The number of carbon atoms of the aralkyl group in (b) is usually 7 or more, and is usually 20 or less, preferably 15 or less, more preferably 11 or less, and still more preferably 9 or less. When the number of carbon atoms is in the above range, curing properties such as chemical resistance tend to be good, and when the resin is used as a resin in a photosensitive resin composition, compatibility with other components tends to be good. Specifically, a benzyl group or a methylenenaphthyl group is preferable, and a benzyl group is more preferable.

In the above formula (II), R¹～R⁴May be the same or different.

Among these groups, R is preferred from the viewpoint of heat resistance¹～R⁴Is a hydrogen atom, and is preferably a methyl group from the viewpoint of chemical resistance.

R in the above formula (II)¹～R⁴The substitution position(s) is not particularly limited, and examples thereof include, among the positions b to f in the following formula (II'), R¹～R⁴When the alkyl group has 1 to 20 carbon atoms, the aryl group has 6 to 20 carbon atoms or the aralkyl group has 7 to 20 carbon atoms, the substitution position is preferably any of b, c, e and f, and more preferably b or f.

In the formula (II), the position of the cycloalkylene group may be any of the positions b to f in the formula (II'), but the position d is preferable from the viewpoint of efficiently obtaining heat resistance due to the cycloalkylene group.

[ chemical formula 13]

In the above formula (II'), R¹～R⁵K and l are as defined above for formula (II).

Specific examples of the partial structure of the formula (II) include, but are not limited to, the following structures. In the following chemical formula, the numerical values described in the cycloalkylene group indicate the number of carbon atoms in the cycloalkylene group.

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

Of these, the partial structure of the formula (II) is preferably any structure selected from the group consisting of (A-1-9) to (A-1-12) and (A-1-33) to (A-1-40), more preferably any structure selected from the group consisting of (A-1-9) to (A-1-12), still more preferably any structure selected from the group consisting of (A-1-9) to (A-1-11), and particularly preferably (A-1-9).

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

The resin (a-1) may contain any structure selected from the following (A-1-29) to (A-1-32) as a structure including a partial structure of (A-1-1).

[ chemical formula 18]

[ chemical formula 19]

In the present invention, as long as the partial structure of the general formula (II) satisfies the general formula (II), 1 species may be used alone, or 2 or more species may be used in combination.

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

[ partial Structure represented by the formula (III) ]

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

[ chemical formula 20]

In the above formula (III), R¹～R⁴The same meaning as in the above formula (II). And each is independently a bonding site.

the reason why the partial structure represented by the formula (II) is preferably the partial structure represented by the formula (III) is that: curing properties such as chemical resistance tend to be good; in addition, when used as a resin in a photosensitive resin composition, the resin tends to have good compatibility with other components and an excellent balance with the effect of the large volume of the cycloalkylidene group; the workability tends to be good; and so on.

the partial structure represented by the above formula (III) contained in the resin (a-1) may be 1 type or 2 or more types. The resin (a-1) may contain a partial structure that does not satisfy the formula (III) and satisfies the formula (II).

In the resin (a-1), the content ratio of the partial structure represented by the formula (III) in the partial structure represented by the formula (II) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less, from the viewpoint of easily exhibiting good resin characteristics.

(partial structure shown in formula (IV))

In the resin (a-1), the partial structure represented by the formula (I) and the partial structure represented by the formula (II) preferably include the partial structure represented by the following formula (IV). That is, the resin having a partial structure represented by the above formulas (I) and (II) is preferably a resin having a partial structure represented by the following formula (IV).

[ chemical formula 21]

In the above formula (IV), R¹¹Each independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 0 to 5. In addition, R¹～R⁵K and l are the same as those of the above formula (II). In addition, R¹²Each independently is synonymous with the above formula (I). And each is independently a bonding site.

The reason why the partial structure represented by the above formula (IV) is preferably contained is as follows: the partial structure has a large-volume cycloalkylidene, and the chemical resistance tends to be good; further, since the partial structure represented by the formula (I) is present apart from the bulky cycloalkylidene group, the influence of steric hindrance caused by the partial structure is small, and crosslinking is likely to occur by ultraviolet irradiation or high heat, and the curing property tends to be further increased. In addition, when the photosensitive resin composition is used as a resin in a photosensitive resin composition, there is a tendency that sensitivity is improved and resistance to an alkali developing solution is improved with an increase in crosslinking reaction.

R in the above formula (IV)¹¹The number of carbon atoms of the alkylene group(s) is usually 1 or more, preferably 2 or more, and usually 5 or less. Within the above range, curing properties such as chemical resistance tend to be good, and the effect of the resin of the present invention tends to be exhibited well. When the resin is used as a resin in a photosensitive resin composition, the effect of steric hindrance by a cycloalkylene group tends to be small when the lower limit value is not less than the lower limit value, and the compatibility with other components tends to be good when the upper limit value is not more than the upper limit value.

R¹¹the alkylene group(s) of (a) may be linear or branched. Specifically, preferred is methylene, ethylene, 1, 3-propylene, 1, 2-propylene, 1, 4-butylene, 1, 2-butylene, 1, 5-pentylene, 1, 2-pentylene, 1, 3-pentylene or cyclopentylene, and more preferred is ethylene, 1, 3-propylene, 1, 2-propylene, 1, 4-butylene, 1, 2-butylene, 1, 5-pentylene, 1, 2-pentylene or 1, 3-pentylene.

In the formula (IV), m is an integer of 0 to 5, preferably an integer of 2 or less, more preferably 0 or 1, and still more preferably 0. When the amount is within the above range, curing properties such as chemical resistance tend to be good, and the effect of the resin (a-1) tends to be exhibited well. When the resin (a-1) is used as a resin in a photosensitive resin composition, the influence of steric hindrance of a cycloalkylene group tends to be small, and the compatibility with other components tends to be good. When m is an integer of 2 or more, R¹¹May be the same or different.

Each of the groups represented by the above formula (IV) is independently a bonding site. For example, the bonding site may be bonded to a hydrogen atom, or to a bonding site of formula (VI) and/or formula (VII) described later.

The partial structure represented by the above formula (IV) contained in the resin (a-1) may be 1 type alone or 2 or more types.

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

[ partial Structure represented by formula (V) ]

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

[ chemical formula 22]

In the above formula (V), R¹～R⁴、R¹¹、R¹²And m are each independently synonymous with formula (IV) above. Each independently is a bonding site.

The reason why the partial structure represented by the above formula (V) is preferable is as follows: when the cycloalkylidene group is cyclododecylidene, curing characteristics such as chemical resistance tend to be good, and the effect of the resin of the present invention tends to be exhibited most favorably. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, the cyclododecylidene tends to have a high resistance to an alkali developing solution due to its large volume, and the steric hindrance of the partial structure represented by the above formula (I) also tends to have a small influence, and the sensitivity and the resistance to an alkali developing solution tend to be good.

The partial structure represented by the above formula (V) contained in the resin (a-1) may be 1 type alone or 2 or more types. The resin (a-1) may have a partial structure satisfying the formula (IV) and not satisfying the formula (V).

From the viewpoint of easily exhibiting the characteristics of the present invention, the content ratio of the partial structure represented by the formula (V) in the partial structure represented by the formula (IV) contained in the resin (a-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 50% by mass or more, and particularly preferably 80% by mass or more. In addition, usually, the content is 100 mass% or less.

Each of the groups represented by the above formula (V) is independently a bonding site. For example, the bonding site may be bonded to a hydrogen atom, or to a bonding site of formula (VI) and/or formula (VII) described later.

[ partial structures of the formulae (VI) and (VII) ]

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

[ chemical formula 23]

[ chemical formula 24]

In the above formula (VI), X is a 2-valent carboxylic acid residue. In the formula (VII), Y is a 4-valent carboxylic acid residue. And each is independently a bonding site.

When the resin (a-1) contains a partial structure represented by the above formula (VI), that is, when the resin (a-1) has at least 1 carboxyl group, adhesion to a substrate tends to be improved by the carboxyl group of the polar group when the resin (a-1) is applied to the substrate. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, and the adhesion to the substrate tends to be improved.

X in the formula (VI) is not particularly limited as long as it is a 2-valent carboxylic acid residue, but is preferably a 2-valent carboxylic acid residue of a 2-membered acid anhydride (dicarboxylic anhydride) from the viewpoint of ease of synthesis, as described in the synthesis section below.

Examples of the 2-valent carboxylic acid residue include a 2-valent hydrocarbon group optionally having a substituent. The hydrocarbon group may be an aliphatic or aromatic hydrocarbon. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. The hydrocarbon group may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less, from the viewpoint of improving the substrate adhesion and the chemical resistance. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, and a carbonyl group, and preferably are unsubstituted.

Specific examples thereof include: and 2-valent carboxylic acid residues such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride, and more preferably 2-valent carboxylic acid residues of tetrahydrophthalic anhydride or succinic anhydride. These 2-membered anhydrides may be used alone in 1 kind of the 2-valent carboxylic acid residue, or 2 or more kinds may be used in combination.

When X is the above-mentioned 2-valent carboxylic acid residue, there is a tendency to improve substrate adhesion and chemical resistance. In addition, when used as a resin in a photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, and the adhesion to a substrate tends to be improved.

Specific examples of the partial structure represented by the formula (VI) include the following structures, but the present invention is applicable to the structure having the formula (VI), and is not limited to the following structures.

[ chemical formula 25]

Further, by incorporating the partial structure represented by the above formula (VII) in the resin (a-1), that is, by providing the resin (a-1) with at least 2 carboxyl groups, the substrate adhesiveness and the chemical resistance tend to be improved. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, and the adhesion to the substrate tends to be improved.

Further, since the partial structure represented by the formula (VII) has 2 bonding positions, it is considered that in the case of the partial structure represented by the formula (IV) or (V) containing 2 or more ethylenically unsaturated groups, the molecular weight can be increased, and the content of the ethylenically unsaturated group can be increased along with this, the crosslinking reaction can be enhanced even at the time of curing, and the substrate adhesion and the chemical resistance can be improved.

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

examples of the 4-valent carboxylic acid residue include a 4-valent hydrocarbon group optionally having a substituent. The hydrocarbon group may have a hetero atom such as an oxygen atom or a sulfur atom.

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

Specifically, for example, a 4-valent carboxylic acid residue of tetracarboxylic dianhydride such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, or biphenyl ether tetracarboxylic dianhydride is preferable, and a 4-valent carboxylic acid residue of biphenyltetracarboxylic anhydride is more preferable. These 4-membered acid anhydrides may be used alone in 1 kind of the 4-valent carboxylic acid residue, or 2 or more kinds may be used in combination.

When Y is the above-mentioned 4-valent carboxylic acid residue, curing properties such as substrate adhesion and chemical resistance tend to be improved. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, the alkali resistance of the image portion tends to be good, and the adhesion to the substrate tends to be improved.

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

[ chemical formula 26]

The resin (a-1) may contain, in addition to the above-mentioned partial structure, a partial structure similar to the partial structure represented by the formula (VI) and/or the partial structure represented by the formula (VII) derived from a polybasic acid anhydride. Among them, the partial structure represented by the following formula (VI') derived from a 3-membered acid anhydride is preferably contained.

[ chemical formula 27]

In the above formula (VI '), X' is a 3-valent carboxylic acid residue. In addition, denotes a bonding site.

When the resin (a-1) contains a partial structure represented by the above formula (VI'), that is, when the resin (a-1) has at least 2 carboxyl groups, the curing properties such as substrate adhesion and chemical resistance tend to be improved. In addition, when the resin (a-1) is used as a resin in the photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, and the adhesion to the substrate tends to be good.

X 'in the formula (VI') is not particularly limited as long as it is a 3-membered carboxylic acid residue, but is preferably a 3-valent carboxylic acid residue of a 3-membered acid anhydride (tricarboxylic acid anhydride) from the viewpoint of ease of synthesis as described later.

Examples of the 3-valent carboxylic acid residue include a 3-valent hydrocarbon group optionally having a substituent. The hydrocarbon group may have a hetero atom such as an oxygen atom or a sulfur atom.

Specifically, a carboxylic acid residue having a valence of 3 such as trimellitic anhydride or hexahydrotrimellitic anhydride is preferable, and a carboxylic acid residue having a valence of 3 of trimellitic anhydride is more preferable. These 3-membered acid anhydrides may be used alone in 1 kind of the 3-valent carboxylic acid residue, or 2 or more kinds may be used in combination.

when X' is the above-mentioned 3-valent carboxylic acid residue, curing properties such as substrate adhesion and chemical resistance tend to be improved. In addition, when used as a resin in a photosensitive resin composition, the solubility during alkali development tends to be easily adjusted, and the adhesion to a substrate tends to be improved.

The bonding site in the partial structure represented by the above formula (VI), the partial structure represented by the above formula (VI'), or the partial structure represented by the above formula (VII) may be bonded to, for example, the bonding site in the partial structure represented by the above formula (IV) or (V), independently of each other.

The bonding site in the partial structure represented by the formula (IV) or the partial structure represented by the formula (V) may be independently bonded to, for example, a hydrogen atom, or the bonding site in the partial structure represented by the formula (VI) and/or the partial structure represented by the formula (VII).

Among the partial structure represented by the above formula (VI), the partial structure represented by the above formula (VI'), or the partial structure represented by the above formula (VII), the partial structure represented by the above formula (VII) is preferable. In the case where the partial structure represented by the formula (VII) is contained alone, the bonding ratio between the bonding sites of the partial structure represented by the formula (VII) and the bonding sites of the partial structure represented by the formula (IV) is usually 10 to 90%, preferably 20 to 85%, and more preferably 30 to 80% when the total number of the bonding sites in the formula (IV) is 100%. The bonding position in the above formula (IV) which is not bonded to the bonding position in the above formula (VII) may be bonded to a hydrogen atom, for example.

When the ratio of the bonding sites in the formula (IV) to the bonding sites in the formula (VII) is within the above range, the curing properties such as substrate adhesion and chemical resistance can be improved, and when the resin composition is used as a resin in a photosensitive resin composition, the resin composition tends to have good solubility in an alkali developing solution and adhesion to a substrate.

In view of curing characteristics such as substrate adhesion and chemical resistance, it is preferable that the resin of the present invention include a partial structure represented by the formula (VI) in addition to the partial structure represented by the formula (VII).

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

The content of the partial structure represented by the formula (VI) is preferably 1 mol% or more, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII).

The content of the partial structure represented by the formula (VII) is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 99 mol% or less, based on the total content of the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII).

When the content ratio of the partial structure represented by the formula (VII) is not less than the lower limit, the decrease in the film properties of the obtained coating film tends to be suppressed, and when the content ratio of the partial structure represented by the formula (VI) is not less than the lower limit, the increase in the viscosity of the obtained resin solution tends to be suppressed, and the workability tends to be good.

In the case where the partial structure represented by the formula (VI) and the partial structure represented by the formula (VII) are contained in combination, the content of the partial structure represented by the formula (VI ') is not particularly limited, but from the viewpoint of curing characteristics such as substrate adhesion and chemical resistance, the bonding ratio between the bonding sites of the partial structure represented by the formula (VI') and the bonding sites of the partial structure represented by the formula (IV) is usually 5 to 70%, preferably 10 to 40%, when the total number of the bonding sites in the formula (IV) is 100%.

When the partial structure represented by the formula (VII) and the partial structure represented by the formula (VI) are contained, or when the partial structure represented by the formula (VI), the partial structure represented by the formula (VII), and the partial structure represented by the formula (VI ') are contained, the ratio of bonding to the bonding positions of the formulae (VI), (VI'), and (VII) is usually 10 to 90%, preferably 20 to 85%, more preferably 30 to 80%, where the total number of the bonding positions in the formula (IV) is 100%.

The bonding sites of the above formula (IV) that are not bonded to the bonding sites of the above formulae (VI), (VI') and (VII) may be bonded to, for example, hydrogen atoms. When the amount is within the above range, curing properties such as substrate adhesion and chemical resistance tend to be good.

The bonding sites in the above formula (VI) and the above formula (VII) may each independently bond to the bonding sites in the above formula (IV) or (V). Each of the bonding sites in the formula (IV) or (V) may be independently bonded to a hydrogen atom, a bonding site in the formula (VI), or a bonding site in the formula (VII). Thus, the resin of the present invention can be used in various forms.

When the bonding site in the formula (V) is bonded to a hydrogen atom, the bonding site in the formula (VI) or the bonding site in the formula (VII), main specific examples of the partial structure are as follows. When the formula (IV) is used instead of the formula (V), the same examples can be given.

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

[ chemical formula 32]

[ chemical formula 33]

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

As described above, the resin (a-1) preferably 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). The bonding site in formula (VI') may be bonded to the bonding site in formula (IV) and/or formula (V).

When the bonding site in the formula (V) is bonded to the bonding site in the formula (VI'), the following are main examples of the partial structure. When the formula (IV) is used instead of the formula (V), the same examples can be given.

[ chemical formula 34]

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

among these specific examples, preferred is a structure having a partial structure of the above-mentioned (A-2-3), (A-2-5), (A-2-6) or (A-2-9) having a partial structure represented by the above-mentioned formula (VII). Particularly preferred is a partial structure of (A-2-6) having 2 partial structures represented by the above formula (VII), or a partial structure of (A-2-5) having a partial structure represented by the above formula (VII) and a partial structure represented by the above formula (VI).

The reason for this is as follows: by containing the partial structure represented by the formula (VII), the bonding position in the formula (VII) is further bonded to the partial structure represented by the formula (IV) or the partial structure represented by the formula (V) to increase the molecular weight, and the content of the ethylenically unsaturated group structure is increased, and further the content of the carboxyl group is increased, whereby the improvement of curing characteristics such as substrate adhesion and chemical resistance tends to be good.

In addition, the bonding site in the above formula (IV) or (V) may be bonded to a bonding site of a partial structure derived from another polybasic acid anhydride within a range not adversely affecting the effect of the present invention, in addition to being independently bonded to a hydrogen atom, the bonding site in the above formula (VI), the bonding site in the above formula (VI'), or the bonding site in the above formula (VII).

[ partial Structure represented by the formula (VIII) ]

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

[ chemical formula 38]

In the above formula (VIII), Z is a polyhydric alcohol residue. n is an integer of 2 to 8. In addition, denotes a bonding site.

By incorporating the partial structure represented by the above formula (VIII) into the resin (a-1), the molecular weight of the resin (a-1) can be increased, and the amount of carboxyl groups and ethylenically unsaturated groups introduced can be increased, and the curing properties such as substrate adhesion and chemical resistance tend to be further improved.

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

Z in the formula (VIII) is a polyol residue, and specifically, an alcohol residue such as 1,2, 3-propanetriol or the like, a polyol residue of a sugar alcohol described later or the like can be mentioned, and any polyol residue satisfying the formula (VIII) can be used without particular limitation.

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

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

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

[ chemical formula 39]

[ chemical 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 above formula (VIII).

[ chemical formula 41]

In the above formula (IX), Z' is a polyhydric hydroxymethyl residue. n' is an integer of 2 to 6. In addition, denotes a bonding position.

N' in the formula (IX) is an integer of 2 to 6, but is preferably an integer of 2 to 4 from the viewpoint of curing properties such as substrate adhesion and chemical resistance.

Z' in the above formula (IX) is a polyvalent methylol residue, preferably a polyvalent methylol residue of trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol or trimethylolethane, and when the above formula (IX) is satisfied, other polyvalent methylol residues may be used. Specific examples of the partial structure represented by the above formula (IX) are shown below.

[ chemical formula 42]

[ chemical formula 43]

[ chemical formula 44]

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

examples of the polyvalent methylol residue include an n' -valent hydrocarbon group optionally having a substituent. The hydrocarbon group may be an aliphatic or aromatic hydrocarbon. The aliphatic hydrocarbon and the aromatic hydrocarbon may be linked. The hydrocarbon group may be a linear or branched chain hydrocarbon group, or a cyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and particularly preferably 5 or less, from the viewpoint of improving the substrate adhesion and the chemical resistance. Examples of the substituent include a halogen atom, a hydroxyl group, an ether group, and a carbonyl group, but are preferably unsubstituted.

The partial structure represented by the formula (VIII) and/or the partial structure represented by the formula (IX) may be used singly or in combination of 2 or more.

Each of the bonding sites in the formula (VIII) and the formula (IX) may be independently bonded to a hydrogen atom, a bonding site in the formula (VI), a bonding site in the formula (VII), or a bonding site in the formula (VI'). Various embodiments can be exemplified by a combination of the bonding.

When the bonding site in the formula (VIII) and the formula (IX) is bonded to the bonding site in the formula (VI), the resin (a-1) of the present invention may be a resin having at least 1 carboxyl group.

When the bonding site in the formula (VIII) and the formula (IX) is bonded to the bonding site in the formula (VI'), the resin (a-1) of the present invention may have at least 2 carboxyl groups.

Examples of the bonding position in the formulae (VIII) and (IX) to the bonding position in the formula (VII) include an embodiment in which the bonding position is bonded to all of the 2 bonding positions in the formula (VII) and an embodiment in which the bonding position is bonded to only the 1 bonding position.

When the resin (a-1) of the present invention is bonded to all of the 2 bonding positions in the formula (VII), the resin may have at least 2 carboxyl groups and may have a further increased branched structure.

In addition, in the case of bonding to only 1 bonding site in the above formula (VII), for example, bonding to bonding sites of partial structures of the above formulae (A-2-3), (A-2-5), (A-2-6) and (A-2-9) having a partial structure represented by the above formula (VII) is possible. Thus, the molecular weight of the resin (a-1) of the present invention can be increased and the content of carboxyl groups or ethylenically unsaturated groups can be increased.

The bonding position in the above formulae (VIII) and (IX) may be bonded to a hydrogen atom. This is because, as described later, the partial structures represented by the above formulae (VIII) and (IX) may be introduced from the polyol, and when the hydroxyl group of the polyol is not reacted during the synthesis, a structure bonded to a hydrogen atom may be formed.

Among these, from the viewpoint of curing characteristics such as substrate adhesion and chemical resistance, the bonding sites in the formulae (VIII) and (IX) are preferably bonded to the bonding sites in the formulae (A-2-3), (A-2-5), (A-2-6) and (A-2-9).

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

[ Properties of resin (a-1) ]

The acid value of the resin (a-1) is usually not less than 10mg-KOH/g, preferably not less than 50mg-KOH/g, and the acid value is preferably not more than 200mg-KOH/g, more preferably not more than 150 mg-KOH/g. When the amount is within the above range, curing properties such as substrate adhesion and chemical resistance tend to be exhibited well.

The weight average molecular weight of the resin (a-1) is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 4,000 or more, and particularly preferably 5,000 or more. Further, it is preferably 40,000 or less, more preferably 30,000 or less. When the amount is within the above range, curing properties such as substrate adhesion and chemical resistance tend to be exhibited satisfactorily.

[ Synthesis of resin (a-1) ]

The resin (a-1) is preferably a resin obtained by reacting at least the following (A-1) and the following (A-2).

(A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.

From the viewpoint of adjusting adhesion to a substrate or solubility in alkali development, a resin obtained by further reacting the resin obtained by reacting (a-1) and (a-2) with (a-3) a polybasic acid anhydride is more preferable.

[ chemical formula 45]

In the above formula (X), R¹～R⁴Each 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, R⁵Is alkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms, aralkyl with 7-20 carbon atoms, R¹¹An alkylene group having 1 to 5 carbon atoms. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5.

To synthesize the resin (a-1), for example, (A-1) an epoxy group-containing compound represented by the above formula (X) and (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester are first reacted to obtain a reactant (hereinafter referred to as "epoxyacrylate resin").

In this case, the partial structure represented by the formula (II) can be obtained from (A-1) the epoxy group-containing compound represented by the formula (X), and the partial structure represented by the formula (I) can be obtained from (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. Further, as the epoxy acrylate resin, a resin containing a partial structure represented by the above formula (IV) can be obtained.

Then, the epoxy acrylate resin is reacted with the polybasic acid anhydride (A-3) to obtain a resin. In this case, the partial structures represented by the above formulae (VI), (VI') and (VII) can be obtained from the polybasic acid anhydride (A-3).

[ (A-1): epoxy group-containing Compound

R in the above formula (X)¹～R⁴、R⁵、R¹¹And k, l and m are synonymous with the above formulae (I) to (IV), and are preferably those listed in the above formulae (I) to (V).

Specific examples of the epoxy group-containing compound represented by the formula (X) include the following compounds (A-1-1 ') to (A-1-20') and (A-1-29 ') to (A-1-40') corresponding to the above-mentioned compounds (A-1-1) to (A-1-20) and (A-1-29) to (A-1-40). The epoxy group-containing compound is applicable to the present invention as long as it satisfies the above formula (X), but is not limited to these compounds. In the following chemical formula, the numerical value described in the cycloalkylene group represents the number of carbon atoms in the cycloalkylene group.

[ chemical formula 46]

[ chemical formula 47]

[ chemical formula 48]

[ chemical formula 49]

[ chemical formula 50]

[ chemical formula 51]

[ chemical formula 52]

[ chemical formula 53]

The epoxy group-containing compound represented by the formula (X) is preferably any compound selected from the group consisting of the compounds (A-1-9 ') to (A-1-12 ') and (A-1-29 ') to (A-1-40 '), more preferably any compound selected from the group consisting of (A-1-9 ') to (A-1-12 '), still more preferably any compound selected from the group consisting of (A-1-9 ') to (A-1-11 '), and particularly preferably (A-1-9 ').

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

In the present invention, 1 kind of the epoxy group-containing compound represented by the above formula (X) may be used alone, or 2 or more kinds may be used in combination.

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

[ chemical formula 54]

In the above formula (XI), R¹～R⁴、R¹¹And m are each independently synonymous with the above formula (X).

As the reason why the compound represented by the above formula (XI) is preferable, as described above, there can be mentioned: there is a tendency that curing properties such as chemical resistance are good, the effect of the resin (a-1) is well exhibited, and the like, and there is a tendency that the epoxy group-containing compound of the formula (XI) is easy to handle and easy to produce.

Further, as a method for synthesizing the compounds of the above-mentioned formulae (X) and (XI), a known method can be used, and for example, the method described in Japanese patent application laid-open No. 2013-253153 can be used.

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

Examples of the unsaturated carboxylic acid that can be used in the synthesis reaction of the resin (a-1) of the present invention include: unsaturated carboxylic acids having ethylenically unsaturated groups. Specific examples thereof include: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, and (meth) acrylic acid substituted at the α -position with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl adipate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxypropyl succinate, 2- (meth) acryloyloxypropyl adipate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxypropyl maleate, 2- (meth) acryloyloxybutyl succinate, 2- (meth) acryloyloxybutyl adipate, 2- (meth) acryloyloxybutyl hydrophthalate, 2- (meth) acryloyloxyethyl acrylate, (meth) acryloyloxyalkyl esters of 2-membered acids such as 2- (meth) acryloyloxybutyl phthalate and 2- (meth) acryloyloxybutyl maleate; monomers obtained by adding lactones such as epsilon-caprolactone, beta-propiolactone, gamma-butyrolactone and delta-valerolactone to (meth) acrylic acid; (meth) acrylic acid dimer, and the like.

Further, there may be mentioned, for example: compounds obtained by adding a hydroxyl group-containing unsaturated compound to an acid anhydride such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or phthalic anhydride, such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, an acrylic acid adduct of glycidyl methacrylate, or a methacrylic acid adduct of glycidyl methacrylate.

Particularly preferred is (meth) acrylic acid. These unsaturated carboxylic acids or unsaturated carboxylic acid esters may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In the synthesis reaction of the resin (a-1), an unsaturated carboxylic acid ester may be used instead of the unsaturated carboxylic acid. For example, α, β -unsaturated monocarboxylic acid esters may also be used. Specific examples thereof include: 2-succinyloxyethyl acrylate, 2-maleyloxyethyl acrylate, 2-phthaloyl ethyl acrylate, 2-hexahydrobenzoylethyl acrylate, 2-succinyloxyethyl methacrylate, 2-maleyloxyethyl methacrylate, 2-phthaloyl ethyl methacrylate, 2-hexahydrophthaloyl ethyl methacrylate, 2-succinyloxyethyl crotonate and the like. 2-maleoyloxyethyl acrylate or 2-phthaloyl ethyl acrylate is preferred, 2-maleoyloxyethyl acrylate being particularly preferred.

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

the amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.3 to 5% by mass, based on the total amount of the reaction raw material mixture (epoxy group-containing compound and unsaturated carboxylic acid). In order to prevent polymerization during the reaction, a polymerization inhibitor (e.g., p-hydroxyanisole, hydroquinone, methyl-p-dihydroxybenzene, p-methoxyphenol, pyrogallol, t-butyl catechol, phenothiazine, etc.) is preferably used in an amount of 0.01 to 10% by mass, particularly preferably 0.03 to 0.5% by mass, based on the reaction raw material mixture.

The proportion of the unsaturated carboxylic acid added to the epoxy group of the epoxy group-containing compound is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol% with respect to the epoxy group. Since the storage stability is adversely affected by the residual epoxy group, the unsaturated carboxylic acid is reacted in a proportion of usually 0.8 to 1.5 equivalents, particularly preferably 0.9 to 1.1 equivalents, based on 1 equivalent of the epoxy group in the epoxy group-containing compound.

As described above, an epoxy acrylate resin having a partial structure of the formula (IV) (hereinafter also referred to as "A-5 epoxy acrylate resin") can be obtained by an addition reaction of (A-1) the epoxy group-containing compound represented by the formula (X) and (A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester.

An ethylenically unsaturated group can be introduced into the epoxy group-containing compound by an addition reaction of the epoxy group-containing compound and the unsaturated carboxylic acid, and ultraviolet reactivity, that is, photocurability can be imparted thereto.

Further, it is considered that the carboxyl group can be introduced or the molecular weight can be increased as described later by further performing an addition reaction of the (a-3) polybasic acid anhydride described later on the hydroxyl group generated by the addition reaction of the epoxy group-containing compound and the unsaturated carboxylic acid.

[ (A-3): polybasic acid anhydride ]

As the polybasic acid anhydride which can be used in the synthesis reaction of the resin (a-1), 2-membered acid anhydride, 3-membered acid anhydride, 4-membered acid anhydride and the like can be preferably used.

The partial structure represented by the above formula (VI) can be obtained from a 2-membered acid anhydride, the partial structure represented by the above formula (VI') can be obtained from a 3-membered acid anhydride, and the partial structure represented by the above formula (VII) can be obtained from a 4-membered acid anhydride.

as the 4-membered acid anhydride (tetracarboxylic dianhydride), known ones can be used, and examples thereof include: tetracarboxylic acid dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride. These 4-membered acid anhydrides (tetracarboxylic dianhydrides) may be used alone in 1 kind or in combination of 2 or more kinds.

Among the above-mentioned exemplary compounds, a biphenyl tetracarboxylic dianhydride is particularly preferable as the 4-membered acid anhydride. When a 4-membered acid anhydride is used as the polybasic acid anhydride, the following tendency is exhibited: when the resin of the present invention is used as a resin in a photosensitive resin composition, effects such as increasing the molecular weight by a crosslinking reaction, improving the adhesion to a substrate, adjusting the solubility, and improving the sensitivity or alkali resistance can be obtained.

Examples of the 2-membered acid anhydride (dicarboxylic anhydride) include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, and the like. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferable. These 2-membered acid anhydrides may be used alone in 1 kind, or 2 or more kinds may be used in combination.

When a 2-membered acid anhydride is used as the polybasic acid anhydride, the following tendency is exhibited: when the resin of the present invention is used as a resin in a photosensitive resin composition, the solubility can be easily adjusted, and the adhesion to a substrate can be improved.

Examples of the 3-membered acid anhydride (tricarboxylic acid anhydride) include trimellitic anhydride and hexahydrotrimellitic anhydride, and trimellitic anhydride is particularly preferable. These 3-membered acid anhydrides may be used alone in 1 kind, or 2 or more kinds may be used in combination.

When a 3-membered acid anhydride is used as the polybasic acid anhydride, the following tendency is exhibited: the amount of the acid group introduced into the resin molecule can be increased, and when the resin composition is used as a resin in a photosensitive resin composition, the sensitivity, adhesion, developability, and the like can be easily balanced.

among the polybasic acid anhydrides, 4-membered acid anhydrides are particularly preferably used. When the 4-membered acid anhydride is used alone, the addition rate of the 4-membered acid anhydride to the hydroxyl group of the (a-5) epoxy acrylate resin is usually 10 to 90 mol%, preferably 20 to 85 mol%, and more preferably 30 to 80 mol%.

Among the hydroxyl groups of the epoxy acrylate resin (A-5), the portion which is not subjected to addition reaction with the 4-membered acid anhydride may remain as hydroxyl groups. On the other hand, when the addition rate of the 4-membered acid anhydride (d) is in the above range, curing properties such as substrate adhesion and chemical resistance tend to be good.

When used as a resin in a photosensitive resin composition, it is preferable to use the 4-membered acid anhydride and use a 2-membered acid anhydride in combination, from the viewpoint of adjusting viscosity or solubility.

When a 4-membered acid anhydride and a 2-membered acid anhydride are used in combination, the molar ratio of the 2-membered acid anhydride to the 4-membered acid anhydride is preferably 70:30 to 1:99, and more preferably 60:40 to 1: 99. When the ratio of the 4-membered acid anhydride is not less than the lower limit, the film properties of the obtained coating film tend to be inhibited from decreasing, and when the ratio of the 2-membered acid anhydride is not less than the lower limit, the workability tends to be inhibited from decreasing due to an increase in the viscosity of the obtained resin solution.

When a 4-membered acid anhydride, a 2-membered acid anhydride and a 3-membered acid anhydride are used in combination, the amount of the 3-membered acid anhydride used is usually 5 to 70 mol%, preferably 10 to 40 mol%, based on the hydroxyl group of the (a-5) epoxy acrylate resin, from the viewpoint of curing characteristics such as substrate adhesion and chemical resistance due to the use of the 3-membered acid anhydride.

When 2 kinds of 4-membered acid anhydride and 2-membered acid anhydride are used or 3 kinds of 4-membered acid anhydride, 2-membered acid anhydride and 3-membered acid anhydride are used as the polybasic acid anhydride, the addition ratio of all the polybasic acid anhydrides to the hydroxyl group of the (a-5) epoxy acrylate resin is usually 10 to 90 mol%, preferably 20 to 85 mol%, more preferably 30 to 80 mol%. In the hydroxyl group of the epoxy acrylate resin (A-5), a portion which is not subjected to addition reaction with the polybasic acid anhydride may remain as a hydroxyl group. When the addition ratio of the polybasic add anhydride is not less than the lower limit value, there is a tendency that the curing properties such as substrate adhesion and chemical resistance are good.

[ (A-4): polyhydric alcohols ]

When the (A-5) epoxy acrylate resin is added to the polybasic acid anhydride, it is preferable to use the polybasic acid anhydride and, at the same time, to use the (A-4) polyhydric alcohol and/or polyhydric methylol group (hereinafter, simply referred to as "polyhydric alcohol") capable of being added to the polybasic acid anhydride to carry out the reaction. By simultaneously reacting the polyhydric alcohols, the acid value tends to be increased or the molecular weight tends to be increased by adding the polyhydric alcohols to the polybasic acid anhydride.

The partial structures of the above formulae (VIII) and (IX) can be obtained from the polyhydric alcohols used in the synthesis reaction of the resin (a-1).

The polyol used in the synthesis reaction of the resin (a-1) is not particularly limited as long as it is a compound having 2 or more hydroxyl groups, and is preferably at least one polyol selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2, 3-propanetriol, from the viewpoints of curing characteristics of substrate adhesion and chemical resistance and ease of handling.

By using the polyhydric alcohol, the molecular weight of the resin (a-1) tends to be increased, branching is introduced into the molecule, and a balance between the molecular weight and the viscosity tends to be obtained. Further, the introduction rate of the acid group introduced into the molecule tends to be increased, and curing properties such as substrate adhesion and chemical resistance tend to be improved. The amount of the polyhydric alcohol used is usually about 0.5 to 6% by mass, preferably about 1 to 4% by mass, based on the (A-5) epoxy acrylate resin, from the viewpoints of the effects and workability due to use.

[ reaction of epoxy acrylate resin with polybasic acid anhydride and polyhydric alcohol ]

As a method for obtaining the (a-5) epoxy acrylate resin as described above and then adding the epoxy acrylate resin to a polybasic acid anhydride or to a polybasic acid anhydride and a polyhydric alcohol, a known method can be used.

the reaction temperature is usually 80-130 ℃, preferably 80-110 ℃, and the reaction is carried out for 4-15 hours until the given acid value, molecular weight, viscosity and the like are reached. When the amount is less than the above upper limit, a rapid increase in molecular weight due to polymerization of the unsaturated group tends to be suppressed, and when the amount is too low, the reaction may not proceed smoothly and the polybasic acid anhydride may remain.

< photosensitive resin composition >

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

The photosensitive resin composition preferably contains a photopolymerization initiator (b) in addition to the resin (a-1). It is preferable that the composition further contains a photopolymerizable monomer (c), a coloring material (d), and a dispersant (e), and further contains other compounding ingredients such as thiols, a dispersing aid (pigment derivative), an adhesion improving agent, a coatability improving agent, a development improving agent, an ultraviolet absorber, an antioxidant, and a surfactant as necessary, and each compounding ingredient can be usually used in a state of being dissolved or dispersed in a solvent.

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

by containing the resin (a-1) in the photosensitive resin composition of the present invention, as described later, there is a tendency that sensitivity, development adhesion, stability during development, substrate adhesion, and the like are excellent. The photosensitive resin composition of the present invention may contain other resin (a-2) in addition to the resin (a-1).

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

The photosensitive colored resin composition containing the resin (a-1) tends to be excellent in sensitivity, development adhesion, substrate adhesion, and the like. The reason for this is considered to be due to: since the resin (a-1) has a bulky cycloalkylidene group in the partial structure of the formula (II), the resistance to an alkali developing solution tends to be high; due to the presence of the bisphenol structure in the partial structure of the formula (II) and the ethylenically unsaturated group structure in the formula (I), the steric hindrance structure around the ethylenically unsaturated group is small, and hence the crosslinking reaction tends to occur easily.

In addition, it is considered that the bulky property of the whole tends to be further increased by crosslinking by ultraviolet irradiation. As a result, the line width is also increased, the resistance to alkali developing solutions is also increased, and the mechanical strength of the cured film is also increased, and it is considered that sensitivity, development adhesion, substrate adhesion, and the like are also likely to be improved.

[ other resin (a-2) ]

The other resin (a-2) that can be used in combination with the resin (a-1) is not particularly limited, but is preferably an alkali-soluble resin in which the solubility of the exposed portion and the unexposed portion with respect to alkali development is changed after exposure of a cured film obtained by applying and drying a photosensitive resin composition, more preferably an alkali-soluble resin having a carboxyl group, and still more preferably an alkali-soluble resin having an ethylenically unsaturated bond and a carboxyl group.

Specific examples thereof include: epoxy (meth) acrylate resin having a carboxyl group and acrylic copolymer resin. More specifically, the resins described as (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4) described later are preferable examples, and 1 kind or 2 or more kinds of these resins may be used. Among the above, the epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group are particularly preferable.

In order to dissolve the unexposed portion in an alkali developer in the production of a color filter, a resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group can be used. Among these resins, resins having a carboxyl group are preferable. By providing the resin with a carboxyl group, the resin tends to be more soluble in an alkali developing solution than a hydroxyl group.

In addition, although the acidity of the phosphoric acid group or sulfonic acid group is higher than that of the carboxylic acid group, the phosphoric acid group or sulfonic acid group tends to react with an initiator, a monomer, a dispersant, or other additives having basicity in the photosensitive resin composition, thereby deteriorating the storage stability.

As described above, as the other resin, the epoxy (meth) acrylate resins (A1-1) and (A1-2) having a carboxyl group and an ethylenically unsaturated group are particularly preferable. The reason for this is considered to be due to: the resins (A1-1) and (A1-2) may contain a large amount of added unsaturated groups or carboxyl groups, a large amount of aromatic ring structures, or an alicyclic structure having a large steric bulk, and have good compatibility with the resin (a-1), as in the resin (a-1), and can have good properties such as developability and pattern shape without deteriorating the effect of the resin (a-1).

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

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

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

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

An alkali-soluble resin obtained by adding an epoxy resin to an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and further reacting the resulting mixture with a polyhydric alcohol and a polybasic acid and/or an anhydride thereof.

As the epoxy (meth) acrylate resin (A1-1) and the epoxy (meth) acrylate resin (A1-2), an alkali-soluble resin (c1) and an alkali-soluble resin (c2) described in Japanese patent application laid-open No. 2013-195681, respectively, can be used.

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

Examples of the acrylic copolymer resin include: various polymer compounds described in Japanese patent laid-open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, 2003-233179, 2007-270147 and the like. The following resins (A2-1) to (A2-4) are preferable, and among them, the resin (A2-1) is particularly preferable.

(A2-1): a resin obtained by adding an unsaturated monobasic acid to at least a part of epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, or a resin obtained by adding a polybasic acid anhydride to at least a part of hydroxyl groups generated by the addition reaction (hereinafter, also referred to as "(a 2-1) resin")

(A2-2): straight-chain alkali-soluble resin having a carboxyl group in the main chain (hereinafter, also referred to as "(A2-2) resin")

(A2-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group moiety of the resin (A2-2) (hereinafter, also referred to as "A2-3 resin")

(A2-4): (meth) acrylic resin (hereinafter, also referred to as "(A2-4) resin")

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

Among these, as the (A2-1) resin, the [2-1-1] resin described in Japanese patent laid-open No. 2009-052010 can be used. Similarly, the (A2-2) resin to the (A2-4) resin may be [2-1-2] resin to [2-1-4] resin described in Japanese patent laid-open publication No. 2009-052010.

Of these resins, the photosensitive resin composition of the present invention preferably contains at least 1 of (A1-1), (A1-2), (A2-1), (A2-2), (A2-3) and (A2-4) as another resin to be used in combination with the resin (a-1).

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

In addition, it is particularly preferable that the other resin contains at least 1 of (A1-1) and (A1-2) as the alkali-soluble resin containing an ethylenically unsaturated group as the epoxy acrylate resin.

As another resin of the present invention, an alkali-soluble resin other than the above-described one may be used. There is no particular limitation as long as it is a resin selected from those generally used for photosensitive resin compositions for color filters. Examples thereof include: alkali-soluble resins described in, for example, Japanese patent laid-open Nos. 2007-271727, 2007-316620, and 2007-334290.

< photopolymerization initiator (b) >

The photosensitive resin composition of the present invention is a resin composition containing a resin (a) and a photopolymerization initiator (b). The photopolymerization initiator is a component having a function of generating a polymerization active radical by directly absorbing light to cause a decomposition reaction or a dehydrogenation reaction.

The photosensitive resin composition of the present invention contains the photopolymerization initiator (b), and can improve the crosslinking property by ultraviolet irradiation or the like, and can improve the effect of the resin (a-1). In particular, when an oxime ester compound is contained as the photopolymerization initiator (b), the effect tends to be further improved.

Examples of the photopolymerization initiator include: a metallocene compound containing a titanocene compound as described in Japanese unexamined patent publication No. Sho 59-152396 and Japanese unexamined patent publication No. Sho 61-151197; hexaarylbiimidazole derivatives as described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503Radical activators and α -aminoalkylphenone derivatives such as oxadiazole derivatives, halomethyl s-triazine derivatives, and N-aryl- α -amino acids such as N-phenylglycine, N-aryl- α -amino acid salts, and N-aryl- α -amino acid esters; oxime ester derivatives described in, for example, Japanese patent application laid-open Nos. 2000-80068 and 2006-36750.

Specifically, for example, as titanocene derivatives, there can be mentioned: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5, 6-pentafluoro-1-yl) titanium, dicyclopentadienyl bis (2,3,5, 6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,4, 6-trifluorophenyl-1-yl) titanium, dicyclopentadiene bis (2, 6-difluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2, 4-difluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl-1-yl) titanium and dicyclopentadienyl [2], 6-difluoro-3- (pyrrol-1-yl) -phen-1-yl ] titanium and the like.

Examples of the bisimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, and (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer, and the like.

In addition, as halomethylationOxadiazole derivatives, for example: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-oxadiazole and 2-trichloromethyl-5-furyl-1, 3,4-Oxadiazoles, and the like.

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

Further, as α -aminoalkylphenone derivatives, for example: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopentylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin And 4- (diethylamino) chalcone.

As the photopolymerization initiator, oxime derivatives (oximes and ketoximes) are effective particularly in terms of sensitivity, and may be disadvantageous in terms of sensitivity when an alkali-soluble resin containing a phenolic hydroxyl group is used, and the like. Among the oxime derivatives, oxime esters are preferred, particularly from the viewpoint of high sensitivity at high pigment concentration.

The photopolymerization initiator of oxime ester has a structure that absorbs ultraviolet light, transmits light energy, and generates radicals, and therefore, can be designed using a small amount of a photosensitive resin composition, i.e., having high sensitivity and stable against thermal reaction, and can realize high sensitivity in a small amount.

In particular, an oxime ester compound having a carbazole ring is more preferable because the structural characteristics are exhibited well. At present, the market demands high opacity, thin film BM (black matrix), and pigment concentration is becoming higher and higher. In such a context, it is particularly effective.

The resin (a-1) contained in the photosensitive resin composition of the present invention has a structure in which a biphenyl structure and a largely extended alicyclic structure having 10 or more carbon atoms are largely distorted by a bonding portion thereof, and a structure having an ethylenically unsaturated group is formed by the biphenyl structure, and therefore, a crosslinked structure extending in a three-dimensional distorted manner can be produced by irradiation with ultraviolet light. Therefore, it is considered that the sensitivity is improved, the line width is widened, the alkali-resistant developing solution property is also improved, and the stability to an alkali developing solution is also increased. In particular, it is considered that these effects are further improved when a small amount of a photopolymerization initiator of oxime ester, which can exhibit high sensitivity, is combined.

Examples of the oxime compound include compounds containing a structural moiety represented by the following general formula (22), and oxime ester compounds represented by the following general formula (23) are preferred.

[ chemical formula 55]

In the above formula (22), R²²Represents an 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, a cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a heteroarylacyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, which are optionally substituted.

[ chemical formula 56]

In the above formula (23), R^21aRepresents hydrogen, or optionally substituted alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 25 carbon atoms, aryl having 6 to 20 carbon atoms, heteroarylalkyl having 1 to 20 carbon atoms, alkoxycarbonylalkyl having 3 to 20 carbon atoms, phenoxycarbonylalkyl having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl or heteroarylsulfanyl having 1 to 20 carbon atoms, aminoalkyl having 1 to 20 carbon atoms, alkanoyl having 2 to 12 carbon atoms, alkenoyl having 3 to 25 carbon atoms, cycloalkoyl having 3 to 8 carbon atoms, aroyl having 7 to 20 carbon atoms, heteroaroyl having 1 to 20 carbon atoms, alkoxycarbonyl having 2 to 10 carbon atoms, aryloxycarbonyl having 7 to 20 carbon atoms, or cycloalkylalkyl having 1 to 10 carbon atoms. R^21bRepresents any substituent comprising an aromatic or heteroaromatic ring.

In addition, R is^21aOr with R^21bForm a ring together, and examples of the linking group include an optionally substituted alkylene group having 1 to 10 carbon atoms, and a polyethylene group (- (CH ═ CH)_r-), polyethyleneinyl (- (C.ident.C)_r-) or a combination thereof (where r is an integer of 0 to 3). R^22aR in the above formula (22)²²The same groups.

Among these groups, R in the above general formula (22) is a group represented by formula (22) from the viewpoint of sensitivity²²And R in the above general formula (23)^22aThe alkanoyl group preferably includes an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms, more preferably an alkanoyl group having 2 to 10 carbon atoms, and still more preferably an alkanoyl group having 2 to 5 carbon atoms.

R in the above general formula (23) is^21aFrom the viewpoint of solubility in a solvent and sensitivity, preferred examples thereof include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkylalkyl group having 1 to 10 carbon atoms, and an optionally substituted aryl group having 6 to 20 carbon atoms. More preferred are methyl, ethyl, propyl, cyclopentylethyl, propyl optionally substituted with 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl or N-acetyl-N-acetoxyamino.

R in the above general formula (23) is^21bPreferred examples thereof include an optionally substituted carbazolyl group, an optionally substituted thioxanthone group and an optionally substituted thiophenyl group. For the reasons described above, it is more preferable to contain a carbazolyl group as R^21bThe case (1). In addition, oxime ester initiators having a carbazolyl group containing a nitro group are also effective.

As the oxime ester initiator, it is preferable to contain a carbazolyl group as R for the reasons described above^21b. Further, preferred is a carbazolyl group having at least one group selected from the group consisting of: 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, an optionally substituted heteroarylcarbonyl group having 6 to 25 carbon atoms, and a nitro group. In particular, from the viewpoint of sensitivity, a carbazolyl group having at least one group selected from the group consisting of: benzoyl, toluoyl, naphthoyl, thienylcarbonyl, and nitro. In addition, the first and second substrates are,Preferably, these groups are bonded to the 3-position of the carbazolyl group. Similarly, the C atom in the above formula (23) is preferably bonded to the 6-position of the carbazolyl group.

The H atom bonded to the N atom of the carbazolyl group may be substituted with an optional substituent, and as an optional substituent, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is even more preferable, from the viewpoint of solubility in a solvent.

As the initiator used in the present invention, oxime esters are useful. Oxime ester initiators having carbazolyl groups are preferred. More preferably, R of the above general formula (23) is used^21aAn oxime ester initiator having a straight chain alkyl group and a cycloalkyl group or an oxime ester initiator having a nitro group on a carbazolyl group. Examples of such commercially available initiators include: OXE-02 manufactured by BASF corporation, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power electronics.

Specific examples of oxime ester compounds preferable in the present invention include the following compounds, but are not limited to these compounds at all.

[ chemical formula 57]

[ chemical formula 58]

[ chemical formula 59]

[ chemical formula 60]

[ chemical formula 61]

[ chemical formula 62]

[ chemical formula 63]

[ chemical formula 64]

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

[ chemical formula 65]

In the above general formula (24), R²⁴And R in the above general formula (22)²²Synonymously.

[ chemical formula 66]

In the above general formula (25), R^23aRepresents an 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, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or 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 aroyl group having 7 to 20 carbon atomsA heteroaromatic acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

R^23bRepresents any substituent comprising an aromatic or heteroaromatic ring. In addition, R is^23aOr with R^23bForm a ring together, and examples of the linking group include an optionally substituted alkylene group having 1 to 10 carbon atoms, and a polyethylene group (- (CH ═ CH)_r-), polyacetylene (- (C.ident.C)_r-) or a combination thereof (where r is an integer of 0 to 3).

R^24aRepresents an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaroyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, each of which is optionally substituted.

As R in the above general formula (24)²⁴And R in the above general formula (25)^24aPreferred examples thereof include alkanoyl groups having 2 to 12 carbon atoms, heteroarylalkanoyl groups having 1 to 20 carbon atoms, cycloalkanoyl groups having 3 to 8 carbon atoms and aroyl groups having 7 to 20 carbon atoms.

As R in the above general formula (25)^23aPreferred examples thereof include an unsubstituted ethyl group, a propyl group, a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.

R in the above general formula (25) is^23bPreferred examples thereof include an optionally substituted carbazolyl group and an optionally substituted thiophenyl group. For the reasons mentioned above, R is more preferably R^23bAnd carbazolyl group.

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

[ chemical formula 67]

[ chemical formula 68]

[ chemical formula 69]

[ chemical formula 70]

These oxime and ketoxime ester compounds are known per se, and are, for example, one of a series of compounds described in Japanese patent laid-open Nos. 2000-80068 and 2006-36750. The photopolymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Further, for example: benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthrone derivatives such as 2-methylanthrone, 2-ethylanthrone, 2-tert-butylanthrone and 1-chloroanthrone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; acetophenone derivatives such as 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxy-2-methylphenyl acetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4' -methylthiophenyl) -2-morpholino-1-propanone and 1,1, 1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone; benzoate derivatives such as ethyl p- (dimethylamino) benzoate and ethyl p- (diethylamino) benzoate; acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9, 10-dimethylbenzophenazine; anthrone derivatives such as benzanthrone and the like. Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the reasons described above.

In the photosensitive resin composition of the present invention, the following accelerator, sensitizing dye and other additives may be used in combination with the photopolymerization initiator as required.

< Accelerator >

As the accelerator, for example: 2-mercaptobenzothiazole, 2-mercaptobenzothiazoleHeterocyclic mercapto compounds such as oxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds. The accelerator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

< sensitizing dye >

For the purpose of improving the sensitivity, a sensitizing dye corresponding to the wavelength of the image exposure light source may be used in combination as necessary in the photopolymerization initiator. Examples of the sensitizing dye include xanthene dye described in Japanese patent application laid-open No. 4-221958, xanthene dye described in Japanese patent application laid-open No. 4-219756, coumarin dye having a heterocyclic ring described in Japanese patent application laid-open No. 3-239703, coumarin dye having a heterocyclic ring described in Japanese patent application laid-open No. 5-289335, 3-oxocoumarin compound described in Japanese patent application laid-open No. 3-239703, 3-oxocoumarin compound described in Japanese patent application laid-open No. 5-289335, and tolylpyrrole dye described in Japanese patent application laid-open No. 6-19240, and further, Japanese patent application laid-open Nos. 47-2528, 54-155292, 45-37377, 48-84183, 52-112681, 58-03, 60-88005, And pigments having a dialkylaminobenzene skeleton as described in Japanese patent laid-open Nos. 59-56403, 2-69, 57-168088, 5-107761, 5-210240, and 4-288818.

Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example: benzophenone compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoAzole, 2- (p-diethylaminophenyl) benzoAzole, 2- (p-dimethylaminophenyl) benzo [4, 5]]Benzo (b) isAzole, 2- (p-dimethylaminophenyl) benzo [6, 7]]Benzo (b) isOxazole, 2, 5-bis (p-diethylaminophenyl) 1,3,4-P-dialkylaminophenyl group-containing compounds such as 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. Among them, the most preferable is 4, 4' -dialkylaminobenzophenone. The sensitizing dye may be used alone in 1 kind, or may be used in combination of 2 or more kindsThe application is as follows.

< photopolymerizable monomer (c) >

The photosensitive resin composition of the present invention preferably contains a photopolymerizable monomer (c) from the viewpoint of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least 1 ethylenically unsaturated group in the molecule (hereinafter also referred to as "ethylenic monomer"). Specific examples thereof include: and monoesters of (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, and carboxylic acids having 1 ethylenically unsaturated bond with polyhydric or 1-membered alcohols.

In the present invention, a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in 1 molecule is particularly preferably used. Examples of such polyfunctional olefinic monomers include: esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polycarboxylic acid.

Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include: examples of the acrylic acid ester include acrylic acid esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic acid esters obtained by replacing acrylic acid esters of these exemplified compounds with methacrylic acid esters, itaconic acid esters obtained by replacing acrylic acid esters of these exemplified compounds with itaconic acid esters, crotonic acid esters obtained by replacing crotonic acid esters, and maleic acid esters obtained by replacing maleic acid esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.

The esters obtained by esterification of polycarboxylic acids and unsaturated carboxylic acids with polyhydric hydroxyl compounds are not necessarily a single substance, and representative examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol, and the like.

Further, as the polyfunctional olefinic monomer used in the present invention, for example, there can be mentioned: urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate. These monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

< color Material (d) >

The photosensitive resin composition of the present invention preferably contains a coloring material (d) when used for formation of a pixel of a color filter, a black matrix, or the like. By containing the color material (d), the color filter can be provided with light-shielding properties or color characteristics. The coloring material is a material for coloring the photosensitive resin composition of the present invention. As the color material, a dye pigment can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance, and the like, and from the viewpoint of light-shielding properties and color characteristics, and further, a dispersant described later is preferably contained in order to disperse the pigment well.

Examples of pigments include: pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, violet pigment, orange pigment, brown pigment and black pigment. In addition, as the structure thereof, in addition toFor example azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, bisindolinoneIn addition to organic pigments such as oxazines, indanthrene and perylene, various inorganic pigments can be used.

Specific examples of pigments that can be used in the present invention are shown below by the pigment numbers. Note that the terms "c.i. pigment red 2" and the like listed below refer to the pigment reference number (c.i.).

Examples of the red pigment include: c.i. pigment red 1,2,3, 4,5,6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:2, 53:1, 53:2, 53:3, 57:1, 57:2, 58:4, 60, 63:1, 63:2, 64:1, 68, 69, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101:1, 104, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 169, 151, 166, 168, 149, 170, 172, 176, 187, 188, 194, 185, 194, 187, 194, 187, 194, 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 them, c.i. pigment red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 are preferable, and c.i. pigment red 177, 209, 224, and 254 are more preferable.

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

Among them, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4 and 15:6 are preferable, and c.i. pigment blue 15:6 is more preferable.

Examples of the green pigment include: c.i. pigment green 1,2,4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Among them, c.i. pigment green 7, 36 and 58 are preferably listed.

Examples of the yellow pigment include: pigment yellow 1, 1:1, 2,3,4,5,6, 9,10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 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, 127:1, 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, 185, 188, 193, 198, 195, 185, 193, 195, 197, 190, 194, 197, 200, 199, 200, 199, 196, 200, 199, 200, 150, and 199, 203. 204, 205, 206, 207 and 208. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150 and 180 are more preferable.

Examples of orange pigments include: pigment orange 1,2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among them, c.i. pigment orange 38 and 71 are preferred.

Examples of violet pigments include: c.i. pigment violet 1, 1:1, 2:2, 3:1, 3:3, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. Among them, c.i. pigment violet 19 and 23 are preferable, and c.i. pigment violet 23 is more preferable.

In the case where the photosensitive resin composition of the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black color material can be used as the color material (d). The black color material may be a single black color material or a mixture of red, green, blue, and the like. The color materials may be appropriately selected from inorganic or organic pigments and dyes.

Examples of color materials that can be used in combination for preparing a black color material include: victoria pure blue (42595), basic Sophora Yellow O (41000), カチロンブリリアントフラビン (basic 13), rhodamine 6GCP (45160), rhodamine B (45170), safranine OK70:100(50240), Papaver Red X (42080), No. 120/Reynolds Yellow (Lionol Yellow) (21090), Reonol Yellow GRO (21090), Schlemlerian fast Yellow 8GF (21105), benzidine Yellow 4T-564D (21095), Schlemlerian fast Red 4015(12355), Reonol Red 7B4401(15850), Fasttogen BlueTGR-L (74160), Reonol blue SM 26150, Reonol blue ES (pigment blue 15:6), Lionogren red GD (pigment Red 168), and Reonol Green 2YS (pigment Green 36) [ to be noted, the above is the number () used to indicate the index (I.C.).

Further, as other pigments which can be used in combination, there can be mentioned, for example, the following pigments, if they are represented by C.I. symbol: c.i. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, and 166, c.i. orange pigments 36, 43, 51, 55, 59, and 61, c.i. red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, and 240, c.i. violet pigments 19, 23, 29, 30, 37, 40, 50, c.i. blue pigments 15, 15:1, 15:4, 22, 60, and 64, c.i. green pigment 7, and c.i. brown pigments 23, 25, and 26, and the like.

As the black color material which can be used alone, a black pigment is preferable in order to obtain high light-shielding properties. Examples of the black pigment include: carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, Sabinan black, titanium black, and the like.

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

Mitsubishi chemical corporation: MA7, MA77, MA8, MA11, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, # 0, #3750, #4000, #4010, # 7B, OIL9B, OIL11B, OIL30B and OIL31B

Manufactured by Degussa: printex (registered trademark, the same below) 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, Special Black550, Special Black350, Special Black250, Special Black100, Special Black6, Special Black5, Special Black4, Color FW1, Color FW2, Color FW2V, Color FW18, Color FW18, Color FW 160, Color FW 170, Color FW S200

Manufactured by Cabot corporation: monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same below) XC72R, and ELFTEX (registered trademark) -8

Manufactured by Colombiyan Carbon corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, and RAVEN7000

As the other black pigment, for example, titanium black, aniline black, and iron oxide-based black pigments, and a mixture of three color organic pigments of red, green, and blue can be used as the black pigment.

Carbon black coated with a resin may be used as the carbon black. When carbon black coated with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. The carbon black coated with a resin is preferably, for example, carbon black described in Japanese patent application laid-open No. 09-71733.

The carbon black to be coated preferably has a total content of Na and Ca of 100ppm or less. Carbon black generally contains ash of Na, Ca, K, Mg, Al, Fe, or the like in a composition that is mixed from a raw oil or fuel (or gas) at the time of production, water at which reaction stops or granulating water, or furnace material of a reaction furnace, or the like. Among them, the content of Na or Ca is usually several hundred ppm or more, respectively, because if they are present in a large amount, they may penetrate into the transparent electrode (ITO) or other electrodes to cause electrical short circuits.

As a method for reducing the content of these ashes containing Na or Ca, it is possible to strictly select a substance having as small an ash content as possible as a raw oil or a fuel oil (or gas) and stop water of reaction at the time of producing carbon black, and to reduce the amount of an alkali substance for adjusting the structure as much as possible. As another method, there is a method of removing Na or Ca by dissolving it by washing carbon black discharged from a furnace with water, hydrochloric acid, or the like.

Since the surfaces of these black pigments are often acidic, it is preferable that the dispersant to be combined is a polymer compound having a basic functional group in order to disperse the black pigment well.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, lead yellow, iron oxide red, chromium oxide, or the like can be used. A plurality of the above-mentioned pigments may be used in combination. For example, a green pigment may be used in combination with a yellow pigment, or a blue pigment may be used in combination with a violet pigment, in order to adjust the chroma.

< particle size of pigment >

In the photosensitive resin composition of the present invention, the average primary particle size of the pigment that can be used as the color material (d) is not particularly limited as long as a desired color development can be obtained when the colored layer of the color filter is formed, and varies depending on the type of the pigment used, but is preferably within a range of 10 to 100nm, more preferably within a range of 10 to 70 nm.

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

When the pigment is carbon black, the average primary particle size of the pigment is preferably 100nm or less, more preferably 60nm or less, and still more preferably 50nm or less. When the pigment is carbon black, the average primary particle diameter of the pigment is preferably 20nm or more. If the pigment is too large, scattering becomes large, and color characteristics such as light-shielding property or contrast are deteriorated. Further, if the pigment particle diameter is too small, the necessary amount of the dispersant increases, and the dispersibility decreases.

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

The photosensitive resin composition of the present invention preferably contains at least a pigment, but in addition to this, a dye may be used in combination within a range not affecting the effects of the present invention. Examples of dyes that can be used in combination include: azo dyes, anthrone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.

As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, and the like.

Examples of the anthrone dyes include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, and the like.

Further, as phthalocyanine-based dyes, for example: c.i. vat blue 5, etc.; examples of the quinoneimine-based dye include: c.i. basic blue 3, c.i. basic blue 9, and the like.

Examples of quinoline dyes include: c.i. solvent yellow 33, c.i. acid yellow 3, c.i. disperse yellow 64, and the like; examples of the nitro dye include: c.i. acid yellow 1, c.i. acid orange 3, c.i. disperse yellow 42, and the like.

< dispersant (e) >

In the case where the color material (d) is used in the photosensitive resin composition of the present invention, it is important to finely disperse the color material and stabilize the dispersed state thereof in order to ensure stability of quality, and therefore, a dispersant is preferably contained.

The dispersant is preferably a polymer dispersant having a functional group, and further preferably a polymer dispersant having the following functional group from the viewpoint of dispersion stability: a carboxyl group; a phosphate group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; and groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine.

Among them, those having a primary amino group, a secondary amino group or a tertiary amino group are particularly preferable; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. By using such a polymer dispersant having a basic functional group, the dispersibility can be improved, and particularly when a black pigment is used as a coloring material, high light-shielding properties tend to be achieved.

Examples of the polymeric dispersant include: polyurethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of an amino group-containing monomer and a macromolecular monomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersant include: EFKA (registered trademark, made by EFKA Chemicals BV (EFKA)), Disperbyk (registered trademark, made by BYK-Chemie Co., Ltd.), BYK-Disparlon (registered trademark, made by Nanguo Kabushiki Kaisha), SOLSPERSE (registered trademark, made by Lubrizol Co., Ltd.), KP (made by shin-Etsu chemical Co., Ltd.), Polyflow, Floren (made by Kyoho chemical Co., Ltd.), Ajiser (registered trademark, made by Ajinomoto Fine-Techno Co., Ltd.), and the like. These polymeric dispersants may be used alone in 1 kind, or in combination of 2 or more kinds.

Among these dispersants, it is particularly preferable that the dispersant (e) contains a polyurethane-based polymer dispersant and/or an acrylic polymer dispersant having a basic functional group, from the viewpoint of adhesion and linearity. Particularly, polyurethane-based polymer dispersants are preferred in view of adhesion. In addition, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and/or a polyether bond is preferable.

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

Examples of the polyurethane and acrylic polymer dispersant include: disperbyk 160-167 and 182 series (both polyurethanes), and Disperbyk2000 and 2001 (both acrylics) (both manufactured by BYK-Chemie, Inc.). Among the above-mentioned polyurethane polymer dispersants having a basic functional group and a polyester and/or polyether bond, examples of particularly preferable dispersants having a weight average molecular weight of 30,000 or less include Disperbyk167 and 182.

(polyurethane polymer dispersant)

If the chemical structure preferred as the polyurethane-based polymeric dispersant is to be specifically exemplified, there are exemplified: and a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule.

Examples of the polyisocyanate compound include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4,4 '-diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate and dimethylbiphenyl diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4, 4' -methylenebis (cyclohexyl isocyanate) and omega, omega '-diisocyanate dimethylcyclohexane, aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and alpha, alpha' -tetramethylxylylene diisocyanate, and the like, Triisocyanates such as lysine ester triisocyanate, 1,6, 11-undecane triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate and triphenylthiophosphate triisocyanate, trimers and water adducts thereof, and polyol adducts thereof.

As the polyisocyanate, a trimer of an organic diisocyanate is preferable, and a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate are most preferable. These polyisocyanate compounds can be used alone in 1, or can be used in combination of 2 or more.

Examples of the method for producing an isocyanate trimer include the following methods: the polyisocyanate is partially trimerized with an isocyanate group using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the objective isocyanurate group-containing polyisocyanate.

Examples of the compound having a number average molecular weight of 300 to 10,000 and 1 or 2 hydroxyl groups in the same molecule include: a compound obtained by alkoxylating one terminal hydroxyl group of the compound with an alkyl group having 1 to 25 carbon atoms, such as polyether diol, polyester diol, polycarbonate diol, and polyolefin diol, and a mixture of 2 or more of them.

Examples of polyether diols include: polyether diol, polyether ester diol and a mixture of more than 2 of the polyether diol and the polyether ester diol. Examples of the polyether glycol include polyether glycols obtained by homopolymerizing or copolymerizing alkylene oxides, such as: polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and mixtures of 2 or more thereof.

As the polyether ester diol, there may be mentioned: polyether ester diols obtained by reacting a diol having an ether group or a mixture with another diol with a dicarboxylic acid or an anhydride thereof, or by reacting an alkylene oxide with a polyester diol, such as poly (polyoxytetramethylene) adipate.

The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound obtained by alkoxylating one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester diol include: dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and diols (e.g., 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, etc.), 2,2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octamethylene glycol, aliphatic diols such as 2-methyl-1, 8-octamethylene glycol and 1, 9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, aromatic diols such as benzenedimethanol and bis (hydroxyethoxy) benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine). Specific examples thereof include: polyethylene glycol adipate, polybutylene adipate, 1, 6-hexanediol adipate, polyethylene glycol/propylene glycol adipate, and the like.

Further, examples thereof include: a polylactone diol or polylactone monool obtained by using the above diol or monohydric alcohol having 1-25 carbon atoms as an initiator. Specific examples thereof include: polycaprolactone diol, polymethylvalerolactone and a mixture of more than 2 of the polycaprolactone diol and the polymethylvalerolactone. The polyester diol is most preferably polycaprolactone diol or polycaprolactone obtained using an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of the polycarbonate diol include: poly (1, 6-hexanediol) carbonate, poly (3-methyl-1, 5-pentanediol) carbonate, and the like. Examples of the polyolefin glycol include: polybutadiene diol, hydrogenated polyisoprene diol, and the like. These polycarbonate diols may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

The compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. As the active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, there may be exemplified: among the hydrogen atoms in the functional groups such as a hydroxyl group, an amino group, and a thiol group, the hydrogen atom of an amino group, particularly a primary amino group, is preferable.

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, a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

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

In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ringNitrogen-containing 6-membered hetero rings such as an N5-membered hetero ring, e.g., an azole ring, a benzothiazole ring, or a benzothiadiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, or an isoquinoline ring. Among these nitrogen-containing heterocycles, preferred is an imidazole ring or a triazole ring.

Among these, examples of the compound having an imidazole ring and an amino group include: 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole, and the like.

In addition, 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-amino-1, 4-diphenyl-1, 2, 3-triazole, and 3-amino-1-benzyl-1H-2, 4-triazole, and the like. Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1, 2, 4-triazole are preferable. These compounds may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The preferable mixing ratio of the raw materials for producing the polyurethane polymer dispersant is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the same molecule, and 0.2 to 25 parts by mass, and preferably 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule, based on 100 parts by mass of the polyisocyanate compound.

The polyurethane polymer dispersant is produced by a known method for producing a polyurethane resin. As the solvent for the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, hydrocarbons such as benzene, toluene, xylene and hexane, partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tert-butyl alcohol, chlorides such as dichloromethane and chloroform, ethers such as tetrahydrofuran and diethyl ether, and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide are generally used. These solvents may be used alone in 1 kind, or 2 or more kinds may be used in combination.

In the above production, a urethane reaction catalyst is usually used. Examples of the catalyst include: 1 or more than 2 kinds of tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octylate, iron compounds such as iron acetylacetonate and iron chloride, and tertiary amines such as triethylamine and triethylenediamine.

< method for measuring amine value >

The tertiary amine value of a dispersant such as a block copolymer is represented by the mass of KOH equivalent to the amount of base per 1g of solid content excluding a solvent in a dispersant sample, and can be measured by the following method. Firing at 100mL0.5 to 1.5g of a dispersant sample was precisely weighed in a cup and dissolved in 50mL of acetic acid. Using an automatic titration apparatus equipped with a pH electrode, 0.1mol/L of HClO was used₄(perchloric acid) acetic acid solution the solution was subjected to a neutralization titration. The inflection point of the titration pH curve was used as the end point of titration, and the amine value was determined by the following equation.

Amine value [ mgKOH/g ] (561 XV)/(W. times.S)

[ wherein, W: represents the weighed amount [ g ] of the dispersant sample, V: the titration amount [ mL ] at the end of the titration, and S, the solid content concentration [ mass% ] of the dispersant sample. ]

The amount of the compound having an active hydrogen and a tertiary amino group introduced in the same molecule is preferably controlled in the range of 1 to 100mgKOH/g, more preferably 5 to 95mgKOH/g, based on the amine value after the reaction. The amine number is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the amine value is less than the above range, the dispersibility tends to be lowered, and when the amine value exceeds the above range, the developability tends to be lowered.

In the case where an isocyanate group remains in the polymer dispersant in the above reaction, it is preferable that the isocyanate group is further destroyed by an alcohol or an amino compound because the stability of the product with time is increased.

The weight average molecular weight (Mw) of the polyurethane polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 30,000 or less. When the molecular weight is less than 1,000, dispersibility and dispersion stability are poor, and when it exceeds 200,000, solubility is lowered, dispersibility is poor, and control of the reaction tends to be difficult. When the molecular weight is 30,000 or less, the alkali developability tends to be good particularly even when the pigment concentration is high. Examples of such particularly preferred commercially available polyurethane dispersants include Disperbyk167 and 182 (BYK-Chemie).

(acrylic Polymer dispersant)

As the acrylic polymer dispersant, a random polymer, a graft copolymer, or a block copolymer of an unsaturated group-containing monomer having a functional group (the functional group mentioned here is a functional group described above as a functional group contained in the polymer dispersant) and an unsaturated group-containing monomer having no functional group is preferably used. These copolymers can be produced by a known method.

Examples of the unsaturated group-containing monomer having a functional group include: unsaturated monomers having a tertiary amino group or quaternary ammonium salt group, such as unsaturated monomers having a carboxyl group, e.g., (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or quaternary ammonium salt group, e.g., dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternary ammonium salts thereof. These monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the unsaturated group-containing monomer having no functional group include: n-substituted maleimides such as 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, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, alpha-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide, and the like, Acrylonitrile, vinyl acetate, polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly (meth) acrylic acid 2-hydroxyethyl ester macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and the like. These monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(acrylic block copolymer)

In the photosensitive resin composition of the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant in order to improve the dispersibility of the colorant and the dispersion stability. It is considered that the nitrogen atom-containing acrylic block copolymer as described above contributes to improvement of dispersion stability as a whole because the nitrogen atom contained therein has affinity for the surface of the coloring agent and the portion other than the nitrogen atom has improved affinity for the medium. The performance of a dispersant is the adsorption behavior with respect to its solid surface. The detailed mechanism of the excellent adsorption behavior of the block copolymer is not clear, but the following is presumed.

That is, in the case of a conventional random copolymer, the probability that the monomers constituting the copolymer are spatially and/or electrically stably arranged in the copolymer at the time of copolymerization is increased. On the other hand, since the portion (molecule) where the monomer is stably arranged is spatially and/or electrically stable, adsorption to the colorant may be an obstacle.

In contrast, in the resin having a controlled molecular arrangement such as a block copolymer, a portion that inhibits adsorption of the dispersant can be disposed at a position distant from the adsorption portion between the pigment and the dispersant. That is, a portion optimal for adsorption may be disposed in the adsorption portion between the colorant and the dispersant, and a portion appropriate for solvent affinity may be disposed in a portion requiring solvent affinity. In particular, it is presumed that the molecular arrangement affects the favorable dispersibility of the colorant containing a colorant having a small crystallite size.

From the viewpoint of enabling the colorant used in the present invention to be dispersed extremely efficiently, an acrylic block copolymer containing a nitrogen atom is preferable. The reason is not clear, but it is presumed that: since the molecular arrangement is controlled, there is little structure that becomes an obstacle when the dispersant adsorbs to the colorant.

The acrylic block copolymer is preferably an a-B block copolymer and/or a B-a-B block copolymer composed of an a block having a quaternary ammonium salt group and/or an amino group in a side chain and a B block having no quaternary ammonium salt group and no amino group.

in the case where the A block has a quaternary ammonium salt group, the quaternary ammonium salt group is preferably represented by-N⁺R⁵¹R⁵²R⁵³·M^-(wherein, R⁵¹、R⁵²And R⁵³Each independently represents a hydrogen atom or an optionally substituted cyclic or linear hydrocarbon group. Alternatively, R may be substituted with⁵¹、R⁵²And R⁵³2 or more of them are bonded to each other to form a ring structure, M^-Representing a counter anion). The quaternary ammonium salt group may be directly bonded to the main chain, but may be bonded to the main chain via a 2-valent linking group.

in-N⁺R⁵¹R⁵²R⁵³In (1) as represented by R⁵¹、R⁵²And R⁵³The cyclic structure formed by bonding at least 2 of them to each other includes, for example: 5-7 membered ring nitrogen-containing heterocyclic monocyclic ring or condensed ring formed by condensing 2 of them. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring. Specific examples thereof include the following. These cyclic structures may further have a substituent.

[ chemical formula 71]

In the above formula, R represents R⁵¹～R⁵³Any 1 group of (1). as-N⁺R⁵¹R⁵²R⁵³R in (1)⁵¹～R⁵³more preferred is an optionally substituted alkyl group having 1 to 3 carbon atoms, an optionally substituted phenyl group, or an optionally substituted benzyl group.

In addition, as with quaternary ammonium salt group A block, especially preferably containing the following general formula (e1) shown in the partial structure.

[ chemical formula 72]

In the above formula (e1), R⁵¹、R⁵²、R⁵³Each independently represents a hydrogen atom or an optionally substituted cyclic or linear hydrocarbon group. Alternatively, R may be substituted with⁵¹、R⁵²And R⁵³2 or more of them are bonded to each other to form a ring structure. R⁵⁴Represents a hydrogen atom or a methyl group. X represents a 2-valent linking group, M^-Represents a counter anion.

In the above general formula (e1), R⁵¹、R⁵²、R⁵³The hydrocarbyl group(s) is (are) preferably an alkyl group having 1 to 10 carbon atoms or a substituent having an aromatic group having 6 to 20 carbon atoms. Specific examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl, phenyl and the like. Among them, methyl, ethyl, propyl, and benzyl are preferable.

In the general formula (e1), examples of the linking group X having a valence of 2 include: alkylene group having 1 to 10 carbon atoms, arylene group, -CONH-R⁵⁵-、-COO-R⁵⁶- (wherein, R)⁵⁵And R⁵⁶Represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (-R)⁵⁷-O-R⁵⁸-:R⁵⁷And R⁵⁸Each independently represents an alkylene group)), etc., preferably-COO-R⁵⁶-。

In addition, as a counter anion M^-Examples thereof include: cl^-、Br^-、I^-、ClO₄ ^-、BF₄ ^-、 CH₃COO^-And PF₆ ^-And the like.

The partial structure containing a specific quaternary ammonium salt group as described above may contain 2 or more kinds in 1 a block. In this case, 2 or more kinds of quaternary ammonium salt group-containing partial structures may be contained in the a block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing such a quaternary ammonium salt group may be contained in the a block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer described later.

The content of such a partial structure not containing a quaternary ammonium salt group in the a block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, and most preferably such a partial structure not containing a quaternary ammonium salt group is not contained in the a block.

The a block of the acrylic block copolymer may have an unreacted tertiary amino group which is not quaternized.

When the a block has an amino group, the amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. The content of the monomer having a primary amino group, a secondary amino group, and a tertiary amino group is preferably 20 mol% or more, and more preferably 50 mol% or more of the monomer composition constituting the acrylic block copolymer. The amino group may be directly bonded to the main chain or may be bonded to the main chain via a linking group having a valence of 2.

The primary amino group, secondary amino group and tertiary amino group are preferably represented by-NR⁶¹R⁶²(wherein, R⁶¹And R⁶²Each independently represents a cyclic or linear alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent), and a partial structure (repeating unit) containing the group preferably includes, for example, a structure represented by the following general formula.

[ chemical formula 73]

Wherein R is⁶¹And R⁶²And R as defined above⁶¹And R⁶²Synonymy, R⁶³Represents an alkylene group having 1 or more carbon atoms, R⁶⁴Represents a hydrogen atom or a methyl group. Wherein R is⁶¹And R⁶²Preferably methyl, R⁶³Preferably methylene, ethylene, R⁶⁴Preferably 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 or the like is particularly preferably used.

[ chemical formula 74]

In the above formula, R⁶⁴Are synonymous with the foregoing.

Further, the amino group-containing partial structure may contain 2 or more kinds in 1 a block. In this case, 2 or more kinds of amino group-containing partial structures may be contained in the a block in any form of random copolymerization or block copolymerization.

In addition, a partial structure containing no amino group may be partially contained in the A block. Examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. The content of such a partial structure not containing an amino group in the a block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, and most preferably such a partial structure not containing an amino group is not contained in the a block.

The a block may have either a quaternary ammonium salt group or an amino group, or both.

On the other hand, the B block constituting the acrylic block copolymer is not particularly limited as long as it is a block formed of a monomer which does not have the quaternary ammonium salt group and the amino group and is copolymerizable with the monomer constituting the a block. The B block is a solvent-philic site having no nitrogen atom-containing functional group serving as a pigment adsorption group, and has an affinity with a solvent, and therefore has an effect of stabilizing a pigment adsorbed on a dispersant in the solvent.

Examples of the B block include a polymer structure obtained by copolymerizing the following comonomers: styrene monomers such as styrene and alpha-methylstyrene; (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethacrylate, and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide, N-methylolacrylamide, N-dimethylacrylamide, and N, N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and crotonic acid glycidyl ether; n-methacryloylmorpholine and the like.

The B block particularly preferably contains a partial structure derived from a (meth) acrylate monomer represented by the following formula (e 2).

[ chemical formula 75]

in the above formula (e2), R⁶¹Represents a hydrogen atom or a methyl group. R⁶²Represents a cyclic or linear alkyl group optionally having a substituent, an allyl group optionally having a substituent, or an aralkyl group optionally having a substituent.

The partial structure derived from the (meth) acrylate monomer may contain 2 or more species in 1B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from 2 or more kinds of monomers is present in a B block not containing a quaternary ammonium salt group, each partial structure may be contained in the B block in any form of random copolymerization or block copolymerization.

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

The acrylic dispersant used in the present invention is an a-B block or B-a-B block copolymer type polymer compound composed of such a block and a block, and such a block copolymer can be produced by, for example, living polymerization.

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 described in Japanese patent laid-open No. 2007-270147 is mentioned.

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

That is, in the a-B block copolymer and the B-a-B block copolymer of the present invention, when the a block has a quaternary ammonium salt group, the amount of the quaternary ammonium salt group in 1g of the copolymer is preferably 0.1 to 10mmol in general, and when it is not within this range, good heat resistance and dispersibility may not be compatible.

in general, such a block copolymer may contain an amino group generated in the production process, but the amine value thereof is usually about 1 to 100mgKOH/g, preferably 1 to 80mgKOH/g, and more preferably 1 to 50 mgKOH/g.

when the block A does not contain a quaternary ammonium salt group, the amine value of the copolymer is usually about 50 to 300mgKOH/g, preferably 50 to 200mgKOH/g, more preferably 80mgKOH/g or more and 150mgKOH/g or less, and further preferably 90 to 150 mgKOH/g.

The acid value of such an acrylic block copolymer depends on the presence or absence and the type of the acid group from which the acid value is derived, but it is usually preferably a low acid value, and is usually 100mgKOH/g or less, preferably 50mgKOH/g or less, and more preferably 40mgKOH/g or less.

The molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of the weight average molecular weight (Mw) of polystyrene measured by GPC. If the molecular weight of the acrylic block copolymer is too small, the dispersion stability tends to be lowered, and if it is too large, the developability and the resolution tend to be lowered.

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

In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by mass or more and 90% by mass or less, preferably 5% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 40% by mass or less with respect to the pigment. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained, and if it is too large, the ratio of other components is relatively reduced, and the voltage holding ratio is lowered, and on the other hand, the shape and level difference of the colored spacer may not be formed.

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

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

(graft copolymer containing nitrogen atom)

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

[ chemical formula 76]

In the general formulae (i), (ii), R⁹¹The alkylene group is a linear or branched alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, etc., preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. A represents a hydrogen atom or any of the following general formulae (iii) to (v), but is preferably a hydrogen atomThe following general formula (iii).

[ chemical formula 77]

In the general formula (III), W¹Represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as a butylene group, a pentylene group, or a hexylene group is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

[ chemical formula 78]

In the general formula (IV), G¹The linking group having a valence of 2 is preferably an alkylene group having 1 to 4 carbon atoms such as ethylene group or propylene group, or an oxyalkylene group having 1 to 4 carbon atoms such as oxyethylene group or oxypropylene group. W²The alkylene group has 2 to 10 carbon atoms and is a linear or branched alkylene group such as ethylene, propylene or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.

G²Represents a hydrogen atom or-CO-R⁹²(R⁹²Represents an alkyl group having 1 to 10 carbon atoms such as an ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc., and among them, an alkyl group having 2 to 5 carbon atoms such as an ethyl group, propyl group, butyl group, pentyl group, etc.) is preferable. q represents an integer of 1 to 20, preferably an integer of 5 to 10.

[ chemical formula 79]

In the general formula (V), W³Represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 hydroxyl groups and having 1 to 50 carbon atoms, and among them, an alkyl group having 10 to 20 carbon atoms such as a stearyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms such as a monohydroxystearyl group is preferable.

The content of the repeating unit represented by the general formula (i) or (ii) in the graft copolymer containing a nitrogen atom is preferably high, and is usually 50 mol% or more, preferably 70 mol% or more, based on the total amount.

The content ratio of both the repeating unit represented by the general formula (i) and the repeating unit represented by the general formula (ii) is not particularly limited, but it is preferable to contain a large amount of the repeating unit represented by the general formula (i).

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

The graft copolymer may contain a repeating unit other than the repeating units represented by the general formulae (i) and (ii), and examples of the other repeating units include alkylene groups and oxyalkylene groups. The graft copolymer in the present invention is preferably-NH-at the terminal thereof₂and-R⁹¹-NH₂(R⁹¹Synonymous with those in the general formulae (i) and (ii).

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

The graft copolymer preferably has a weight average molecular weight of 3,000 or more, particularly preferably 5,000 or more, preferably 100,000 or less, particularly preferably 50,000 or less, as measured by GPC. If the weight average molecular weight is less than 3,000, the color material cannot be prevented from aggregating, and may cause high viscosity or gelation, and if it exceeds 100,000, the viscosity itself becomes high and the solubility in an organic solvent is insufficient, which is not preferable.

the method for synthesizing the dispersant may be a known method, and for example, the method described in Japanese patent publication No. 63-30057 may be used.

< thiols >

In order to achieve high sensitivity and improve adhesion to a substrate, it is preferable to add a thiol compound to the photosensitive resin composition of the present invention. Examples of the thiol group include: hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), and propylene glycol bis (3-mercaptobutyrate); (abbreviated as PGMB), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutanoyloxy) butane; [ trade name; karenz (registered trademark, the same below) MT BD1, manufactured by Showa Denko K.K. ], butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; manufactured by Karenz MT PE1, Showa Denko K.K.), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptobutyrate) (TPMB for short), trimethylolpropane tris (2-mercaptoisobutyrate) (TPMIB for short), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione; (trade name; Karenz MTNR1, manufactured by Showa Denko K.K.) and the like. These thiols may be used alone as 1 of each species, or as a mixture of 2 or more species. The above polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are preferable, among which Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MTPE1 is particularly preferable.

< solvent >

The photosensitive resin composition of the present invention is generally used in a state in which a resin (a), a photopolymerization initiator (b), a photopolymerizable monomer (c), a color material (d), a dispersant (e), various materials used as needed, and the like are dissolved or dispersed in an organic solvent.

The organic solvent is preferably selected to have a boiling point (pressure of 1013.25[ hPa ], hereinafter, the same applies to all boiling points) in the range of 100 to 300 ℃. More preferably a solvent having a boiling point of 120 to 280 ℃.

Examples of such an organic solvent include the following organic solvents. Examples thereof include:

Glycol monoalkyl ethers such as 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 tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol 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;

Glycol alkyl ether acetates such as 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, methoxyamyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

Glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether; ketones such as acetone, methylethylketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone; 1-or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, 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; linear or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile. Examples of commercially available solvents that meet the above-mentioned requirements include: mineral spirits (Mineral spirits), Varsol #2, Apco #18 solvent, Apco triner, sonal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (all trade names), and the like.

These organic solvents may be used alone, or 2 or more kinds thereof may be used in combination.

When the pixels of the color filter or the black matrix are formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ℃ as the organic solvent. More preferably an organic solvent having a boiling point of 120 to 170 ℃.

Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like and high solubility of the constituent components in the composition.

In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. The organic solvent used in combination is particularly preferably a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is particularly preferable in view of solubility of the components in the composition.

The diol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate easily, and the storage stability of the photosensitive resin composition obtained later tends to be lowered, for example, the viscosity of the photosensitive resin composition increases, and therefore the proportion of the diol monoalkyl ethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

In addition, it is also preferable to use an organic solvent having a boiling point of 150 ℃ or higher (hereinafter also referred to as "high-boiling solvent") in combination. The combined use of such high boiling point solvents has the effect of preventing the uniform dispersion state of the pigment in the composition from being broken by rapid drying, although the photosensitive resin composition is not easily dried.

That is, for example, the slit nozzle has an effect of preventing the occurrence of foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a color material or the like. Among the various solvents mentioned above, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of the remarkable effect.

The content ratio of the high-boiling solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, and particularly preferably 5 to 10% by mass. If the amount of the high boiling point solvent is too small, for example, foreign matter defects may be caused at the tip of the slit nozzle by precipitation and solidification of a color material or the like, and if the amount of the high boiling point solvent is too large, the drying rate of the composition may be lowered, which may cause problems such as a tact failure in a reduced pressure drying process or pin hole marks in pre-baking (pre-bake) in a color filter manufacturing process described later.

The high boiling point solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be contained.

Examples of the preferred high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin among the various solvents described above.

< other compounding ingredients of photosensitive resin composition >

In addition to the above components, the photosensitive resin composition of the present invention may contain a bonding improver, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, a surfactant, a pigment derivative, and the like as appropriate.

(Adhesives)

The photosensitive resin composition of the present invention may contain an adhesion improving agent for improving adhesion to a substrate, and examples thereof include a silane coupling agent, a phosphoric acid-based adhesion improving agent, and other adhesion improving agents.

The silane coupling agent may be 1 kind of epoxy, acrylic, or amino silane coupling agent, or 2 or more kinds of silane coupling agents may be mixed and used.

Preferred silane coupling agents include, for example: (meth) acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane, (meth) acryloyloxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, and isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane are particularly preferred, and epoxysilane-based silane coupling agents are particularly preferred.

The phosphate adhesion improver is preferably a (meth) acryloyloxy group-containing phosphate, and more preferably a (meth) acryloyloxy group-containing phosphate represented by the following general formulae (g1), (g2) and (g 3).

[ chemical formula 80]

In the above general formulae (g1), (g2) and (g3), R⁵¹Represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1,2 or 3.

Examples of other adhesion improving agents include: TEGO^*Add Bond LTH (Evonik Co., Ltd.). These phosphoric acid group-containing compounds and other sealing agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(surfactant)

In order to improve coatability, a surfactant may be contained in the photosensitive resin composition of the present invention. Examples of the surfactant include various surfactants such as anionic, cationic, nonionic and amphoteric surfactants. Among them, nonionic surfactants are preferably used from the viewpoint of low possibility of exerting adverse effects on various properties, and among them, fluorine-based or silicon-based surfactants are effective from the viewpoint of coatability.

Examples of such surfactants include: TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by NEOS Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie Co., Ltd.), KP340 (manufactured by shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-559(DIC Co., Ltd.), SH7PA (manufactured by Toray Silicone Co., Ltd.), DS-401 (manufactured by Dajin Co., Ltd.), L-77 (manufactured by Nissan Youka Co., Ltd.), FC4430 (manufactured by Sumitomo 3M Co., Ltd.), and the like. The surfactant may be used in 1 kind, or 2 or more kinds may be used in combination in any combination and ratio.

(other Components)

The photosensitive resin composition of the present invention may further contain, 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 anhydride, a development modifier, a thermal polymerization inhibitor, and the like.

(pigment derivative)

The photosensitive coloring composition of the present invention may contain a pigment derivative for the purpose of improving dispersibility and storage stability. Examples of the pigment derivative include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, bisindanoneAzines, anthracenones, indanthrenes, perylenes, perinones, diketopyrrolopyrroles and diketopyrrolopyrrolesDerivatives of azines and the like. Among them, phthalocyanines and quinophthalones are preferable.

Examples of the substituent of the pigment derivative include: sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, and the like, and sulfonic acid groups are preferred. In addition, a plurality of these substituents may be substituted on one pigment skeleton.

Examples of the pigment derivative include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthrone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and bisSulfonic acid derivatives of oxazines, and the like. These pigment derivatives can be used alone in 1, also can be used in 2 or more combinations.

< component compounding ratio in photosensitive resin composition >

The content of the resin (a) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less, relative to the total solid content of the photosensitive resin composition of the present invention.

If the content ratio of the resin (a) is significantly small, the solubility of the unexposed portion in the developer is reduced, and thus development failure tends to be easily caused. On the other hand, if the content ratio of the resin (a) is too large, the permeability of the developer to the exposed portion tends to be high, which may result in a decrease in the definition or adhesiveness of the pixel.

As described above, in the photosensitive resin composition of the present invention, the resin (a) may contain the other resin (a-2) in addition to the resin (a-1), but when it is particularly necessary to improve the performance such as sensitivity and adhesion based on the resin (a-1), the content of the resin (a-1) is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and usually 100% by mass or less, based on the total mass of the resin (a).

The resin (a) may contain another resin (a-2) in addition to the resin (a-1). In this case, the mass ratio of the resin (a-1) to the other resin (a-2) is not particularly limited, but is preferably 1:99 to 99:1, more preferably 5:95 to 95:5, and even more preferably 10:90 to 90:10, from the viewpoint of achieving a balance between the sensitivity, adhesion, and properties of the resin (a-1) according to the present invention and those of the other resin.

When it is desired to obtain the performance based on the other resin (a-2), the content of the resin (a-1) relative to the resin (a) is preferably 1% by mass or more, and is preferably 90% by mass or less, more preferably 50% by mass or less, and still more preferably 60% by mass or less.

The content of the photopolymerization initiator (b) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, further preferably 1% by mass or more, further preferably 3% by mass or more, further preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition of the present invention. If the content of the photopolymerization initiator (b) is too small, sensitivity may be lowered, whereas if it is too large, solubility of an unexposed portion in a developer may be lowered, and development failure may be easily caused.

In particular, the proportion of the oxime ester compound in the photopolymerization initiator (b) is usually 10% by mass or more, preferably 50% by mass or more, more preferably 90% by mass or more, and usually 100% by mass or less. When the lower limit value is not less than the above-described lower limit value, the following tendency is present: after the ultraviolet irradiation, the increase of the line width due to the improvement of the sensitivity and the development stability due to the improvement of the alkali-resistant developing solution can be improved.

When the photopolymerization initiator (b) is used together with an accelerator, the content of the accelerator is usually 0.01% by mass or more, preferably 0.02% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition of the present invention.

The accelerator is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the photopolymerization initiator (b). By using the photopolymerization initiator (b) and the accelerator having the lower limit or more, there is a tendency that sensitivity to exposure light becomes sufficient, and by using the photopolymerization initiator (b) and the accelerator having the upper limit or less, there is a tendency that solubility of an unexposed portion in a developer becomes good.

When a sensitizing dye is used, the amount of the sensitizing dye to be incorporated in the photosensitive resin composition of the present invention is usually 0 to 20% by mass, preferably 0 to 15% by mass, and more preferably 0 to 10% by mass of the total solid content in the photosensitive resin composition.

The content of the photopolymerizable monomer (c) is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition. When the content ratio of the photopolymerizable monomer is not more than the upper limit, the permeability of the developer to the exposed portion tends to be appropriate, and a good image tends to be obtained.

The lower limit of the content of the photopolymerizable monomer (c) is usually 1% by mass or more, preferably 5% by mass or more. When the content is not less than the lower limit, photocuring by ultraviolet irradiation tends to be improved, and alkali developability tends to be good.

The content of the color material (d) is usually selected within the range of 1 to 70% by mass relative to the total solid content of the photosensitive resin composition. In this range, the content is more preferably 20 to 70% by mass.

As described above, the photosensitive resin composition of the present invention can be used for various applications, but its excellent image formability is particularly effective when used for forming a black matrix for a color filter. When the pigment is used for forming a black matrix, the above-described black pigment such as carbon black or titanium black, or a mixture of a plurality of other pigments except black may be used as the pigment (d). Among them, carbon black is particularly preferably used.

The present invention is particularly effective in a range where the pigment concentration of the black pigment is large. In particular, in recent years, it has been required to increase the black pigment concentration in order to improve the light-shielding degree. The content of such a black pigment that can exert a significant effect is preferably 40% by mass or more, more preferably more than 40% by mass, still more preferably 45% by mass or more, particularly preferably 50% by mass or more, and usually 70% by mass or less, based on the total solid content of the photosensitive resin composition.

By setting the content of the black pigment in the photosensitive resin composition within the above range, a photosensitive resin composition having high light-shielding properties (optical density, OD value) can be obtained. Specifically, for example, when the content of the black pigment is 45% by mass or more, the optical density in the case of forming a black matrix having a thickness of 1 μm using the colored photosensitive resin composition of the present invention can be set to a value of 4.0 or more.

The optical density is more preferably 4.2 or more. In the range of high light-shielding property, it is difficult for ultraviolet rays to transmit to deep parts, and particularly, in the portions where the substrate and the thin lines are in close contact, crosslinking by photopolymerization is weak, but when the photosensitive resin composition of the present invention is used, particularly when the pigment concentration is high, the effects of the present invention can be sufficiently confirmed.

When the pigment is used for the purpose of forming a pixel of a color filter or the like, the pigment concentration is particularly effective when the pigment concentration is 40 to 65 mass% based on the total solid content. When the content of the color material is not less than the lower limit, the following tendency is present: the film thickness is not excessively increased with respect to the color density, and adverse effects on gap control and the like in the formation of a liquid crystal cell can be prevented. Further, when the upper limit value is less than or equal to the above upper limit value, sufficient image formability tends to be obtained.

When a color material is used in the photosensitive resin composition, the amount of the resin (a) is usually not less than 20 parts by mass, preferably not less than 30 parts by mass, and more preferably not less than 40 parts by mass, and is usually not more than 500 parts by mass, preferably not more than 300 parts by mass, more preferably not more than 200 parts by mass, and still more preferably not more than 100 parts by mass, relative to 100 parts by mass of the color material (d).

When the content of the resin (a) to the color material (d) is not less than the lower limit, solubility of an unexposed portion in a developer tends to be sufficient, and when the content is not more than the upper limit, a desired pixel film thickness tends to be easily obtained.

when the thiol compound is used, the content of the thiol compound is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, based on the entire solid content of the photosensitive resin composition of the present invention. When the content of the thiol compound is not less than the lower limit, the sensitivity tends to be sufficient, and when the content is not more than the upper limit, the storage stability tends to be good.

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

The content of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, and usually 200 parts by mass or less, preferably 80 parts by mass or less, and more preferably 50 parts by mass or less, with respect to 100 parts by mass of the coloring material (d). When the content of the dispersant is not less than the lower limit, sufficient dispersibility tends to be easily obtained, and when the content is not more than the upper limit, the ratio of other components tends to be relatively sufficient, and the color density, sensitivity, film-forming property, and the like tend to be good.

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

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

When the content of the surfactant is not less than the lower limit, the smoothness and uniformity of the coating film tend to be improved, and when the content is not more than the upper limit, the smoothness and uniformity of the coating film are improved and the deterioration of other properties is suppressed.

The photosensitive resin composition of the present invention can be prepared into a solution using the organic solvent described above so that the solid content concentration thereof is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less.

< method for producing photosensitive resin composition >

The photosensitive resin composition (hereinafter also referred to as "resist") of the present invention can be produced by a conventional method.

In general, it is preferable that the color material (d) is subjected to dispersion treatment in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. The dispersion treatment makes the color material (d) fine-particle, thereby improving the coating properties of the resist. In addition, when a black color material is used as the color material (d), it contributes to improvement of light shielding ability.

The dispersion treatment is usually preferably performed in a system in which a part or all of the color material (d), the dispersant (e), the organic solvent, and the resin (a) are used in combination as needed (hereinafter, the mixture for dispersion treatment and the composition obtained by the treatment are also referred to as "ink" or "pigment dispersion liquid"). In particular, the use of a polymeric dispersant as a dispersant is preferable because the thickening of the resulting ink and resist with time can be suppressed (excellent dispersion stability).

When a liquid to be mixed with all the components in the photosensitive resin composition is subjected to dispersion treatment, the highly reactive components may be modified due to heat generation during the dispersion treatment. Therefore, the dispersion treatment is preferably performed in a system containing a polymeric dispersant.

When the color material (d) is dispersed by a sand mill, glass beads or zirconia beads having a diameter of about 0.1 to 8mm are preferably used. The temperature is usually 0 to 100 ℃ and preferably room temperature to 80 ℃ in terms of dispersion treatment conditions. The dispersion time is adjusted as appropriate because it is appropriate depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like.

The approximate criteria for dispersion are: the gloss of the ink is controlled so that the 20-degree specular gloss [ JIS Z8741 (1997) ] of the resist falls within the range of 100 to 200. When the gloss of the resist is low, the dispersion treatment is insufficient, and coarse pigment (color material) particles often remain, and there is a possibility that the developability, adhesion, resolution, and the like may become insufficient. Further, if the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is broken and a large number of ultrafine particles are generated, and therefore, the dispersion stability tends to be impaired on the contrary.

Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the resist to prepare a uniform solution. In the resist production process, since fine dust is often mixed into the liquid, it is preferable to perform a filtration treatment using a filter or the like on the obtained resist.

< cured product >

By curing the photosensitive resin composition of the present invention, a cured product can be obtained. The cured product obtained by curing the photosensitive resin composition can be preferably used as a black matrix or a colored spacer.

< Black matrix >

Hereinafter, a black matrix using the photosensitive resin composition of the present invention will be described according to a method for producing the black matrix.

(1) Support body

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

In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent and a urethane resin, or the like, as necessary.

The thickness of the transparent substrate is usually 0.05 to 10mm, preferably 0.1 to 7 mm. When a thin film forming treatment is performed on various resins, the thickness of the film is usually 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black matrix

In order to form the black matrix of the present invention from the photosensitive resin composition of the present invention, a black matrix can be formed by applying the photosensitive resin composition of the present invention on a transparent substrate, drying the composition, placing a photomask on the sample, performing image exposure and development through the photomask, and further performing thermal curing or photo curing as necessary.

(3) Formation of black matrix

(3-1) coating of photosensitive resin composition

The photosensitive resin composition for a black matrix can be applied to a transparent substrate by, for example, a spin coating method, a Wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among these, the die coating method is preferable from the overall viewpoint of being able to greatly reduce the amount of the coating liquid used, being able to suppress the generation of foreign matter without being affected by the fogging or the like adhering when the spin coating method is employed.

If the thickness of the coating film is too thick, pattern development becomes difficult, and gap adjustment in a liquid crystal cell process sometimes becomes difficult, and if the thickness of the coating film is too thin, it becomes difficult to increase the pigment concentration, and a desired color may not be developed.

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

(3-2) drying of coating film

The coating film after coating the photosensitive resin composition on the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like.

The drying time is generally selected within a range of from 15 seconds to 5 minutes at a temperature of from 40 to 200 ℃ and preferably within a range of from 30 seconds to 3 minutes at a temperature of from 50 to 130 ℃, depending on the kind of solvent component and the performance of the dryer used.

The higher the drying temperature, the more the adhesiveness of the coating film to the transparent substrate can be improved, but if the drying temperature is too high, the alkali-soluble resin may be decomposed to cause thermal polymerization and further cause development failure. The drying step of the coating film may be a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without raising the temperature.

(3-3) Exposure

The image exposure is performed by superimposing a negative mask pattern on a coating film of the photosensitive resin composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent the decrease in sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed to light as necessary.

The light source used for the image exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. When light of a specific wavelength is irradiated and used, an optical filter may be used.

(3-4) development

The black matrix of the present invention can be made as follows: the coating film formed from the photosensitive resin composition is image-exposed by the light source, and then developed using an organic solvent or an aqueous solution containing a surfactant and an alkali compound, thereby forming an image on a substrate. The aqueous solution may further comprise an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the basic compound include: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more.

Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters, anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates and sulfosuccinates, 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, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited, and the development temperature may be usually set to a range of 10 to 50 ℃, preferably 15 to 45 ℃, particularly preferably 20 to 40 ℃, and any of the immersion development method, the spray development method, the magnetic brush development method, the ultrasonic development method, and the like may be used as the development method.

(3-5) Heat curing treatment

The developed substrate is subjected to a heat curing treatment or a light curing treatment, and preferably subjected to a heat curing treatment. The heat curing conditions in this case may be selected within a range of 100 to 280 ℃, preferably 150 to 250 ℃, and the time may be selected within a range of 5 to 60 minutes.

The width of the bottom of the black matrix formed as described above is usually 3 to 50 μm, preferably 4 to 30 μm, and particularly in the case of a high-definition line, it is preferably 4 to 8 μm, and the height is usually 0.5 to 5 μm, preferably 1 to 4 μm.

Further, the volume resistivity was 1X 10¹³Omega cm or more, preferably 1X 10¹⁴Omega cm or more, and a relative dielectric constant of 6 or less, preferably 5 or less. Further, the Optical Density (OD) per 1 μm thickness is 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.2 or more.

[ formation of other color filter pixels ]

A photosensitive coloring resin composition containing a coloring material of one of red, green and blue colors is applied to a transparent substrate provided with a black matrix by the same process as in the above (3-1) to (3-5) and dried, then a photomask is laminated on the applied film, image exposure and development are performed through the photomask, and a pixel image is formed by thermal curing or photo curing as necessary, thereby producing a colored layer. This operation is performed for each of the photosensitive colored resin compositions of three colors of red, green, and blue, whereby pixels of the color filter can be formed. Their order is not limited to the above.

[ colored spacer ]

the colored photosensitive composition of the present embodiment can be used as a black matrix and also as a resist for a colored spacer. When the spacer is used in a TFT-type LCD, the TFT as a switching element may malfunction due to light incident on the TFT, and a colored spacer is used to prevent this. For example, Japanese patent application laid-open No. 8-234212 discloses that spacers are made light-shielding. The colored spacer can be formed by the same method as the black matrix described above, except that a colored spacer mask is used.

(3-6) formation of transparent electrode

The color filter may be used as a part of a member of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image in an original state, but a top coat layer such as polyamide or polyimide may be provided on the image as necessary for the purpose of improving surface smoothness and durability. In some applications such as an in-plane alignment driving method (IPS mode), a transparent electrode is not formed.

[ image display apparatus ]

The image display device of the present invention is not particularly limited as long as it is a device for displaying images or videos, and examples thereof include a liquid crystal display device, an organic EL display, and the like described below.

[ liquid Crystal display device ]

the liquid crystal display device of the present invention is manufactured using the black matrix of the present invention, and the order of formation, the position of formation, and the like of the color pixels and the black matrix are not particularly limited.

Liquid crystal display devices are generally made as follows: after an alignment film is formed on a color filter and spacers are scattered on the alignment film, a liquid crystal cell is formed by bonding the color filter to a counter substrate, a liquid crystal is injected into the formed liquid crystal cell, and a wiring is formed between the liquid crystal cell and a counter electrode, thereby completing a liquid crystal display device. The alignment film is preferably a resin film such as polyimide.

The alignment film may be formed by a gravure printing method and/or a flexographic printing method, and the thickness of the alignment film may be several 10 nm. After the alignment film is cured by thermal baking, the alignment film is subjected to surface treatment by irradiation with ultraviolet rays or treatment with a rubbing cloth, and is processed into a surface state in which the tilt of the liquid crystal can be adjusted.

The spacer is preferably 2 to 8 μm, and is preferably a spacer suitable for the size of the gap (gap) between the counter substrate and the counter substrate. It is also possible to form a Photosensitive Spacer (PS) of a transparent resin film on the color filter substrate by photolithography, and to effectively use the Photosensitive Spacer (PS) instead of the spacer. As the counter substrate, an array substrate is generally used, and a TFT (thin film transistor) substrate is particularly preferable.

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

After the liquid crystal cell having the sealed periphery is cut into a panel unit, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the pressure is released in the vacuum chamber, whereby the liquid crystal is injected into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1X 10^-2～1×10^-7Pa, preferably 1X 10^-3～1×10^-6Pa。

In addition, the liquid crystal cell is preferably heated at a temperature of usually 30 to 100 ℃ and more preferably 50 to 90 ℃ during the pressure reduction. The liquid crystal is immersed in the liquid crystal after the heating for reduced pressure is maintained for 10 to 60 minutes. The liquid crystal cell into which the liquid crystal is injected is sealed at the liquid crystal injection port by curing the UV curable resin, thereby completing the liquid crystal display device (panel).

The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, and any of them is possible.

[ organic EL display ]

The organic EL display of the present invention is manufactured using the color filter of the present invention.

When an organic EL display is produced using the color filter of the present invention, as shown in fig. 1, a color filter is first produced by forming a pattern of a colored resin composition (i.e., pixels 20 and a resin black matrix (not shown) provided between adjacent pixels 20) on a transparent support substrate 10, and an organic light emitter 500 is laminated on the color filter through an organic protective layer 30 and an inorganic oxide film 40, whereby an organic EL element 100 can be produced. At least one of the pixels 20 and the resin black matrix is produced by using the photosensitive colored resin composition of the present invention.

As a lamination method of the organic light-emitting body 500, there can be mentioned: a method of sequentially forming 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, a method of bonding an organic light emitting body 500 formed on another substrate to the inorganic oxide film 40, and the like.

The organic EL element 100 thus fabricated can be used to fabricate an organic EL display by a method described in, for example, "organic EL display" (Ohmsha, ltd., 2004, 20 th/8 th/l, wainshi, andea kyushui, cuntian english-fortunate).

The color filter of the present invention can be applied to an organic EL display of a passive drive system, and can also be applied to an organic EL display of an active drive system.

Examples

The present invention will be described in more detail below with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples within the scope not exceeding the gist of the present invention.

< preparation of carbon Black Dispersion ink >

A pigment, a dispersant, a dispersion aid and a solvent were prepared according to the following compositions, and a carbon black dispersed ink was prepared by the following method.

First, the pigment, the dispersant, the solid components of the dispersion aid, and the solvent were prepared in the following manner.

Pigment:

R1060 (carbon black manufactured by Columbia corporation): 100 parts by mass

Dispersant:

BYK167 (alkali polyurethane dispersant manufactured by BYK-Chemie Co.): 20 parts by mass (converted to solid content)

Dispersing aid (pigment derivative):

S12000 (phthalocyanine pigment derivative having an acid group, manufactured by Lubrizol corporation): 2 parts by mass

Solvent:

propylene glycol methyl ether acetate: 226.6 parts by mass

The above ingredients were thoroughly stirred and mixed.

Subsequently, the dispersion was dispersed for 6 hours at 25 to 45 ℃ by a paint shaker to obtain a dispersion. As the beads, zirconia beads having a diameter of 0.5mm were used, and 60 parts by mass of the dispersion and 180 parts by mass of the beads were added. After the end of the dispersion, the beads were separated by a filter, and a carbon black-dispersed ink having a solid content of 35 mass% was prepared.

< examples 1 to 4: synthesis of alkali-soluble resins (1) to (4) >

[ chemical formula 81]

7.3g of the epoxy compound having the above chemical structure (epoxy equivalent 240), 2.2g of acrylic acid, 6.4g of propylene glycol monomethyl ether acetate, 0.18g of tetraethylammonium chloride and 0.007g of p-methoxyphenol were put into a flask equipped with a thermometer, a stirrer and a condenser, and the reaction was carried out at 100 ℃ while stirring until the acid value reached 5mg-KOH/g or less. The reaction took 9 hours to obtain an epoxyacrylate solution.

The obtained epoxy acrylate solution, Trimethylolpropane (TMP), biphenyltetracarboxylic dianhydride (BPDA), tetrahydrophthalic anhydride (THPA), and Propylene Glycol Monomethyl Ether Acetate (PGMEA) were prepared in amounts shown in table 1 below, and added to a flask equipped with a thermometer, a stirrer, and a condenser, and while stirring, the temperature was gradually increased to 105 ℃. The content ratio of the partial structure contained in the alkali-soluble resins (1) to (4) is shown in table 2, for example.

< comparative example 1: synthesis of alkali-soluble resin (5) >

[ chemical formula 82]

50g of the epoxy compound having the above chemical structure (epoxy equivalent 264), 13.65g of acrylic acid, 60.5g of methoxybutyl acetate, 0.936g of triphenylphosphine and 0.032g of methoxyphenol were put in a flask equipped with a thermometer, a stirrer and a condenser, and the mixture was reacted at 90 ℃ with stirring until the acid value reached 5mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

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) were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was gradually increased to 105 ℃ while stirring, thereby carrying out the reaction.

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

< comparative example 2: synthesis of alkali-soluble resin (6) >

[ chemical formula 83]

7.1g of the epoxy compound having the above structure (epoxy equivalent 217), 2.4g of acrylic acid, 6.4g of propylene glycol monomethyl ether acetate, 0.18g of tetraethylammonium chloride and 0.008g of p-methoxyphenol were put into a flask equipped with a thermometer, a stirrer and a condenser, and the mixture was reacted at 100 ℃ while stirring until the acid value reached 5mg-KOH/g or less. The reaction took 9 hours to obtain an epoxy acrylate solution.

16 parts by mass of the obtained epoxy acrylate solution, 0.42 part by mass of Trimethylolpropane (TMP), 3.7g of biphenyltetracarboxylic dianhydride (BPDA), 0.076 part by mass of tetrahydrophthalic anhydride (THPA), and 15 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a thermometer, a stirrer, and a condenser, and while stirring, the temperature was slowly increased to 105 ℃ to effect reaction, whereby an alkali-soluble resin (6) having an acid value of 114mg-KOH/g, a weight average molecular weight in terms of polystyrene as measured by GPC of 9300, and a solid content of 40 mass% was obtained.

< synthetic example 1: synthesis of photopolymerization initiator (1) >

(diketone body)

Ethylcarbazole (5g, 25.61mmol) and o-naphthoyl chloride (5.13g, 26.89mmol) were dissolved in 30ml of dichloromethane, cooled to 2 ℃ in an ice-water bath and stirred, to which AlCl was added₃(3.41g, 25.61 mmol). After further stirring at room temperature for 3 hours, a solution of crotonyl chloride (2.81g, 26.89mmol) in 15ml of methylene chloride was added to the reaction mixture, and AlCl was added₃(4.1g, 30.73mmol) and stirring was continued for 1 hour 30 minutes. The reaction mixture was added to 200ml of ice water, 200ml 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 (10g) of a diketone.

(Oxime body)

In 30ml of isopropyl alcohol, diketone (3.00g, 7.19mmol) and NH were mixed₂OH/HCl (1.09g, 15.81mmol) and sodium acetate (1.23g, 15.08mmol) were refluxed for 3 hours.

After completion of the reaction, the reaction mixture was concentrated, and 30ml of ethyl acetate was added to the obtained residue, which was washed with 30ml of a saturated aqueous sodium bicarbonate solution and 30ml of a saturated saline solution, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82g of a solid. This solid was purified by column chromatography to obtain 2.22g of oxime as a pale yellow solid.

(Oxime ester forms)

Oxime (2.22g, 4.77mmol) and acetyl chloride (1.34g, 17.0mmol) were added to 20ml of dichloromethane, the mixture was cooled in an ice bath, and triethylamine (1.77g, 17.5mmol) was added dropwise thereto, and the reaction was allowed to proceed for 1 hour while maintaining this state. After confirming the disappearance of the starting material by thin layer chromatography, the reaction was terminated by adding water. The reaction mixture was washed 2 times with 5ml of a saturated aqueous sodium bicarbonate solution and 2 times with 5ml of a 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 0.79g of a pale yellow solid photopolymerization initiator (1). Method for producing photopolymerization initiator (1)¹Chemical shifts of H-NMR are shown below.

¹H-NMR(CDCl₃):σ1.17(d,3H),1.48(t,3H),1.53(s,3H),1.81(s,3H),2.16(s,3H), 2.30(s,3H),3.17-3.32(m,2H),4.42(q,2H),4.78-4.94(br,1H),7.45-7.59(m,5H),7.65(dd,1H),7.95(m,2H),8.04(m,2H),8.14(dd,1H),8.42(d,1H),8.64(d,1H)

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

[ chemical formula 84]

< example 5>

(preparation of Black resist 1)

Using the carbon black dispersion inks prepared in < preparation of carbon black dispersion ink >, the components described in table 3 were mixed at the ratios shown in table 3, and stirred with a stirrer to be dissolved, thereby preparing a black resist 1.

[ Table 3]

in table 3, the amounts of the respective components used in the carbon black dispersed ink and others are values of solid components. The amount of the solvent used is the total amount of the solvent used including the solvents contained in the carbon black-dispersed ink and other components.

The specific conditions of the components in the table are as follows.

Alkali-soluble resin (1): the resin synthesized in example 1.

Photopolymerization initiator (1): the photopolymerization initiator synthesized in synthesis example 1 was synthesized.

Photopolymerizable monomer (1): dipentaerythritol hexaacrylate (manufactured by Nippon Kabushiki Kaisha)

Surfactants: f559(DIC Co., Ltd.)

< example 6>

(preparation of Black resist 2)

A black resist 2 was produced in the same manner as in example 5, except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (2) synthesized in example 2.

< example 7>

(preparation of Black resist 3)

A black resist 3 was produced in the same manner as in example 5, except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (3) synthesized in example 3.

< example 8>

(preparation of Black resist 4)

A black resist 4 was produced in the same manner as in example 5, except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (4) synthesized in example 4.

< example 9>

(preparation of Black resist 5)

a black resist 5 was prepared in the same manner as in example 5, except that the photopolymerization initiator was changed to the photopolymerization initiator (2) (TR-PBG-304, manufactured by yokoku corporation).

< example 10>

(preparation of Black resist 6)

A black resist 6 was produced in the same manner as in example 5, except that the photopolymerization initiator was changed to the photopolymerization initiator (3) (NCI-831 manufactured by ADEKA corporation).

< example 11>

(preparation of Black resist 7)

A black resist 7 was produced in the same manner as in example 5, except that the photopolymerization initiator was changed to the photopolymerization initiator (4) (OXE02, BASF).

< example 12>

(preparation of Black resist 8)

A black resist 8 was produced in the same manner as in example 5, except that the content of each component was changed to the content shown in table 4 so that the content of carbon black with respect to the total solid content became 45 mass%.

< example 13>

(preparation of Black resist 9)

A black resist 9 was produced in the same manner as in example 5, except that the content of each component was changed to the content shown in table 4 so that the content of carbon black with respect to the total solid content became 40 mass%.

< comparative example 3>

(preparation of comparative Black resist 10)

A comparative black resist 10 was prepared in the same manner as in example 5, except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (5) synthesized in comparative example 1.

< comparative example 4>

(preparation of comparative Black resist 11)

A comparative black resist 11 was prepared in the same manner as in example 5, except that the alkali-soluble resin (1) was changed to the alkali-soluble resin (6) synthesized in comparative example 2.

(evaluation of resist)

(I) evaluation of line width formation/evaluation of development adhesion

(1) Method for making Black Matrix (BM) resist pattern

The prepared black resists 1 to 9 and comparative black resists 10 and 11 were applied to a glass substrate by a spin coater, and dried under reduced pressure, and then dried at 100 ℃ for 120 seconds by a hot plate to obtain a dry coating film. Next, the resulting dried coating film was subjected to pattern exposure through an exposure mask described later at 40mJ by a high pressure mercury lamp, and then spray development was performed at room temperature (23 ℃) for 80 seconds, 100 seconds, or 120 seconds using a KOH aqueous solution adjusted to 0.04 mass% by ultrapure water as an alkali developing solution, thereby obtaining various BM resist patterns. The BM resist pattern thus formed was evaluated for line width (sensitivity) and resolution (development adhesion) according to the criteria described in (2) and (3) described later, and the results are shown in table 5.

(2) Line width evaluation method (sensitivity)

The line width of the BM resist pattern obtained by the method (1) was observed under a microscope at a magnification of 200 times using an exposure mask having a10 μm opening (stripe-shaped opening having a width of 10 μm), and the line width was measured. In the case of evaluation at the same exposure amount and the same development time, the larger the line width is, the higher the sensitivity is.

(3) Development adhesion evaluation method (resolution)

A BM resist pattern was produced by the method (1) above using an exposure mask having an opening of 1 to 10 μm (stripe-shaped opening having a width of 1 to 10 μm and a span of 1 μm). The BM resist pattern was observed by visual observation or using an optical microscope. In the BM resist pattern which is not chipped, has a rough surface, and remains on the glass substrate, the value of the opening width of the exposure mask corresponding to the pattern having the finest line width is set as the value of development adhesion. The smaller the value of development adhesion, the better the adhesion to the substrate and the higher the resolution.

(II) evaluation of opacity

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), each BM resist pattern prepared in (1) of the above (I) was baked in an oven at 230 degrees for 30 minutes to prepare a BM. The film thickness was measured by an Alpha-Ste pair 500 (KLA-Tencor) using a height difference measuring device, and the OD value was measured by a GretagMacbeth D200-II (GretagMacbeth) using a permeation concentration measuring device. The OD value (unit OD value) was determined for each 1 μm. As a result, the OD value of all BM was 4.0/. mu.m.

(III) evaluation of substrate adhesion force

the substrate adhesion force of the prepared black resist 1 (example 5), comparative black resists 10 (comparative example 3) and 11 (comparative example 4) was evaluated using BM fabricated as described below. The substrate adhesion force was determined as follows.

A substrate having a BM with a film thickness of 1.20 μm and a square width of 2.5cm was produced by the same process as in the above (II) (wherein the entire surface was exposed without using an exposure mask). An aluminum stud pin (P/N: 901106U, 2.7mm in diameter) (manufactured by Quad Group) was joined to a thermosetting sealant Structure-Bond XN-21-S (manufactured by Mitsui chemical Co., Ltd.). The prepared sample was subjected to a tensile test at a speed of 2.0kg/s using a film adhesion strength measuring machine Romulus (manufactured by Quad Group Co.), and the substrate adhesion stress was determined from the breaking strength and the bonding area at the time of breaking of the black matrix and the glass substrate by the following formula.

Stress (kg/cm) for substrate adhesion²) Breaking strength (kg)/bonding area (cm)²)

The results are shown in Table 6. The substrate adhesion force (%) in table 6 is the substrate adhesion stress (kg/cm) in example 5²) The value of (b) is set as a relative value (%) at 100%.

[ Table 6]

	Alkali soluble resin	OD value [/μm ]]	Substrate adhesion (%)
				Example 5	Alkali soluble resin (1)	4.0	100
comparative example 3	Alkali soluble resin (5)	4.0	74

As shown in tables 5 and 6, the resin of the present invention is excellent in sensitivity (line width formation), resolution (development adhesion) and substrate adhesion when applied to a photosensitive resin composition.

As shown in Table 5, the photosensitive resin compositions of examples 5 to 13 of the present invention exhibited good development adhesion and a large line width in the development time of 80 to 120 seconds, and high sensitivity was obtained. This is considered to be because the resin in the photosensitive resin compositions of examples 5 to 13 of the present invention has a bulky ring structure in which an alkylidene group at a diphenoxy group site is largely extended in a planar shape as in the above formula (II), and therefore has high hydrophobicity and high resistance to an alkali developing solution, and further, because of the diphenoxy structure, steric hindrance at the peripheral portion of an acryloyl group is small as described above, and a crosslinking reaction is likely to occur. Further, it was confirmed by comparing example 5 with examples 12 and 13 that the composition was excellent in both the line width and the development adhesion, regardless of the pigment content.

On the other hand, the photosensitive resin composition of comparative example 4 had no pattern remaining in the range of 1 to 10 μm in the developing time of 120 seconds in developing adhesion, and also had poor developing stability.

This is presumably because the resin in the photosensitive resin composition of comparative example 4 has an alkylidene ring structure at the diphenoxy site, but the number of carbon atoms forming the ring is 6, and the resin has lower hydrophobicity and smaller bulkiness than the resins of examples 5 to 13.

As shown in Table 4, the photosensitive resin composition of comparative example 3 also had a smaller line width, lower sensitivity than those of examples 1 to 4, and also had poorer development adhesion than those of examples 5 to 13. In addition, in the evaluation of the adhesion of the substrate in table 4, the amount was reduced to about 3/4 as compared with that of example 1.

This is considered to be because the resin in the photosensitive resin composition of comparative example 3 has 2 adamantyl structures, and therefore, although the number of carbon atoms is large, it does not have a bulky structure extending in a planar shape, and does not have a diphenoxy structure, and therefore, resistance and high sensitivity to an alkali developing solution cannot be obtained.

While the present invention has been described in detail with reference to the specific embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. The present application is completed based on japanese patent application (japanese patent application 2014-138870) proposed on 7/4/2014, and the entire contents thereof are incorporated herein by reference.

Claims

1. 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), R¹²A 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), R¹～R⁴Each 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 each is independently a bonding site.

2. The resin according to claim 1, wherein the resin having a partial structure represented by the formulae (I) and (III) is a resin having a partial structure represented by the formula (V),

In the formula (V), R¹¹Each independently an alkylene group having 1 to 5 carbon atoms, m is an integer of 0 to 5,

In addition, R¹～R⁴Synonymous with said formula (III), further, R¹²Each independently synonymous with said formula (I),

And each is independently a bonding site.

3. The resin according to claim 1, 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 2-valent carboxylic acid residue,

In the formula (VII), Y is a 4-valent carboxylic acid residue,

And each is independently a bonding site.

4. The resin according to claim 2, 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 2-valent carboxylic acid residue,

In the formula (VII), Y is a 4-valent carboxylic acid residue,

And each is independently a bonding site.

5. The resin according to claim 3, which further has 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,

In addition, is a bonding site.

6. The resin according to claim 4, which further has a partial structure represented by the following formula (VIII),

In addition, is a bonding site.

7. The resin according to claim 3, which further has a partial structure represented by the following formula (IX),

In the formula (IX), Z 'is a polyhydric hydroxymethyl residue, n' is an integer of 2 to 6,

In addition, is a bonding site.

8. The resin according to claim 4, which further has a partial structure represented by the following formula (IX),

In addition, is a bonding site.

9. A resin obtained by reacting at least the following (A-1) and the following (A-2),

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

(A-2) an unsaturated carboxylic acid or an unsaturated carboxylic acid ester,

In the formula (XI), R¹～R⁴Each 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, R¹¹An alkylene group having 1 to 5 carbon atoms,

m is an integer of 0 to 5.

10. A resin obtained by reacting the resin according to claim 9 with (a-3) a polybasic acid anhydride.

11. The resin according to claim 10, which is obtained by reacting with (a-3) polybasic acid anhydride and further with (a-4) polyhydric alcohol.

12. The resin according to claim 11, wherein the (a-4) polyol is at least one polyol selected from the group consisting of: trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol.

13. the resin according to any one of claims 1 to 12, which is a resin for a color filter.

14. A photosensitive resin composition, comprising at least:

The resin according to any one of claims 1 to 13, and

A photopolymerization initiator (b).

15. The photosensitive resin composition according to claim 14, further comprising a coloring material (d).

16. The photosensitive resin composition according to claim 15,

The color material (d) is a pigment,

The photosensitive resin composition further contains a dispersant (e).

17. The photosensitive resin composition according to claim 16,

The color material (d) is a black pigment,

The dispersant (e) is a polymer compound having a basic functional group.

18. The photosensitive resin composition according to claim 17, wherein a content ratio of the black pigment is 45 mass% or more in all solid components.

19. The photosensitive resin composition according to any one of claims 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 claims 14 to 19.

21. A color filter comprising at least one of a pixel and a black matrix formed from the cured product according to claim 20.

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