CN111221217B

CN111221217B - Color material dispersion, photosensitive coloring resin composition, color filter, liquid crystal display device, and organic light-emitting display device

Info

Publication number: CN111221217B
Application number: CN202010024592.6A
Authority: CN
Inventors: 长井健朗; 中村和彦; 冢本力飞; 五十岚一贵; 上森理惠; 市川裕司
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2014-12-24
Filing date: 2015-12-22
Publication date: 2024-03-12
Anticipated expiration: 2035-12-22
Also published as: TW202022055A; WO2016104493A1; CN111221217A; TWI743635B

Abstract

The color material dispersion liquid for the color filter comprises a color material, a dispersing agent and a solvent; the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2); p1: a block copolymer having an A block comprising constituent units represented by the following general formula (I) and a B block comprising constituent units derived from a carboxyl group-containing monomer; p2: a salt-type block copolymer in which at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) of the block copolymer is salified with 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3); the acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃.

Description

Color material dispersion, photosensitive coloring resin composition, color filter, liquid crystal display device, and organic light-emitting display device

The present application is a divisional application of application No. 2015, 12 and 22, and application No. 201580065051.5, entitled "color material dispersion, photosensitive coloring resin composition, color filter, liquid crystal display device, and organic light emitting display device".

Technical Field

The invention relates to a color material dispersion liquid for a color filter, a photosensitive coloring resin composition for a color filter, a liquid crystal display device and an organic light emitting display device.

Background

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, an organic light emitting display device such as an organic EL display which emits light and has high visibility has been attracting attention as a next-generation image display device. In the performance of these image display apparatuses, further improvement of image quality, such as improvement of contrast and color reproducibility, and reduction of power consumption have been strongly desired.

The existing display devices are mostly based on international standard specification sRGB (IEC 61966-2-1) of the chromaticity space. However, in order to seek a more physical expression and further improve color reproducibility, there is an increasing demand for a display device corresponding to AdobeRGB having a wider color gamut than sRGB. The AdobeRGB specification is defined by the chromaticity space advocated by Adobe Systems, and the three primary colors in AdobeRGB are determined by chromaticity coordinates x and y in the XYZ color system as follows. The AdobeRGB specification is characterized by a wider color gamut in the green direction than the sRGB specification.

Red: x=0.64; y=0.34

Green: x=0.21; y=0.71

Blue: x=0.15; y=0.06

In addition, there is also a demand for a display device conforming to the DCI (Digital Cinema Initiatives) specification which has a wide color gamut in the red and green directions as compared with sRGB.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, a color image of a liquid crystal display device is formed by directly coloring light passing through a color filter into colors of pixels constituting the color filter, and synthesizing the light of these colors. As a light source in this case, there are cases of an organic light emitting device that emits white light and an inorganic light emitting device that emits white light, in addition to a conventional cold cathode ray tube. In addition, in the organic light emitting display device, a color filter is used for color adjustment and the like.

In this case, there is a demand for improvement in brightness, contrast, and color reproducibility in the color filter.

Here, the color filter generally includes a transparent substrate, a colored layer formed on the transparent substrate and including colored patterns of three primary colors of red, green, and blue, and a light shielding portion formed on the transparent substrate to divide each colored pattern.

Among them, a pigment dispersion method having an average excellent characteristic is most widely used as a method for forming pixels in a color filter from the viewpoints of spectroscopic characteristics, durability, pattern shape, accuracy, and the like.

In a color filter having pixels formed by a pigment dispersion method, miniaturization of pigments has been studied in order to achieve high brightness and high contrast. It is considered that the miniaturization of the pigment reduces scattering of light passing through the color filter by the pigment particles, thereby achieving high brightness and high contrast.

However, since fine pigment particles are likely to aggregate, there is a problem that dispersibility or dispersion stability is lowered.

As a method for improving the dispersion method of the fine pigment, it is known to use a dispersant effectively. For example, patent document 1 discloses a coloring composition for a color filter, which has excellent chromaticity characteristics and good developability and storage stability, and which uses a block copolymer as a pigment dispersant, the block copolymer comprising: an A block having a specific repeating unit having an amino group or an ammonium salt group, and a B block having a specific repeating unit having an alkyleneoxy chain derived from an alcohol moiety of a carboxylic acid ester and a repeating unit having an acidic group.

Further, patent document 2 discloses a coloring composition for a color filter which is excellent in chromaticity characteristics, developability and storage stability, and which uses a copolymer containing: the specific repeating unit having an amino group or an ammonium salt group, the repeating unit containing a carboxylic acid ester, and the repeating unit having an acidic group are set to a specific ratio, and the ratio of the weight average molecular weight to the number average molecular weight is set to a specific ratio.

On the other hand, in the color filter, a region of 3 dots connecting red, green, and blue pixels becomes a boundary of reproducible colors. That is, the larger the triangle obtained at 3 points of the red, green, and blue pixels, the wider the range of colors reproducible on the screen by the display device.

In order to realize a chromaticity space having a wide color gamut such as AdobeRGB or DCI, it is particularly required to set the green pixels of the color filter to a region where the green chromaticity of the high color density { (x=0.14 to 0.30, y=0.55 to 0.75), more preferably (x=0.14 to 0.30, y=0.57 to 0.75), still more preferably (x=0.14 to 0.30, y=0.61 to 0.75) }.

Examples of Green pigments widely used for Green pixels include c.i. pigment Green (c.i. pigment Green) 7 (hereinafter, abbreviated as PG 7), c.i. pigment Green 36 (hereinafter, abbreviated as PG 36), and c.i. pigment Green 58 (hereinafter, abbreviated as PG 58).

However, when a green pixel is manufactured using PG7 so as to realize the above-described green region of high color density, there is a problem in that the luminance of the green pixel is lowered. When a green pixel is formed using PG7 as a main green color material, a darker color filter is formed.

In addition, when a green pixel is manufactured using PG36 so as to realize the above-described green region of high color density, there is a problem in that the luminance of the green pixel is lowered, although it is not as serious as PG 7.

In addition, when PG58 is used, although the luminance is high, in manufacturing a green pixel including the green region of high color density, the green pixel must be made very thick, which causes problems in mass production and also makes it difficult to maintain the color filter performance because only the green pixel is made thick. Even if only PG58 is used, there is an unrealizable region in the green region of the high color density, and there is a limit in creating green pixels so as to be a larger triangle.

Patent document 3 describes that a pigment containing highly chlorinated zinc phthalocyanine is used as a colored resin composition for a color filter which achieves a green target chromaticity with a high color density without thickening and which can form a green pixel with a high brightness. However, higher brightness is also required.

On the other hand, patent document 4 has been proposed for the purpose of providing a color curable resin composition for a color filter in which occurrence of foreign matter failure due to a zinc bromide phthalocyanine pigment which has recently been attracting attention as a green pixel formation agent is suppressed, and discloses a color filter color composition comprising a pigment dispersant which is an amine polymer containing a specific constituent unit and a block copolymer aggregation inhibitor which contains a constituent unit having a 4-stage ammonium salt group and a constituent unit having no 4-stage ammonium salt group in a side chain as an aggregation inhibitor. However, the zinc phthalocyanine bromide pigment described in patent document 4 is substantially only c.i. pigment green 58 (PG 58), and a green pigment dispersion exhibiting bluish green and having high brightness cannot be obtained.

In addition, the green pixel has a problem that display failure is likely to occur. More specifically, in the liquid crystal display device of the transverse electric field system, a colored layer of a color filter exists in a liquid crystal driving electric field, and thus is greatly affected by the electrical characteristics of the colored layer. When PG36 is used for the green pixel, various display defects such as disorder of liquid crystal alignment due to electric characteristics of the green pixel and a sintering phenomenon due to a switching threshold deviation occur in the liquid crystal display device of the transverse electric field system. Such display failure occurs more remarkably when PG58 is used for the green pixel, which causes a problem.

Patent document 5 discloses that, in a liquid crystal display device of a transverse electric field type, the electric properties of a colored layer as a color filter do not adversely affect the switching performance of liquid crystals, a sufficient performance can be ensured even without providing a protective layer of a transparent resin, and as a color filter that can cope with high color reproducibility, a colored layer forming a green pixel contains PG36 in a specific amount or less and has a specific dielectric loss tangent (tan δ) value.

However, with the technique disclosed in patent document 5, even if display failure is reduced, luminance is insufficient, and this is also insufficient in terms of wide color reproducibility.

On the other hand, patent document 6 discloses a green composition for a color filter, which contains PG58 and a yellow organic pigment and contains any one selected from blue pigment, red pigment, violet pigment and orange pigment, as a green composition for a color filter, which can adjust luminance without deteriorating high contrast.

However, the technique disclosed in patent document 6 is insufficient in terms of wide color reproducibility.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2011-237769

Patent document 2: japanese patent application laid-open No. 2012-32767

Patent document 3: japanese patent laid-open publication No. 2013-20558

Patent document 4: japanese patent laid-open publication No. 2012-108266

Patent document 5: japanese patent laid-open No. 2009-162979

Patent document 6: japanese patent laid-open publication No. 2011-118051

Disclosure of Invention

Problems to be solved by the invention

In recent color filters, various problems in mass production of color filters have to be solved with a technique for improving dispersibility of color materials in order to achieve a high brightness and a high contrast. That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the dispersant, and there are problems such as occurrence of development residues and delay of development time. Further, if the color material concentration is increased and the dispersant content is increased, the binder amount is relatively reduced, and therefore, the colored resin layer tends to be peeled off from the base substrate during development. Therefore, the colored resin composition is required to have high development adhesion, but has a problem that the practical level is not achieved. In the process for producing a color filter, it is required that the solid content of the once dried colored resin composition is dissolved in a solvent again, that is, the resolubility in a solvent is excellent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip during coating by a die coater, a cured product is produced by drying, and if the cured product is not easily dissolved in the photosensitive colored resin composition during the coating restart, the cured product on the die lip is partially peeled off and easily adheres to the colored layer of the color filter, which causes a foreign matter defect. In particular, when the color material concentration of the colored resin composition is increased, there are problems such as a lack of solvent resolubility, a decrease in yield due to the generation of the foreign matter in the process of manufacturing the color filter, and the like.

However, according to the methods described in patent documents 1 and 2, in addition to the dispersibility of the color material, it is difficult to solve all of the problems in mass production of color filters, the occurrence of development residues, development adhesion, and solvent resolubility at the same time as those described in comparative examples described below.

In view of the above, a first object of the present invention is to provide: a color material dispersion liquid which has excellent color material dispersion stability, can inhibit development residues, and can produce photosensitive coloring resin composition with excellent development adhesion and solvent resolubility; a photosensitive colored resin composition for a color filter, which has excellent color material dispersion stability, excellent development adhesion while suppressing development residues, excellent solvent resolubility, and can form a colored layer having excellent contrast; a color filter formed by using the photosensitive coloring resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device excellent in display characteristics by using the color filter.

In addition, a blue pigment dispersion liquid exhibiting bluish green and having high brightness is desired in order to achieve high brightness and high contrast while forming the high-color density green chromaticity region without thickening the green pixels of the color filter, but there has been no conventional one.

In view of the above, a second object of the present invention is to provide: a blue green color material dispersion liquid which exhibits excellent dispersion stability of a blue color material and has high brightness; a photosensitive colored resin composition for a color filter, which is excellent in solvent resolubility, high in brightness and contrast, and capable of forming a colored layer excellent in color reproducibility, using the color material dispersion; a color filter having high brightness, high contrast and excellent color reproducibility using the photosensitive colored resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device having high brightness and excellent color reproducibility by using the color filter.

Technical means for solving the problems

A color material dispersion for a color filter according to a first aspect of the present invention for solving the first object is a color material dispersion containing a color material, a dispersant, and a solvent; the method is characterized in that:

the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2);

p1: a block copolymer having an A block comprising constituent units represented by the following general formula (I) and a B block comprising constituent units derived from a carboxyl group-containing monomer;

p2: a salt-type block copolymer in which at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) of the block copolymer is salified with 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3);

The acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃;

[ chemical formula 1]

(in the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R ² R is R ³ R is independently a hydrogen atom or a hydrocarbon group which may contain a hetero atom ² R is R ³ Can be bonded to each other to form a ring structure;

in the general formula (1), R ^a Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R ^b 、R ^b′ R is R ^b″ Each independently represents a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or-O-R ^f ，R ^f A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group which is bonded via an alkylene group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c R is R ^d Independently represent a hydrogen atomSub-, hydroxy-, C1-20 straight-chain, branched or cyclic alkyl, vinyl, phenyl or benzyl which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; wherein R is ^c R is R ^d At least one of which contains a carbon atom. )

A color material dispersion liquid for a color filter according to a second aspect of the present invention for solving the second object is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the method is characterized in that:

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the following general formula (I);

[ chemical formula 2]

(in the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R ² R is R ³ R is independently a hydrogen atom or a hydrocarbon group which may contain a hetero atom ² R is R ³ Can be bonded to each other to form a ring structure. )

The photosensitive colored resin composition for a color filter of the present invention is characterized by comprising the color material dispersion liquid of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

The color filter of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a colored layer formed by curing the photosensitive colored resin composition for a color filter of the present invention.

The present invention provides a liquid crystal display device comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

In addition, the present invention provides an organic light emitting display device having the color filter of the present invention described above, and an organic light emitter.

ADVANTAGEOUS EFFECTS OF INVENTION

According to a first aspect of the invention, there may be provided: a color material dispersion liquid which has excellent color material dispersion stability, can inhibit development residues, and can produce photosensitive coloring resin composition with excellent development adhesion and solvent resolubility; a photosensitive colored resin composition for a color filter, which has excellent color material dispersion stability, excellent development adhesion while suppressing development residues, excellent solvent resolubility, and can form a colored layer having excellent contrast; a color filter formed by using the photosensitive coloring resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device excellent in display characteristics by using the color filter.

Further, according to the second aspect of the invention, there may be provided: a blue green color material dispersion liquid which exhibits excellent dispersion stability of a blue color material and has high brightness; a photosensitive colored resin composition for a color filter, which is excellent in solvent resolubility and can form a colored layer excellent in color reproducibility with high brightness and high contrast, using the color material dispersion; a color filter having high brightness, high contrast and excellent color reproducibility using the photosensitive colored resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device having high brightness and excellent color reproducibility by using the color filter.

Drawings

Fig. 1 is a schematic diagram showing an example of a color filter according to the present invention.

Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.

Fig. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention.

Detailed Description

I. First aspect of the invention

The color material dispersion liquid for a color filter, the photosensitive colored resin composition for a color filter, the liquid crystal display device, and the organic light emitting display device according to the present invention will be described in order.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation including, for example, microwaves and electron beams. Specifically, electromagnetic waves having a wavelength of 5 μm or less and electron beams.

In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid, respectively, and (meth) acrylic acid ester means acrylic acid ester and methacrylic acid ester, respectively.

In the present specification, unless otherwise specified, the chromaticity coordinates x and y are chromaticity coordinates in the XYZ color system of JIS Z8701 using the color measured by the C light source.

I-1 the color Material Dispersion of the first aspect of the present invention

The color material dispersion liquid for a color filter according to the first aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the method is characterized in that:

The acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃.

[ chemical formula 3]

(in the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, A represents a valence of 2Linking group, R ² R is R ³ R is independently a hydrogen atom or a hydrocarbon group which may contain a hetero atom ² R is R ³ Can be bonded to each other to form a ring structure;

in the general formula (1), R ^a Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R ^b 、R ^b′ R is R ^b″ Each independently represents a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or-O-R ^f ，R ^f A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group which is bonded via an alkylene group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c R is R ^d Independently of each other, a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; wherein R is ^c R is R ^d At least one of which contains a carbon atom. )

The color material dispersion liquid of the present invention uses at least 1 of the block copolymer (P1) having the specific acid value and the specific glass transition temperature and containing the specific constituent unit and the salt-type block copolymer (P2) in which the block copolymer and the specific compound form a salt as a dispersant, and thus can produce a photosensitive colored resin composition excellent in color material dispersion stability, development adhesion while suppressing development residue generation, and solvent resolubility. Further, a colored layer excellent in contrast can be formed using the photosensitive colored resin composition for a color filter prepared from the color material dispersion.

The effect of using at least 1 of the block copolymer (P1) having the specific acid value and the specific glass transition temperature and containing the specific constituent unit and the salt-type block copolymer (P2) in which the block copolymer forms a salt with the specific compound as a dispersant is not clarified, but is presumed as follows.

Conventionally, as pigment dispersants, it has been known that dispersibility, dispersion stability, and alkali developability can be improved by a block copolymer having an a block containing a specific repeating unit having an amino group or an ammonium salt group and a B block containing a repeating unit having an acidic group (for example, patent documents 1, 2, and 4).

However, as a result of the studies by the present inventors, the method described in patent document 1 has not reached a practical level, particularly in terms of development adhesion. As shown in comparative examples described below, the method described in patent document 1 is presumed to be because the portion of the block copolymer containing the carboxylic acid ester derived from the alcohol contains a specific repeating unit of the alkylene oxide chain, and thus the glass transition temperature is low. If the glass transition temperature of the block copolymer as the pigment dispersant is lower than or close to the developer temperature, the molecular motion of the dispersant increases during development, and as a result, it is presumed that the development adhesion is lowered.

In addition, in the methods described in patent documents 2 and 4, in particular, the development adhesion thereof is not yet practical. In the methods described in patent documents 2 and 4, as shown in comparative examples described below, it is assumed that the reason for this is that the acid value of the dispersant is higher than the value defined in the present application, and therefore the development property is excellent, but the polarity is too high and peeling is easily generated instead. In the methods described in patent documents 2 and 4, it is assumed that the development adhesion does not reach a practical level because the idea of satisfying both a specific low acid value and a specific high glass transition temperature of the dispersant is not present.

As a result of intensive studies, the present inventors have found that if the acid value of a specific block copolymer or a salt-type block copolymer is high, the development adhesion does not reach a practical level, and the solvent resolubility is deteriorated; however, if the acid value is a low value of not more than a specific value, the development residue can be suppressed, and good development adhesion in which peeling is difficult to occur can be obtained, and the solvent resolubility is excellent. On the other hand, it was found that even if the specific block copolymer or the salt-type block copolymer has a low acid value equal to or lower than the specific value, if the glass transition temperature is lower than the specific value, the development adhesion does not reach a practical level; when a block copolymer or a salt-type block copolymer having a glass transition temperature of 30℃or higher than the developer temperature is used, the development adhesion is excellent. It is presumed that when a block copolymer or a salt-type block copolymer having a glass transition temperature of 30℃or higher than the developer temperature is used, the molecular movement of the dispersant during development is suppressed, and therefore the reduction of development adhesion is suppressed.

The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

The components of the color material dispersion liquid of the present invention will be described below in order from the dispersant characteristic in the present invention.

< dispersant >

In the present invention, at least 1 of the block copolymer (P1) and the salt-type block copolymer (P2) is used as a dispersant, wherein the dispersant has an acid value of 1 to 18mgKOH/g and a glass transition temperature of 30℃or higher.

The constituent unit represented by the general formula (I) contained in the a block has basicity and functions as an adsorption site to the color material. In addition, when at least a part of the nitrogen portion of the terminal of the constituent unit represented by the general formula (I) forms a salt with 1 or more compounds selected from the group consisting of the general formulae (1) to (3), the salt forming portion functions as a stronger adsorption portion to the color material. On the other hand, the B block containing a constituent unit derived from a carboxyl group-containing monomer functions as a block having solphilicity. Therefore, the block copolymer of the present invention functions as a color material dispersant by sharing the function of the a block adsorbed to the color material with the B block having solvent affinity.

[ Block copolymer ]

{ A block }

(constituent units represented by the general formula (I))

In the general formula (I), A is a direct bond or a 2-valent connecting group. The term "directly bonded" means that a has no atom, that is, C (carbon atom) and N (nitrogen atom) in the general formula (I) are bonded to each other without any other atom.

Examples of the 2-valent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-group, -COO-group, an ether group having 1 to 10 carbon atoms (-R '-OR "-: R' and R" are each independently an alkylene group), and a combination of these.

Among them, from the viewpoint of dispersibility, a in the general formula (I) is preferably a 2-valent linking group directly bonded, containing a-CONH-group, or a-COO-group.

R ² R is R ³ Examples of the hydrocarbon group among hydrocarbon groups which may contain a hetero atom include an alkyl group, an aralkyl group, an aryl group and the like.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl, and the number of carbon atoms of the alkyl group is preferably 1 to 18, and among these, methyl or ethyl groups are more preferred.

Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. The number of carbon atoms of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, and xylyl. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12. The preferred number of carbon atoms does not include a substituent.

The heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and the like.

The hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, or a bromine atom.

So-called R ² And R is R ³ Bonded to each other to form a ring structure, which means R ² R is R ³ A ring structure is formed via the nitrogen atom. R is R ² And R is R ³ The ring structure formed may contain heteroatoms. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholine ring, and the like.

In the present invention, R is preferably ² And R is R ³ Independently of each other, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² And R is R ³ Bonding to form a pyrrolidine ring, a piperidine ring, a morpholine ring.

Examples of the constituent unit represented by the above general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and other alkyl-substituted amino-containing (meth) acrylates, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and other alkyl-substituted amino-containing (meth) acrylamides. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide are preferably used from the viewpoint of improving dispersibility and dispersion stability.

The constituent unit represented by the general formula (I) may be 1 or 2 or more constituent units.

In the A block containing the constituent unit represented by the general formula (I), the constituent unit represented by the general formula (I) preferably contains 3 or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to contain 3 to 100, more preferably 3 to 50, still more preferably 3 to 30.

Within the scope of achieving the object of the present invention, the A block may have a constituent unit other than the constituent unit represented by the general formula (I), and may be contained as long as it is a constituent unit copolymerizable with the constituent unit represented by the general formula (I). For example, as the constituent unit other than the constituent unit represented by the general formula (I) which may be contained in the basic block, the "other constituent unit" mentioned in the B block described later may be used, and specifically, for example, the constituent unit represented by the general formula (II) described later may be mentioned.

The content of the constituent unit represented by the general formula (I) in the A block in the block copolymer before salification is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and most preferably 100% by mass based on the total mass of all constituent units in the A block. This is because the higher the proportion of the constituent unit represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. The content of the constituent units is calculated from the packing mass when synthesizing an a block having the constituent units represented by the general formula (I).

In addition, the content of the constituent unit represented by the general formula (I) in the block copolymer before salification is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of all constituent units of the block copolymer, from the viewpoint of good dispersibility and dispersion stability. The content of each constituent unit in the block copolymer is calculated from the packing mass of the block copolymer before salt synthesis.

The constituent unit represented by the general formula (I) may be 1 or 2 or more constituent units as long as it has affinity with the color material.

{ B block }

The B block is a block containing no constituent unit represented by the above general formula (I) and a constituent unit derived from a carboxyl group-containing monomer. The B block is preferably selected from monomers having an unsaturated double bond which are copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and used appropriately depending on the solvent so as to have solphilicity. As a standard, the B block is preferably introduced so that the solubility of the copolymer at 23℃is 20 (g/100 g of solvent) or more relative to the solvent used in combination.

(constituent units derived from carboxyl group-containing monomers)

As the carboxyl group-containing monomer used in the present invention, a monomer containing an unsaturated double bond and a carboxyl group which can be copolymerized with a monomer from which the constituent unit represented by the general formula (I) is derived can be used.

Examples of such monomers include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic anhydride, ω -carboxy-polycaprolactone mono (meth) acrylate, or the like can be used. As the precursor of the carboxyl group, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The content of the constituent units derived from the carboxyl group-containing monomer in the block copolymer before salification is not particularly limited as long as the acid value of the block copolymer is appropriately set within the above-mentioned specific acid value range, and is preferably 0.05 to 4.5 mass%, more preferably 0.07 to 3.7 mass% relative to the total mass of all constituent units of the block copolymer.

The content ratio of the constituent unit derived from the carboxyl group-containing monomer is set to the above lower limit or more, whereby the effect of suppressing the development residue is excellent, and the content ratio is set to the above upper limit or less, whereby deterioration of the development adhesion or deterioration of the solvent resolubility can be prevented.

The constituent unit derived from the carboxyl group-containing monomer may be 1 or 2 or more constituent units as long as it has the above-mentioned specific acid value.

(other constituent Unit)

In the B block, from the viewpoint of improving the solphilicity, in general, a constituent unit that improves the solphilicity may be further contained in addition to a constituent unit derived from the carboxyl group-containing monomer.

The constituent unit constituting the B block may be a monomer having an unsaturated double bond copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and among these, the constituent unit represented by the general formula (II) is preferable.

[ chemical formula 4]

(in the general formula (II), A' is a direct bond or a 2-valent linking group, R ⁴ Represents a hydrogen atom or a methyl group, R ⁵ Represents a hydrocarbon group, - [ CH (R) ⁶ )-CH(R ⁷ )-O] _x -R ⁸ Or- [ (CH) ₂ ) _y -O] _z -R ⁸ A 1-valent group as shown. R is R ⁶ R is R ⁷ Each independently is a hydrogen atom or a methyl group, R ⁸ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ⁹ The 1-valent radical shown, R ⁹ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The above-mentioned hydrocarbon group may have a substituent.

x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the general formula (II), A' may be set to be the same as A in the general formula (I). Among them, from the viewpoint of solubility in an organic solvent, a 2-valent linking group containing a-CONH-group or-COO-group is preferable.

In the general formula (II), R ⁵ Represents a hydrocarbon group, - [ CH (R) ⁶ )-CH(R ⁷ )-O] _x -R ⁸ Or- [ (CH) ₂ ) _y -O] _z -R ⁸ 。

As R ⁵ The hydrocarbon group in (a) is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group.

The alkyl group having 1 to 18 carbon atoms may be any of a linear, branched, and cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-ethylhexyl group, a 2-ethoxyethyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, and a lower alkyl-substituted adamantyl group.

The alkenyl group having 2 to 18 carbon atoms may be any of linear, branched, and cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of reactivity of the obtained polymer, it is preferable to have a double bond at the terminal of the alkenyl group.

Examples of the substituent of the aliphatic hydrocarbon group such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12.

Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl groups, which may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

Examples of the substituent of the aromatic ring such as an aryl group or an aralkyl group include an alkenyl group, a nitro group, a halogen atom, and the like, in addition to a linear branched alkyl group having 1 to 4 carbon atoms.

The preferred number of carbon atoms does not include a substituent.

R is as described above ⁵ Wherein x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2; y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3.z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

R is as described above ⁸ The hydrocarbon group in (2) may be set as the same as R ⁵ The same is shown.

R ⁹ The alkyl group having 1 to 5 carbon atoms may be a linear, branched or cyclic alkyl group.

In addition, R in the constituent unit represented by the above formula (II) ⁵ May be the same or different from each other.

As R as above ⁵ Among them, a solvent having excellent compatibility with a solvent to be described later is preferably selected, specifically, for exampleAmong the above solvents, the solvents generally used as solvents for color filter colored resin compositions, such as glycol ether acetates, ethers, esters, and the like, are preferably methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, and the like.

Furthermore, R is as described above ⁵ The substituent may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group, or may be added by reacting the block copolymer with a compound having the substituent after synthesis, within a range not to impair the dispersibility of the block copolymer.

The number of the constituent units constituting the B block is not particularly limited, but is preferably 10 to 300, more preferably 10 to 100, still more preferably 10 to 70, from the viewpoint of effectively functioning the solvophilic site and the chromotropic site and improving the dispersibility of the chromotropic.

The content of the constituent units represented by the general formula (II) in the B block in the block copolymer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total mass of all the constituent units of the B block, from the viewpoint of improving the solvophilicity or the color material dispersibility. The content of the constituent units is calculated from the packing mass when synthesizing the B block having the constituent units derived from the carboxyl group-containing monomer.

In the block copolymer before salification, the content of the constituent unit represented by the general formula (II) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of all constituent units of the block copolymer, from the viewpoint of improving the dispersibility of the color material. The content of the constituent units is calculated from the packing mass of the block copolymer before synthesis of the salt.

The B block may be any block that can be appropriately selected so as to function as a solvent-philic moiety, and the constituent unit represented by the general formula (II) may be 1 or 2 or more constituent units. The constituent units of 2 or more kinds contained in the B block may be randomly arranged in the block.

In the present invention, the B block of the block copolymer preferably contains a constituent unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion. When the constituent unit derived from the hydroxyl group-containing monomer is contained, it is considered that the development adhesion is improved because the constituent unit easily interacts with glass, metal, or the like that is generally used as a substrate. In the case where the B block contains a constituent unit derived from a hydroxyl group-containing monomer, the development speed is further improved.

The hydroxyl group herein means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the constituent unit derived from the hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group which can be copolymerized with a monomer from which the constituent unit represented by the general formula (I) is derived can be used. Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, epsilon-caprolactone 1 molar adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.

From the viewpoint of improving the developability, a hydroxyl group having a 1-order hydroxyl group is more preferable than a hydroxyl group having a 2-order hydroxyl group. The 1-order hydroxyl group means a hydroxyl group having a 1-order carbon atom as a carbon atom to which the hydroxyl group is bonded; the 2-order hydroxyl group means a hydroxyl group having a 2-order carbon atom as a carbon atom to which the hydroxyl group is bonded.

As described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving development adhesion, among them, a hydroxyl group-containing monomer having a glass transition temperature (Tgi) of 0 ℃ or more, and more preferably a hydroxyl group-containing monomer having a glass transition temperature of 10 ℃ or more, are preferably used.

Among them, 1 or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is preferable from the viewpoint of improving development adhesion.

In the block copolymer (P1) before salification, the content of the constituent units derived from the hydroxyl group-containing monomer is preferably 1 mass% or more, more preferably 2 mass% or more, still more preferably 3 mass% or more, and particularly preferably 4 mass% or more, based on the total mass of all the constituent units of the block copolymer. If the lower limit is not less than the above, a product preferable for development adhesion can be obtained. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less. If the ratio is not more than the upper limit, a preferable product can be obtained from the viewpoint of increasing the ratio of other useful monomers to be introduced. The content of the constituent units was calculated from the charge mass in the synthesis of the block copolymer before salt formation.

In the present invention, the B block preferably contains a constituent unit derived from an aromatic group-containing monomer from the viewpoint of improving the solvent resolubility. When the aromatic group-containing monomer is contained, the compatibility with the solvent or other components is easily improved, and therefore, the solvent resolubility is considered to be improved.

As the constituent unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group which can be copolymerized with a monomer from which the constituent unit represented by the general formula (I) is derived can be used. Examples of such monomers include acrylates such as benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrenes such as styrene, and vinyl ethers such as phenyl vinyl ether.

As described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving development adhesion, among them, an aromatic group-containing monomer having a glass transition temperature value (Tgi) of 0 ℃ or more, and more preferably an aromatic group-containing monomer having a glass transition temperature value (Tgi) of 10 ℃ or more, are preferably used.

Among them, 1 or more selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and phenoxyethyl (meth) acrylate is preferable, and 1 or more selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable from the viewpoint of easy improvement of the resolubility.

In addition, the content of the constituent unit derived from the aromatic group-containing monomer in the block copolymer (P1) before salifying is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the total mass of all the constituent units of the block copolymer, from the viewpoint of improving the solvent resolubility. When the ratio is not less than the above lower limit, a product having preferable solvent resolubility can be obtained. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less. If the ratio is not more than the upper limit, a preferable product can be obtained from the viewpoint of increasing the ratio of other useful monomers to be introduced.

Among them, the B block having solphilicity preferably contains (i) a constituent unit derived from a hydroxyl group-containing monomer and (ii) a constituent unit derived from an aromatic group-containing monomer, from the viewpoint of improving development adhesion and solvent resolubility; and (ii) at least 1 kind of constituent units derived from a carboxyl group-containing and aromatic group-containing monomer.

When the constituent unit derived from the hydroxyl group-containing monomer and the constituent unit derived from the aromatic group-containing monomer are contained in the respective components (i), the constituent unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 0.15 parts by mass or more, more preferably 0.5 parts by mass or more, based on 1 part by mass of the constituent unit derived from the aromatic group-containing monomer. When the lower limit is not less than the above, a product excellent in development adhesion can be obtained. In the same manner, the aromatic group-containing monomer preferably contains 15 parts by mass or less, more preferably 7 parts by mass or less of the constituent unit derived from the hydroxyl group-containing monomer, relative to 1 part by mass of the constituent unit derived from the aromatic group-containing monomer. This is because, if the upper limit is less than or equal to the above-mentioned upper limit, a product excellent in solvent resolubility can be produced. Among them, 1 part by mass of a constituent unit derived from an aromatic group-containing monomer having a glass transition temperature (Tgi) of 10 ℃ or higher relative to the homopolymer is particularly preferable, and a constituent unit derived from a hydroxyl group-containing monomer having a glass transition temperature (Tgi) of 10 ℃ or higher is contained in the above range. When each component is contained at the lower limit or more, a product having more excellent development adhesion can be obtained, and when each component is contained at the upper limit or less, a product having more excellent solvent solubility can be obtained.

Examples of the monomer (ii) having a hydroxyl group and an aromatic group in the constituent unit derived from a hydroxyl group-and aromatic group-containing monomer include 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid. The value (Tgi) of the glass transition temperature of the homopolymer of 2-hydroxy-3-phenoxypropyl (meth) acrylate is 10 ℃ or higher, and is preferably used from the viewpoint that any one of effects derived from the constituent unit derived from the hydroxyl group-containing monomer and effects derived from the constituent unit derived from the aromatic group-containing monomer can be obtained. That is, it is preferable from the viewpoints of improving the development adhesion, development speed, and solvent resolubility.

(ii) When the monomer contains a constituent unit derived from a hydroxyl group-containing monomer and an aromatic group-containing monomer, the development adhesion, development speed and solvent resolubility can be improved by using 1 constituent unit, and therefore, there is an advantage that the introduction ratio of other functional monomers can be improved.

In addition, as described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesion, it is preferable to set the value (Tgi) of the glass transition temperature of the homopolymer of the monomer to 10 ℃ or more, and the total content in the B block is set to 75 mass% or more, more preferably 85 mass% or more.

In the block copolymer (P1), the ratio m/n of the number m of the constituent units of the A block to the number n of the constituent units of the B block is preferably in the range of 0.05 to 1.5, more preferably in the range of 0.1 to 1.0 from the viewpoints of dispersibility and dispersion stability of the color material.

The amine value of the block copolymer (P1) before salification is not particularly limited, but is preferably 40mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 60mgKOH/g or more from the viewpoints of color material dispersibility and dispersion stability. The upper limit is preferably 140mgKOH/g or less, more preferably 130mgKOH/g or less, still more preferably 120mgKOH/g or less. When the content is not less than the above lower limit, the dispersion stability is further excellent. When the amount is equal to or less than the upper limit, the compatibility with other components is excellent, and the solvent resolubility is good.

In the present invention, the amine value of the block copolymer before salification means the mass (mg) of potassium hydroxide equivalent to 1g of hydrochloric acid required for neutralizing the solid content of the block copolymer before salification, and is a value measured according to the method described in JIS K7237.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 3000 to 12000, from the viewpoint of improving the dispersibility and dispersion stability of the color material.

The weight average molecular weight (Mw) was determined by Gel Permeation Chromatography (GPC) as a standard polystyrene equivalent.

In the present invention, the weight average molecular weight Mw of the block copolymer is obtained by GPC (gel permeation chromatography) as a standard polystyrene equivalent. Measurement was performed using HLC-8120GPC manufactured by Tosoh, inc., using N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added as an elution solvent, mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories Co., ltd.) as a calibration curve polystyrene standard, mw1090000 (manufactured by Tosoh, inc.), and TSK-GEL ALPHA-MX2 (manufactured by Tosoh, inc.) as a measurement column. The macromer, the salt-type block copolymer, and the graft copolymer, which are the raw materials of the block copolymer, are also prepared under the above-described conditions.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like can be used. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferable.

The method for producing the block copolymer is not particularly limited, and the block copolymer can be produced by a known method, and among them, a living polymerization method is preferable. This is because chain rotation or deactivation is less likely to occur, a copolymer having a uniform molecular weight can be produced, dispersibility can be improved, and the like. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and group transfer polymerization methods, living cationic polymerization methods, and the like. By these methods, the monomers are polymerized sequentially, and a copolymer can be produced. For example, a block is first produced, and constituent units constituting a B block are polymerized on the a block, whereby a block copolymer can be produced. In the above production method, the polymerization order of the a block and the B block may be reversed. Alternatively, the a block and the B block may be separately manufactured, after which the a block and the B block are coupled.

[ salt type Block copolymer ]

In the present invention, a salt-type block copolymer in which at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) of the block copolymer is salified with 1 or more compounds selected from the group consisting of the compounds represented by the general formulae (1) to (3) can be used.

The salt-forming site in the constituent unit represented by the general formula (I) is preferably the salt-form block copolymer from the viewpoint of further improving the color material adsorption property and the color material dispersibility.

(1 or more compounds selected from the group consisting of the compounds represented by the above general formulae (1) to (3))

In the general formulae (1) to (3), R is ^a 、R ^b 、R ^b′ 、R ^b″ 、R ^c 、R ^d 、R ^e R is R ^f The straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms may be either straight-chain or branched, or may have a cyclic structure, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl may be mentionedGroup, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, dodecyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl and the like. The alkyl group may be preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and more preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

In addition, R ^a 、R ^c 、R ^d R is R ^e Examples of the substituent of the phenyl group or benzyl group which may have a substituent include an alkyl group having 1 to 5 carbon atoms, an acyl group, an acyloxy group, and the like.

R ^b 、R ^b′ 、R ^b″ R is R ^f Examples of the substituent of the phenyl group or benzyl group which may have a substituent include an acidic group or an ester group thereof, an alkyl group having 1 to 5 carbon atoms, an acyl group, an acyloxy group, and the like.

In addition, R ^b 、R ^b′ 、R ^b″ R is R ^f Examples of the substituent of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or vinyl group which may have a substituent include an acidic group or an ester group thereof, a phenyl group, an acyl group, an acyloxy group and the like.

R ^b 、R ^b′ 、R ^b″ R is R ^f The acidic group refers to a group that releases a proton in water to exhibit acidity. Specific examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO) ₃ H) Phosphate (-P (=O) (OH) ₂ ) A phosphosubunit (> P (=o) (OH)), a boronic acid group (-B (OH) ₂ ) The boric acid subunit (> BOH) and the like may be anions such as carboxylate groups (-COO-) and the like in which hydrogen atoms have been dissociated, or may be acidic salts which form salts with alkali metal ions such as sodium ions and potassium ions.

Examples of the ester group of the acidic group include a carboxylic acid ester group (-COOR) and a sulfonic acid ester group (-SO) ₃ R), phosphate group (-P (=o) (OR) ₂ ) Phosphate subunits (> P (=o) (OR)), borate groups (-B (OR) ₂ ) Borate subunit (> BOR), and the like. Wherein the ester group as the acidic group is from the viewpoints of dispersibility and dispersion stabilityFrom this point of view, carboxylic acid ester groups (-COOR) are preferred. R is a hydrocarbon group, but is not particularly limited thereto, and is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoints of dispersibility and dispersion stability.

The compound of the above general formula (2) preferably has a functional group selected from the group consisting of a carboxyl group, a boric acid subunit, anions of these, alkali metal salts of these, and esters of these, and more preferably has a functional group selected from the group consisting of a carboxyl group, a carboxylate group, and a carboxylate ester group, from the viewpoints of dispersibility, dispersion stability, alkali developability, and development residue inhibition.

In the case where the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter, referred to as an acidic group or the like), it is presumed that the terminal nitrogen site and the halogen atom side hydrocarbon stably form a salt, as compared with the case where the terminal nitrogen site and the acidic group or the like form a salt, because either one of the acidic group or the like and the halogen atom side hydrocarbon of the compound can form a salt with the terminal nitrogen site. Further, it is estimated that the dispersibility and dispersion stability can be improved by adsorbing the coloring material at the stably existing salt forming site.

In the case where the compound of the general formula (2) has the acid group or the like, the compound may have 2 or more acid groups or the like. In the case where the acid group is 2 or more, the plurality of acid groups may be the same or different. The number of the acidic groups and the like of the compound of the general formula (2) is preferably 1 to 3, more preferably 1 to 2, still more preferably 1.

R in the above general formula (1) ^a R in the above general formula (2) ^b 、R ^b′ R is R ^b″ At least one of (3), R in the above general formula (3) ^c R is R ^d When at least one of the (c) and (d) has an aromatic ring, affinity with the skeleton of a color material to be described later can be improved, and the color material is preferably excellent in dispersibility and dispersion stability, from the viewpoint that a color composition excellent in contrast can be obtained.

The molecular weight of 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) is preferably 1000 or less, more preferably 50 to 800, still more preferably 50 to 400, still more preferably 80 to 350, and most preferably 100 to 330, from the viewpoint of improving the dispersibility of the color material.

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfuric acid, monoethyl sulfuric acid, and mono-n-propylsulfuric acid. It is to be noted that a hydrate such as p-toluenesulfonic acid monohydrate may be used. Examples of the compound represented by the general formula (2) include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α -chlorophenyl acetic acid, α -bromophenyl acetic acid, α -iodophenyl acetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenyl benzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, α -bromophenyl acetic acid methyl ester, 3- (bromomethyl) phenylboronic acid, and the like. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphoric acid, and dimethylaminoacryloxyethyl acid type phosphoric acid.

From the viewpoint of particularly excellent dispersion stability, 1 or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethylaminoethyl acid phosphoric acid, dibutylphosphoric acid, benzyl chloride, benzyl bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate is preferable, and 1 or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl bromide, and p-toluenesulfonic acid monohydrate is preferable.

In addition, from the viewpoints of excellent dispersion stability and improved effect of inhibiting development residues by combination with the block copolymer (P1) having an acid value, the compound represented by the general formula (2) having an acid group and an ester group thereof is also suitably used, and among them, 1 or more selected from the group consisting of α -chlorophenyl acetic acid, α -bromophenyl acetic acid, α -iodophenyl acetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl benzoic acid, and 4-iodophenyl benzoic acid are also suitably used.

Since the content of 1 or more compounds selected from the group consisting of the above-mentioned general formulae (1) to (3) forms a salt with the terminal nitrogen site of the constituent unit represented by the general formula (I), the content of 1 or more compounds selected from the group consisting of the above-mentioned general formulae (1) to (3) is 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and particularly preferably 0.3 mol or more, based on 1 mol of the terminal nitrogen site of the constituent unit represented by the general formula (I). When the lower limit is not less than the above, the effect of improving the dispersibility of the color material due to salt formation is easily obtained. Similarly, the amount is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When the content is not more than the above-mentioned upper limit, a product excellent in development adhesion and solvent resolubility can be obtained.

1 or more compounds selected from the group consisting of the general formulae (1) to (3) may be used alone or 2 or more compounds may be combined. When 2 or more kinds are combined, the total content thereof is preferably within the above range.

As a method for preparing the salt-type block copolymer, there are mentioned a method in which 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) are added to a solvent in which the block copolymer is dissolved or dispersed, stirred, and then heated as necessary.

The nitrogen site at the terminal of the constituent unit represented by the general formula (I) of the block copolymer, the formation of a salt with 1 or more compounds selected from the group consisting of the general formulae (1) to (3), and the ratio thereof can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer (P2) is smaller than that of the block copolymer (P1) before salt formation, only the portion where salt is formed. However, since the salt forming site is the same as or a stronger member at the nitrogen site at the end corresponding to the amino group, there is a tendency that the dispersibility or dispersion stability of the color material is improved by salt formation. In addition, if the salt formation site is too large, the solvent resolubility is adversely affected, as in the case of the amino group. Therefore, in the present invention, the amine value of the block copolymer (P1) before salification can be used as an index for improving the dispersion stability of the color material and the solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably 0 to 130mgKOH/g, more preferably 0 to 120mgKOH/g.

When the content is not more than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility is good.

In the salt-type block copolymer (P2), the amine value of the salt-type block copolymer obtained by forming a salt from the compound represented by the general formula (2) can be determined by the method described in JIS K7237. In the compound of the above general formula (2), since the terminal nitrogen portion of the constituent unit represented by the general formula (I) forms a salt with the halogen atom side hydrocarbon, the amine value can be measured without changing to a salt state even by this measurement method.

On the other hand, in the salt-type block copolymer (P2), the amine value of the salt-type block copolymer obtained by forming a salt with the compound represented by the above general formula (1) or (3) is calculated from the amine value of the block copolymer before salt formation as described below. In the compounds represented by the general formulae (1) or (3), since the terminal nitrogen moiety of the constituent unit represented by the general formula (I) forms a salt with an acidic group, when the amine value of such a salt-type block copolymer is measured by the method described in JIS K7237, the state of salt formation is changed, and thus the accurate value cannot be measured.

First, the amine value of the block copolymer (P1) before salification was obtained by the above-described method. Next, 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance apparatus, and in the obtained spectrum data, the reaction rate (nitrogen site ratio of the salt-forming terminal) of 1 or more compounds selected from the group consisting of the above-mentioned general formulae (1) and (3) was measured on the nitrogen site of the terminal of the salt-type block copolymer with respect to the nitrogen site of the terminal of the constituent unit of the general formula (I) by using the ratio of the integral value of the carbon atom peak adjacent to the non-salt-forming nitrogen atom and the carbon atom peak adjacent to the salt-forming nitrogen atom. The amine value of the terminal nitrogen site of the constituent unit represented by the general formula (I) after salifying 1 or more compounds selected from the group consisting of the above general formulae (1) and (3) is calculated by (the amine value of the block copolymer (P1) before salifying measured by the method described in JIS K7237) × (the nitrogen site ratio (%)/100 at the terminal of salified formed calculated by 13C-NMR spectrum) by subtracting the amine value consumed by salifying from the amine value of the block copolymer before salifying.

Amine value = { amine value of salt-forming block copolymer (P1) measured by the method described in JIS K7237 } × { nitrogen site ratio (%)/100 at the end of formed salt calculated from 13C-NMR spectrum }

The acid value of the dispersant used in the present invention is 1mgKOH/g or more as the lower limit from the viewpoint of the effect of suppressing the development residue. Among these, the acid value of the dispersant is more preferably 2mgKOH/g or more from the viewpoint of more excellent suppression effect of the development residue. The acid value of the dispersant used in the present invention is limited to 18mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and deterioration of solvent resolubility. Among them, the acid value of the dispersant is more preferably 16mgKOH/g or less, still more preferably 14mgKOH/g or less, from the viewpoint of good development adhesion and solvent resolubility.

In the dispersant used in the present invention, the acid value of the block copolymer (P1) before salification is preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more. This is because the inhibition effect of the development residues can be improved. The upper limit of the acid value of the block copolymer (P1) before salification is 18mgKOH/g or less, preferably 16mgKOH/g or less, more preferably 14mgKOH/g or less. This is to improve the development adhesion and the solvent resolubility.

As described above, the acid value of the block copolymer (P1) before salification represents the mass (mg) of potassium hydroxide required for neutralizing the acid component contained in 1g of the solid content of the block copolymer, and is measured according to the method described in JIS K0070.

The acid value of the salt-type block copolymer (P2) obtained by forming a salt from the compound represented by the above general formula (2) is also measured by the method described in JIS K0070. The compound of the above general formula (2) can be measured because the nitrogen site at the terminal of the constituent unit represented by the general formula (I) forms a salt with a halogen atom-side hydrocarbon, and the state of salt formation does not change even by this measurement method.

On the other hand, in the case of a salt-type block copolymer (P2) in which a compound represented by the above general formula (1) or (3) is used to form a salt, the acid value is calculated by removing the acid groups used for salt formation. This is because the acid group used for salification does not function as an acid group that increases the acid value of the dispersant. Accordingly, in the present application, the acid value of the salt-type block copolymer which is a salt formed by using the compound represented by the above general formula (1) or (3) is calculated from the value obtained by the following formula. This is because, when the acid value of the salt-type block copolymer obtained by forming a salt from the compound represented by the general formula (1) or (3) is measured by the method described in JIS K0070, the state of salt formation is changed, and the accurate value cannot be measured.

Acid value of salt-type block copolymer (P2) = { total acid value of the compound represented by the above general formula (1) or (3) for salification-acid value consumed by salification } + acid value of block copolymer (P1) before salification }

The total acid value of the compound represented by the general formula (1) or (3) used for the salt formation can be measured by the method described in JIS K0070. On the other hand, the acid value consumed by salt formation was calculated by using the salt formation ratio obtained by NMR.

Specifically, for example, the 13C-NMR spectrum of the salt-type block copolymer is measured by using a nuclear magnetic resonance device, and the ratio of the number of terminal nitrogen sites to the total number of terminal nitrogen sites forming a salt is calculated from the ratio of the integral values of the peaks of carbon atoms adjacent to the nitrogen atoms not forming a salt and the peaks of carbon atoms adjacent to the nitrogen atoms forming a salt in the obtained spectral data. The amine value consumed was calculated using { the amine value of the block copolymer before salt formation (P1) measured by the method described in JIS K7237 } × { the nitrogen site ratio (%)/100 at the end of the formed salt calculated from the 13C-NMR spectrum }, and this value was the same as the acid value consumed by salt formation.

However, in the case where the compound represented by the general formula (1) is salified at 1 mol or less relative to 1 mol of the terminal nitrogen portion of the constituent unit represented by the general formula (I), in the case where the compound represented by the general formula (3) having 1 acid group is salified at 1 mol or less, or in the case where the compound represented by the general formula (3) having 2 acid groups is salified at 0.5 mol or less, the total amount of the acid groups may be the same as the acid value of the block copolymer before salifying because the acid groups do not affect the acid value in the salified block copolymer if the total amount of the acid groups forms a salt with the terminal nitrogen portion of the constituent unit represented by the general formula (I).

On the other hand, when the compound represented by the general formula (3) having 2 acid groups is added in an amount exceeding the above molar amount, since the acid groups which do not form salts are present in the dispersant after salification, the acid value of the acid groups which do not form salts is added to the acid value of the block copolymer before salification as described above, and the acid value of the dispersant is calculated.

In the present invention, the glass transition temperature of the dispersant is 30℃or higher. That is, the dispersant is either a block copolymer (P1) or a salt-type block copolymer (P2) and has a glass transition temperature of 30℃or higher.

When the glass transition temperature of the dispersant is lower than 30 ℃, the development adhesion is lowered, particularly when the temperature of the developer is equal to or lower than the developer temperature (usually about 23 ℃). This is presumably because: when the glass transition temperature is equal to or lower than the developer temperature, the movement of the dispersant during development increases, and as a result, the development adhesion is deteriorated.

The glass transition temperature of the dispersant is preferably 32 ℃ or higher, more preferably 35 ℃ or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of ease of handling in use, such as ease of accurate weighing, it is preferably 200℃or less.

The glass transition temperature of the dispersant of the present invention is determined by measurement by differential scanning calorimeter measurement (DSC) based on JIS K7121.

Among them, the glass transition temperature (Tg) of the block copolymer which does not form a salt is calculated by the following formula and can be used as an index.

1/Tg＝∑(Xi×Tgi)

Here, the block copolymer is formed by copolymerizing n monomer components i=1 to n. Xi is the weight fraction of the ith monomer (Σxi=1), tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Where Σ is the sum taken as i=1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer may be the value of Polymer Handbook 3rd Edition (J.Brandrup, E.H.Immergut, wiley-Interscience, 1989).

The glass transition temperature obtained from the calculated value is almost the same as the measured value obtained by DSC, as shown in examples described later, and therefore can be used as an index of the glass transition temperature of a block copolymer in which no salt is formed.

In the color material dispersion liquid of the present invention, at least 1 of the block copolymer and the salt-type block copolymer is used as the dispersing agent, and the content thereof is appropriately selected according to the type of the color material used, the solid content concentration in a photosensitive colored resin composition for a color filter to be described later, and the like.

The content of the dispersant is preferably 3 to 45 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion. When the lower limit is not less than the above, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is further excellent. In addition, if the upper limit value is less than or equal to the above, the developability is good.

In particular, when a coating film or a colored layer having a high color material concentration is formed, the content of the dispersant is preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion.

In the present invention, the solid component includes all the substances other than the above-mentioned solvents, and includes monomers dissolved in the solvents.

< color Material >

In the present invention, the color material is not particularly limited as long as it can give a desired color when forming a colored layer of a color filter, and various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination of 2 or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of the organic Pigment include a compound classified as Pigment (Pigment) in the Pigment index (c.i.; issued by The Society of Dyers and Colourists company), and specifically, a Pigment to which a Pigment index (c.i.) number is attached as described below.

C.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and c.i. pigment yellow 150;

c.i. pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

C.i. pigment violet 1, 19, 23, 29, 32, 36, 38;

c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 215, 216, 226, 242, 224, 254, 255.

C.i. pigment blue 15, 15:3, 15:4, 15:6, 60;

c.i. pigment green 7, 36, 58, 59;

c.i. pigment brown 23, 25;

c.i. pigment black 1, 7.

Among them, when the c.i. pigment green 59 is contained as the color material, a green color material dispersion liquid exhibiting bluish green color, excellent color material dispersion stability, and high brightness is preferable. When the green material dispersion is used, the green pixels of the color filter can be formed into green chromaticity regions of high color density without thickening, and high brightness and high contrast can be achieved. Regarding the c.i. pigment green 59, details will be described in the following description of the second aspect of the present invention. The derivative pigment of c.i. pigment yellow 150 is also described in detail in the following description of the second aspect of the present invention.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, indian red (bengal, red iron (III) oxide), cadmium red, ultramarine, cyanosis, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when a light-shielding layer pattern is formed on a substrate of a color filter using the color material dispersion liquid of the present invention as a photosensitive colored resin composition for a color filter described later, a black pigment having high light-shielding property is blended in an ink. As the black pigment having high light-shielding properties, for example, an inorganic pigment such as carbon black or ferroferric oxide, or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include dyes that are dispersible by insolubilizing in a solvent by adding various substituents to the dye or by using a known method of laking (salifying), or dyes that are dispersible by using a combination of solvents having low solubility. By using such a dispersible dye in combination with the above-mentioned dispersant, the dispersibility and dispersion stability of the dye can be improved.

As the dispersible dye, one selected appropriately from the existing dyes can be used. Examples of such dyes include azo dyes, metal double salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.

When the amount of the dye dissolved in 10mg or less of the solvent (or mixed solvent) is 10g or less, it can be determined that the dye is dispersible in the solvent (or mixed solvent) as a standard.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as a desired color can be emitted when a colored layer of a color filter is formed, and is preferably in the range of 10 to 100nm, more preferably 15 to 60nm, depending on the type of the color material used. By setting the average primary particle diameter of the color material to the above range, a display device provided with a color filter manufactured using the color material dispersion liquid of the present invention can be made high-contrast and high-quality display device.

The average primary particle diameter of the color material of the present invention means "volume distribution median particle diameter (D50)". In a scanning electron microscope (S-4800) manufactured by hitachi High Technologies corporation, field emission type, a dedicated bright field STEM placement table and a selective detector were attached to make the scanning electron microscope usable as a scanning transmission electron microscope (hereinafter simply referred to as "STEM"), a STEM photograph of 20 ten thousand times was taken, 100 color materials were arbitrarily selected on the photograph, diameters (cross lengths) thereof were measured, and an average primary particle diameter of the color materials was obtained as a 50% cumulative particle diameter by volume from a distribution of volume references.

The color material and toluene were mixed and added dropwise to a collodion film-sticking net to prepare a measurement sample to be supplied to STEM. When the volume-based particle size distribution or the volume-distribution median particle size (D50) is obtained from STEM photographs, image analysis type particle size distribution measuring software "Mac-View ver.4" manufactured by Mountech corporation is used.

The average dispersion particle diameter of the color material in the color material dispersion liquid varies depending on the type of color material used, but is preferably in the range of 10 to 100nm, more preferably in the range of 15 to 60 nm.

The average dispersion particle diameter of the color material in the color material dispersion liquid is the dispersion particle diameter of the color material particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser scattering particle size distribution meter. As the particle diameter measurement by the laser scattering particle size distribution meter, the color material dispersion may be diluted appropriately with the solvent used for the color material dispersion to a concentration (for example, 1000 times or the like) at which the measurement by the laser scattering particle size distribution meter is possible, and the measurement may be performed by a dynamic light scattering method at 23 ℃ by using the laser scattering particle size distribution meter (for example, a nanotch particle size distribution measuring apparatus UPA-EX150 manufactured by the daily nectar corporation). The average distribution particle diameter herein is a volume average particle diameter.

The color material used in the present invention can be produced by a known method such as recrystallization or solvent salt milling. Further, a commercially available color material may be used by being subjected to a fine-scale treatment.

The content of the color material in the color material dispersion liquid of the present invention is not particularly limited. The color material content is preferably blended in a proportion of 5 to 80 parts by mass, more preferably 8 to 70 parts by mass, relative to 100 parts by mass of the total solid content in the color material dispersion from the viewpoints of dispersibility and dispersion stability.

In particular, when a coating film or a colored layer having a high color material concentration is formed, the composition is preferably formulated in a proportion of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, relative to 100 parts by mass of the total solid content in the color material dispersion.

< solvent >

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the components in the color material dispersion liquid and can dissolve or disperse them. The solvent may be used alone or in combination of 2 or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; a carbitol acetate solvent such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and Butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as gamma-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; organic solvents such as aromatic hydrocarbons including toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used in view of the solubility of other components. Among them, the solvent used in the present invention is preferably 1 or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate from the viewpoint of solubility of other components and coating suitability.

The color material dispersion liquid of the present invention contains the above solvent in a range of usually 55 to 95 mass%, preferably 65 to 90 mass%, more preferably 70 to 88 mass%, based on the total amount of the color material dispersion liquid containing the solvent. If the solvent is too small, the viscosity tends to increase and the dispersibility tends to decrease. If the solvent is too much, the color material concentration may be reduced, and it may be difficult to achieve the chromaticity coordinates of the target.

< other ingredients >

In the color material dispersion liquid of the present invention, a dispersion auxiliary resin and other components may be further blended as needed without impairing the effects of the present invention.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by photosensitive colored resin compositions for color filters described below. The steric hindrance of the alkali-soluble resin makes the color material particles less likely to contact each other, and there are cases where dispersion stabilization occurs and the effect of the dispersing agent is reduced by utilizing the dispersion stabilization effect.

Examples of the other components include a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, a shrinkage inhibitor, an antioxidant, an anticoagulant, and an ultraviolet absorber.

The color material dispersion liquid of the present invention is used as a pre-prepared product for preparing a photosensitive colored resin composition for a color filter, which will be described later. That is, the color material dispersion liquid is a color material dispersion liquid having a relatively high ratio of (mass of color material component in the composition)/(mass of solid component other than the color material component in the composition) which is pre-prepared in a stage before preparing a photosensitive color resin composition for a color filter described later. Specifically, the ratio of (the mass of the color material component in the composition)/(the mass of the solid component other than the color material component in the composition) is usually 1.0 or more. The photosensitive colored resin composition for a color filter having excellent dispersibility can be prepared by mixing the color material dispersion liquid with each component described below.

< method for producing color Material Dispersion >

In the present invention, the method for producing the color material dispersion liquid is not particularly limited as long as the color material dispersion liquid is obtained by dispersing the color material in a solvent using the dispersant of the block copolymer or the salt-type block copolymer. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the color material, any of the following 2 production methods is preferable.

That is, the first production method of the color material dispersion liquid of the present invention includes: preparing a dispersant for the block copolymer or the salt-type block copolymer; and dispersing the color material in a solvent in the presence of the dispersing agent.

In addition, the second production method of the color material dispersion liquid of the present invention, which uses the dispersant that is a salt-type block copolymer, includes: and a step of mixing a solvent, the block copolymer, at least 1 compound selected from the group consisting of the general formulae (1) to (3), and a color material, and dispersing the color material while forming a salt with the compound at least in part of the terminal nitrogen portion of the constituent unit represented by the general formula (I).

In the case of using a salt-type block copolymer, the salt-type block copolymer is prepared according to the first production method, and then the salt-type block copolymer is used as a dispersant to disperse the color material, so that it is preferable from the viewpoint that the reaction end point and the reaction rate of the block copolymer before salt formation and 1 or more compounds in the group consisting of the general formulae (1) to (3) can be accurately confirmed.

In addition, according to the second production method, the dispersing agent of the salt-type block copolymer is prepared and the color material is dispersed, so that the salt-type block copolymer does not self-agglomerate, the color material dispersion liquid can be efficiently prepared, and the dispersibility can be improved.

In the first manufacturing method and the second manufacturing method, the color material may be dispersed using a conventional dispersing machine.

Specific examples of the dispersing machine include a roll mill such as a twin roll mill or a triple roll mill, a ball mill such as a ball mill or a vibration ball mill, a paint conditioner, a continuous disc type bead mill, a continuous ring type bead mill, and the like. As preferable dispersion conditions of the bead mill, the diameter of the beads to be used is preferably 0.03 to 3.0mm, more preferably 0.05 to 2.0mm.

Specifically, for example, the pre-dispersion is performed by using 2.0mm zirconium dioxide beads having a large bead diameter, and the main dispersion is performed by using 0.1mm zirconium dioxide beads having a small bead diameter. After the dispersion, filtration is preferably performed by a filter of 0.5 to 2. Mu.m.

I-2A photosensitive colored resin composition for a color filter according to the first aspect of the invention

The photosensitive colored resin composition for a color filter according to the first aspect of the present invention is characterized by comprising the color material dispersion liquid according to the first aspect of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

The photosensitive colored resin composition for a color filter according to the first aspect of the present invention can form a colored layer excellent in color material dispersion stability, suppressed development residues, excellent in development adhesion and solvent resolubility, and excellent in contrast by using the color material dispersion liquid according to the first aspect of the present invention.

The photosensitive colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, the respective components contained in the photosensitive colored resin composition for a color filter of the present invention will be described, but since the dispersing agent, the color material and the solvent are the same as those described in the color material dispersion liquid of the present invention, the description thereof will be omitted.

< alkali-soluble resin >

The alkali-soluble resin of the present invention has an acidic group, can function as a binder resin, and can be suitably selected from alkali-soluble resins which are soluble in a developer used for patterning, particularly preferably an alkali developer.

Preferred alkali-soluble resins in the present invention are resins having a carboxyl group as an acidic group, and specifically, there can be mentioned: acrylic copolymers having a carboxyl group, styrene-acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like. Of these, particularly preferred is an alkali-soluble resin having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain. The reason for this is that the film strength of the formed cured film can be improved by containing the photopolymerizable functional group. In addition, these acrylic copolymers, styrene-acrylic copolymers and epoxy acrylate resins may be used in combination of 2 or more.

The acrylic copolymer having a carboxyl group and the styrene-acrylic copolymer having a carboxyl group can be obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with other ethylenically unsaturated monomers.

Specific examples of the acrylic copolymer having a carboxyl group include those described in, for example, japanese patent application laid-open No. 2013-029832, and specific examples thereof include: a copolymer is formed from a monomer having no carboxyl group such as methyl (meth) acrylate or ethyl (meth) acrylate, and 1 or more selected from (meth) acrylic acid and its acid anhydride. Examples of the copolymer include, but are not limited to, a polymer obtained by introducing an ethylenically unsaturated bond by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the copolymer.

Among these, the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly preferable in view of the sensitivity of the colored layer, the film strength being more stable, and the like.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5 mass%, the solubility of the obtained coating film in an alkaline developer is reduced, and patterning becomes difficult. If the copolymerization ratio exceeds 50 mass%, pattern deletion or film roughening on the pattern surface tends to occur easily when developing with an alkali developer.

The carboxyl group-containing copolymer preferably has a weight average molecular weight (Mw) in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If the weight average molecular weight is less than 1,000, the function of the cured binder is significantly reduced, and if the weight average molecular weight exceeds 50,000, the development by an alkaline developer may be difficult to form a pattern.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth) acrylate compound obtained by reacting an unsaturated group-containing monocarboxylic acid with an acid anhydride is preferable.

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be appropriately selected from known ones.

Among them, epoxy (meth) acrylate resins having carboxyl groups, those having carboxyl groups, in which a fluorene skeleton represented by the following chemical formula (a) is bonded to two benzene rings (Cardo structure), are preferable in terms of improving the effect of suppressing defects, improving the curability of the colored layer, and improving the residual film rate of the colored layer.

[ chemical formula 5]

The exact mechanism of the epoxy (meth) acrylate resin having a carboxyl group (hereinafter referred to as Cardo resin) containing the Cardo structure has not been elucidated, but it is considered that since the fluorene skeleton contains pi-conjugated system, it exhibits high sensitivity to free radicals, and the combination of the oxime ester photoinitiator described later with Cardo resin can improve the required performances such as sensitivity, developability, development adhesion, and the like. Further, cardo resin is preferable from the viewpoint that it can be designed into a colored resin composition free of aggregates even at a high color density because it has high solvent resolvability.

Examples of the Cardo resin include polymerizable compounds represented by the following general formula (B) described in japanese patent application laid-open No. 2007-119720, and reactants (condensates) of epoxy (meth) acrylate resins having a fluorene skeleton and polybasic acids described in japanese patent application laid-open No. 2006-308698.

[ chemical formula 6]

/>

(in the general formula (B), X represents a group represented by the following general formula (D), Y independently represents a polycarboxylic acid or anhydride thereof, and R ⁱ The group represented by the following general formula (C) is represented by the following formula (C), j is an integer of 0 to 4, k is an integer of 0 to 3, and n is an integer of 1 or more. )

[ chemical formula 7]

(in the general formula (C), R is ⁱⁱ Represents a hydrogen atom or a methyl group, R ⁱⁱ¹ Each independently represents a hydrogen atom or a methyl group. )

[ chemical formula 8]

(in the general formula (D), R is ^iv Each independently represents a hydrogen atom, a C1-5 alkyl group, a phenyl group, or a halogen atom, R ^v represents-O-or-OCH ₂ CH ₂ O-。)

The Cardo resin used in the present invention can be obtained, for example, by epoxidizing a fluorene bisphenol compound to obtain an epoxy compound of the fluorene bisphenol compound, reacting the epoxy compound with (meth) acrylic acid to obtain an epoxy (meth) acrylate resin, and reacting the epoxy (meth) acrylate resin with a polybasic acid or an acid anhydride thereof.

As the fluorene bisphenol compound, R in the above general formula (D) can be exemplified ^v Fluorene bisphenol compounds that are-O-, preferably the-O-is-OH.

As the fluorene bisphenol compound, examples thereof include 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene bisphenol compounds such as 9, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, and 9, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, and mixtures thereof.

Examples of the polybasic acid and the acid anhydride thereof used for the reaction of the epoxy (meth) acrylate resin having a fluorene skeleton include dicarboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic anhydride, chlormycolic acid, methyltetrahydrophthalic acid, glutaric acid, and the acid anhydrides thereof; tetracarboxylic acids such as biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl sulfone tetracarboxylic acid, 4- (1, 2-dicarboxyethyl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, butane tetracarboxylic acid, and pyromellitic acid, or acid dianhydrides thereof; tricarboxylic acids such as trimellitic acid and its anhydride, and their anhydrides. These may be used alone or in combination of 2 or more.

The Cardo resin used in the present invention is preferably an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride.

As commercial products of Cardo resins usable in the present invention, INR-16M (manufactured by Nagase ChemteX Co., ltd.) and the like are mentioned.

The epoxy (meth) acrylate resin having a carboxyl group may be used alone or in combination of 1 or more than 2 kinds.

The alkali-soluble resin used in the photosensitive colored resin composition for a color filter may be used alone or in combination of 1 or more than 2, and the content thereof is not particularly limited, but is preferably in the range of 5 to 60 mass%, more preferably 10 to 40 mass% relative to the total solid content of the photosensitive colored resin composition for a color filter. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, film roughness or pattern deletion may occur during development. In the present invention, the solid component is any substance other than the above-mentioned solvent, and includes a liquid polyfunctional monomer and the like.

< multifunctional monomer >

The polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited as long as it is a polyfunctional monomer polymerizable by a photoinitiator described below, and a compound having 2 or more ethylenically unsaturated double bonds can be generally used, and a polyfunctional (meth) acrylate having 2 or more acryl groups or methacryl groups is particularly preferable.

Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include polyfunctional (meth) acrylates described in Japanese patent application laid-open No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of 1 or more than 2. In addition, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition for a color filter of the present invention, the polyfunctional monomer preferably has 3 or more (trifunctional) polymerizable double bonds, more preferably poly (meth) acrylic esters of a 3-or more-membered polyol, or dicarboxylic acid modifications thereof, and specifically, it is preferable that: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modification of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modification of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited, but is preferably in the range of 5 to 60 mass%, more preferably 10 to 40 mass% relative to the total solid content of the photosensitive colored resin composition for a color filter. If the content of the polyfunctional monomer is less than the above-mentioned lower limit, the photocuring may not be sufficiently performed, and the exposed portion may be eluted during development, and if the content of the polyfunctional monomer is more than the above-mentioned upper limit, there is a concern that the alkali developability may be lowered.

< photoinitiator >

The photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, and 1 or 2 or more photoinitiators can be used in combination from various conventional photoinitiators. Specific examples thereof include photoinitiators described in Japanese patent application laid-open No. 2013-029832.

As the photoinitiator, only 1 kind may be used, or two or more kinds may be used in combination. Among these photoinitiators, oxime ester photoinitiators are preferably contained in view of their high effect of suppressing pattern defects and high effect of suppressing water penetration. When a dispersant having an acid value is used, water-bleeding tends to occur particularly easily, but it is preferable to use the dispersant from the viewpoint that water-bleeding can be suppressed by using an oxime ester photoinitiator in combination. The water-bleeding is a phenomenon in which marks such as water-bleeding occur after alkali development and after rinsing with pure water. The water-bleeding is not problematic as a product because it disappears after post baking, but is detected as uneven abnormality in the appearance inspection of the pattern surface after development, and there is a problem that normal products cannot be distinguished from abnormal products. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, the yield of the final color filter product is lowered as a result, which is a problem.

Among these, the oxime ester photoinitiator is preferably an oxime ester photoinitiator having an aromatic ring, more preferably an oxime ester photoinitiator having a condensed ring containing an aromatic ring, and still more preferably an oxime ester photoinitiator having a condensed ring containing a benzene ring and a heterocyclic ring, from the viewpoint of reducing contamination of the photosensitive colored resin composition for a color filter due to decomposition products or contamination of devices.

The oxime ester-based photoinitiator may be appropriately selected from oxime ester-based photoinitiators described in 1, 2-octanedione-1- [4- (phenylthio) -, 2- (o-benzoyl) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime), japanese patent application laid-open No. 2000-80068, japanese patent laid-open No. 2001-233836, japanese patent publication No. 2010-527339, japanese patent publication No. 2010-527338, japanese patent application laid-open No. 2013-04153, and the like. As the commercial products, irgacure OXE-01, irgacure OXE-02, irgacure OXE-03 (manufactured by BASF corporation, above), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (manufactured by ADEKA corporation, above), TR-PBG-304, TR-PBG-326, TR-PBG-3057 (manufactured by strong electronic new materials, co., ltd., above), and the like can be used.

The oxime ester photoinitiator used in the present invention is preferably an oxime ester photoinitiator that generates alkyl radicals, more preferably an oxime ester photoinitiator that generates methyl radicals, from the viewpoints of excellent curability and excellent development resistance, inhibition effect of pattern deletion, and inhibition effect of water penetration and hair dye generation even in a photosensitive colored resin composition in which the color material concentration is increased to achieve a wide color gamut by using PG 59. It is presumed that alkyl radicals are easier to activate radical rotation than aryl radicals. As the oxime ester-based photoinitiator generating an alkyl radical, there may be mentioned ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyloxime) (trade name: irgacure OXE-02, manufactured by BASF), methanone, [8- [ [ (acetoxy) imino ] [2- (2, 3-tetrafluoropropoxy) phenyl ] methyl ] -11- (2-ethylhexyl) -11H-benzo [ a ] carbazol-5-yl ] -, (2, 4, 6-trimethylphenyl) (trade name: irgacure OXE-03, manufactured by BASF), ethanone, 1- [ 9-ethyl-6- (1, 3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl ] -,1- (o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), methanone, (9-ethyl-6-nitro-9H-carbazol-5-yl ] -, (trade name: 2,4, 6-trimethylphenyl) (trade name: irgacure OX-03, manufactured by BASF), 1- [ 9-ethyl-6- (2-methoxyphenoxy) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime ]) (trade name: ADEKA-2-methyl-62), 3-cyclopentyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (trade name TR-PBG-304, manufactured by Hezhou powerful electronic New Co., ltd.), 1-propanone, 3-cyclopentyl-1- [2- (2-pyrimidothio) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (trade name TR-PBG-314, manufactured by Hezhou powerful electronic New Co., ltd.), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidyloxy) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (trade name TR-PBG-326, manufactured by Hezhou powerful electronic New Co., ltd.), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidothio) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (trade name TR-PBG-331, manufactured by Hezhou powerful electronic Co., ltd.), 1-octanone, 1- [4- [3- [1- [ (1-acetoxy) imino ] ethyl ] -4- [ (4 ], 6-dimethyl-2-pyrimidinyl) thio ] -2-methylbenzoyl ] -9H-carbazol-9-yl ] phenyl ] -,1- (o-acetyl oxime) (trade name EXTA-9, manufactured by UNION CHEMICAL Co., ltd.), and the like.

In addition, among the oxime ester-based photoinitiators, a photoinitiator having a 3-stage amine structure is preferably used in combination from the viewpoint of improvement in sensitivity. This is because a photoinitiator having a 3-stage amine structure has a 3-stage amine structure as an oxygen quenching body in the molecule, so that radicals generated by the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved. Examples of the commercially available photoinitiator having a 3-stage amine structure include 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one (for example, irgacure907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, irgacure369, manufactured by BASF), 4' -bis (diethylamino) diphenyl ketone (for example, hicure ABP, manufactured by Sichuan).

The content of the photoinitiator used in the photosensitive color resin composition for a color filter is not particularly limited, but is preferably in the range of 3 to 40 mass%, more preferably 10 to 30 mass%, based on the total solid content of the photosensitive color resin composition for a color filter. If the content is less than the lower limit, the photocuring may not be sufficiently performed, and the exposed portion may be eluted during development; on the other hand, if the amount is more than the upper limit, yellowing of the obtained colored layer may be increased and brightness may be lowered.

< optional additional Components >

The photosensitive colored resin composition for a color filter may contain various additives as required.

Examples of the additives include, in addition to antioxidants, polymerization stoppers, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

The photosensitive colored resin composition for a color filter of the present invention preferably further contains an antioxidant from the viewpoint of heat resistance. The antioxidant is selected from the existing materials. Specific examples of the antioxidant include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like, and from the viewpoint of heat resistance, hindered phenol antioxidants are preferably used.

In the case of using an antioxidant, the amount to be blended is not particularly limited as long as the effect of the present invention is not impaired, but the amount to be blended is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, based on the total amount of the solid content in the photosensitive colored resin composition for a color filter. When the lower limit is not less than the above-mentioned lower limit, heat resistance is excellent. On the other hand, if the upper limit value is less than or equal to the above, the photosensitive colored resin composition for a color filter of the present invention can be made into a photosensitive colored resin composition for a color filter having high sensitivity.

Further, specific examples of the surfactant and the plasticizer include those described in Japanese patent application laid-open No. 2013-029832.

< proportion of ingredients in photosensitive colored resin composition for color Filter >

The total content of the color materials is preferably 3 to 65 mass%, more preferably 4 to 60 mass% relative to the total solid content of the photosensitive colored resin composition for a color filter. When the thickness is equal to or larger than the lower limit, the colored layer has a sufficient color density when the photosensitive colored resin composition for a color filter is coated to a predetermined film thickness (usually 1.0 to 5.0 μm). In addition, when the upper limit value is less than or equal to the above, the storage stability is excellent, and a colored layer having sufficient hardness and adhesion to a substrate can be obtained. In particular, when forming a colored layer having a high color material concentration, the color material content is preferably blended at a ratio of 15 to 65 mass%, more preferably 25 to 60 mass%, with respect to the photosensitive colored resin composition for a color filter.

The content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed, and for example, 1 to 40 mass% relative to the total solid content of the photosensitive colored resin composition for a color filter can be used. The photosensitive colored resin composition for a color filter is preferably blended in a proportion of 2 to 30% by mass, particularly preferably 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition. When the content is not less than the above lower limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is further excellent. In addition, when the above upper limit value or less, the developability is good. In particular, when forming a colored layer having a high color material concentration, the content of the dispersant is preferably 2 to 25 mass%, more preferably 3 to 20 mass%, relative to the photosensitive colored resin composition for a color filter. In the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer before salification and 1 or more compounds selected from the group consisting of the general formulae (1) to (3).

The solvent content may be appropriately set within a range where the colored layer can be formed with good precision. The content of the solvent is usually in the range of 55 to 95 mass%, and more preferably in the range of 65 to 88 mass%, based on the total amount of the photosensitive colored resin composition for a color filter. The content of the solvent is within the above range, whereby a product excellent in coatability can be produced.

< method for producing photosensitive colored resin composition for color Filter >

The method for producing the photosensitive colored resin composition for a color filter of the present invention is not particularly limited, and for example, the photosensitive colored resin composition for a color filter of the present invention can be obtained by adding an alkali-soluble resin, a polyfunctional monomer, a photoinitiator and other components as necessary to the color material dispersion of the present invention and mixing the mixture by a known mixing means.

I-3. Color filter of the first aspect of the invention

The color filter according to the first aspect of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the first aspect of the present invention.

The color filter according to the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. According to fig. 1, a color filter 10 of the present invention includes a transparent substrate 1, a light shielding portion 2, and a colored layer 3.

< coloring layer >

The colored layer used in the color filter of the present invention is at least one colored layer formed by curing the photosensitive colored resin composition for a color filter of the present invention.

The colored layer is usually formed in an opening of a light shielding portion on a transparent substrate described later, and is usually formed of a colored pattern of 3 or more colors.

The arrangement of the coloring layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement. The width, area, etc. of the colored layer can be arbitrarily set.

The thickness of the colored layer is suitably controlled by adjusting the coating method, the solid content concentration, viscosity, and the like of the photosensitive colored resin composition for a color filter, and is preferably in the range of 1 to 5 μm.

The colored layer can be formed by the following method, for example.

First, the photosensitive colored resin composition for a color filter of the present invention is applied to a transparent substrate described later by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, or die coating, to form a wet coating film. Among them, spin coating and die coating can be preferably used.

Next, the wet coating film is dried using a heating plate, an oven, or the like, and then exposed to light through a mask of a predetermined pattern, whereby an alkali-soluble resin and a polyfunctional monomer or the like are subjected to photopolymerization, thereby forming a cured coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halogen lamp, and electron beams. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

In addition, a heat treatment may be performed after the exposure in order to promote the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for a color filter to be used, the thickness of the coating film, and the like.

Next, a developing treatment is performed using a developing solution to dissolve and remove the unexposed portions, thereby forming a coating film in a desired pattern. As the developer, a solution in which alkali is dissolved in water or a water-soluble solvent is generally used. To the alkali solution, a surfactant or the like may be added in an appropriate amount. In addition, the development method may employ a general method.

After the development treatment, the development solution is usually washed, and a cured coating film of the photosensitive colored resin composition for a color filter is dried to form a colored layer. After the development treatment, a heating treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.

< light shielding portion >

The light shielding portion in the color filter of the present invention is a light shielding portion formed in a pattern on a transparent substrate described later, and may be the same as a light shielding portion used as a light shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light shielding portion may be a resin layer containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin adhesive. In the case of the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

The film thickness of the light shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case of dispersing or dissolving the black pigment in the binder resin.

< transparent substrate >

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate; or a transparent flexible material having flexibility such as a transparent resin film, an optical resin sheet, or flexible glass.

The thickness of the transparent substrate is not particularly limited, and for example, a transparent substrate of about 100 μm to 1mm can be used according to the application of the color filter of the present invention.

In addition to the transparent substrate, the light shielding portion, and the colored layer, the color filter of the present invention may be formed with, for example, a protective layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like.

I-4A liquid Crystal display device of the first aspect of the invention

A liquid crystal display device according to a first aspect of the present invention is characterized by comprising the color filter according to the first aspect of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in fig. 2, the liquid crystal display device 40 of the present invention has: a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a known configuration of a liquid crystal display device used as a general color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used for a general liquid crystal display device can be used. Examples of such driving methods include a TN method, an IPS method, an OCB method, and an MVA method. Any of these modes can be suitably used in the present invention.

The counter substrate may be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies, and mixtures thereof can be used according to the driving method and the like of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include: vacuum injection, liquid crystal dropping, and the like.

In the vacuum injection method, for example, a liquid crystal cell is prepared by using a color filter and a counter substrate in advance, an isotropic liquid is prepared by heating liquid crystal, the liquid crystal is injected into the liquid crystal cell in the isotropic liquid state by capillary effect, and sealing is performed with an adhesive agent, thereby forming a liquid crystal layer. Thereafter, the liquid crystal cell is cooled slowly to room temperature, whereby the enclosed liquid crystal can be aligned.

In the liquid crystal dropping method, for example, a sealant is applied to the edge of a color filter, the color filter is heated to a temperature at which liquid crystal becomes isotropic phase, the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like, and the color filter and a counter substrate are overlapped under reduced pressure and bonded via the sealant, whereby a liquid crystal layer can be formed. Thereafter, the liquid crystal cell is cooled slowly to room temperature, whereby the enclosed liquid crystal can be aligned.

I-5. Organic light emitting display device of the first aspect of the present invention

An organic light-emitting display device of a first aspect of the present invention is characterized by having: the color filter and the organic light-emitting body of the present invention are described above.

The organic light emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As illustrated in fig. 3, the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting element 80.

As a lamination method of the organic light-emitting body 80, for example, there can be mentioned: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; a method of bonding the organic light-emitting element 80 formed on the other substrate to the inorganic oxide film 60. In the organic light-emitting body 80, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components can be appropriately used. The organic light emitting display device 100 thus manufactured can be applied to, for example, a passive driving type organic EL display or an active driving type organic EL display.

The organic light-emitting display device of the present invention is not limited to the configuration shown in fig. 3, and may be a known configuration of an organic light-emitting display device used as a general color filter.

Second aspect of the invention

The color material dispersion liquid for a color filter, the photosensitive colored resin composition for a color filter, the liquid crystal display device, and the organic light emitting display device according to the second aspect of the present invention will be described in order.

II-1. Color material dispersion liquid according to the second aspect of the present invention

(i) First aspect of the second aspect of the present invention

The color material dispersion liquid for a color filter according to the first aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent,

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the following general formula (I).

[ chemical formula 9]

In the color material dispersion liquid according to the first embodiment of the second aspect of the present invention, the color material contains c.i. pigment green 59 (hereinafter, may be simply referred to as PG 59), and the polymer having the constituent unit represented by the general formula (I) is used in combination as the dispersing agent, so that a green color material dispersion liquid exhibiting bluish green color, excellent color material dispersion stability, and high brightness can be obtained.

In the second aspect of the present invention, since PG59 is used as a color material, a chromaticity region which is not achieved by PG58 can be achieved, and since a polymer having a constituent unit represented by the general formula (I) is used in combination, a color filter having high brightness and high contrast, and a large triangle connected by 3 dots of red, green, and blue pixels and excellent color reproducibility can be produced.

In addition, in the color material dispersion liquid according to the first embodiment of the second aspect of the present invention, the polymer having the structural unit represented by the general formula (I) is combined with PG59 as a dispersant, so that a photosensitive colored resin composition having excellent color material dispersion stability and excellent solvent resolubility can be produced. Since the polymer having the constituent unit represented by the general formula (I) is combined with the PG 59-containing color material as the dispersant, it is presumed that the PG 59-containing color material is strongly adsorbed to the nitrogen site contained in the constituent unit represented by the general formula (I) to make the color material excellent in dispersibility, and the PG 59-containing color material strongly adsorbed to the nitrogen site and surrounded by the dispersant is easily washed out by the resolubilized solvent in a state of being adsorbed to the dispersant. In addition, when a polymer having a constituent unit represented by the general formula (I) is incorporated as a dispersant in a color material containing PG59, development residues tend to be easily suppressed. The reason for this is presumed that the PG 59-containing color material firmly adsorbed to the nitrogen portion and surrounded by the dispersant is easily washed away in a state of being adsorbed to the dispersant during development, and the color material is not left on the substrate, thereby easily suppressing the occurrence of development residues.

(ii) Second aspect of the present invention

The color material dispersion liquid for a color filter according to a second aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent,

the color material contains C.I. pigment green 59 and yellow color material;

the dispersant may be a polymer having a constituent unit represented by the general formula (I).

In the color material dispersion liquid according to the second aspect of the present invention, the color material contains PG59 and a yellow color material, and the polymer having the constituent unit represented by the general formula (I) is used in combination as the dispersant, so that a colored layer having excellent color material dispersion stability, suppressed occurrence of display failure, high luminance, and excellent color reproducibility can be formed.

In the second aspect of the present invention, PG59 used as a color material is monochromatic and exhibits bluish green, and has a strong coloring power and high brightness, so that by combining with a yellow color material, even if the content of PG59 in the color material or the ratio of the P/V ratio ((the mass of color material components in the composition)/(the mass of solid components other than the color material components in the composition)) is suppressed, a green pixel contained in the green region of the high color density can be produced. Since display failure is likely to occur in the green pixel, it is presumed that the occurrence of display failure is suppressed by using the color material dispersion of the present invention, since the content of the green material having a phthalocyanine skeleton in the pixel can be reduced and the P/V ratio can be reduced.

In addition, the PG59 used as the color material in the second aspect of the present invention can realize a chromaticity region which is not realized by the PG58 in the above-described green chromaticity region of high color density. Further, in the second embodiment of the present invention, since PG59 and a yellow color material are used in combination with a polymer having a constituent unit represented by the general formula (I), the color material dispersibility and the color material dispersion stability are excellent, and therefore a color filter having a large triangle connected by 3 points of red, green, and blue pixels, and excellent color reproducibility can be produced while achieving high brightness and high contrast.

In addition, in the color material dispersion liquid according to the second aspect of the present invention, the polymer having the structural unit represented by the general formula (I) is combined with the PG59 and the yellow color material as the dispersant, so that a photosensitive colored resin composition excellent in the solvent resolubility can be produced. It is presumed that since the polymer having the structural unit represented by the general formula (I) is combined with the PG59 and the yellow coloring material as the dispersant, the PG59 and the yellow coloring material which are firmly adsorbed to the nitrogen site and surrounded by the dispersant are easily washed away by the resolubilized solvent in a state of being adsorbed to the dispersant.

In the color material dispersion for a color filter according to the second aspect of the present invention, the PG59 is preferably contained in the color material in an amount of 5 to 95% by mass, from the viewpoint of suppressing occurrence of display failure and increasing color reproducibility to increase brightness.

In the color material dispersion for a color filter according to the second aspect of the present invention, the yellow color material is preferably 1 or more selected from the group consisting of c.i. pigment yellow 138 (hereinafter, abbreviated as PY 138), c.i. pigment yellow 139 (hereinafter, abbreviated as PY 139), c.i. pigment yellow 185 (hereinafter, abbreviated as PY 185), c.i. pigment yellow 150 (hereinafter, abbreviated as PY 150) and derivative pigments thereof, from the viewpoint of easily forming a colored layer excellent in color reproducibility while suppressing occurrence of display failure and having high brightness and high contrast.

In the color material dispersion for a color filter according to the second aspect of the present invention, the color material preferably contains at least 1 of c.i. pigment green 58 and c.i. pigment green 7, in addition to PG 59. Among them, PG58 is preferably contained in addition to PG59 from the viewpoint of achieving a target chromaticity, suppressing display defects, and forming a green pixel of high brightness. On the other hand, from the viewpoint of achieving a target chromaticity, suppressing display defects, further reducing the P/V ratio, and improving platemaking properties such as development resistance, it is preferable to contain PG7 in addition to PG 59. Further, from the viewpoint of achieving a target chromaticity, suppressing display defects, and improving the balance between luminance and platemaking due to the reduction of the P/V ratio, it is preferable to include PG58 and PG7 in addition to PG 59.

(iii) Third aspect of the second aspect of the present invention

The color material dispersion for a color filter according to a third aspect of the present invention is a color material dispersion for a color filter comprising a color material, a dispersant, and a solvent,

the color material contains C.I. pigment green 59, blue color material and yellow color material; the yellow color material is (Y1) at least 1 yellow color material containing C.I. pigment yellow 185, or (Y2) at least 2 yellow color material containing C.I. pigment yellow 139 as an essential component and further containing 1 or more selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 150 and derivative pigments thereof;

In the color material dispersion liquid according to the third aspect of the present invention, since the specific color material is contained and the polymer having the constituent unit represented by the general formula (I) is used in combination as the dispersant, a colored layer having excellent color material dispersion stability, suppressed occurrence of display failure, high brightness, and excellent color reproducibility can be formed.

According to the color material dispersion liquid according to the third aspect of the present invention, it is estimated that by combining either (Y1) or (Y2) as a yellow color material with PG59 and a blue color material, a wavelength portion which is not sufficiently absorbed by PG59 and the blue color material can be efficiently absorbed, and the total amount of color material can be reduced, whereby the P/V ratio can be reduced, and color can be reproduced. Therefore, in the green degree of the high color density, a colored layer which suppresses display failure and has high luminance can be formed while realizing a (x=0.14 to 0.30, y=0.61 to 0.75) region and further (x=0.14 to 0.30, y=0.66 to 0.75) region which is green of the high color density.

Further, since the specific yellow color material has excellent dispersibility when combined with a specific dispersant described later, the contrast can be easily improved, and a photosensitive colored resin composition having excellent solvent resolubility can be produced.

In the color material dispersion liquid according to the third aspect of the second aspect of the present invention, the blue color material preferably contains at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15:4 from the viewpoint of brightness.

The color material dispersion liquid according to the second aspect of the present invention is a color material dispersion liquid containing at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

The components of the color material dispersion liquid according to the second aspect of the present invention will be described in detail below in order.

< color Material >

In the second aspect of the present invention, the color material contains c.i. pigment green 59 as a zinc phthalocyanine pigment.

As chromaticity coordinates in the XYZ color system of JIS Z8701 in which color measurement is performed using the C light source alone, PG59 is a color material capable of expressing x=0.10 to 0.30 and y=0.30 to 0.64, and particularly a color material capable of expressing x=0.13 to 0.20 and y=0.32 to 0.60.

The PG59 is characterized in that it can represent an xy chromaticity coordinate region surrounded by the following equations 1, 2 and 3 in the XYZ color system of JIS Z8701 using the color measured by the C light source alone.

(equation 1)

y＝6.715×x-0.286

Wherein, in equation 1, 0.121 < x < 0.133

(equation 2)

y＝7147.200×x ⁵ -8466.000×x ⁴ +3891.400×x ³ -854.200×x ² +86.380×x-2.579

In equation 2, 0.133 < x < 0.310

(equation 3)

y＝1189.500×x ⁶ +1817.000×x ⁵ -3011.300×x ⁴ +1447.800×x ³ -307.420×x ² +27.628×x-0.285

Wherein, in equation 3, 0.121 < x < 0.310

Of the xy chromaticity coordinate regions surrounded by the above equations 1, 2 and 3, the region where x=0.13 to 0.20 and y=0.32 to 0.60 is most characteristic and effective.

When the transmittance at 450nm of PG59 used in the present invention is 5%, the wavelength (Tmax) at which the spectral transmittance spectrum at 400 to 700nm has the maximum transmittance is 505 to 535nm. Further, the transmittance at the wavelength (Tmax) is 70% or more. The transmittance of the spectral transmittance spectrum of PG59 used in the present invention at 435nm is 15% or less, and the transmittance of the spectral transmittance spectrum at 575nm is 5% or less.

In order to coat the PG59 alone and measure the color, a coating liquid may be prepared by blending an appropriate dispersant, binder component and solvent into the PG59, and the coating liquid may be applied to a transparent substrate, dried, and cured as necessary. As the binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin composition may be used, provided that a transparent coating capable of color measurement can be formed. In addition, in the photosensitive colored resin composition of the present invention described later, a coating film containing only PG59 as a color material can be formed by using a composition containing only PG59 as a color material, and measurement can be performed.

The transparent coating film containing a dispersant and a binder component and capable of color measurement may be, for example, a transparent coating film having a film thickness of 2.0 μm and a spectral transmittance spectrum at 380 to 780nm, the transmittance being 95% or more.

The spectral transmittance spectrum may be measured using a spectral measuring apparatus (for example, an Olympus microscope apparatus OSP-SP 200). The measurement conditions were C light sources.

In the color material dispersion liquid of the present invention, only PG59 may be used as a color material alone. On the other hand, a color material different from PG59 as exemplified in the color material item of the color material dispersion liquid of the first aspect of the present invention described above may be combined with PG59 as another color material without impairing the effect of the present invention. As the other color material, for example, other green color material, yellow color material, blue color material can be suitably used.

In the color material dispersion liquid according to the second aspect of the present invention, when another color material different from PG59 is used, the content of PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of enhancing color reproducibility and increasing brightness, PG59 is preferably contained in an amount of 5 mass% or more, more preferably 10 mass% or more, relative to the entire color material containing PG 59.

In the color material dispersion liquid according to the second aspect of the present invention, it is preferable to further use a yellow color material as a color material in combination with PG59, in order to suppress occurrence of defective display of green pixels and to form a colored layer having high brightness and excellent color reproducibility (the second aspect of the present invention).

Examples of the yellow color material include c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and derivative pigments of c.i. pigment yellow 150.

Specific examples of the derivative pigment of c.i. pigment yellow 150 include metal complexes of monoanions, dians, trianions, and tetraanions of the azo compounds of the following chemical formula (i) or one of their tautomeric structures which act as a host of at least 1 guest compound, and examples of the metal include Li, cs, mg, cd, co, al, cr, sn, pb, preferably Na, K, ca, sr, ba, zn, fe, ni, cu, mn, and La. Among these metals, ni is preferable, and at least 1 of the derivative pigment of c.i. pigment yellow 150 containing Ni and Zn and the derivative pigment of c.i. pigment yellow 150 containing Ni and Cu is more preferable. Among them, at least 1 of the derivative pigment of c.i. pigment yellow 150 described above containing Ni and Zn in a ratio (molar ratio) of Ni to zn=8:2 to 2:8 and the derivative pigment of c.i. pigment yellow 150 described above containing Ni and Zn in a ratio (molar ratio) of Ni to cu=5:5 to 9.8:0.2 is preferable.

[ chemical formula 10]

Chemical formula (i)

(in the chemical formula (i), R is independently-OH, -NH ₂ -NH-CN, acylamino or arylamino, R' are each independently-OH or-NH ₂ 。)

Pigment yellow 150 and its derivative pigment can be obtained by referring to Japanese patent application laid-open No. 2001-354869, no. 2005-325350, no. 2007-25687, no. 2007-23287, no. 2007-23288 and No. 2008-24927.

The yellow color material may be commercially available.

In the color material dispersion liquid according to the second aspect of the present invention, 1 kind or 2 or more kinds of yellow color materials may be used singly or in combination by appropriately selecting them. The same yellow color material is preferably used for the same reasons as those described in the photosensitive colored resin composition for a color filter to be described later.

In the color material dispersion liquid according to the second aspect of the present invention, other color materials exemplified by the photosensitive colored resin composition described later may be used in combination with the yellow color material in the PG59 without impairing the effects of the present invention. As the other color material, for example, other green color materials, blue color materials, orange color materials, and the like can be suitably used. Examples of other green materials than PG59 include phthalocyanine green pigments such as PG58, PG7, and PG 36. As a preferable other color material, the same other color material is preferably used for the same reason as described in the photosensitive colored resin composition for a color filter to be described later.

In the color material dispersion liquid according to the second aspect of the present invention, when another green color material is further contained, at least 1 of PY150 and its derivative pigment and PY138 are preferably used in combination in the yellow color material from the viewpoint of suppressing occurrence of display failure and easily realizing a high-luminance colored layer.

In the color material dispersion liquid according to the second aspect of the present invention, the content ratio of PG59 to the entire color material, the content ratio of yellow color material to PG59, and the content ratio when PG59, yellow color material, and other color materials are used are preferably the same content ratio as the photosensitive colored resin composition described later. However, since the photosensitive colored resin composition can be produced by mixing 2 or more kinds of color material dispersions appropriately, the same content ratio as the photosensitive colored resin composition described later can be used appropriately.

In the color material dispersion liquid according to the second aspect of the present invention, as the color material, a blue color material and a yellow color material are combined in PG59, and the yellow color material preferably contains (Y1) at least 1 yellow color material of PY 185; or (Y2) at least 2 yellow color materials containing PY139 as an essential component and 1 or more selected from the group consisting of PY138, PY150 and derivative pigments of PY150 (third embodiment of the second aspect of the present invention).

In the present invention, when the spectral transmittance spectrum is measured as in the case of PG59, the blue color material is a color material having a peak top in a range of 435nm to 490 nm.

Examples of the blue color material include c.i. pigment blue 15, 15:3, 15:4, 15:6, and 60. Among the dispersible dyes described in the photosensitive colored resin composition described below, a color material falling within the range of the blue color material can be appropriately selected and used.

In the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, the blue color material may be used singly or in combination of 1 or more than 2 kinds.

Among them, the blue color material used in the third embodiment of the present invention is preferably a β -type copper phthalocyanine pigment from the viewpoint of being able to suppress a decrease in brightness when PG59 is combined with the specific yellow color material or from the viewpoint of being excellent in dispersibility when the specific dispersant is combined, and at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15:4 is preferably contained, and these β -type copper phthalocyanine pigments are preferably contained in an amount of 60 to 100 mass% in the total amount of the blue color material.

Among them, from the viewpoint of brightness, the blue color material is preferably at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15:4.

In a third embodiment of the second aspect of the present invention, the yellow color material (Y1) containing at least 1 of PY185 may further contain other yellow color materials in addition to PY185, and examples of the yellow color material include derivative pigments of PY1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, and PY 150.

In the third embodiment of the second aspect of the present invention, as the yellow color material combined with PY185, 1 or more pigments selected from the group consisting of PY139, PY150 and derivative pigments thereof are preferable from the viewpoint of excellent color material dispersion stability, suppression of occurrence of display failure, easy realization of a colored layer with high brightness and excellent color reproducibility.

In the third embodiment of the second aspect of the present invention, the (Y2) contains PY139 as an essential component, and further contains 1 or more of at least 2 yellow color materials selected from the group consisting of PY138, PY150 and derivative pigments thereof, and may further contain other yellow color materials in addition to the above-mentioned at least 2 yellow color materials, and examples of the yellow color materials include PY1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 151, 152, 153, 154, 155, 156, 166, 168, 175, and the like.

In the third embodiment of the second aspect of the present invention, when the above (Y1) is used as the yellow color material, it is preferable because higher brightness can be easily achieved. On the other hand, when the above (Y2) is used as a yellow color material, it is preferable because high contrast is easily achieved.

In a third embodiment of the second aspect of the present invention, the above (Y2) contains PY139 as an essential component and further contains at least 2 kinds of yellow color materials of 1 or more selected from the group consisting of PY138, PY150 and derivative pigments thereof, and among them, from the viewpoint of suppressing occurrence of defective display and easily realizing a high-brightness and high-contrast colored layer, it is preferable to contain PY139 as an essential component and further contains at least 2 kinds of yellow color materials of 1 or more selected from the group consisting of PY150 and derivative pigments thereof.

In the color material dispersion liquid according to the third aspect of the present invention, other color materials exemplified by the photosensitive colored resin composition described below may be used in combination with PG59, the blue color material, and the specific yellow color material without impairing the effects of the present invention. As the other color material, for example, other green color materials, orange color materials, and the like can be suitably used. As an appropriate other color material, the same other color material is preferably used for the same reasons as those described in the photosensitive colored resin composition for a color filter to be described later. In the present invention, the term "green" refers to a green having a peak top in a range of over 490nm and 580nm or less as a standard when the spectral transmittance spectrum is measured as described above.

In the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, the content ratio of each of PG59, the blue color material, and the yellow color material, and further, the content ratio when other color materials are used, is preferably the same content ratio as the photosensitive colored resin composition described later. Among them, the color material dispersion liquid can be used in a mixture of 2 or more kinds to produce a photosensitive colored resin composition, and therefore can be used appropriately without the necessity of having the same content ratio as the photosensitive colored resin composition described later.

The average primary particle diameter of the color material used in the second aspect of the present invention and the average dispersion particle diameter of the color material in the color material dispersion liquid may be the same as those described for the color material item in the color material dispersion liquid of the first aspect of the present invention, and therefore, the description thereof is omitted here.

In the color material dispersion liquid according to the second aspect of the present invention, the color material content may be the same as that described for the color material item in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

< dispersant >

In the second aspect of the present invention, a polymer having a constituent unit represented by the above general formula (I) is used as a dispersant. The constituent unit represented by the above general formula (I) has basicity and functions as an adsorption site to a color material.

The color material dispersion liquid according to the second aspect of the present invention improves the adsorption performance to the color material and improves the dispersibility and dispersion stability of the color material by using the polymer having the constituent unit represented by the general formula (I).

The constituent units represented by the general formula (I) may be the same as those described in the dispersant item in the color material dispersion liquid according to the first aspect of the present invention, and therefore, description thereof will be omitted here.

Among the polymers having the constituent units represented by the above general formula (I), it is preferable that at least a part of the terminal nitrogen portion of the constituent unit represented by the above general formula (I) forms a salt with 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3) from the viewpoint of further improving the color material adsorption property, color material dispersion stability and solvent resolubility in the salt-forming portion.

The 1 or more compounds selected from the group consisting of the following general formulae (1) to (3) may be the same as those described in the above-mentioned salt-type block copolymer item of the dispersant in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof will be omitted here.

[ chemical formula 11]

(the symbols in the general formulae (1) to (3) are as described above.)

In the dispersant used in the second aspect of the present invention, the content of 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) in the polymer having the constituent unit represented by the general formula (I) is the same as that described in the item of the salt-type block copolymer of the dispersant in the color material dispersion liquid of the first aspect of the present invention, and therefore, the description thereof is omitted here.

The polymer having the structural unit represented by the general formula (I) preferably contains a site having affinity for a solvent from the viewpoint of improving dispersibility. The solvent affinity site is preferably selected appropriately according to the solvent so as to have solvent affinity among monomers having ethylenic unsaturated bonds, which are polymerizable with monomers derived from the constituent unit represented by the general formula (I). As a standard, it is preferable to introduce the solvent affinity site so that the solubility of the polymer at 23℃is 20 (g/100 g solvent) or more with respect to the solvent used in combination.

Among the polymers having the structural unit represented by the general formula (I) used in the second aspect of the present invention, block copolymers or graft copolymers are preferable, and block copolymers are particularly preferable, from the viewpoints of improving the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, and forming a colored layer having high brightness and high contrast. The block copolymers which are particularly preferred are described in detail below.

[ Block copolymer ]

If a block containing a constituent unit represented by the general formula (I) is used as the a block, the a block has basicity as the constituent unit represented by the general formula (I), and functions as an adsorption site to the color material. In addition, when at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) forms a salt with 1 or more compounds selected from the group consisting of the following general formulae (1) to (3), the salt-forming portion functions as a stronger adsorption portion to the color material. On the other hand, the B block containing no constituent unit represented by the above general formula (I) functions as a block having solvent affinity. Therefore, the block copolymer used in the present invention functions as a color material dispersant by sharing the function of the a block adsorbed to the color material with the B block having solvent affinity.

The dispersant used in the second aspect of the present invention is a block copolymer having a constituent unit represented by the general formula (I), and the amine value of the block copolymer is 40mgKOH/g or more and 130mgKOH/g or less, and is preferable from the viewpoint that the dispersibility and dispersion stability of the c.i. pigment green 59 are improved.

In the dispersant used in the second aspect of the present invention, the lower limit is preferably 50mgKOH/g or more, more preferably 60mgKOH/g or more, from the viewpoints of dispersibility and dispersion stability of the color material. The upper limit is preferably 120mgKOH/g or less. When the content is not less than the above lower limit, the dispersion stability is further excellent. When the content is not more than the upper limit, the compatibility with other components is excellent, and the solvent resolubility is good.

The amine value in the case of the salt-type block copolymer is smaller than that of the block copolymer before salt formation only in the portion where salt is formed. However, since the salt forming site is the same as the terminal nitrogen site corresponding to the amino group or a more reinforced color material adsorption site, there is a tendency to improve the color material dispersibility or color material dispersion stability by salt formation. In addition, the salt formation site is similar to the amino group, and if too large, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer before salification can be used as an index for improving the dispersion stability of the color material and the solvent resolubility. The amine value of the obtained salt-type block copolymer (P2) is preferably from 0 to 130mgKOH/g, more preferably from 0 to 120 mgKOH/g.

{ A block }

The A block is a block containing a constituent unit represented by the above general formula (I), and the constituent unit represented by the above general formula (I) is as described above, and therefore, description thereof is omitted here.

The constituent unit represented by the general formula (I) may be 1 or 2 or more constituent units as long as it functions as a color material adsorption site.

The a block may have a constituent unit other than the constituent unit represented by the general formula (I) within a range for achieving the object of the present invention, and may be contained as long as it is a constituent unit copolymerizable with the constituent unit represented by the general formula (I). For example, the constituent unit other than the constituent unit represented by the general formula (I) which may be contained in the basic block may be specifically a constituent unit represented by the following general formula (II), for example.

The content of the constituent unit represented by the general formula (I) in the A block in the block copolymer before salification is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and most preferably 100% by mass based on the total mass of all constituent units in the A block. This is because the higher the proportion of the constituent unit represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. The content of the constituent units is calculated from the packing mass at the time of synthesizing the a block having the constituent units represented by the general formula (I).

In the block copolymer before salification, the content of the constituent unit represented by the general formula (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of all constituent units of the block copolymer, from the viewpoint of improving dispersibility and dispersion stability. The content of each constituent unit in the block copolymer is calculated from the packing mass of the block copolymer before salt synthesis.

{ B block }

The B block is a block which does not contain a constituent unit represented by the above general formula (I). The B block is preferably selected from monomers having an unsaturated double bond which are copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and used appropriately depending on the solvent so as to have solphilicity. As a standard, it is preferable to introduce the B block so that the solubility of the copolymer at 23℃is 20 (g/100 g solvent) or more with respect to the solvent used in combination.

The constituent unit constituting the B block may be a monomer having an unsaturated double bond copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and among these, the constituent unit represented by the following general formula (II) is preferable.

The constituent units represented by the following general formula (II) may be the same as those described in the dispersant item in the color material dispersion liquid of the first aspect of the present invention, and therefore, description thereof is omitted here.

[ chemical formula 12]

(each symbol in the general formula (II) is as described above.)

The number of the constituent units constituting the B block is not particularly limited, but is preferably 10 to 300, more preferably 10 to 100, still more preferably 10 to 70, from the viewpoint of effectively acting the solvent affinity site and the color material adsorption site and improving the dispersibility of the color material.

The content of the constituent units represented by the general formula (II) in the B block of the block copolymer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total mass of all the constituent units of the B block, from the viewpoint of improving the solvophilicity and the color material dispersibility. The content of the constituent units was calculated from the packing mass at the time of synthesizing the B block.

In the block copolymer before salification, the content of the constituent unit represented by the general formula (II) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of all constituent units of the block copolymer, from the viewpoint of improving the dispersibility and dispersion stability of the color material. The content of the constituent units is calculated from the packing mass of the block copolymer before synthesis of the salt.

The B block may be appropriately selected so as to function as a solvophilic moiety, and the constituent unit represented by the general formula (II) may be 1 or 2 or more constituent units. The constituent units of 2 or more types contained in the B block may be randomly arranged in the block.

In addition, as the above-mentioned dispersant, the following dispersant is preferably used from the viewpoints of being capable of making excellent in dispersion stability of a color material, excellent in generation suppressing effect of development residues, excellent in solvent resolubility, and further having high development adhesion when producing a colored resin composition; the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2);

p1: a block copolymer having an A block comprising constituent units represented by the above general formula (I) and a B block comprising constituent units derived from a carboxyl group-containing monomer;

p2: a salt-type block copolymer in which at least a part of the terminal nitrogen portion of the constituent unit represented by the general formula (I) of the block copolymer is salified with 1 or more compounds selected from the group consisting of compounds represented by the general formulae (1) to (3);

the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more.

When the color material concentration is increased and the dispersant content is increased, the binder amount is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. The dispersant contains a B block containing a constituent unit derived from a carboxyl group-containing monomer, and has the above-described specific acid value and glass transition temperature, thereby improving development adhesion. It is estimated that when the acid value is too high, although the developability is excellent, the polarity is too high, and peeling easily occurs during development.

Such a dispersant may be the same as that described in the dispersant item for the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof will be omitted here.

In the color material dispersion liquid according to the second aspect of the present invention, at least 1 of the polymers having the constituent units represented by the above general formula (I) is used as the dispersant, and the content thereof is appropriately selected according to the type of color material used, and further the solid content concentration in the photosensitive colored resin composition for a color filter to be described later.

The content of the dispersant in the color material dispersion liquid according to the second aspect of the present invention may be the same as that described for the dispersant used in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof will be omitted here.

The solvent and the content thereof, other components which can be blended as needed, and the method for producing the color material dispersion liquid according to the second aspect of the present invention can be the same as those described for the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof will be omitted here.

The color material dispersion liquid according to the second aspect of the present invention is used as a pre-prepared product for preparing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention described later. That is, the color material dispersion liquid is a color material dispersion liquid which is pre-prepared in a stage before the preparation of a photosensitive color resin composition for a color filter described later, and has a high ratio of (mass of color material component in the composition)/(mass of solid component other than the color material component in the composition). Specifically, the ratio of (the mass of the color material component in the composition)/(the mass of the solid component other than the color material component in the composition) is usually 1.0 or more. The photosensitive colored resin composition for a color filter according to the second aspect of the present invention having excellent dispersibility can be prepared by mixing the color material dispersion liquid according to the second aspect of the present invention with the respective components described later.

II-2A photosensitive colored resin composition for a color filter according to a second aspect of the invention

(i) First aspect of the second aspect of the present invention

A photosensitive coloring resin composition for a color filter according to a first embodiment of the present invention is a photosensitive coloring resin composition for a color filter comprising a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator and a solvent, characterized in that,

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the general formula (I).

In the photosensitive colored resin composition for a color filter according to the first aspect of the present invention, the c.i. pigment green 59 is contained in the color material, whereby a green region having a high color density can be formed, and a colored layer having high brightness and high contrast can be formed. The photosensitive colored resin composition for a color filter according to the first aspect of the present invention can form a colored layer excellent in solvent resolubility, high brightness, high contrast, and excellent in color reproducibility by the same actions as described in the color material dispersion liquid according to the first aspect of the present invention.

(ii) Second aspect of the present invention

A photosensitive coloring resin composition for a color filter according to a second aspect of the present invention is a photosensitive coloring resin composition for a color filter comprising a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent, characterized in that,

the color material contains C.I. pigment green 59 and yellow color material;

the dispersant may be a polymer having a constituent unit represented by the following general formula (I).

Since the photosensitive colored resin composition for a color filter according to the second aspect of the present invention contains the c.i. pigment green 59 and the yellow color material and the polymer having the structural unit represented by the general formula (I) is used in combination as the dispersant, a colored layer excellent in color material dispersion stability, suppressed in occurrence of display failure, high in luminance and excellent in color reproducibility can be formed by the same action as described in the color material dispersion liquid according to the second aspect of the present invention.

(iii) Third aspect of the second aspect of the present invention

The photosensitive coloring resin composition for a color filter according to a third embodiment of the second aspect of the present invention is a photosensitive coloring resin composition for a color filter comprising a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, since the color material contains the c.i. pigment green 59, the blue color material, and the specific yellow color material, and the polymer having the constituent unit represented by the general formula (I) is used in combination as the dispersant, a colored layer having excellent color material dispersion stability, suppressed occurrence of display failure, high brightness, and excellent color reproducibility can be formed by the same actions as described in the color material dispersion liquid according to the third embodiment of the present invention.

The photosensitive colored resin composition for a color filter according to the second aspect of the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and may further contain other components within a range that does not impair the effects of the present invention. The respective components contained in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention will be described below, but the c.i. pigment green 59 and the dispersant, which are essential components among the color materials, are the same as those described in the color material dispersion liquid according to the second aspect of the present invention, and therefore, the description thereof will be omitted here. The solvent may be the same as that described for the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here. The alkali-soluble resin, the polyfunctional monomer, the photoinitiator, and other components may be the same as those described in the photosensitive colored resin composition for a color filter according to the first aspect of the present invention, and therefore, the description thereof will be omitted here.

< color Material >

The color material in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention contains c.i. pigment green 59 as an essential component, but other color materials may be further used in combination for adjusting the color tone.

The color filter is not particularly limited as long as a desired color can be produced when a colored layer of the color filter is formed, and 2 or more kinds of various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination. Among them, the organic pigment is preferably used because of its high color development and high heat resistance. Examples of the organic Pigment include a compound classified as Pigment (Pigment) in the Pigment index (c.i.; issued by The Society of Dyers and Colourists company), and specifically, a Pigment to which a Pigment index (c.i.) number is attached as described below.

As another color material, a color material different from PG59 as exemplified in the color material items of the color material dispersion liquid of the first aspect of the present invention described above may be used as another color material. Among them, a yellow color material, another green color material, and a blue color material are preferably used.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, it is preferable to further use a yellow color material as a color material in PG59 from the viewpoint of suppressing occurrence of defective display of green pixels and forming a colored layer having high brightness and excellent color reproducibility (the second embodiment of the present invention). The yellow color material used in the second embodiment of the present invention may be the same as that described in the color material dispersion liquid in the second embodiment of the present invention. As the other color material used in the second embodiment of the second aspect of the present invention, other green color material, blue color material, orange color material are preferably used.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, at least 1 of PG58 and PG7 is preferably contained in addition to PG 59. Among them, from the viewpoint of achieving a target chromaticity, suppressing display failure, and forming a green pixel of high luminance, PG58 is preferably contained in addition to PG 59. If PG59 and PG58 are used in combination, the color reproducibility can be enhanced, the P/V ratio can be reduced, and the luminance can be improved, as compared with the case where PG58 is used alone. On the other hand, from the viewpoints of achieving a desired chromaticity, suppressing display defects, further reducing the P/V ratio, and improving platemaking properties such as development resistance, it is preferable to include PG7 in addition to PG 59. In order to achieve the target chromaticity, suppress display failure, and improve the balance between luminance and platemaking due to the reduction of the P/V ratio, it is preferable to include PG58 and PG7 in addition to PG 59.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the content ratio of PG59 to the entire color material can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of improving the brightness by suppressing occurrence of defective display and simultaneously increasing color reproducibility, 5 to 95 mass% of PG59 is preferably contained, more preferably 10 to 90 mass%, and still more preferably 20 to 80 mass% with respect to the entire color material containing PG 59.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the content ratio of the yellow color material to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and increasing the brightness by increasing the color reproducibility, it is preferable to contain 10 to 900 parts by mass, more preferably 20 to 400 parts by mass of the yellow color material per 100 parts by mass of PG 59.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, 1 or 2 or more yellow color materials may be used singly or in combination, and among them, 1 or more selected from the group consisting of PY138, PY139, PY185, PY150 and pigment derivatives thereof are preferable from the viewpoint of easily realizing a colored layer excellent in color reproducibility with high brightness and high contrast while suppressing occurrence of display failure.

In the second embodiment of the second aspect of the present invention, the PY150 and its derivative pigment are preferably used in the chromaticity region where y=0.550 to 0.610 and x=0.205 to 0.324, and are preferable from the standpoint that the P/V ratio is more easily reduced in the chromaticity region.

Further, PY138 is preferably used in the case of realizing high luminance in the chromaticity region of y=0.550 to 0.610 and x=0.205 to 0.324, and is more preferably used in the case of realizing high luminance in the chromaticity region of x=0.246 to 0.324.

Further, PY185 is suitable for an enlarged color gamut, and even in the case of y=0.610 to 0.626, it is preferable to represent a chromaticity region of x=0.205 to 0.324, and more preferable to represent a chromaticity region of y= 0.659.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, when at least 1 of PY150 and its derivative pigment is used in combination with PY138, the total amount of at least 1 of PY150 and its derivative pigment and the ratio of PY138 are preferably 5:95 to 95:5, and may be appropriately adjusted according to the desired chromaticity, brightness, and film thickness. Among them, the total amount of at least 1 of PY150 and its derivative pigments and the ratio of PY138 are more preferably 10:90 to 90:10 from the viewpoint of the luminance and the above-mentioned P/V ratio, and still more preferably 20:80 to 80:20 from the viewpoint of the luminance and the P/V.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, when a green material other than PG59 is further contained, the content ratio of the green material containing PG59 to the entire color material can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and enhancing color reproducibility to increase brightness, the green color material containing PG59 is preferably contained in an amount of 10 to 90% by mass, more preferably 20 to 80% by mass, relative to the entire color material.

The content ratio of the yellow color material to the green color material containing PG59 is appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and enhancing color reproducibility to increase brightness, the yellow color material is preferably contained in an amount of 10 to 900 parts by mass, more preferably 20 to 400 parts by mass, relative to 100 parts by mass of the green color material containing PG 59.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, when at least one of PG58 and PG7 is further contained, at least 1 of PG58 and PG7 is preferably contained in an amount of 5 to 50% by mass, and more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, from the standpoint of poor display and luminance to the above-described P/V ratio, relative to the entire green material containing PG 59.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the color material may further contain other color materials than the green color material and the yellow color material, and the total content of the green color material containing PG59 and the yellow color material is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass, based on the entire color material, within a range that does not impair the effects of the present invention.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, a blue color material and a yellow color material are combined as a color material in PG 59; the yellow color material (Y1) contains at least 1 yellow color material of c.i. pigment yellow 185, or (Y2) contains at least 2 yellow color materials of 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and derivative pigments thereof, with c.i. pigment yellow 139 as an essential component (third embodiment of the second aspect of the present invention). The blue color material and the specific yellow color material used in the third embodiment of the second aspect of the present invention may be the same as those described in the color material dispersion liquid of the third embodiment of the present invention. As the other color material used in the third embodiment of the second aspect of the present invention, other green color materials and orange color materials are preferably used.

Among these, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, PG7 is more preferably contained from the viewpoints of achieving a target chromaticity, suppressing display failure, further reducing the above P/V ratio, suppressing development residues, and improving development adhesion and platemaking.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of PG59 to the entire color material can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of improving the brightness by suppressing occurrence of defective display and increasing color reproducibility, 5 to 80 mass% of PG59 is preferably contained, more preferably 10 to 70 mass%, and still more preferably 10 to 60 mass% of the entire color material containing PG 59.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of the blue color material to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and increasing the brightness by increasing the color reproducibility, it is preferable to contain 10 to 300 parts by mass, more preferably 20 to 200 parts by mass of the blue color material per 100 parts by mass of PG 59.

The content of the blue color material is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass, based on the total amount of the color material.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of the yellow coloring material to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and increasing the brightness by increasing color reproducibility, it is preferable to contain 10 to 800 parts by mass, more preferably 20 to 600 parts by mass of the yellow color material per 100 parts by mass of PG 59.

The yellow color material is preferably contained in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 70% by mass, based on the total amount of the color material.

In the photosensitive colored resin composition for a color filter according to the third aspect of the second aspect of the present invention, the content ratio of the yellow color material to the blue color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing occurrence of display failure and increasing the brightness by increasing the color reproducibility, the yellow color material is preferably contained in an amount of 10 to 800 parts by mass, more preferably 20 to 600 parts by mass, relative to 100 parts by mass of the blue color material.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, when (Y1) at least 1 yellow color material of c.i. pigment yellow 185 is used, the content of PY185 is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, relative to the total amount of yellow color material. PY185 has a strong coloring power, and even when it is contained in an amount of about 10 mass% relative to the total amount of the yellow color material, it has an effect of reducing the P/V ratio.

In the case where PY139 is contained in addition to PY185 in (Y1), the content of PY139 is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, based on the total amount of the yellow color material, corresponding to (Y1).

In the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, (Y2) contains c.i. pigment yellow 139 as an essential component, and further contains at least 2 yellow color materials selected from 1 or more of the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150 and derivative pigments thereof, wherein the content of PY139 is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, relative to the total amount of yellow color materials. The content of 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150 and its derivative pigments is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the total amount of the yellow color material.

Among these, in view of suppressing occurrence of defective display and easily realizing a high-luminance and high-contrast colored layer, it is preferable that PY139 is an essential component and at least 2 yellow color materials selected from 1 or more of the group consisting of PY150 and its derivative pigments are contained as the above (Y2). Further, as (Y2), it is preferable to combine at least 2 kinds of yellow color materials containing PY139 and 1 or more kinds of pigments selected from PY150 and its derivatives with the PG59 and blue color materials, from the viewpoint of further reducing the P/V ratio, suppressing development residues, and improving development adhesion and platemaking.

In the above combination, from the viewpoint of improving the brightness and easily reducing the P/V ratio, at least 2 kinds of yellow color materials containing PY139 as an essential component and further containing a derivative pigment of PY150 containing a nickel complex are preferable.

In the case of combining PY139 with 1 or more selected from the group consisting of PY150 and its derivative pigment, the content of 1 or more selected from the group consisting of PY150 and its derivative pigment is preferably more than the content of PY139, more preferably 150 to 700 parts by mass, still more preferably 200 to 600 parts by mass, per 100 parts by mass of PY139, from the viewpoint of easily realizing a colored layer with high brightness and high contrast.

In the photosensitive colored resin composition for a color filter according to the third aspect of the second aspect of the present invention, 1 or 2 or more specific yellow color materials may be used singly or in combination by appropriately selecting the specific yellow color materials.

In the second aspect of the present invention, PY185 is suitable for an enhanced color reproduction region, and is preferably used for a case where y=0.610 to 0.720 and x=0.140 to 0.230 are indicated, and is preferably used for a case where x=0.140 to 0.210 are indicated even in a case where y=0.720 to 0.750.

Further, PY139 is preferably used for expressing a chromaticity region where y=0.570 to 0.710 and x=0.180 to 0.265.

In the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, when a green material other than PG59 is further contained, the content ratio of the green material containing PG59 to the entire color material can be appropriately adjusted according to the desired chromaticity, and is not particularly limited.

Even when a green material other than PG59 is further contained, the content ratio of the green material containing PG59 to the entire color material, the content ratio of the blue material to the green material containing PG59, the content ratio of the blue material to the entire color material, the content ratio of the yellow material to the green material containing PG59, and the content ratio of the yellow material to the entire color material are preferably the same as the content ratio of PG59 to the entire color material, the content ratio of the blue material to PG59, the content ratio of the blue material to the entire color material, the content ratio of the yellow material to PG59, and the content ratio of the yellow material to the entire color material, respectively.

In the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, when PG7 is further contained, 5 to 50 mass% of PG7 is preferably contained with respect to the total amount of the green material containing PG59, and from the viewpoint of poor display, brightness, and the P/V ratio, 5 to 45 mass% is more preferably contained.

In the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, the color material may further contain other color materials than the green color material, the blue color material, and the yellow color material, and the total content of the green color material, the blue color material, and the specific yellow color material containing PG59 is preferably 70 to 100 mass%, and more preferably 80 to 100 mass%, with respect to the entire color material, within a range that does not impair the effects of the present invention.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the P/V ratio ((mass of color material component in the composition)/(mass of solid component other than the color material component in the composition)) is preferably 0.1 or more, more preferably 0.2 or more from the viewpoint of degassing and heat shrinkage; on the other hand, from the viewpoints of poor display and excellent manufacturing convenience, that is, excellent solvent re-solvability, development residues, development adhesion, development resistance, water penetration occurrence inhibition effect, and the like, it is preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.

< cured film of photosensitive colored resin composition for color Filter >

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, it is preferable that a cured film having chromaticity coordinates in the range of x=0.180 to 0.330 and y=0.500 to 0.750 in the XYZ color system of JISZ8701 for color measurement using a C light source be formed.

Among them, from the viewpoint of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the second aspect of the present invention is preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.188 to 0.324 and y=0.550 to 0.750 in the XYZ color system of JIS Z8701 in which color measurement is performed using a C light source, more preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.200 to 0.324 and y=0.570 to 0.750, and still more preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.205 to 0.324 and y=0.580 to 0.750.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, in the chromaticity coordinates in the XYZ color system of JIS Z8701 in which the film thickness is 2.8 μm or less and color measurement is performed using a C light source in a single pixel, the chromaticity space in the range of x=0.200 to 0.300, y=0.570 to 0.750, and the stimulus value Y is 37.ltoreq Y is preferable, and the chromaticity space in the range of x=0.200 to 0.300, y=0.570 to 0.750, and the stimulus value Y is 40.ltoreq Y is more preferable.

The total content of the color materials is 20 to 45 mass% relative to the total solid content of the photosensitive coloring resin composition for color filter, which is a good blending ratio or combination of chromaticity space capable of representing 37 to Y; as a combination of the color materials, the ratio (G: Y) of the green color material (G) containing PG59 to the yellow color material (Y) is preferably 80:20 to 20:80. Among the above, the content of PG59 with respect to the green color material (G) containing PG59 is more preferably 30 mass% or more. The film thickness of the cured film here was obtained by applying and drying a photosensitive colored resin composition for a color filter, exposing the resultant to light, curing the resultant, and then post-baking the resultant by a dust-free oven at 230℃for 30 minutes.

The photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention is preferably capable of forming a cured film having chromaticity coordinates in the range of x=0.140 to 0.330 and y=0.500 to 0.750 in the XYZ color system of JIS Z8701 in which color measurement is performed using a C light source.

Among these, from the viewpoint of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the third aspect of the present invention is preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.140 to 0.280 and y=0.570 to 0.730 in the XYZ color system of JIS Z8701 in which color measurement is performed using a C light source, more preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.140 to 0.265 and y=0.610 to 0.720, and still more preferably capable of forming a cured film having a chromaticity coordinate in the range of x=0.180 to 0.230 and y=0.690 to 0.710.

In the cured film of the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, the cured film has a film thickness of 2.8 μm or less, and in chromaticity coordinates in the XYZ color system of JIS Z8701 in which color measurement is performed using a C light source in a single pixel, chromaticity spaces in which x=0.140 to 0.265, y=0.570 to 0.720, and a stimulus value Y is 16.ltoreq.y are preferably displayed, and chromaticity spaces in which x=0.140 to 0.230, y=0.610 to 0.720, and a stimulus value Y is 18.ltoreq.y are more preferably displayed. The film thickness of the cured film here was obtained by applying and drying a photosensitive colored resin composition for a color filter, exposing the resultant to light, curing a polyfunctional monomer, and then post-baking the resultant film by a dust-free oven at 230℃for 30 minutes.

The yellow color material (Y1) is preferably used as a preferable ratio or combination of chromaticity space in which x=0.140 to 0.230, y=0.610 to 0.720, and the stimulus value Y is 18.ltoreq.y in chromaticity coordinates in the XYZ color system of JIS Z8701 in which the film thickness is 2.8 μm or less and the color is measured by using a C light source in a single pixel; the amount of the green color material containing c.i. pigment green 59 is preferably 10 to 70 mass%, the amount of the blue color material is preferably 5 to 50 mass%, and the amount of the yellow color material is preferably 10 to 70 mass% with respect to the total amount of the color materials; the amount of the green color material containing c.i. pigment green 59 is more preferably 15 to 60% by mass, the amount of the blue color material is preferably 10 to 40% by mass, and the amount of the yellow color material is preferably 20 to 60% by mass, based on the total amount of the color materials.

The yellow color material (Y2) is preferably used as a preferable blending ratio or combination of the chromaticity space in which x=0.180 to 0.265, y=0.570 to 0.710, and the stimulus value Y is 16.ltoreq.y; the amount of the green color material containing c.i. pigment green 59 is preferably 10 to 70 mass%, the amount of the blue color material is preferably 5 to 50 mass%, and the amount of the yellow color material is preferably 10 to 70 mass% with respect to the total amount of the color materials; the amount of the green color material containing c.i. pigment green 59 is more preferably 15 to 60% by mass, the amount of the blue color material is preferably 10 to 40% by mass, and the amount of the yellow color material is preferably 20 to 60% by mass, based on the total amount of the color materials.

The method for producing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention is not particularly limited, and the photosensitive colored resin composition can be obtained, for example, by adding an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and other components as necessary to the color material dispersion according to the second aspect of the present invention and mixing the resultant mixture by a known mixing means. Alternatively, when a different color material than PG59 is contained as in the second embodiment or the third embodiment, a color material dispersion of PG59, a color material dispersion of a yellow color material, and a color material dispersion of another color material as needed are prepared using the above-described dispersing agent, and a color material dispersion of PG59, a color material dispersion of a yellow color material, and a color material dispersion of another color material as needed, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and another component as needed are mixed by using a known mixing means, whereby a photosensitive color resin composition for a color filter can be obtained.

II-3 color filter according to second aspect of the invention

The color filter according to the second aspect of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention.

The color filter according to the second aspect of the present invention can be a color filter having high brightness and high contrast and excellent color reproducibility by providing at least one of the colored layers with a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention.

The color filter according to the second aspect of the present invention may have the same other components as those described for the color filter according to the first aspect of the present invention, as long as the color filter has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, and therefore, the description thereof will be omitted here.

II-4, 5. Liquid crystal display device and organic light emitting display device of the second aspect of the present invention

A liquid crystal display device according to a second aspect of the present invention is characterized by comprising the color filter according to the second aspect of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

An organic light-emitting display device of a second aspect of the present invention is characterized by having: the color filter and the organic light-emitting body according to the second aspect of the present invention are described above.

In the second aspect of the present invention, by using the color filter of the second aspect, a liquid crystal display device having high brightness and excellent color reproducibility, and an organic light emitting display device can be provided.

The liquid crystal display device and the organic light emitting display device according to the second aspect of the present invention may have the same other configurations as those described for the liquid crystal display device and the organic light emitting display device according to the first aspect of the present invention, as long as the color filter according to the second aspect of the present invention is provided, and therefore, the description thereof is omitted here.

Examples

The following examples are given to illustrate the invention in detail. The present invention is not limited by these descriptions.

The acid value of the block copolymer before salification and the acid value of the salt-type block copolymer salified by the compound represented by the above general formula (2) are obtained by a method based on the method described in JIS K0070.

The amine value of the block copolymer before salification and the amine value of the salt-type block copolymer salified by the compound represented by the above general formula (2) are obtained by a method based on the method described in JIS K7237.

The glass transition temperatures (Tg) of the block copolymers before and after salification were measured by Differential Scanning Calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nano Technology) using a method described in JIS K7121.

The weight average molecular weight (Mw) of the block copolymer before salification was determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent according to the measurement method of the present invention.

The glass transition temperatures (Tg) of the block copolymers A-1 and A-26 of the following synthesis examples and the block copolymers A-22 and A-24 of the comparative examples were calculated by the following formulas. As a result, it was found that the block copolymer A-1 was 37 ℃ (DSC measurement 38 ℃), the block copolymer A-26 was 64 ℃ (DSC measurement 66 ℃), the block copolymer A-22 was 0 ℃ (DSC measurement 2 ℃), and the block copolymer A-24 was 20 ℃ (DSC measurement 20 ℃), which showed almost the same measurement as that of DSC.

1/Tg＝∑(Xi/Tgi)

Here, the block copolymer is formed by copolymerizing n monomer components i=1 to n. Xi is the weight fraction of the ith monomer (Σxi=1), tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Where Σ is the sum taken as i=1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer was determined by the method of Polymer Handbook,3rd Edition (J.Brandrup, E.H.Immergut, wiley-Interscience, 1989). Specifically, the values (Tgi) of the homopolymer glass transition temperatures of the respective monomers used in the examples and comparative examples are shown below.

Methacrylic acid (MAA): 185 DEG C

2-hydroxyethyl methacrylate (HEMA): 55 DEG C

2-ethylhexyl methacrylate (EHMA): -10 DEG C

n-Butyl Methacrylate (BMA): 20 DEG C

Benzyl methacrylate (BzMA): 54 DEG C

Methyl Methacrylate (MMA): 105 DEG C

Cyclohexyl methacrylate (CHMA): 83 DEG C

Dimethylaminoethyl methacrylate (DMMA): 18 DEG C

Dimethylaminopropyl methacrylamide (DMAPMA): 96 DEG C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-100, manufactured by solar oil Co., ltd., BLEMMER-PME-100, ethyleneoxy repeat number=2): -26 DEG C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-200, manufactured by solar oil Co., ltd., BLEMMER-PME-200, ethyleneoxy repeat number=4): -59 DEG C

2-hydroxy-3-phenoxypropyl acrylate (HPhPA) (trade name: M-600A, manufactured by Kabushiki Kaisha Co., ltd.): 17 DEG C

Example I series: first aspect of the invention

Synthesis example 1 preparation of Block copolymer A-1

Into a 500mL round-bottom four-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 part by mass of lithium chloride were charged, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to-60 ℃, 4.9 parts by mass of butyllithium (15% by mass of hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. 0.37 part by mass of 1-ethoxyethyl methacrylate (EEMA), 18.6 parts by mass of 2-ethylhexyl methacrylate (EHMA), 15.4 parts by mass of n-Butyl Methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 29.3 parts by mass of Methyl Methacrylate (MMA) as monomers for the B block were added dropwise using an addition funnel over a period of 60 minutes. After 30 minutes, 27.0 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for the A block was added dropwise over 20 minutes. After the reaction was performed for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, dried under vacuum, and diluted with PGMEA to a solution having a solid content of 30 mass%. 32.5 parts by mass of water was added thereto, and the mixture was heated to 100℃and reacted for 7 hours, whereby the constituent units derived from EEMA were deprotected to prepare constituent units derived from methacrylic acid (MAA). The resulting block copolymer PGMEA solution was reprecipitated in hexane, and then purified by filtration and vacuum drying to obtain a block copolymer A-1 (acid value: 1mgKOH/g, tg: 38 ℃ C.) comprising an A block comprising a constituent unit represented by the general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solphilicity. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography) to give a weight average molecular weight Mw of 7600. The amine value was 96mgKOH/g.

Synthesis examples 2 to 3 Synthesis of Block copolymers A-2 to A-3

In Synthesis example 1, block copolymers A-2 to A-3 were synthesized in the same manner as in Synthesis example 1 except that the content shown in Table 1 was changed. In Synthesis example 2, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used; in Synthesis example 3, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid value, tg and amine value of the obtained block copolymer are shown in Table 1.

Synthesis example 4 Synthesis of salt type Block copolymer A-4

First, a block copolymer A-2 was synthesized in the same manner as in Synthesis example 2 (the block copolymer before salifying the salt-type block copolymer A-4 was the same as the block copolymer A-2).

In a 100mL round-bottomed flask, 10.0 parts by mass of block copolymer A-2 was dissolved in 41.93 parts by mass of PGMEA, and 0.48 parts by mass (0.20 mol per 1 mol of DMMA unit, which is block copolymer A-2, as the compound represented by the general formula (3)) was added as a phenylphosphonic acid (Tokyo formation) compound represented by the general formula (3), followed by stirring at a reaction temperature of 30℃for 20 hours, to obtain a salt-type block copolymer A-4 solution having a solid content of 20% by mass. The acid value of the block copolymer after salification was the same as that of the block copolymer A-2, and the amine value after salification was specifically calculated as follows.

A solution (1 g) containing 9 parts by mass of the salt-type block copolymer A-4 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was placed in an NMR sample tube, and the 13C-NMR spectrum was measured at room temperature under 10000 times of accumulation by using a nuclear magnetic resonance apparatus (FT NMR, JNM-AL 400). In the obtained spectrum data, the ratio of the number of amino groups to the total number of amino groups in the salt formation was calculated from the ratio of the peak of carbon atoms adjacent to the nitrogen atom which did not form a salt and the integral value of the peak of carbon atoms adjacent to the nitrogen atom which did not form a salt at the terminal nitrogen site (amino group), and it was confirmed that the ratio was not different from the theoretical salt formation ratio (all phenylphosphonic acid forms a salt with the terminal nitrogen site of DMMA of the block copolymer a-2).

The amine value after salification was calculated to be 76mgKOH/g by subtracting the amine value (19 mgKOH/g) of 0.20 molar parts of DMMA units from the amine value before salification of 95 mgKOH/g. Tg's of the block copolymers before and after salt formation are also shown in Table 1.

( Synthesis examples 5 to 10: synthesis of salt type Block copolymers A-5 to A-10 )

In Synthesis example 4, the same procedure as in Synthesis example 4 was repeated except that the salt-forming compound was changed to the compound and the amount shown in Table 1, to obtain solutions of salt-type block copolymers A-5 to A-10.

In the salt-type block copolymers A-5 to A-10, the acid value, tg and amine value of the block copolymer before salt formation, and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) are shown in Table 1.

In table 1, the amount of 1 or more compounds selected from the group consisting of the compounds represented by the above general formulae (1) to (3) is expressed by the number of moles of the above compound per 1 mole of nitrogen site (DMMA) of the constituent unit represented by the general formula (I).

( Synthesis examples 11 to 12: synthesis of salt type Block copolymers A-11 to A-12 )

In Synthesis example 1, block copolymers A-11 to A-12 used in comparative examples were synthesized in the same manner as in Synthesis example 1 except that the contents shown in Table 1 were changed. The acid value, tg and amine value of the obtained block copolymer are shown in Table 1.

Synthesis example 13 preparation of Block copolymer A-13

In a 500mL round bottom four-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of Tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyltrimethylsilyl acetal as an initiator were added via the addition funnel, and nitrogen substitution was sufficiently performed. 0.5 part by mass of a 1mol/L acetonitrile solution of tetrabutylammonium orthochlorobenzoic acid of the catalyst was injected using a syringe, and 18.7 parts by mass of HEMA, 12.8 parts by mass of EHMA, 13.7 parts by mass of BMA, 9.5 parts by mass of BzMA9, and 19.5 parts by mass of MMA of the B block monomer were added dropwise over 60 minutes using an addition funnel. The reaction flask was cooled with an ice bath to maintain the temperature below 40 ℃. After 1 hour, 25.8 parts by mass of DMMA as a monomer for the A block was added dropwise over 20 minutes. After 1 hour of reaction, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, and then purified by filtration and vacuum drying to obtain a block copolymer A-13 (Tg 37 ℃ C.) comprising an A block comprising the constituent unit represented by the formula (I) and a B block having solvophilicity. The block copolymer A-13 thus obtained was confirmed by GPC (gel permeation chromatography) to give a weight average molecular weight Mw of 7320. The amine value was 92mgKOH/g.

( Synthesis examples 14 to 17: synthesis of salt type Block copolymers A-14 to A-17 )

In Synthesis example 4, the same procedure as in Synthesis example 4 was repeated except that block copolymer A-13 of Synthesis example 13 (the block copolymer before salifying salt of salt-form block copolymers A-14 to A-17 was identical to block copolymer A-13) was used as the block copolymer before salifying salt, and the compound as salifying salt was changed to the compound and the amount shown in Table 1, to obtain a solution of salt-form block copolymers A-14 to A-17.

The acid value, tg and amine value of the block copolymer before salt formation and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) are shown in Table 1, among the salt-type block copolymers A-14 to A-17.

( Synthesis examples 18 to 34: synthesis of Block copolymers A-18 to A-34 )

In Synthesis example 1, block copolymers A-18 to A-34 used in Synthesis examples or comparative examples were prepared in the same manner as in Synthesis example 1 except that the contents shown in Table 2 or Table 3 were changed. The acid value, tg and amine value of the obtained block copolymer are shown in Table 2 or Table 3.

( Synthesis examples 35 to 37: synthesis of salt type Block copolymers A-35 to A-37 )

In Synthesis example 4, the same procedure as in Synthesis example 4 was repeated except that block copolymer A-33 of Synthesis example 33 (the block copolymer before salifying salt of salt-type block copolymers A-35 to A-37 was identical to block copolymer A-33) was used as the block copolymer before salifying salt, and the compound as salifying salt was changed to the compound and the amount shown in Table 3, to obtain a solution of salt-type block copolymers A-35 to A-37.

The acid value, tg and amine value of the block copolymer before salt formation and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) in the salt-type block copolymers A-35 to A-37 are shown in Table 3.

( Synthesis examples 38 to 40: synthesis of Block copolymers A-38 to A-40 )

The block copolymers A-38 to A-40 used in the comparative examples were synthesized in the same manner as described in synthesis examples 1, 2 and 5 (B-1, B-2 and B-5) of patent document 2. The acid value, tg and amine value of the obtained block copolymer are shown in Table 4.

TABLE 1

TABLE 2

TABLE 3

Table 3.

TABLE 4

Table 4.

Synthesis example 41 (Synthesis of alkali-soluble resin A solution)

After 300 parts by mass of PGMEA was charged into the polymerization vessel and the temperature was raised to 100℃under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of PERBUTYL O (manufactured by Nikko Co., ltd.) and 2 parts by mass of a chain transfer agent (n-dodecylmercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued at 100℃and after 2 hours from the end of the dropwise addition of the above-mentioned mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization.

Subsequently, 20 parts by mass of Glycidyl Methacrylate (GMA) was added as an epoxy group-containing compound while blowing air, and after the temperature was raised to 110 ℃, 0.8 parts by mass of triethylamine was added thereto and the reaction was carried out at 110 ℃ for 15 hours to obtain an alkali-soluble resin a solution (weight average molecular weight (Mw) 8500, acid value 75mgKOH/g, solid content 40 mass%).

In the method for measuring the weight average molecular weight, polystyrene was used as a standard substance, and THF was used as an eluent to measure the weight average molecular weight by Shodex GPC system-21H (Shodex GPC system-21H). The method for measuring the acid value was carried out based on JIS K0070.

Example 1

(1) Production of color Material Dispersion G-1

3.25 parts by mass of the block copolymer A-I of Synthesis example 1 as a dispersant, 11.7 parts by mass of C.I. pigment Green 58 (PG 58) as a colorant, 1.3 parts by mass of C.I. pigment yellow 138 (PY 138), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated for 1 hour with a pigment vibrator (manufactured by light Tian Tiegong Co., ltd.) as a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly dispersed for 4 hours with the pigment vibrator as a main pulverization, to obtain a colorant dispersion G-1.

(2) Production of photosensitive colored resin composition G-1 for color Filter

0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.60 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 0.09 parts by mass of 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropan-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF JAPAN Co., ltd.), 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF JAPAN Co., ltd.), 0.04 parts by mass of ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (photo initiator: trade name IRGACURE JAXE 02, (manufactured by BASF PAN Co., ltd.), 0.02 parts by BASF surfactant (trade name IRGACURE JAPAN Co., ltd.), and 0.04 parts by fluorine-based surfactant (trade name) and color resin (light-sensitive color composition) (1.14.07 parts by BASF) were added to obtain a color composition.

Examples 2 to 26

(1) Production of color Material dispersions G-2 to G-26

In example 1 (1), the same procedure as in example 1 (1) was repeated except that, instead of the block copolymer A-1, the block copolymers A-2 to A-3 of Synthesis examples 2 to 3, the salt-type block copolymers A-4 to A-10 of Synthesis examples 4 to 10, the block copolymers A-18 to A-21 of Synthesis examples 18 to 21, the block copolymers A-26 to A-32 of Synthesis examples 26 to 32, the block copolymers A-33 to A-34 of Synthesis examples 33 to 34, and the salt-type block copolymers A-35 to A-37 of Synthesis examples 35 to 37 were used in such a manner that the solid content was the same as the mass part of the block copolymer A-1, and the amounts of PGMEA were adjusted to 100 mass parts in total, to obtain color material dispersions G-2 to G-26.

(2) Production of photosensitive colored resin compositions G-2 to G-26 for color filters

In the same manner as in (2) of example 1, except that the above-mentioned color material dispersions G-2 to G-26 were used in place of the color material dispersion G-1, photosensitive colored resin compositions G-2 to G-26 for color filters were obtained in the same manner as in (2) of example 1.

Example 35

(1) Production of color Material Dispersion G-27

3.25 parts by mass of the block copolymer A-2 of Synthesis example 2 as a dispersant, 13 parts by mass of C.I. pigment Green 59 (PG 59, trade name of FASTOGEN GREEN C100, manufactured by DIC Co., ltd.) as a color material, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated by a pigment vibrator (manufactured by light Tian Tiegong Co.) for 1 hour as a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly dispersed by the pigment vibrator for 4 hours as a main pulverization, to obtain a color material dispersion G-27.

(2) Production of photosensitive colored resin composition G-27 for color Filter

In the same manner as in (2) of example 1, except that the above-mentioned color material dispersion liquid G-27 was used instead of the color material dispersion liquid G-1, a photosensitive colored resin composition G-27 for a color filter was obtained.

Examples 36 to 38

(1) Production of color Material dispersions G-28 to G-30

In example 35 (1), the same procedure as in example 35 (1) was repeated except that the salt-type block copolymer A-8 solution of Synthesis example 8, the block copolymer A-33 of Synthesis example 33 and the salt-type block copolymer A-35 solution of Synthesis example 35 were used in place of the block copolymer A-2 so that the solid content was the same as the mass parts of the block copolymer A-2, respectively, and the amounts of PGMEA were adjusted to 100 mass parts in total, as shown in Table 8, to obtain color material dispersions G-28 to G-30.

(2) Production of photosensitive colored resin compositions G-28 to G-30 for color filters

In example 35 (2), photosensitive colored resin compositions G-28 to G-30 for color filters were obtained in the same manner as in example 35 (2), except that the above-mentioned color material dispersions G-28 to G-30 were used in place of the color material dispersion G-27.

Example 39

In the same manner as in (1) of example 1 except that c.i. pigment green 59 (PG 59, trade name fastageren C100, manufactured by DIC corporation) was used instead of c.i. pigment green 58 (PG 58) as a color material and block copolymer a-2 of synthesis example 2 was used instead of block copolymer a-1 of synthesis example 1 as a dispersant, a color material dispersion G-31 was obtained.

(2) Production of photosensitive colored resin composition G-31 for color Filter

In the same manner as in (2) of example 1, except that the above-mentioned color material dispersion liquid G-31 was used instead of the color material dispersion liquid G-1, a photosensitive colored resin composition G-31 for a color filter was obtained.

Examples 40 to 42

(1) Production of color Material dispersions G-32 to G-34

In example 39 (1), color material dispersions G-32 to G-34 were obtained in the same manner as in example 39 (1) except that the salt-type block copolymer A-8 solution of Synthesis example 8, the block copolymer A-33 of Synthesis example 33 and the salt-type block copolymer A-35 solution of Synthesis example 35 were each used in the same mass parts as the block copolymer A-2 in terms of solid content, respectively, as shown in Table 8, in place of the block copolymer A-2, and the amount of PGMEA was adjusted to 100 mass parts in total.

(2) Production of photosensitive colored resin compositions G-32 to G-34 for color filters

Photosensitive colored resin compositions G-32 to G-34 for color filters were obtained in the same manner as in (2) of example 39, except that the above-mentioned color material dispersions G-32 to G-34 were used in place of the color material dispersion G-31 in (2) of example 39.

Comparative examples 1 to 14

(1) Production of comparative color material dispersions G-1 to G14

In example 1 (1), the same procedure as in example 1 (1) was repeated except that, instead of the block copolymer A-1, the block copolymers A-11 to A-13 of Synthesis examples 11 to 13, the salt-type block copolymers A-14 to A-17 of Synthesis examples 14 to 17, the block copolymers A-22 to A-25 of Synthesis examples 22 to 25, and the block copolymers A-38 to A-40 of Synthesis examples 38 to 40 were used in such a manner that the solid content was the same parts by mass as the block copolymer A-1, and the amounts of PGMEA were adjusted to 100 parts by mass in total, respectively, to obtain comparative color material dispersions G-1 to G-14.

(2) Production of photosensitive colored resin compositions G-1 to G-14 for comparative color filters

In the same manner as in (2) of example 1, except that the comparative color material dispersions G-1 to G-11 were used in place of the color material dispersion G-1, photosensitive colored resin compositions G-1 to G-14 for comparative color filters were obtained.

Example 27

(1) Production of color Material Dispersion R-1

3.25 parts by mass of the block copolymer A-1 of Synthesis example 1 as a dispersant, 6.5 parts by mass of C.I. pigment Red 177 (PR 177) as a pigment, 6.5 parts by mass of C.I. pigment Red 254 (PR 254), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of the zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated for 1 hour with a pigment vibrator (made by light Tian Tiegong Co.) as a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of the zirconia beads having a particle diameter of 0.1mm were added, and similarly dispersed for 4 hours with the pigment vibrator as a main pulverization, to obtain a color material dispersion R-1.

(2) Production of photosensitive colored resin composition R-1 for color filter

The color material dispersion liquid R-1.40 parts by mass obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.60 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 0.02 parts by mass of 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF JAPAN), 0.09 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF JAPAN), 0.04 parts by mass of ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (photo initiator: trade name IRGACURE XE02, manufactured by BASF JAPAN), 0.02 parts by fluorine-based surfactant (trade name 380862, manufactured by DIC, manufactured by BASF JAPAN), and 0.07 parts by color filter (light-sensitive color resin composition of the color resin of the color filter 1, 14 parts by color resin composition were obtained.

Examples 28 to 30

(1) Production of color Material dispersions R-2 to R-4

In example 27 (1), color material dispersions R-2 to R-4 were obtained in the same manner as in example 27 (1) except that the solutions of block copolymers A-27, A-3 and salt type block copolymer A-4 of Synthesis examples 27, 3 and 4 were used in such a manner that the solid content was the same parts by mass as in block copolymer A-1, respectively, as shown in Table 9, instead of block copolymer A-1, and the amount of PGMEA was adjusted to 100 parts by mass.

(2) Production of photosensitive colored resin compositions R-2 to R-4 for color filters

In example 27 (2), photosensitive colored resin compositions R-2 to R-4 for color filters were obtained in the same manner as in example 27 (2), except that the above-mentioned color material dispersions R-2 to R-4 were used in place of the color material dispersion R-1.

Comparative examples 15 to 18

(1) Production of comparative color Material Dispersion solutions R-1 to R-4

Comparative color material dispersions R-1 to R-4 were obtained in the same manner as in (1) of example 27, except that in (1) of example 27, the block copolymers A-11, A-13, A-24 and A-25 of Synthesis examples 11, 13, 24 and 25 were used in such a manner that the solid content was the same mass parts as in the block copolymer A-1, respectively, as shown in Table 9, instead of the block copolymer A-1, and the amount of PGMEA was adjusted to 100 mass parts as a total.

(2) Production of photosensitive colored resin compositions R-1 to R-4 for comparative color filters

In example 27 (2), photosensitive colored resin compositions R-1 to R-4 for a comparative color filter were obtained in the same manner as in example 27 (2), except that the comparative color material dispersions R-1 to R-4 were used in place of the color material dispersion R-1.

Example 31

(1) Production of color Material Dispersion B-1

The block copolymer A-1.25 parts by mass of Synthesis example 1 as a dispersant, C.I. pigment blue 15:6 (PB 15:6) 10.4 parts by mass of pigment, C.I. pigment violet 23 (PV 23) 2.6 parts by mass, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, PGMEA67.5 parts by mass, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated for 1 hour with a pigment vibrator (manufactured by light Tian Tiegong Co.) as a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, and zirconium beads having a particle diameter of 0.1mm were added for 200 parts by mass, and similarly dispersed for 4 hours with the pigment vibrator as a main pulverization, to obtain a color material dispersion B-1.

(2) Production of photosensitive colored resin composition B-1 for color Filter

1.05 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.98 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 0.15 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE907, manufactured by BASF JAPAN), 0.07 parts by mass of ethyl ketone, 0.9- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (photo initiator: IRGACURE XE02, manufactured by BASF PAN), 0.03 parts by weight of a fluorine-based surfactant (trade name 380862, manufactured by DIC JAPAN), and 0.06 parts by color resin composition (trade name of light-sensitive resin B, manufactured by BASF JAEA) were added to the color material dispersion liquid B-18.59 parts by the above (1).

Examples 32 to 34

(1) Production of color Material dispersions B-2 to B-4

In example 31 (1), color material dispersions B-2 to B-4 were obtained in the same manner as in example 31 (1) except that the solutions of block copolymers A-27, A-3 and salt type block copolymer A-4 of Synthesis examples 27, 3 and 4 were used in such a manner that the solid content was the same parts by mass as in block copolymer A-1, respectively, as shown in Table 10, and the amount of PGMEA was adjusted to 100 parts by mass in total.

(2) Production of photosensitive colored resin compositions B-2 to B-4 for color filters

In example 31 (2), photosensitive colored resin compositions B-2 to B-4 for color filters were obtained in the same manner as in example 31 (2) except that the above-mentioned color material dispersions B-2 to B-4 were used in place of the color material dispersion B-1.

Comparative examples 19 to 22

(1) Production of comparative color Material dispersions B-1 to B-4

Comparative color material dispersions B-1 to B-4 were obtained in the same manner as in (1) of example 31, except that in (1) of example 31, block copolymers A-11, A-13, A-24 and A-25 of Synthesis examples 11, 13, 24 and 25 were used in such a manner that the solid content was the same parts by mass as in block copolymer A-1, respectively, as shown in Table 10, and the amount of PGMEA was adjusted to 100 parts by mass in total.

(2) Production of photosensitive colored resin compositions B-1 to B-4 for comparative color filters

In example 31 (2), photosensitive colored resin compositions B-1 to B-4 for a comparative color filter were obtained in the same manner as in example 31 (2), except that the comparative color material dispersions B-1 to B-4 were used in place of the color material dispersion B-1.

[ evaluation method ]

< evaluation of dispersibility of color Material Dispersion >

The viscosities of the color material dispersions obtained in examples and comparative examples were measured immediately after the preparation and after the storage at 25℃for 30 days, and the viscosity change rates were calculated from the viscosities before and after the storage, to evaluate the viscosity stability. In the viscosity measurement, a vibration viscometer was used to measure the viscosity at 25.0.+ -. 0.5 ℃. The results are shown in tables 5 to 10.

(evaluation criterion for Dispersion stability)

A: the viscosity change rate before and after preservation is less than 15%

B: the viscosity change rate before and after storage is 15% or more and less than 25%

C: the viscosity change rate before and after storage is 25% or more and less than 40%

D: the viscosity change rate before and after preservation is more than 40%

Here, the value is a value when 13 mass% of the color material is set with respect to the total mass of the solvents containing the color material dispersion liquid.

The color material dispersion liquid can be practically used even if the evaluation result is C, but the color material dispersion liquid is more favorable if the evaluation result is B, and the dispersion stability of the color material dispersion liquid is excellent if the evaluation result is a.

< evaluation of optical Property, evaluation of contrast >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied to Glass substrates (NH Techno Glass Co., ltd., "NA 35") having a thickness of 0.7mm and 100mm X100 mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, thereby forming colored layers. Irradiation of the colored layer with an ultra-high pressure mercury lamp of 60mJ/cm ² Is a ultraviolet ray of (a).

Subsequently, the colored substrate was post-baked in a dust-free oven at 230℃for 30 minutes, and the contrast, chromaticity (x, Y) and luminance (Y) of the resulting colored substrate were measured by using a pot plate electric contrast measuring apparatus CT-1B and an Olympus micro-spectroscopic measuring apparatus OSP-SP 200. The results are shown in tables 5 to 10.

(contrast evaluation reference)

A: green exceeds 7000, red exceeds 5000, blue exceeds 5000

B: green is 6300-7000, red is 4300-5000, blue is 4300-5000

C: green below 6300, red below 4300, blue below 4300

Here, the values are the values when Green in examples 1 to 26 and comparative examples 1 to 11 under the C light source is set to y=0.570, green in examples 35 to 38 is set to y=0.420, green in examples 39 to 42 is set to y=0.480, red in examples 27 to 30 and comparative examples 12 to 15 is set to x=0.650, and Blue in examples 31 to 34 and comparative examples 16 to 19 is set to y=0.107, respectively.

< evaluation of development residue >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied to Glass substrates (NH Techno Glass Co., ltd., "NA 35") having a thickness of 0.7mm and 100mm X100 mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, whereby a colored layer having a thickness of 2.5 μm was formed. The glass plate on which the colored layer was formed was subjected to spray development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. After the unexposed portion (50 mm. Times.50 mm) of the glass substrate on which the colored layer was formed was visually observed, the glass substrate was sufficiently wiped with a lens cleaning cloth (trade name TORAYSEE MK cleaning cloth manufactured by Toli Co., ltd.) containing ethanol to visually observe the degree of coloration of the lens cleaning cloth. The results are shown in tables 5 to 10.

(development residue evaluation reference)

A: the development residue was not visually confirmed, and the lens cleaning cloth was completely free of coloration

B: the development residue was not visually recognized, and slight coloration of the lens cleaning cloth was recognized

C: to visually confirm a slight development residue and a slight coloring of the lens cleaning cloth

D: to visually confirm a slight development residue and to confirm the coloration of the lens cleaning cloth

E: to visually confirm the development residues and confirm the coloring of the lens cleaning cloth

When the development residue evaluation criterion is A, B or C, it is evaluated that the development residue is sufficiently suppressed, and the development residue evaluation criterion can be practically used without any problem.

< evaluation of development adhesion >

Photosensitive coloring tree for color filter obtained in example and comparative exampleThe grease composition was applied onto a Glass substrate (NA 35, manufactured by NH Techno Glass Co., ltd.) having a thickness of 0.7mm and 100mm X100 mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, thereby forming a colored layer having a thickness of 2.5. Mu.m. Irradiating the colored layer with 60mJ/cm by using an ultra-high pressure mercury lamp through a photomask with a shielding opening width of 2-80 μm ² Is a ultraviolet ray of (a). The glass plate on which the colored layer was formed was subjected to spray development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. The developed substrate was observed with an optical microscope, and the presence or absence of a colored layer for masking the line width of the opening was observed. The results are shown in tables 5 to 10.

(development adhesion evaluation criterion)

A: the coloring layer was observed at a portion where the line width of the shielding opening was less than 10. Mu.m

B: the coloring layer was observed at a portion where the line width of the shielding opening was 10 μm or more and less than 20 μm

C: the coloring layer was observed at a portion where the line width of the shielding opening was 20 μm or more and less than 50 μm

D: the coloring layer was observed at a portion where the line width of the shielding opening was 50 μm or more and less than 80 μm

E: no coloring layer was observed at a portion where the line width of the masked opening was 80 μm or less

Even if the evaluation result is C, the photosensitive colored resin composition for a color filter can be practically used; however, if the evaluation result is B, the photosensitive colored resin composition for a color filter is suitable for a case of higher definition; when the evaluation result is A, the photosensitive colored resin composition for a color filter can be suitably used in the case of higher definition.

< evaluation of solvent resolubility >

The front end of a glass substrate having a width of 0.5cm and a length of 10cm was immersed in the photosensitive colored resin composition for color filters obtained in examples and comparative examples, and coated on a portion of 1cm in length of the glass substrate. The pulled-up glass substrate was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23℃and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually determined and evaluated. The results are shown in tables 5 to 10.

(solvent resolubility evaluation criterion)

A: the dried coating film is completely dissolved

B: flakes in solvent which give dry film coating which dissolve shortly

C: flakes producing a dry film in a solvent, solution coloration

D: flakes producing a dry film in solvent, the solution being uncolored

E: flakes which did not produce a dry film in the solvent, the solution was uncolored

When the development residue evaluation criterion is A, B or C, the solvent resolubility is evaluated to be good, and the development residue evaluation criterion can be practically used without any problem.

TABLE 5

TABLE 6

TABLE 7

Table 7.

TABLE 8

Table 8.

TABLE 9

Table 9.

TABLE 10

Table 10.

[ integration of results ]

As apparent from the results of tables 1 to 10, as the dispersant, a block copolymer comprising an A block containing a constituent unit represented by the above general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer and having solvophilicity was used; and the color material dispersion of examples 1 to 42 of the dispersant of at least one of salt-type block copolymers wherein at least a part of nitrogen sites of the constituent units represented by the general formula (I) of the block copolymer and at least one compound selected from the group consisting of compounds represented by the general formulae (1) to (3) form salts, wherein the dispersant has an acid value of 1 to 18mgKOH/g and a glass transition temperature of 30 ℃ or higher. The photosensitive colored resin compositions for color filters of examples 1 to 42 prepared using the color material dispersions of examples 1 to 42 were excellent in color material dispersion stability, and in development adhesion and solvent resolubility while suppressing development residues.

Among these, examples 4 to 10 and 24 to 26, 30, 34, 36, 38, 40 and 42 using the above-mentioned salt-type block copolymer were excellent in color material dispersibility and further excellent in contrast of the resulting colored layer.

On the other hand, although the glass transition temperature of the dispersant was 30℃or higher, the development adhesion of comparative examples 1, 2, 12 to 14, 15 and 19 having an acid value higher than the specific value of the present application was poor, and the solvent resolubility of comparative examples 2 and 12 to 14 having a higher acid value was also deteriorated. On the other hand, although the dispersant had a glass transition temperature of 30℃or higher, the comparative examples 3 to 7, 16 and 20, in which the acid value was lower than the specific value in the present application, were inferior in evaluation of the development residues. Although the acid value of the dispersant was a specific value of the present application, the development adhesion of comparative examples 8 to 10, 17 and 21 in which the glass transition temperature of the dispersant was lower than the specific value of the present application was poor. The dispersant had a glass transition temperature of 23℃and the development adhesion was poor in comparative examples 11, 18 and 22 having an acid value higher than the specific value of the present application.

Example II series: first aspect of the second aspect of the present invention

Synthesis example II-1 preparation of dispersant a

After drying a 500ml four-necked separation flask under reduced pressure, ar (argon) substitution was performed.

While Ar was blown, 100g of dehydrated THF, 2.0g of methyltrimethylsilyl dimethylketene acetal, 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB), and 0.2g of mesitylene were added. 36.7g of Methyl Methacrylate (MMA) was added dropwise thereto over 45 minutes using a dropping funnel. Since the reaction proceeds with heat generation, the temperature was kept below 40 ℃ by ice bath cooling. After 1 hour, 13.3g of dimethylaminoethyl methacrylate (DMMA) were added dropwise over a period of 15 minutes. After 1 hour of reaction, 5g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give block copolymer II-A1. The mass average molecular weight was 6,000 as determined by GPC measurement (NMP LiBr10 mM), and the amine value was 95mgKOH/g.

In a 100mL round-bottomed flask, 29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and 3.17 parts by mass (0.20 mol per 1 mol of DMMA unit of block copolymer 1 as the compound represented by the general formula (3)) of phenylphosphonic acid (PPA, tokyo formation) as the compound represented by the general formula (3) was added and stirred at a reaction temperature of 30℃for 20 hours to obtain a salt type block copolymer II-A1 (dispersant a) solution. The amine number after salt formation was calculated specifically as follows.

9 parts by mass of a solution containing 9 parts by mass of a salt type block copolymer II-A1 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was placed in an NMR sample tube, and a 13C-NMR spectrum was measured at room temperature under 10000 times of accumulation by using a nuclear magnetic resonance apparatus (FT NMR, JNM-AL 400). In the obtained spectrum data, the ratio of the number of amino groups to the total number of amino groups in the salt formation was calculated from the ratio of the peak of carbon atoms adjacent to the nitrogen atom which did not form a salt and the integral value of the peak of carbon atoms adjacent to the nitrogen atom which did not form a salt at the terminal nitrogen site (amino group), and it was confirmed that the ratio was not different from the theoretical salt formation ratio (all 2 acid groups of phenylphosphonic acid form salts with the terminal nitrogen site of DMMA of the block copolymer II-A1).

The amine value after salification was calculated as 57mgKOH/g by subtracting 0.40 molar parts of the amine value (38 mgKOH/g) of the DMMA unit from 95mgKOH/g before salification. The Tg's of the block copolymers before and after salt formation are shown in Table 11.

Synthesis example II-2 preparation of dispersant b

A solution of a salt-type block copolymer II-A2 (dispersant b) was obtained in the same manner as in Synthesis example 8 of example I series. The acid value of the block copolymer after salification was the same as that of the block copolymer II-A2 before salification, and the amine value after salification was specifically calculated in the same manner as in Synthesis example II-1.

Synthesis example II-3 preparation of dispersant c

While Ar was blown, 100g of dehydrated THF, 2.0g of methyltrimethylsilyl dimethylketene acetal, 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB), and 0.2g of mesitylene were added. In which 33g of methyl methacrylate was added dropwise over 45 minutes using a dropping funnel. Since the reaction proceeds with heat generation, the temperature was kept below 40 ℃ by ice bath cooling. After 1 hour, 17g of dimethylaminoethyl methacrylate was added dropwise over 15 minutes. After 1 hour of reaction, 5g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give block copolymer II-A3. The mass average molecular weight was 6,000 as determined by GPC measurement (NMP LiBr10 mM), and the amine value was 120mgKOH/g.

In a 100mL round-bottomed flask, 24.15 parts by mass of block copolymer II-A3 was dissolved in 24.15 parts by mass of PGMEA, 3.5 parts by mass (0.20 mol based on 1 mol of DMMA unit, which is block copolymer II-A3, which is a compound represented by the above general formula (3)) as a phenylphosphonic acid (Tokyo formation) compound represented by the above general formula (3) was added, and the mixture was stirred at a reaction temperature of 30℃for 20 hours, thereby obtaining a 20% by mass solid salt type block copolymer II-A3 (dispersant c) solution. The amine number after salt formation was specifically calculated in the same manner as in Synthesis example II-1.

Synthesis example II-4 Synthesis of dispersant d

In Synthesis example II-2, the synthesis of a block copolymer II-A4 before salt formation and a solution of a salt-type block copolymer (dispersant d) were carried out in the same manner as in Synthesis example II-2 except that the content shown in Table 11 was changed. In Synthesis example II-4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid value, tg and amine value of the obtained block copolymer before salt formation and the salt-form block copolymer are shown in Table 11.

Synthesis example II-5 Synthesis of dispersant e

Block copolymer II-A5 (dispersant e) was synthesized in the same manner as in the salt-forming block copolymer II-A2 of Synthesis example II-2 (acid value: 8mgKOH/g, tg: 38 ℃).

( Synthesis examples II-6 to II-7: synthesis of dispersant f and dispersant g )

In Synthesis example II-5, a block copolymer II-A6 (dispersant f) and a block copolymer II-A7 (dispersant g) were synthesized in the same manner as in Synthesis example II-5 except that the monomers and the content shown in Table 11 were changed. The acid value, tg and amine value of the obtained block copolymer are shown in Table 11.

Synthesis example II-8 preparation of dispersant h

In synthesis example II-2, a block copolymer II-A8 before salt formation was synthesized in the same manner as in synthesis example II-2, except that the monomers and the content shown in Table 11 were changed. A solution of a salt-forming block copolymer II-A8 (dispersant h) was obtained in the same manner as in Synthesis example II-2 except that the amount of the salt-forming compound was changed as shown in Table 11 using the block copolymer II-A8 before salt formation. The acid value, tg and amine value of the obtained block copolymer before salt formation and the salt-form block copolymer are shown in Table 11.

Synthesis example II-9 Synthesis of alkali-soluble resin A solution

A mixture of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA and 3 parts by mass of AIBN was added dropwise to a polymerization vessel containing 150 parts by mass of PGMEA at 100℃for 3 hours under a nitrogen stream. After the completion of the dropwise addition, the mixture was heated at 100℃for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.

Then, 20 parts by mass of GMA, 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the resulting polymer solution, and the mixture was heated at 110 ℃ for 10 hours, whereby the reaction of the carboxylic acid group of the main chain methacrylic acid with the epoxy group of glycidyl methacrylate was performed. In the reaction, in order to prevent polymerization of glycidyl methacrylate, air bubbling was performed in the reaction solution. The reaction was followed by measuring the acid value of the solution. The alkali-soluble resin A obtained was a resin in which a side chain having an ethylenic double bond was introduced into a main chain formed by copolymerization of BzMA, MMA and MAA using GMA, and was a resin having a solid content of 40% by mass, an acid value of 74mgKOH/g, and a weight average molecular weight of 12000.

TABLE 11

The abbreviations in the tables are as follows.

PME-200: methoxy polyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nikko Co., ltd., BLEMER-PME-200, ethyleneoxy repeat number=4)

DMAPMA: dimethylaminopropyl methacrylamide

Example II-1

(1) Production of color Material Dispersion II-G1

6.18 parts by mass of the dispersant b solution of Synthesis example II-2 as a dispersant, 13.00 parts by mass of C.I. pigment Green 59 (PG 59, trade name of FASTOGEN GREEN C100, manufactured by DIC Co., ltd.) as a color material, 14.63 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 9, 66.19 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated for 1 hour with a pigment vibrator (manufactured by light Tian Tiegong Co.) as a pre-pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly dispersed for 4 hours with a pigment vibrator as a main pulverization, to obtain a color material dispersion II-G1.

(2) Production of photosensitive colored resin composition II-G1 for color filter

The color material dispersion liquid II-G1.40 parts by mass obtained in the above (1), the alkali-soluble resin A solution obtained in Synthesis example II-9, 0.64 parts by mass, the polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 0.60 parts by mass, the 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF Co., ltd.), 0.09 parts by mass, the 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, the ethyl ketone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (photo initiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA Co., ltd.), the fluorine-based surfactant (trade name DIC MEGAFACE F, manufactured by DIC, manufactured by BASF Co., ltd.) 0.02 parts by color filter, and the photosensitive resin A, and the color filter II (photo initiator) 0.07 parts by color resin were added to obtain the color resin composition II.

(3) Formation of colored layer

The photosensitive colored resin compositions II to G1 obtained in the above (2) were each applied onto a glass substrate (NA 35, manufactured by NH TechnoGlass Co., ltd.) having a thickness of 0.7mm and a thickness of 100mm X100 mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, and irradiated with an ultra-high pressure mercury lamp at 60mJ/cm ² After baking in a dust-free oven at 230 ℃ for 30 minutes, the film thickness was adjusted so that the chromaticity of y=0.4 and x=0.2 was set at the C light source, thereby forming a colored layer II-G1.

(examples II-2 to II-10, comparative examples II-C1 to II-C4)

(1) Production of color Material Dispersion solutions II-G2 to II-G6, II-CG1 to II-CG4

In example II-1 (1), color material dispersions II-G2 to II-G6 and II-CG1 to II-CG4 were obtained in the same manner as in example II-1 (1), except that the type and amount of the dispersant were changed so that the solid content was the same part by mass instead of the dispersant b solution as shown in Table 12, and the amount of PGMEA was adjusted so that the total was 100 parts by mass in the comparative example.

(2) Production of photosensitive colored resin compositions II-G2 to II-G6 and II-CG1 to II-CG4 for color filters

Photosensitive colored resin compositions II-G2 to II-G6 and II-CG1 to II-CG4 for color filters were obtained in the same manner as in (2) of example II-1, except that the above-mentioned color material dispersions II-G2 to II-G6 and II-CG1 to II-CG4 were used in place of the color material dispersion II-G1 of (2) of example II-1 in examples II-2 to II-6 and comparative examples II-C1 to II-C4, respectively.

(3) Formation of colored layer

In example II-1, in (3), colored layers II-G2 to II-G6 and II-CG1 to II-CG4 were obtained in the same manner as in example II-1 except that the photosensitive colored resin compositions II-G2 to II-G6 and II-CG1 to II-CG4 were used in place of the photosensitive colored resin composition II-G1, respectively.

Examples II-7 to II-10

(1) Production of photosensitive colored resin compositions II-G7 to II-G10 for color filters

In examples II-7 to II-10, photosensitive colored resin compositions II-G7 to II-G10 for color filters were obtained in the same manner as in (2) of example II-1, except that the photoinitiator was changed to that described in Table 12.

In example II-9, the same procedure as in (2) of example II-1 was repeated except that 0.02 part by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyloxime) was replaced with 0.10 parts by mass of 2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholinopropane-1-one (photoinitiator: IRGACURE907, manufactured by BASF, IRG 907) and 0.05 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: IRGACURE369, manufactured by BASF, IRG 369) in place of the ethanone in (2) of example II-1, to obtain photosensitive colored resin composition II-G9 for a color filter.

(3) Formation of colored layer

In example II-1, in (3), the same procedure as in example II-1 was repeated except that the photosensitive colored resin compositions II-G7 to II-G10 were used in place of the photosensitive colored resin compositions II-G1, respectively, to obtain colored layers II-G7 to II-G10.

Comparative examples II to C5

In comparative examples II to C5, a colored layer II-CG5 was formed in the same manner as in (3) of example II-1, except that in (3) of example II-1, the photosensitive colored resin composition II-CG2 obtained in comparative example II-C2 was used, and the film thickness was adjusted so that the chromaticity of the light source C was y=0.50, to form a colored layer.

TABLE 12

The table is abbreviated as follows.

G58: C.I. pigment Green 58 (trade name: FASTOGEN GREEN A110, manufactured by DIC Co., ltd.)

And G7: C.I. pigment Green 7 (trade name: CHROMOPINE GREEN 6428EC, manufactured by Dai-day refining industry Co., ltd.)

byk-161: disperbyk-161 (urethane dispersant, 30% by mass of solid content, manufactured by BYK Chemie)

PB822: ajisper PB822 (Weisu FINE TECHNO, inc.), polyester dispersant, solid content 30% by mass

NCI-831: oxime ester-series photoinitiators (ADEKA ARKLS NCI-831, manufactured by ADEKA)

TR-PBG-304: oxime ester photoinitiator (Hengzhou powerful electronic New material Co., ltd.)

OXE03: oxime ester-based photoinitiators (IRGACURE OXE-03, manufactured by BASF)

NCI-930: oxime ester-series photoinitiators (ADEKA ARKLS NCI-930, manufactured by ADEKA)

[ evaluation method ]

< evaluation of dispersibility of color Material Dispersion >

The viscosities of the color material dispersions obtained in examples and comparative examples were measured immediately after the preparation and after the storage at 25℃for 30 days, and the viscosity change rates were calculated from the viscosities before and after the storage, to evaluate the viscosity stability. In the viscosity measurement, a vibration viscometer was used to measure the viscosity at 25.0.+ -. 0.5 ℃. The results are shown in Table 12.

(evaluation criterion for Dispersion stability)

A: the viscosity change rate before and after preservation is less than 10%

B: the viscosity change rate before and after storage is more than 10% and less than 15%

C: the viscosity change rate before and after storage is 15% or more and less than 25%

D: the viscosity change rate before and after preservation is above 25%

< evaluation of optical Property, evaluation of contrast >

The contrast, chromaticity (x, Y) and luminance (Y) of the colored layers obtained in examples and comparative examples were measured by using a contrast measuring device CT-1B made by Karaku electric system and an OSP-SP200 made by Olympus.

In comparative example 1 using PG58 as a pigment, chromaticity of y=0.4 and x=0.2 in the C light source was not achieved.

The results are shown in Table 12.

(color gamut evaluation reference)

Value when y=0.4 to 0.5 under the C light source

A: x=less than 0.21

B：x＝0.21～0.23

C: x=exceeding 0.23

(brightness evaluation reference)

The value when y=0.4 and x=0.2 under the C light source

A: exceeding 50.0

B：47.5～50.0

C: less than 47.5

Value when y=0.5 under C light source

A: exceeding 30.0

B：30.0～25.0

C: less than 25.0

(contrast evaluation reference)

The value when y=0.4 and x=0.2 under the C light source

A: exceeding 15000

B：13500～15000

C: less than 13500

Value when y=0.5 under C light source

A: exceeding 3500

B：2500～3500

C: less than 2500

< evaluation of solvent resolubility >

The front end of a glass substrate having a width of 0.5cm and a length of 10cm was immersed in the photosensitive colored resin composition for color filters obtained in examples and comparative examples, and coated on a portion of 1cm in length of the glass substrate. The pulled-up glass substrate was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23℃and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually determined and evaluated. The results are shown in Table 12.

(solvent resolubility evaluation criterion)

A: the dried coating film is completely dissolved

B: flakes producing a dry film in a solvent, solution coloration

C: flakes which did not produce a dry film in the solvent, the solution was uncolored

The evaluation criterion is a or B, and is practically usable, and the effect is more excellent if the evaluation result is a.

< evaluation of development residue >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied to Glass substrates (NH Techno Glass Co., ltd., "NA 35") having a thickness of 0.7mm and 100mm X100 mm using a spin coater, and then dried at 60℃for 3 minutes using a heating plate, whereby a colored layer having a thickness of 2.5 μm was formed. The glass plate on which the colored layer was formed was subjected to spray development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. After the unexposed portion (50 mm. Times.50 mm) of the glass substrate on which the colored layer was formed was visually observed, the glass substrate was sufficiently wiped with a lens cleaning cloth (trade name TORAYSEE MK cleaning cloth manufactured by Toli Co., ltd.) containing ethanol to visually observe the degree of coloration of the lens cleaning cloth. The results are shown in Table 12.

(development residue evaluation reference)

A: the development residue was not visually confirmed, and the lens cleaning cloth was completely colorless.

B: the development residue was not visually confirmed, and slight coloration of the lens cleaning cloth was confirmed.

C: to visually confirm a slight development residue and a slight coloring of the lens cleaning cloth.

D: the slight development residue was visually confirmed, and the staining of the lens cleaning cloth was confirmed.

E: to visually confirm the development residues and to confirm the coloration of the lens cleaning cloth.

The evaluation criterion A, B or C is practically usable, and the effect is more excellent when the evaluation result is B and further a.

< evaluation of development adhesion >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied to Glass substrates (NH Techno Glass Co., ltd., "NA 35") having a thickness of 0.7mm and 100mm X100 mm using a spin coater, and then dried at 60℃for 3 minutes using a heating plate, whereby a colored layer having a thickness of 2.5 μm was formed. Irradiating the colored layer with 60mJ/cm by using an ultra-high pressure mercury lamp through a photomask with a shielding opening width of 2-80 μm ² Is a ultraviolet ray of (a). The glass plate on which the colored layer was formed was subjected to spray development for 60 seconds using a 0.05 mass% aqueous potassium hydroxide solution as an alkali developer. The developed substrate was observed with an optical microscope, and the presence or absence of a colored layer for masking the line width of the opening was observed. The results are shown in Table 12.

(development adhesion evaluation criterion)

A: the colored layer was observed at a portion where the line width of the shielding opening was less than 10 μm.

B: the colored layer was observed at a portion where the line width of the mask opening was 10 μm or more and less than 20 μm.

C: the colored layer was observed at a portion where the line width of the mask opening was 20 μm or more and less than 50 μm.

D: the colored layer was observed at a portion where the line width of the mask opening was 50 μm or more and less than 80 μm.

E: no coloring layer was observed at a portion where the line width of the mask opening was 80 μm or less.

If the evaluation criterion is A, B or C, the method is practical; however, when the evaluation result is B or even a, the photosensitive colored resin composition for a color filter is suitable for applications with higher definition.

< evaluation of development resistance >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied to Glass substrates (manufactured by NH Techno Glass Co., ltd., "NA 35") having a thickness of 0.7mm using a spin coater. After heating and drying on a heating plate at 80℃for 3 minutes, 40mJ/cm of the mixture was irradiated with an ultra-high pressure mercury lamp ² Is a ultraviolet ray of (a). The film thickness at this time was measured as T1 (. Mu.m). Thereafter, spray development was performed using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developer. The film thickness after development was measured as T2 (. Mu.m). T2/T1X 100 (%) was calculated. The results are shown in Table 12.

(development resistance evaluation reference)

A:95% or more

B: more than 90 percent and less than 95 percent

C: less than 90%

The evaluation result B can be used in practice, but the effect is more excellent if the evaluation criterion a.

< evaluation of Water penetration >

The photosensitive colored resin compositions for color filters obtained in each example and each comparative example were applied to a GLASS substrate (NH TECHNO GLASS, inc. "NA 35") at a film thickness of 1.6 μm after post-baking using a spin coater, and then dried at 60℃for 3 minutes using a heating plate without being subjected to the post-bakingBlanket irradiation of 60mJ/cm by using an ultra high pressure mercury lamp from a photomask ² Is formed on a glass substrate. Then, spin development was performed using 0.05wt% potassium hydroxide (KOH) as a developer, and after 60 seconds of contact with the developer, the substrate was washed with pure water to perform development treatment, and after 10 seconds of spin-drying the washed substrate to remove water by centrifugation, the contact angle of pure water was measured immediately as described below to evaluate water penetration.

The contact angle measurement of pure water was: to the surface of the colored layer immediately after the removal of water by centrifugation, 1.0. Mu.L of a droplet of pure water was dropped, and the static contact angle after 10 seconds of the drop was measured according to the θ/2 method. The measurement device used a contact angle meter DM500 manufactured by Kyowa interface science Co.

(evaluation criterion)

A: contact angle of 80 DEG or more

B: contact angle of 65 degrees or more and less than 80 degrees

C: contact angle of 50 degrees less than 65 degrees

D: contact angle less than 50 DEG

If the water penetration evaluation standard is A or B, the method can be practically used; however, if the evaluation result is a, the effect is more excellent.

[ integration of results ]

As is apparent from the results in Table 12, the viscosity stability of the color material dispersions of examples II-1 to II-6, in which the dispersant which is a polymer having the constituent unit represented by the general formula (I) was combined with the C.I. pigment green 59, was good. On the other hand, the viscosity stability of the color material dispersions of comparative examples II-C3 to II-C4, in which the urethane-based dispersant and the polyester-based dispersant were combined with the C.I. pigment green 59, was significantly deteriorated. In addition, the viscosity stability of the color material dispersion of comparative examples II to C2, in which the dispersant of the polymer having the constituent unit represented by the general formula (I) was combined with c.i. pigment green 7, was significantly deteriorated.

The photosensitive colored resin compositions for color filters of examples II-1 to II-10, in which the dispersant of the polymer having the constituent unit represented by the general formula (I) was combined with c.i. pigment green 59, clearly exhibited bluish green in the region of x=0.20 when y=0.40 or in the region of x=0.16 when y=0.50, and had high brightness. The photosensitive colored resin compositions for color filters of examples II-1 to II-10, in which the c.i. pigment green 59 was combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), exhibited excellent color material dispersion stability, excellent contrast, excellent solvent resolubility, and further suppressed development residue generation.

Wherein a block copolymer comprising an A block comprising a constituent unit represented by the above general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solvophilicity is used as the dispersant; or a salt-type block copolymer which forms a salt with at least a part of a nitrogen site of a constituent unit represented by the general formula (I), particularly in examples II-1, 2, 3 and 6 to 10, the occurrence of development residues is suppressed, and the development adhesion is excellent, wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more.

On the other hand, when c.i. pigment green 58 is used as in comparative examples II to C1, the region of x=0.2 cannot be displayed when y=0.4. In addition, when c.i. pigment green 7 is used as in comparative examples II to C2, the region where x=0.2 can be displayed when y=0.4, but the luminance is low. When c.i. pigment green 7 is used as in comparative examples II to C5, the brightness is low at y=0.50 although the region of x=0.16 can be displayed. Although not shown in the table, the c.i. pigment green 58 cannot show the region of x=0.16 when y=0.50.

In addition, when C.I. pigment green 7 is used as in comparative examples II to C2, the dispersibility is poor even when a dispersant is used in combination as a polymer having a constituent unit represented by the general formula (I), and therefore the contrast is low, and the resolubility and residue are deteriorated.

On the other hand, the dispersibility of the photosensitive colored resin compositions for color filters of comparative examples II to C4, in which the urethane-based dispersing agent or the polyester-based dispersing agent was combined with the c.i. pigment green 59, was degraded, and therefore, the brightness was lowered, the contrast was lowered, and the resolubility and the residue were also degraded, as compared with the examples.

In the examples, the development resistance and the inhibition effect of the occurrence of water bleeding in the examples using the oxime ester photoinitiator as the photoinitiator were significantly improved.

Example III series: second aspect of the present invention

In example III, solutions of dispersants a to h were obtained in the same manner as in Synthesis examples II-1 to II-8 in example II. The alkali-soluble resin A solution was obtained in the same manner as in Synthesis examples II-9 of example II series.

Example III-1

(1) Production of color Material Dispersion III-G1

6.22 parts by mass of a dispersant b solution as a dispersant, 5.33 parts by mass of C.I. pigment Green 59 (PG 59, trade name of FASTOGEN GREEN C100, manufactured by DIC Co., ltd.) as a color material, 7.67 parts by mass of C.I. pigment yellow 138 (PY 138, trade name of CHROMOFINE YELLOW 6206EC, manufactured by Dai Seiki Seisakusho Kogyo Co., ltd.) and 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated by a pigment vibrator (manufactured by light Tian Tiegong Co., ltd.) for 1 hour as a preliminary pulverization, then zirconia beads having a particle diameter of 2.0mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly dispersed by the pigment vibrator for 4 hours as a main pulverization, to obtain a color material dispersion III-G1.

(2) Production of photosensitive colored resin composition III-G1 for color Filter

A color material dispersion liquid III-G1.40 parts by mass, an alkali-soluble resin A solution 0.64 parts by mass, a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.) 0.60 parts by mass, 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF Co., ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -,1- (o-acetyl oxime) (photo initiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA Co., ltd.) 0.02 parts by mass, a fluorine-based surfactant (trade name MEGAFACE F559.559, DIC (manufactured by DIC Co., ltd.) 0.04 parts by photo-1- [ 9-ethyl-6- (2-methylbenzoyl) ] and a photosensitive resin A) 0.04 parts by color resin III were added to obtain a color resin composition III.

(3) Formation of colored layer

The photosensitive colored resin compositions III to G1 obtained in the above (2) were each applied onto a Glass substrate (NA 35, manufactured by NH Techno Glass Co., ltd.) having a thickness of 0.7mm and a thickness of 100mm X100 mm using a spin coater, and then dried at 80℃for 3 minutes using a heating plate, and irradiated with an ultra-high pressure mercury lamp at 60mJ/cm ² After baking in a dust-free oven at 230 ℃ for 30 minutes, the film thickness was adjusted so that the chromaticity of y=0.570 and x=0.260 was set at the C light source, thereby forming a colored layer III-G1.

(examples III-2 to III-6, comparative examples III-C1 to III-C5)

(1) Production of color Material Dispersion solutions III-G2 to III-G6, III-CG1 to III-CG5

In example III-1 (1), color material dispersions III-G2 to III-G6 and III-CG1 to III-CG5 were obtained in the same manner as in example III-1 (1) except that the type and the amount of the dispersant were changed so that the solid content was the same mass part instead of the dispersant b solution as shown in Table 13, and the amount of PGMEA was changed in comparative examples III-C1 to III-C3 so that the total was 100 mass parts.

(2) Production of photosensitive colored resin compositions III-G2 to III-G6 and III-CG1 to III-CG5 for color filters

In examples III-2 to III-6 and comparative examples III-C1 to III-C5, photosensitive colored resin compositions III-G2 to III-G6 and III-CG1 to III-CG5 for color filters were obtained in the same manner as in (2) of example III-1 except that the color material dispersions III-G1 in (2) of example III-1 were replaced with the color material dispersions III-G2 to III-G6 and III-CG1 to III-CG5, respectively, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 13 in order to set the film thicknesses to 2.35. Mu.m.

(3) Formation of colored layer

In example III-1, in (3), colored layers III-G2 to III-G6 and III-CG1 to III-CG5 were obtained in the same manner as in example III-1 except that the photosensitive colored resin compositions III-G2 to III-G6 and III-CG1 to III-CG5 were used in place of the photosensitive colored resin composition III-G1, respectively.

Examples III-7 to III-10, III-33

(1) Production of photosensitive colored resin compositions III-G7 to III-G10 and III-33 for color filters

Photosensitive colored resin compositions III-G7 to III-G8 and III-G33 for color filters were obtained in the same manner as in (2) of example III-1, except that the photoinitiator was changed to that described in Table 13 in examples III-7 to III-8 and III-33.

In example III-9, the same procedure as in (2) of example III-1 was repeated except that 0.02 part by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyloxime) was replaced with 0.10 parts by mass of 2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholinopropane-1-one (photoinitiator: IRGACURE907, manufactured by BASF Co., ltd.) and 0.05 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: IRGACURE369, manufactured by BASF) in place of the ethanone in (2) of example III-1, to obtain a colored resin composition III-G9 for a color filter.

In example III-10, a photosensitive colored resin composition III-G10 for a color filter was obtained in the same manner as in (2) of example III-1, except that the alkali-soluble resin solution A was replaced with an alkali-soluble resin solution B (a carboxylic group-containing epoxy (meth) acrylate resin having a Cardo structure, manufactured by INR-16M,Nagase ChemteX Co., ltd.) and the amount of the resin was adjusted so that the solid content was the same mass part.

(3) Formation of colored layer

In example III-1, in (3), the same procedure as in example III-1 was repeated except that the photosensitive colored resin compositions III-G7 to III-G10 and III-G33 were used in place of the photosensitive colored resin composition III-G1, respectively, to obtain colored layers III-G7 to III-G10 and III-G33.

TABLE 13

The table is abbreviated as follows.

G36: C.I. pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Co., ltd.)

Y138: C.I. pigment yellow 138 (trade name: CHROMOFINE YELLOW 6206EC, manufactured by Dai Ji Summit Co., ltd.)

The series of G58, G7, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, NCI-930 were the same as those of example II.

(examples III-11 to III-16, comparative examples III-C6)

(1) Production of color Material Dispersion III-G11 to III-G16, III-CG6

In example III-1 (1), color material dispersions III-G11 to III-G16 and III-CG6 were obtained in the same manner as in example III-1 (1), except that the types and the amounts of the color materials were changed as shown in Table 14, and the amounts of the dispersants were changed so that the solid content was the same parts by mass, and the PGMEA amounts were adjusted so that the total was 100 parts by mass.

(2) Production of photosensitive colored resin compositions III-G11 to III-G16 and III-CG6 for color filters

Photosensitive colored resin compositions III-G11 to III-G16 and III-CG6 for color filters were obtained in the same manner as in (2) of example III-1 except that the color material dispersions III-G11 to III-G16 and III-CG6 were used in place of the color material dispersion III-G1 of (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each set to the values shown in Table 14 so that the film thicknesses became 2.80. Mu.m.

(3) Formation of colored layer

In example III-1, in (3), the colored layers III-G11 to III-G16 and III-CG6 were obtained in the same manner as in example III-1 except that the photosensitive colored resin compositions III-G11 to III-G16 and III-CG6 were used in place of the photosensitive colored resin composition III-G1, respectively. In comparative examples III to C6 using PG58 as a color material, chromaticity of y=0.610 and x=0.210 under the C light source could not be achieved.

TABLE 14

The table is abbreviated as follows.

Y150: C.I. pigment yellow 150 (trade name: LEVASCREEN YELLOW G, manufactured by LANXESS Co., ltd.)

Ni-azo-1: derivative pigment of C.I. pigment yellow 150 (Ni: zn=1:1 (molar ratio) azo pigment) prepared in the following preparation example

(modulation example)

To 550g of distilled water, 23.1g of diazobarbituric acid and 19.2g of barbituric acid were introduced. Next, an aqueous potassium hydroxide solution was used to prepare azobarbituric acid (0.3 mol), and 750g of the azobarbituric acid was mixed with distilled water. 5g of 30% hydrochloric acid was added dropwise. Thereafter, 38.7g of melamine was introduced. Next, 0.3 mol of nickel chloride solution was added in combination with 0.3 mol of zinc chloride solution, and stirred at 80℃for 8 hours. The pigment was separated by filtration, washed, dried at 120 ℃ and ground with a mortar to give a derivative pigment of c.i. pigment yellow 150.

(examples III-17 to III-21, comparative examples III-C7)

Production of color Material Dispersion III-G17-III-G21, III-CG7

In example III-1 (1), color material dispersions III-G17 to III-G21 and III-CG7 were obtained in the same manner as in example III-1 (1), except that the types and the amounts of the color materials were changed as shown in Table 15, and the amounts of the dispersants were changed so that the solid content was the same parts by mass, and the PGMEA amounts were adjusted so that the total was 100 parts by mass.

(2) Production of photosensitive colored resin compositions III-G17 to III-G21, III-CG7 for color filters

Photosensitive colored resin compositions III-G17 to III-G21 and III-CG7 for a color filter were obtained in the same manner as in (2) of example III-1 except that the color material dispersions III-G17 to III-G21 and III-CG7 were used in place of the color material dispersion III-G1 of (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each set to the values shown in Table 15 in order to set the film thicknesses to 2.80. Mu.m.

(3) Formation of colored layer

In example III-1, in (3), colored layers III-G17 to III-G21 and III-CG7 were obtained in the same manner as in example III-1 except that the photosensitive colored resin compositions III-G17 to III-G21 and III-CG7 were used in place of the photosensitive colored resin composition III-G1, respectively. In comparative examples III to C7 using PG58 as a color material, chromaticity of y=0.626 and x=0.205 cannot be achieved under the C light source.

TABLE 15

The table is abbreviated as follows.

Y185: C.I. pigment Yellow 185 (trade name: paliotol (registered trademark) Yellow D1155, manufactured by BASF corporation)

Examples III-22 to III-24

Production of color Material Dispersion III-G22 to III-G24

In example III-1 (1), color material dispersions III-G22 to III-G24 were obtained in the same manner as in example III-1 (1), except that the types and the amounts of the color materials were changed, and the amounts of the dispersants were changed so that the solid content was the same parts by mass, and the PGMEA amounts were adjusted so that the total was 100 parts by mass, as shown in Table 16.

(2) Production of photosensitive colored resin compositions III-G22 to III-G24 for color filters

Photosensitive colored resin compositions III-G22 to III-G24 for color filters were obtained in the same manner as in (2) of example III-1, except that the color material dispersions III-G22 to III-G24 were used in place of the color material dispersion III-G1 of (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each set to the values shown in Table 16 in order to set the film thicknesses to 3.30. Mu.m.

(3) Formation of colored layer

In example III-1, in (3), colored layers III-G22 to III-G24 were obtained in the same manner as in example III-1 (3), except that the photosensitive colored resin compositions III-G22 to III-G24 were used in place of the photosensitive colored resin composition III-G1.

TABLE 16

Table 16

Examples III-25 to III-27

Production of color Material Dispersion III-G25 to III-G27

In example III-1 (1), color material dispersions III-G25 to III-G27 were obtained in the same manner as in example III-1 (1), except that the types and the amounts of the color materials were changed as shown in Table 17, and the amounts of the dispersants were changed so that the solid content was the same parts by mass and the amount of PGMEA was adjusted so that the total was 100 parts by mass.

(2) Production of photosensitive colored resin compositions III-G25 to III-G27 for color filters

Photosensitive colored resin compositions III-G25 to III-G27 for color filters were obtained in the same manner as in (2) of example III-1, except that the color material dispersions III-G25 to III-G27 were used in place of the color material dispersion III-G1 of (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each set to the values shown in Table 17 in order to set the film thicknesses to 3.30. Mu.m.

(3) Formation of colored layer

In example III-1, in (3), colored layers III-G25 to III-G27 were obtained in the same manner as in example III-1 (3), except that the photosensitive colored resin compositions III-G25 to III-G27 were used in place of the photosensitive colored resin composition III-G1.

TABLE 17

Examples III-28

(1) Production of color Material Dispersion

6.22 parts by mass of a dispersant b solution as a dispersant, 13 parts by mass of C.I. pigment GREEN 59 (PG 59, manufactured by FASTOGEN GREEN C100 DIC Co., ltd.) as a color material, 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated by a pigment vibrator (manufactured by light Tian Tiegong Co., ltd.) for 1 hour as a preliminary pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly the dispersion was dispersed by the pigment vibrator for 4 hours as a main pulverization to obtain a GREEN color material dispersion g.

6.22 parts by mass of a dispersant b solution as a dispersant, 13 parts by mass of C.I. pigment yellow 138 (PY 138, trade name: CHROMOFINE YELLOW 6206EC, manufactured by Dai Kagaku Kogyo Co., ltd.) as a color material, 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated by a pigment vibrator (manufactured by light Tian Tiegong Co., ltd.) for 1 hour as a preliminary pulverization, then zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly, dispersed by the pigment vibrator for 4 hours as a final pulverization, to obtain a yellow color material dispersion y.

(2) Production of photosensitive colored resin composition III-G28 for color Filter

4.67 parts by mass of the green color material dispersion G obtained in the above (1), 6.73 parts by mass of the yellow color material dispersion y, 0.64 parts by mass of an alkali-soluble resin A solution, 0.60 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.), 0.02 parts by mass of 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF Co., ltd.), 0.09 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by BASF), 0.04 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl ] -, 0.02 parts by 1- (o-acetyl oxime) (photo initiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA Co., ltd.), 0.02 parts by fluorine-based surfactant (trade name MEGAFACE F), and 0.07 parts by color filter (manufactured by PGM) were added to obtain a colored composition of the color resin composition of yellow color film (III).

(3) Formation of colored layer

In example III-1, in (3), a colored layer III-G28 was obtained in the same manner as in example III-1 except that the photosensitive colored resin composition III-G28 was used instead of the photosensitive colored resin composition III-G1.

The obtained photosensitive colored resin composition III-G28 for a color filter had the same composition as the photosensitive colored resin composition III-G1 for a color filter of example III-1, and the evaluation results of the photosensitive colored resin composition III-G28 for a color filter and the colored layer III-G28 were the same as the evaluation results of the photosensitive colored resin composition III-G1 for a color filter and the colored layer III-G1.

[ evaluation method of example III series ]

The optical performance evaluation, contrast evaluation and display failure evaluation were performed as follows. The dispersibility, the solvent resolubility, the development residue, the development adhesion, the development resistance and the water-bleeding of the color material dispersion were evaluated in the same manner as in the series of example II.

< evaluation of optical Property, evaluation of contrast >

In comparative example 6 using PG58 as a color material, chromaticity of y=0.610 and x=0.210 under the C light source could not be achieved. In comparative example 7 using PG58 as a color material, chromaticity of y=0.626 and x=0.205 under the C light source cannot be achieved.

(contrast evaluation reference)

Let y=0.570 and x=0.260 be the values for the C light source

A: over 12000

B：12000～10000

C: below 10000

< evaluation of display failure >

The colored layers obtained in examples and comparative examples were evaluated for defective display by using a dielectric impedance measurement system 126096W (manufactured by Toyo Technical).

(display failure evaluation criterion)

A: a dielectric loss tangent (tan delta) at 100Hz of less than 0.023

B: dielectric loss tangent (tan delta) at 100Hz of 0.023-0.048

C: dielectric loss tangent (tan delta) at 100Hz exceeding 0.048

If the evaluation criterion is a or B, the method can be used in practice, and if the evaluation result is a, the effect of suppressing the defective is high.

[ integration of results from example III series ]

As is apparent from the results in tables 13 to 17, the viscosity stability of the color material dispersion liquid of the example in which the dispersant which is the polymer having the constituent unit represented by the general formula (I) was combined with the yellow color material was good. On the other hand, the viscosity stability of the color material dispersions of comparative examples III-C4 to III-C5 in which the urethane-based dispersant or the polyester-based dispersant was combined with PG59 was significantly deteriorated. In addition, the color material dispersions of comparative examples III-C1, III-C2 and III-C3, in which PG58, PG7 and PG36 are combined as dispersants for the polymer having the constituent unit represented by the general formula (I), were significantly inferior in viscosity stability to example III-1. In addition, the dispersion properties of the dispersion liquids of comparative examples III to C2 and III to C3, in which PG7 and PG36 are combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), are deteriorated.

As is apparent from table 13, the photosensitive colored resin compositions for color filters of examples III-1 to III-10, in which the yellow color material PY138 and the dispersant which is the polymer having the constituent unit represented by the general formula (I) were combined in PG59, exhibited a region of x=0.260 when y=0.570, and the occurrence of display defects was suppressed, so that a colored layer with high brightness was formed. It is also apparent that the photosensitive colored resin compositions for color filters of examples III-1 to III-10, in which the yellow color material PY138 and the dispersant which is the polymer having the constituent unit represented by the general formula (I) were combined with PG59, were excellent in color material dispersion stability, excellent in contrast, excellent in solvent resolubility, and further suppressed in development residues.

Wherein a block copolymer comprising an A block comprising a constituent unit represented by the above general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solvophilicity is used as the dispersant; in examples III-1, III-2, III-6 to III-10, III-33, which are block copolymers of a salt form with at least a part of the nitrogen site of the constituent unit represented by the general formula (I), the occurrence of development residues is particularly suppressed, and the development adhesion is excellent, wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more. In addition, example III-10, which used a carboxylic group-containing epoxy (meth) acrylate resin having a Cardo structure as the alkali-soluble resin in the photosensitive colored resin composition, was more excellent in development adhesion, development resistance and water penetration and hair dye growth inhibition effect than example III-1.

In the examples, it is evident from the comparison of examples III-1, III-7, III-8, III-9 and III-33 that the examples using the oxime ester photoinitiator as the photoinitiator have higher development resistance and water penetration and hair growth inhibition effects.

As is apparent from tables 14 and 15, when a yellow coloring material and a dispersant which is a polymer having a constituent unit represented by the general formula (I) are combined in PG59, the color gamut is increased, and even in the case of y=0.570 to 0.626, the chromaticity region of x=0.205 to 0.324 can be displayed, and further, the chromaticity region of y= 0.659 can be displayed, and occurrence of display failure can be suppressed, whereby a high-luminance colored layer can be formed.

In addition, in examples III-23 of Table 16, when PG58 was further combined with a yellow color material, the P/V ratio was significantly reduced and the luminance was further improved as compared with examples III-22 in which PG59 was used alone as a green color material. In examples III to 24, when PG59 and PG58 as green materials and PY138 and PY150 as yellow materials were combined, it was found that the above P/V ratio could be further reduced.

In addition, in examples III to 26 of Table 17, if PG7 is further combined with PG59, the P/V ratio can be remarkably reduced, and the luminance can also be improved. In examples III to 27, when PY138 and PY150 as yellow color materials were combined with PG59 and PG7 as green color materials, the P/V ratio was further significantly reduced.

On the other hand, when PG58 is used as in comparative example III-C1, when y=0.570, the region of x=0.260 can be displayed, but poor display occurs, and the luminance is inferior to that in the case of using PG 59. In addition, the development residue also worsens. In addition, when PG7 and PG36 are used as in comparative examples III to C2 and III to C3, when y=0.570, the region where x=0.260 can be displayed, but the luminance is low. Further, even if a dispersant is used in combination as a polymer having a constituent unit represented by the general formula (I), the dispersibility thereof is deteriorated, and therefore the contrast is low, and the resolubility and residue are also deteriorated.

On the other hand, the photosensitive colored resin compositions for color filters of comparative examples III-C4 to III-C5, in which the urethane-based dispersant and the polyester-based dispersant were combined with PG59, had lower brightness and lower contrast than the examples, and had poor resolubility and residue due to the deterioration of dispersibility.

Example IV series: third aspect of the second aspect of the present invention

In the system of example IV, the solutions of dispersants a to h were obtained in the same manner as in Synthesis examples II-1 to II-8 of example II series, respectively. The alkali-soluble resin A solution was obtained in the same manner as in Synthesis examples II-9 of example II series.

Example IV-1

(1) Production of color Material Dispersion IV-G1

6.22 parts by mass of a dispersant b solution as a dispersant, 6.42 parts by mass of C.I. pigment GREEN 59 (PG 59, trade name FASTOGEN GREEN C100, manufactured by DIC Co., ltd.) as a color material, 15:4 (PB 15:4, trade name CYANINE BLUE CP-1, manufactured by Dairy Seikovian Co., ltd.) as a BLUE color material, 1.39 parts by mass of C.I. pigment YELLOW 139 (PY 139, trade name IRGAPHOR YELLOW 2R-CF, manufactured by BASF) as a YELLOW color material, 1.40 parts by mass of C.I. pigment YELLOW 150 (PY 150, trade name LEVASCREEN YELLOW G, manufactured by LAXESS Co., ltd.) as a YELLOW color material, 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, 100 parts by mass of zirconia beads having a particle size of 2.0mm, and a YELLOW bottle were placed in a pigment vibrator (Tian Tiegong) (1 hour, manufactured by weight was taken out as a pre-vibration particle size, and the same zirconia beads were dispersed in a vibration container having a particle size of 2.0mm, and the same particle size was obtained as a vibration container.

(2) Production of photosensitive colored resin composition IV-G1 for color filter

A color material dispersion IV-G1.41 mass parts, an alkali-soluble resin A solution 2.75 mass parts, a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyama Synthesis Co., ltd.) 0.60 mass parts, a 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photo initiator: trade name IRGACURE907, manufactured by BASF Co., ltd.) 0.09 mass parts, a 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo initiator: trade name IRGACURE369, manufactured by BASF) 0.04 mass parts, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, a 1- (o-acetyl oxime) (photo initiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA Co., ltd.) 0.02 mass parts, a fluorine-based surfactant (trade name MEGAFACE F559, DIC (manufactured by DIC Co., ltd.) 0.07 mass parts), and a photosensitive resin composition 1.72 mass parts were added to the color resin composition.

(3) Formation of colored layer

The photosensitive colored resin compositions IV-G1 obtained in the above (2) were each applied to a Glass substrate (NA 35, manufactured by NH Techno Glass Co., ltd.) having a thickness of 0.7mm and a thickness of 100mm X100 mm using a spin coater, and then heated to 80℃using a heating plateDrying for 3 min, and irradiating with ultra-high pressure mercury lamp at 60mJ/cm ² After baking in a dust-free oven at 230℃for 30 minutes, the film thickness was adjusted so that the film thickness after curing became 2.80. Mu.m, thereby forming a colored layer IV-G1.

(examples IV-2 to IV-6, IV-11 to IV-13, comparative examples IV-C1 to IV-C4)

(1) Production of color Material Dispersion solutions IV-G2 to IV-G6, IV-G11 to IV-G13, IV-CG1 to IV-CG4

In examples IV-2 to IV-6 and comparative examples IV-C3 to IV-C4, color material dispersions IV-G2 to IV-G6 and IV-CG3 to IV-CG4 were obtained in the same manner as in (1) of example IV-1, except that in (1) of example IV-1, the kind and the amount of the dispersant were changed so that the solid content was the same parts by mass instead of the dispersant b solution and the amount of PGMEA was adjusted so that the total was 100 parts by mass, as shown in Table 18. In examples IV-11 to IV-13, color material dispersions IV-G11 to IV-G13 were obtained in the same manner as in (1) of example IV-1, except that the color material was changed and the amount of PGMEA was adjusted to 100 parts by mass in total in (1) of example IV-1. In comparative examples IV-C1 to IV-C2, IV-CG1 to IV-CG2 were obtained in the same manner as in (1) of example IV-1 except that in (1) of example IV-1, a dispersant a solution was used instead of the dispersant b solution and the color material was changed.

(2) Production of photosensitive colored resin compositions IV-G2 to IV-G6, IV-G11 to IV-G13, and IV-CG1 to IV-CG4 for color filters

The same procedure as in (2) of example IV-1 was repeated except that the color material dispersions IV-G2 to IV-G6, IV-G11 to IV-G13, and IV-CG1 to IV-CG4 were used in place of the color material dispersion IV-G1 of (2) of example IV-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each the values shown in Table 18 so that the film thicknesses became 2.8. Mu.m, thereby obtaining photosensitive colored resin compositions IV-G2 to IV-G6, IV-G11 to IV-G13, and IV-CG1 to IV-CG4 for color filters.

(3) Formation of colored layer

In the same manner as in (3) of example IV-1, except that the photosensitive colored resin compositions IV-G2 to IV-G6, IV-G11 to IV-G13, and IV-CG1 to IV-CG4 were used in place of the photosensitive colored resin composition IV-G1, colored layers IV-G2 to IV-G6, IV-G11 to IV-G13, and IV-CG1 to IV-CG4 were obtained in the same manner as in (3) of example IV-1.

Examples IV-7 to IV-10, IV-36

(1) Production of photosensitive colored resin compositions IV-G7 to IV-G10 and IV-G36 for color filters

Photosensitive colored resin compositions IV-G7 to IV-G8 and IV-G36 for color filters were obtained in the same manner as in (2) of example IV-1 except that the photoinitiator was changed to that described in Table 18 in examples IV-7 to IV-8 and IV-36.

In example IV-9, the same procedure as in (2) of example IV-1 was repeated except that 0.02 part by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyloxime) was replaced with 0.10 parts by mass of 2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholinopropane-1-one (photoinitiator: IRGACURE907, manufactured by BASF Co., ltd.) and 0.05 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: IRGACURE369, manufactured by BASF) in place of the ethanone in (2) of example IV-1, to obtain a colored resin composition IV-G9 for a color filter.

In example IV-10, a photosensitive colored resin composition IV-G10 for a color filter was obtained in the same manner as in (2) of example IV-1, except that the alkali-soluble resin a solution was replaced with an alkali-soluble resin B solution (a carboxylic group-containing epoxy (meth) acrylate resin having a Cardo structure, manufactured by type INR-16M,Nagase ChemteX, inc.) and the amount of the alkali-soluble resin was adjusted so that the solid content was the same mass part.

(3) Formation of colored layer

In example IV-1 (3), coloring layers IV-G7 to IV-G10 and IV-G36 were obtained in the same manner as in example IV-1 (3), except that the photosensitive coloring resin compositions IV-G7 to IV-G10 and IV-G36 were used instead of the photosensitive coloring resin composition IV-G1, respectively.

TABLE 18

In this case, the following is the abbreviations.

PB15:4:C.I. pigment BLUE 15:4 (trade name: CYANINE BLUE CP-1, manufactured by Dai Jiuzu industries Co., ltd.)

PB15:3:C.I. pigment blue 15:3 (trade name: CHROMOFINE BLUE A-220JC, manufactured by Dari Seiyi Co., ltd.)

G36, G58, ni-azo-1, Y138, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, NCI-930 are the same as those of the series of examples II or III.

(examples IV-14 to IV-15, comparative examples IV-C5 to IV-C10)

(1) Production of color Material Dispersion IV-G14-IV-G15, IV-CG 5-IV-CG 10

In example IV-1 (1), color material dispersions IV-G14 to IV-G15 and IV-CG5 to IV-CG10 were obtained in the same manner as in example IV-1 (1), except that the types and amounts of the color materials were changed as shown in Table 19, and the amounts of the dispersants were changed so that the solid content was the same parts by mass, and the PGMEA amount was adjusted so that the total was 100 parts by mass.

(2) Production of photosensitive colored resin compositions IV-G14 to IV-G15 and IV-CG5 to IV-CG10 for color filters

Photosensitive colored resin compositions for color filters IV-G14 to IV-G15 and IV-CG6 were obtained in the same manner as in (2) of example IV-1 except that the color material dispersion IV-G1 of (2) of example IV-1 was replaced with the color material dispersions IV-G14 to IV-G15 and IV-CG6, respectively, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each the values shown in Table 19 in order to set the film thicknesses to 2.8. Mu.m.

In the combinations of the color materials of comparative examples IV to C5 and comparative examples IV to C10, the photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing chromaticity of x=0.200 and y=0.710 could not be prepared.

(3) Formation of colored layer

In example IV-1 (3), coloring layers IV-G14 to IV-G15 and IV-CG6 were obtained in the same manner as in example IV-1 (3), except that the photosensitive coloring resin compositions IV-G14 to IV-G15 and IV-CG6 were used in place of the photosensitive coloring resin composition IV-G1, respectively.

TABLE 19

PB15:6:C.I. pigment BLUE 15:6 (manufactured by DIC Co., ltd., product name. FASTOGEN BLUE A510)

Examples IV-16 to IV-30

Production of color Material Dispersion IV-G16 to IV-G30

In example IV-1 (1), color material dispersions IV-G16 to IV-G30 were obtained in the same manner as in example IV-1 (1), except that the types and amounts of the color materials were changed, and the amounts of the dispersants were changed so that the solid content was the same parts by mass, and the PGMEA amounts were adjusted so that the total was 100 parts by mass, as shown in table 20.

(2) Production of photosensitive colored resin compositions IV-G16 to IV-G30 for color filters

Photosensitive colored resin compositions IV-G16 to IV-G30 for color filters were obtained in the same manner as in (2) of example IV-1, except that the color material dispersions IV-G16 to IV-G30 were used in place of the color material dispersion IV-G1 of (2) of example IV-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were each set to the values shown in table 20 in order to set the film thicknesses to 2.8 μm.

(3) Formation of colored layer

In example IV-1 (3), coloring layers IV-G16 to IV-G30 were obtained in the same manner as in example IV-1 (3), except that the photosensitive coloring resin compositions IV-G16 to IV-G30 were used instead of the photosensitive coloring resin composition IV-G1.

TABLE 20

The G7 and Y185 are the same as those in example III.

Examples IV-35

(1) Production of color Material Dispersion

6.22 parts by mass of a dispersant b solution as a dispersant, 13 parts by mass of C.I. pigment GREEN 59 (PG 59, manufactured by FASTOGEN GREEN C100DIC Co., ltd.) as a color material, 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put into a mayonnaise bottle, vibrated by a pigment vibrator (manufactured by light Tian Tiegong Co., ltd.) for 1 hour as a preliminary pulverization, then the zirconia beads having a particle diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle diameter of 0.1mm were added, and similarly the dispersion was dispersed by the pigment vibrator for 4 hours as a main pulverization to obtain a GREEN color material dispersion g.

The GREEN material dispersion b was obtained in the same manner as in the GREEN material dispersion g except that 13 parts by mass of c.i. pigment BLUE 15:4 (PB 15:4 trade name: cyanone BLUE CP-1, manufactured by dai-seminar industries, co.) was used as a color material in place of 13 parts by mass of c.i. pigment GREEN 59 (PG 59, trade name fastagen GREEN C100, manufactured by DIC corporation) as a color material.

The GREEN material dispersion g was prepared in the same manner as the GREEN material dispersion g except that 13 parts by mass of c.i. pigment yellow 139 (PY 139, trade name: irgapolyllow 2R-CF, manufactured by BASF) was used as a color material instead of 13 parts by mass of c.i. pigment GREEN 59 (PG 59, trade name fastagen GREEN C100DIC (manufactured by the trade name) as a color material, to obtain a yellow color material dispersion y1.

The GREEN color material dispersion g was prepared in the same manner as in the GREEN color material dispersion g except that 13 parts by mass of c.i. pigment yellow 150 (PY 150, trade name: LEVASCREEN YELLOW G, manufactured by LAXESS corporation) was used as a color material instead of 13 parts by mass of c.i. pigment GREEN 59 (PG 59, trade name fastagen GREEN C100DIC (manufactured by the trade name of fastagen corporation)) as a color material.

(2) Production of photosensitive colored resin composition IV-G35 for color Filter

5.63 parts by mass of the green material dispersion G obtained in the above (1), 1.22 parts by mass of the blue material dispersion b, 1.23 parts by mass of the yellow material dispersion y, 23.33 parts by mass of the yellow material dispersion y, 2.75 parts by mass of the alkali-soluble resin a solution obtained in synthesis example 9, 0.60 part by mass of a polyfunctional monomer (trade name aromix M-403, manufactured by eastern synthesis co., ltd.) and 2-methyl-1- (4-methylsulfanyl phenyl) -2-morpholinopropane-1-one (photoinitiator: A photosensitive colored resin composition IV-G35 for a color filter was obtained by using 0.09 parts by mass of IRGACURE907, manufactured by BASF, 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photo-initiator: IRGACURE369, manufactured by BASF), 0.02 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime) (photo-initiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA Co., ltd.), 0.07 parts by fluorine-based surfactant (trade name MEGAFACE F559, manufactured by DIC Co., ltd.), and 9.72 parts by PGMEA.

(3) Formation of colored layer

In example IV-1 (3), a colored layer IV-G35 was obtained in the same manner as in example IV-1 (3) except that the photosensitive colored resin composition IV-G35 was used instead of the photosensitive colored resin composition IV-G1.

The obtained photosensitive colored resin composition IV-G35 for a color filter had the same composition as the photosensitive colored resin composition IV-G1 for a color filter of example IV-1, and the evaluation results of the photosensitive colored resin composition IV-G35 for a color filter and the colored layer IV-G35 were the same as the evaluation results of the photosensitive colored resin composition IV-G1 for a color filter and the colored layer IV-G1.

[ evaluation method of example IV series ]

The optical performance evaluation and contrast evaluation were performed as follows. The dispersibility evaluation, the display failure evaluation, the solvent resolubility evaluation, the development residue evaluation, the development adhesion evaluation, the development resistance evaluation, and the water-bleeding evaluation of the color material dispersion were performed in the same manner as in the example II series.

< evaluation of optical Property, evaluation of contrast >

(contrast evaluation reference)

Let y=0.670 and x=0.210 for the C light source

A: over 8000

B：6000～8000

C: below 6000

[ results integration of example IV System ]

As is apparent from the results in tables 18 to 20, the viscosity stability of the color material dispersion liquid of the example in which the PG59 and the blue color material and the specific yellow color material were combined with the dispersant as the polymer having the constituent unit represented by the general formula (I) was good. On the other hand, the color material dispersions of comparative examples IV-C3 to IV-C4, in which the urethane-based dispersant and the polyester-based dispersant were combined with PG59, had significantly deteriorated viscosity stability. In addition, the color material dispersions of comparative examples IV-C1 and IV-C2, in which PG58 and PG36 are combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), were significantly inferior in viscosity stability to those of example IV-1. In addition, the dispersibility of the color material dispersion of comparative example IV-C2 in which PG36 was combined with a dispersant which was a polymer having a constituent unit represented by the general formula (I) was deteriorated.

As is apparent from table 18, the photosensitive colored resin compositions for color filters of examples IV-1 to IV-13 and IV-36, in which the blue color material, the specific yellow color material, and the dispersant which is the polymer having the structural unit represented by the general formula (I) were combined in PG59, exhibited a region of x=0.210 when y=0.670, and the occurrence of display failure was suppressed, so that a colored layer with high brightness was formed. The photosensitive colored resin compositions for color filters of examples IV-1 to IV-13 and IV-36 were excellent in color material dispersion stability, contrast, solvent resolubility, and further suppressed in development residue.

Among them, it is apparent that when a block copolymer comprising an A block containing a constituent unit represented by the above general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer and having solvophilicity is used as a dispersant; or a salt-type block copolymer which forms a salt with at least a part of the nitrogen site of the constituent unit represented by the general formula (I), particularly suppresses the occurrence of development residues, and is excellent in development adhesion (examples IV-1, IV-2, IV-6 to IV-13 and IV-36 in examples IV-1 to IV-13 and IV-36 having the same P/V ratio), wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more. In addition, example IV-10, which uses a carboxylic group-containing epoxy (meth) acrylate resin having a Cardo structure as an alkali-soluble resin in the photosensitive colored resin composition, was more excellent in development adhesion, development resistance and water penetration and hair dye growth inhibition effect than example IV-1.

In the examples, it is evident from the comparison of examples IV-1, IV-7, IV-8, IV-9 and IV-36 that the development resistance and the water penetration dye growth inhibition effect of the examples using the oxime ester photoinitiator as the photoinitiator are improved.

As is apparent from tables 19 and 20, when the blue color material and the specific yellow color material are combined in PG59 as a dispersant for a polymer having a constituent unit represented by the general formula (I), the color gamut is widened, and even when y=0.570 to 0.720, the chromaticity region of x=0.140 to 0.265 can be displayed, and further, the chromaticity region of y=0.750 can be displayed, and occurrence of display failure can be suppressed, and a colored layer having higher luminance than the conventional one can be formed.

In examples IV-29 of table 20, when PG59 was combined with the specific yellow color material and PG7 was further combined, the P/V ratio was significantly reduced and the brightness was also improved as compared with examples IV-28 in which the same color was obtained.

On the other hand, as shown in comparative example IV-C1, even if the blue color material and the specific yellow color material are combined as in the example, when PG58 is used, the region of x=0.210 can be displayed when y=0.670, but poor display occurs, and the luminance is inferior to that in the case where PG59 is used. In addition, development residues and development adhesion are also deteriorated. As shown in comparative example IV-C2, even if a blue color material and a specific yellow color material were combined as in the example, if PG36 was used, when y=0.670, the region of x=0.210 could be displayed, but poor display occurred and the luminance was low. In addition, even if the dispersant is combined as a polymer having a constituent unit represented by the general formula (I), the dispersibility is still poor, and therefore the contrast is low, and the resolubility, development residues, and development adhesion are also deteriorated.

On the other hand, in the photosensitive colored resin compositions for color filters of comparative examples IV-C3 to IV-C4 in which a blue color material and a specific yellow color material, and further a urethane-based dispersant and a polyester-based dispersant were combined in PG59, the dispersibility was deteriorated, and therefore, the brightness was lowered as compared with examples, the contrast was low, and the resolubility and development residues were also deteriorated.

As shown in comparative examples IV-C5, IV-C7 and IV-C10 in table 19, in the composition in which G58 was used, the blue color material was not combined, but the yellow color material was combined, the photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing chromaticity of x=0.200 and y=0.710 could not be prepared. In addition, in the combination of the color materials of comparative examples IV to C8 and IV to C9, the photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing chromaticity of x=0.200 and y=0.710 could not be prepared.

If the green color material is not used and the blue color material and the yellow color material are combined as in comparative examples IV to C6, chromaticity with a film thickness of 2.8 μm, x=0.200, and y=0.710 can be achieved, and no display failure occurs, but the luminance of comparative examples IV to C6 with a large amount of blue color material is significantly deteriorated to such an extent that a practical level cannot be achieved.

Symbol description

1. Transparent substrate

2. Light shielding part

3. Coloring layer

10. Color filter

20. Counter substrate

30. Liquid crystal layer

40. Liquid crystal display device having a light shielding layer

50. Organic protective layer

60. Inorganic oxide film

71. Transparent anode

72. Hole injection layer

73. Hole transport layer

74. Light-emitting layer

75. Electron injection layer

76. Cathode electrode

80. Organic light-emitting body

100. Organic light emitting display device

Claims

1. A color material dispersion liquid for a color filter, which is a color material dispersion liquid containing a color material, a dispersant and a solvent,

the color material includes c.i. pigment green 59 and a yellow color material,

the dispersant is a polymer having a constituent unit represented by the following general formula (I),

in the general formula (I), R ¹ Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R ² R is R ³ R is independently a hydrogen atom or a hydrocarbon group which may contain a hetero atom ² R is R ³ Can be bonded to each other to form a ring structure.

2. The color material dispersion liquid for color filters according to claim 1, wherein the dispersant is a block copolymer having a constituent unit represented by the general formula (I), and the amine value of the block copolymer is 40mgKOH/g or more and 130mgKOH/g or less.

3. The color material dispersion for a color filter according to claim 1 or 2, wherein at least a part of nitrogen sites at the ends of the constituent units represented by the general formula (I) in the dispersant form salts with 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3),

in the general formula (1), R ^a Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R ^b 、R ^b ' and R ^b "each independently represents a hydrogen atom, an acidic group or an ester group thereof, a C1-20 linear, branched or cyclic alkyl group which may have a substituent, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or-O-R ^f ，R ^f A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group which is bonded via an alkylene group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c R is R ^d Independently of each other, a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R ^e ，R ^e Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group bonded via an alkylene group having 1 to 4 carbon atoms; wherein R is ^c R is R ^d At least one of which contains a carbon atom.

4. The color material dispersion for a color filter according to claim 3, wherein the dispersant is a block copolymer containing a block A containing a constituent unit represented by the general formula (I) and a block B containing a constituent unit derived from a carboxyl group-containing monomer.

5. The color material dispersion for a color filter according to claim 3, wherein the dispersant has a glass transition temperature of 30 ℃ or higher.

6. The color material dispersion for a color filter according to claim 1, wherein the c.i. pigment green 59 is contained in an amount of 5 to 95% by mass in the color material.

7. The color material dispersion for a color filter according to claim 1, wherein the yellow color material is 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 185, c.i. pigment yellow 150, and derivative pigments thereof.

8. The color material dispersion liquid for color filter according to claim 1, wherein the yellow color material is a metal complex of mono-, di-, tri-and tetra-anions of azo compounds of the following chemical formula (i) or one of its tautomeric structures with a metal, is a derivative pigment of c.i. pigment yellow 150 containing Ni and Zn, or Ni and Cu as the metal,

(i)

In the chemical formula (i), R is independently-OH or-NH ₂ -NH-CN, acylamino or arylamino, R' are each independently-OH or-NH ₂ 。

9. The color material dispersion liquid for color filters according to claim 1, wherein the color material further comprises at least one of c.i. pigment green 58 and c.i. pigment green 7.

10. The color material dispersion for a color filter according to claim 1 or 2, wherein the color material contains c.i. pigment green 59, a blue color material, and a yellow color material, and the yellow color material is (Y1) at least 1 yellow color material containing c.i. pigment yellow 185, or (Y2) at least 2 yellow color materials containing c.i. pigment yellow 139 as an essential component, and further contains 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and derivative pigments thereof.

11. The color material dispersion liquid for color filters according to claim 10, wherein the blue color material contains at least one of c.i. pigment blue 15:3 and c.i. pigment blue 15:4.

12. A photosensitive coloring resin composition for a color filter, which comprises a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator and a solvent,

the color material includes c.i. pigment green 59 and a yellow color material,

the dispersant is a polymer having a constituent unit represented by the general formula (I),

13. The photosensitive colored resin composition for a color filter according to claim 12, wherein the dispersant is a block copolymer having a constituent unit represented by the general formula (I), and the block copolymer has an amine value of 40mgKOH/g or more and 130mgKOH/g or less.

14. The photosensitive colored resin composition for a color filter according to claim 12 or 13, wherein at least a part of nitrogen sites at the ends of the constituent units represented by the general formula (I) in the dispersant form salts with 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3),

15. The photosensitive colored resin composition for a color filter according to claim 14, wherein the dispersant is a block copolymer comprising a block a comprising the constituent unit represented by the general formula (I) and a block B comprising a constituent unit derived from a carboxyl group-containing monomer.

16. The photosensitive colored resin composition for a color filter according to claim 14, wherein the dispersant has a glass transition temperature of 30 ℃ or higher.

17. The photosensitive colored resin composition for a color filter according to claim 12, wherein the c.i. pigment green 59 is contained in an amount of 5 to 95% by mass in the color material.

18. The photosensitive colored resin composition for a color filter according to claim 12, wherein the yellow color material is 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 185, c.i. pigment yellow 150, and derivative pigments thereof.

19. The photosensitive colored resin composition for a color filter according to claim 12, wherein the yellow color material is a metal complex of mono-, di-, tri-and tetra-anions of an azo compound of the following chemical formula (i) or one of its tautomeric structures with a metal, is a derivative pigment of c.i. pigment yellow 150 containing Ni and Zn, or Ni and Cu as the metal,

(i)

20. The photosensitive colored resin composition for a color filter according to claim 12, wherein the color material further comprises at least one of c.i. pigment green 58 and c.i. pigment green 7.

21. The photosensitive colored resin composition for a color filter according to claim 12 or 13, wherein the color material contains c.i. pigment green 59, a blue color material, and a yellow color material, and the yellow color material is (Y1) at least 1 yellow color material containing c.i. pigment yellow 185, or (Y2) at least 2 yellow color materials containing c.i. pigment yellow 139 as an essential component, and further contains 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and a derivative pigment thereof.

22. The photosensitive colored resin composition for a color filter according to claim 21, wherein the blue color material comprises at least one of c.i. pigment blue 15:3 and c.i. pigment blue 15:4.

23. A color filter is characterized by comprising at least a transparent substrate and a coloring layer provided on the transparent substrate, and is provided with the following coloring layers:

At least one of the colored layers is a cured product of the photosensitive colored resin composition for a color filter according to any one of claims 12 to 22.

24. A liquid crystal display device comprising the color filter according to claim 23, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

25. An organic light-emitting display device comprising the color filter according to claim 23 and an organic light-emitting body.