JP6864341B2 - Pigment dispersion and coloring composition using phthalimide and its derivatives - Google Patents

Description

The present invention relates to a pigment dispersion and a coloring composition using phthalimide and a derivative thereof, and more particularly to a pigment dispersion used for a color filter provided in a flat panel of a display device and a coloring composition containing the same. is there.

Color filters are widely used as constituents of liquid crystal displays (LCDs) and the like. LCDs are widely used in display devices such as monitors, televisions, notebook personal computers, tablet personal computers, and smartphones. Higher image quality is required for these display devices. On the other hand, in recent years, there has been an increasing demand for reduction of power consumption from the viewpoint of global environmental protection. Therefore, the color filters that compose it are required to have high brightness, high contrast, and the like.

The color filter is produced by forming a coating film by a photolithography step using a colored photosensitive composition in which a colorant such as a red, green or blue dye or pigment is dissolved or dispersed in a photosensitive resin as a coating liquid. Is widely practiced. As described above, as a method for improving the image quality of the color filter, it is conceivable to improve the color purity by increasing the concentration of the dye or pigment in the colored photosensitive composition. However, in this case, the light transmittance due to the backlight of the LCD decreases, so that the power consumption increases. Further, in order to achieve high contrast, it is conceivable to eliminate the large particle size particles of the pigment and disperse the pigment as small particle size particles below the wavelength of light in the colored photosensitive composition. However, the smaller the particle size, the easier it is for the pigment to agglomerate, and it tends to be difficult to uniformly disperse the pigment in the colored photosensitive composition. Therefore, there is a demand for the development of a pigment capable of realizing a high-brightness, high-contrast color filter capable of expressing the same brightness with a smaller amount of light than before without increasing the concentration of the pigment or the like. Then, a color filter formed by using such a pigment has been proposed (Patent Document 1).

For example, by using a pigment as disclosed in Patent Document 1, high brightness and high contrast of the color filter can be expected to some extent. However, in general, it is not easy to uniformly disperse the pigment in the colored photosensitive composition. Therefore, for example, a dispersant or a pigment derivative is used as a component constituting the colored photosensitive composition, or a surface-treated pigment is used. Generally, the method of squeezing is adopted. Since the characteristics of these components are related to the dispersibility of the pigment, it is considered that the selection thereof has a corresponding effect on the performance of the color filter.

By the way, as described above, it is widely practiced that a color filter is produced by forming a coating film by a photolithography process. Therefore, a resist composition having good properties as a resist has been proposed (Patent Document 2). Patent Document 2 describes that it is preferable to contain a basic compound for the purpose of suppressing the diffusion rate of acid in the resist film, further improving the resolution, suppressing the change in sensitivity after exposure, and the like. Has been done. Further, it is described that an imide derivative such as phthalimide can be used as the basic compound.

Further, the imide derivative may be used for ink jet ink and recording ink (Patent Documents 3 and 4). Patent Document 3 describes that a hydroxyamide derivative is used in order to have a long waiting time and long-term ejection stability when used in a thermal inkjet printer, and a phthalimide derivative is described as a specific example of the hydroxyamide derivative. ing. Patent Document 4 describes that a recording ink containing water and polyvinylpyrrolidone contains a substance having a pyrrolidone ring in order to prevent a hydration phenomenon between water and polyvinylpyrrolidone. As a specific example thereof, phthalimide is described. Is illustrated.

Japanese Unexamined Patent Publication No. 2016-38584 Japanese Unexamined Patent Publication No. 2006-251296 Japanese Unexamined Patent Publication No. 10-204359 Japanese Unexamined Patent Publication No. 7-331146

The present inventor is a phthalocyanine-based green pigment C.I., manufactured by DIC Corporation, which is a pigment disclosed in Patent Document 1. I. Pigment Green 59 was used to prepare a pigment dispersion containing a dispersant and a solvent and a coloring composition using the same, and a coating film was formed using the coloring composition. It was found that the contrast of the film was lower than that immediately after preparation. In addition, C.I. I. When the same procedure was carried out using another phthalocyanine pigment instead of Pigment Green 59, the viscosity of the pigment dispersion increased when the pigment dispersion was allowed to stand for a certain period of time, which made it difficult to handle when preparing the coloring composition. Was found to occur.

Therefore, an object of the present invention is to suppress an increase in viscosity after preparing a pigment dispersion and to prepare a coloring composition containing the same, regardless of the type of phthalocyanine pigment. An object of the present invention is to provide a pigment dispersion capable of suppressing a decrease in contrast and a coloring composition containing the same.

As a result of diligent studies by the present inventor, it has been found that the above problems can be solved by using phthalimide and a specific phthalimide derivative, and the present invention has been completed. The gist of the present invention is as follows.

（式（１）中、Ｒ¹〜Ｒ⁴は、水素原子又はハロゲン原子であり、Ｑは、（ｉ）水素原子、（ii）末端の炭素原子に結合する置換基Ｘを有してもよい炭素数１〜５のアルキル基又は（iii）芳香環の炭素原子に結合する置換基Ｙを有してもよいアリール基であり、置換基Ｘは、アセチル基、カルボキシル基、リン酸基又はスルホン基であり、置換基Ｙは、メチル基、アセチル基、カルボキシル基、リン酸基又はスルホン基である。） The first aspect of the present invention relates to a pigment dispersion containing at least one selected from phthalimide represented by the following formula (1) and a derivative thereof, a phthalocyanine pigment, a dispersant, and a solvent.

(In the formula (1), R ^{1 to} R ⁴ are hydrogen atoms or halogen atoms, and Q may have a substituent X bonded to (i) a hydrogen atom and (ii) a terminal carbon atom. It is an alkyl group having 1 to 5 carbon atoms or an aryl group which may have a substituent Y bonded to a carbon atom of the (iii) aromatic ring, and the substituent X is an acetyl group, a carboxyl group, a phosphoric acid group or a sulfone. It is a group, and the substituent Y is a methyl group, an acetyl group, a carboxyl group, a phosphate group or a sulfone group.)

In a preferred embodiment of the present invention, the phthalocyanine pigment is a metallic phthalocyanine pigment. Further, a zinc phthalocyanine pigment or a copper phthalocyanine pigment is more preferable. Further, a more preferable embodiment of the zinc phthalocyanine pigment is a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 2 or more, and particularly preferably, an average hydrogen atom contained in the one molecule. It is a halogenated zinc phthalocyanine pigment having a number of 2 or more, and most preferably a chlorinated brominated zinc phthalocyanine pigment.

In a preferred embodiment of the present invention, Q in the formula (1) is (ii) an alkyl group having 2 carbon atoms having a substituent X bonded to a terminal carbon atom, and the substituent X is a carboxyl group or a carboxyl group. It is a phosphate group.

The second aspect of the present invention relates to a coloring composition containing the pigment dispersion and a coating film-forming component. In a preferred embodiment of the present invention, the coating film forming component includes a photopolymerizable component.

According to the present invention, regardless of the type of phthalocyanine pigment, an increase in viscosity after preparing a pigment dispersion is suppressed, and a decrease in contrast of a coating film after preparing a coloring composition containing the pigment dispersion is suppressed. Will be done.

Hereinafter, embodiments of the present invention will be described.

（式（１）中、Ｒ¹〜Ｒ⁴は、水素原子又はハロゲン原子であり、Ｑは、（ｉ）水素原子、（ii）末端の炭素原子に結合する置換基Ｘを有してもよい炭素数１〜４のアルキル基又は（iii）芳香環の炭素原子に結合する置換基Ｘを有してもよいアリール基であり、置換基Ｘは、アセチル基、カルボキシル基、リン酸基又はスルホン基であり、置換基Ｙは、メチル基、アセチル基、カルボキシル基、リン酸基又はスルホン基である。） The embodiment of the pigment dispersion according to the present invention contains at least one selected from phthalimide and its derivatives represented by the following formula (1), a phthalocyanine pigment, a dispersant, and a solvent.

(In the formula (1), R ^{1 to} R ⁴ are hydrogen atoms or halogen atoms, and Q may have a substituent X bonded to (i) a hydrogen atom and (ii) a terminal carbon atom. It is an alkyl group having 1 to 4 carbon atoms or an aryl group which may have a substituent X bonded to a carbon atom of the (iii) aromatic ring, and the substituent X is an acetyl group, a carboxyl group, a phosphoric acid group or a sulfone. It is a group, and the substituent Y is a methyl group, an acetyl group, a carboxyl group, a phosphate group or a sulfone group.)

By using the phthalocyanine pigment in combination with at least one selected from the phthalimide represented by the formula (1) and a specific phthalimide derivative in this way, the mechanism of action is not clear, but the type of phthalocyanine pigment can be selected. Therefore, an increase in viscosity after preparation of the pigment dispersion can be suppressed, and a decrease in contrast of the coating film after preparation of the coloring composition containing the pigment dispersion can be suppressed.

(Ii) The alkyl group having 1 to 5 carbon atoms which may have a substituent X bonded to the terminal carbon atom is not particularly limited, and is an alkyl group having 1 to 5 carbon atoms or a terminal carbon atom. It may be an alkyl group having 1 to 5 carbon atoms having a substituent X bonded to. That is, methyl group (-CH ₄ ), ethyl group (-C ₂ H ₅ ), propyl group (-C ₃ H ₇ ), butyl group (-C ₄ H ₉ ), pentyl group (-C ₅ H ₁₁ ), −CH ₂ −X, −C ₂ H ₄ −X, − (C ₂ H ₄ ) CH ₂ −X, − (C ₃ H ₆ ) CH ₂ −X, − (C ₄ H ₈ ) CH ₂ −X, Anything is fine. The butyl group and the pentyl group may be linear or branched. Of these, alkyl groups having 1 to 4 carbon atoms are preferable, and alkyl groups having 1 to 3 carbon atoms are more preferable, from the viewpoint of further exerting the effect of suppressing the increase in viscosity of the pigment dispersion and the effect of suppressing the decrease in contrast of the coating film. Preferably, an alkyl group having 1 to 2 carbon atoms is more preferable, and an alkyl group having 2 carbon atoms is particularly preferable.

In the case of (ii), the substituent X is preferably an acetyl group, a carboxyl group, a phosphoric acid group or a sulfone group. Of these, an acetyl group, a carboxyl group, and a phosphoric acid group are more preferable, and a carboxyl group and a phosphoric acid group are further preferable, from the viewpoint of further exerting the effect of suppressing the increase in viscosity of the pigment dispersion and the effect of suppressing the decrease in contrast of the coating film. preferable.

(Iii) The aryl group which may have the substituent Y bonded to the carbon atom of the aromatic ring is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is preferable. Is more preferable. Specific examples of the rings constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a pyrene ring, a naphthalene ring, and a biphenyl ring. It may be linked), a terphenyl ring (three phenyl groups may be linked in any linking mode), and the like. In the case of (iii), the substituent Y is preferably a methyl group, an acetyl group, a carboxyl group, a phosphoric acid group or a sulfone group. Further, it is preferable that the substituent has no functional group other than these. The position and number of the substituent Y are not particularly limited.

In the embodiment, at least one selected from the phthalimide represented by the above formula (1) and its derivative can be used. Of these, from the viewpoint of further exerting the effect of suppressing the increase in viscosity of the pigment dispersion and the effect of suppressing the decrease in contrast of the coating film, Q in the formula (1) is (i) a hydrogen atom or (ii) a terminal carbon. It is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent X bonded to an atom, and (ii) an alkyl group having 1 to 4 carbon atoms having a substituent X bonded to a terminal carbon atom. It is more preferable that the substituent X is a carboxyl group or a phosphate group, and (ii) it is an alkyl group having 1 to 2 carbon atoms having a substituent X bonded to a terminal carbon atom, and the substituent X is. It is more preferably a carboxyl group or a phosphate group, (ii) an alkyl group having 2 carbon atoms having a substituent X bonded to a terminal carbon atom, and the substituent X is a carboxyl group or a phosphate group. Is particularly preferable.

(Ii) Specific examples of an alkyl group having 1 to 2 carbon atoms having a substituent X bonded to a terminal carbon atom and the substituent X being a carboxyl group or a phosphoric acid group are −CH ₂ COOH, −. C ₂ H ₄ COOH, −CH ₂ −OPO (OH) ₂ , and −C ₂ H ₄ −OPO (OH) ₂ .

In the formula (1), R ^{1 to} R ⁴ may be hydrogen atoms or halogen atoms, but according to the results of the study by the present inventor, suitable combinations tend to differ depending on the type of Q. For example, when Q is -CH ₂ COOH, it contributes to suppressing the decrease in contrast of the coating film of the coloring composition when ^{R 1 to} R ⁴ _{are hydrogen atoms, and when Q is -C 2} H ₄ COOH, it contributes to suppressing the decrease in contrast. When R ^{1 to} R ⁴ are halogen atoms, they tend to contribute to the improvement of the contrast. When ^{any of R 1 to} R ⁴ is a halogen atom, the number substituted with the halogen atom and which of R ^{1 to} R ⁴ is a halogen atom is not particularly limited. The halogen atom is not particularly limited, but a chlorine atom and a bromine atom are preferable from the viewpoint of suppressing the increase in viscosity of the pigment dispersion and suppressing the decrease in contrast of the coating film of the coloring composition. As the halogen atoms, ^{all of R 1 to} R ⁴ may be the same, or any of them may be different.

The content in at least one pigment dispersion selected from the phthalimide represented by the formula (1) and its derivative is not particularly limited, but is preferably 2 to 10 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment. ~ 6 parts by weight is more preferable.

Commercially available phthalimides can be used. The phthalimide derivative can be produced by a conventionally known method. Alternatively, a commercially available product may be used.

The phthalocyanine pigment is not particularly limited, but a metal phthalocyanine pigment is preferable from the viewpoint of easily enjoying the effects of suppressing an increase in the viscosity of the pigment dispersion and suppressing a decrease in the contrast of the coloring composition. The metal phthalocyanine pigment is composed of a complex in which a metal ion is coordinated in the central portion of the phthalocyanine and a derivative thereof. The metal that can be a coordinating metal ion may be any metal that is common in the art. For example, copper, zinc, vanadium, chromium, manganese, iron, and cobalt are used to form a stable coordination bond. , Nickel, platinum and the like. Of these, zinc and copper are preferable. That is, as the metal phthalocyanine pigment, zinc phthalocyanine pigment and copper phthalocyanine pigment are more preferable.

Further, the phthalocyanine pigment may be a halogen derivative in which at least one of the hydrogen atoms bonded to the benzene ring of phthalocyanine is replaced with a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferable. The halogen atom may be one kind or two or more kinds. It can be appropriately selected according to the desired color.

As the zinc phthalocyanine pigment, a halogenated zinc phthalocyanine pigment is preferable. As such a halogenated zinc phthalocyanine pigment, for example, those described in Patent Document 1 can be used. The outline of the contents is as follows.

Zinc phthalocyanine has 16 hydrogen atoms in one molecule, and the halogenated zinc phthalocyanine pigment is obtained by substituting these hydrogen atoms with halogen atoms such as chlorine atom and bromine atom. Of these, chlorinated brominated zinc phthalocyanine pigments are preferable.

The content ratio of chlorine atoms in the halogenated zinc phthalocyanine pigment is preferably 3.5% by mass or more and 30% by mass or less. The lower limit is more preferably 3.8% by mass or more, further preferably 4.0% by mass or more, and even more preferably 4.3% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 6% by mass or less. The content of halogen atoms contained in the halogenated zinc phthalocyanine pigment is determined by dissolving the pigment in ethyl benzoate and then burning it in a combustion device to absorb the combustion gas into a hydrogen peroxide absorbing solution and ion in the absorbing solution. Can be measured by the combustion gas-ion chromatography method.

The number of chlorine atoms contained in the 16 substituents present in one molecule of the zinc halide phthalocyanine pigment is not particularly limited, but is preferably 1 or more and 14 or less. As the lower limit, it is more preferably two or more, and further preferably three or more. The upper limit is more preferably 10 or less, further preferably 6 or less, and particularly preferably 4 or less. The content of chlorine atoms in one molecule of the pigment is an average value calculated from the average value of the average molecular weight measured by the LDI-MS method described later and the content ratio of chlorine atoms measured by the combustion gas-ion chromatography method described above. Is.

When the halogenated zinc phthalocyanine pigment is a brominated chlorinated zinc phthalocyanine pigment, the molar content ratio of chlorine atoms to the molar content ratio of bromine atoms in one molecule of the pigment is not particularly limited, but is 0.1 or more and 7 or less. Is preferable. The lower limit is more preferably 0.12 or more, further preferably 0.15 or more, and even more preferably 0.2 or more. The upper limit is more preferably 3 or less, further preferably 1 or less, further preferably 0.5 or less, and particularly preferably 0.3 or less.

The content ratio of the bromine atom in the halogenated zinc phthalocyanine pigment is preferably 30% by mass or more and 80% by mass or less. As the lower limit, it is more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more. The upper limit is more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less.

The number of bromine atoms contained in the 16 substituents present in one molecule of the zinc halide phthalocyanine pigment is not particularly limited, but is preferably 5 or more and 15 or less. The lower limit is more preferably 8 or more. The upper limit is more preferably 13 or less, further preferably 12 or less, further preferably 11 or less, and particularly preferably 10 or less. The average number of bromine atoms contained in one molecule of the pigment is an average value calculated in the same manner as in the case of the chlorine atom.

The average number of hydrogen atoms contained in one molecule of the zinc halide phthalocyanine pigment is not particularly limited, but is preferably 2 or more and 14 or less. As the lower limit, it is more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and most preferably 6 or more. The upper limit is more preferably 12 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 7 or less. The average number of hydrogen atoms in one molecule of zinc phthalocyanine halogenated pigment contains the average value of the average molecular weight measured by the LDI-MS method described later and the bromine atom and the chlorine atom measured by the combustion gas-ion chromatography method described above. It is an average value calculated from the ratio. Details can be obtained by the following procedure.

First, the average molecular weight is measured by a laser desorption / ionization (LDI) -mass spectrometry (MS). The average molecular weight is measured four times, and the average value of the four measurement results is taken (hereinafter, abbreviated as "average value of average molecular weight").
Next, the chlorine atom content ratio [mass%] and the bromine atom content ratio [mass%] in the pigment are measured by a combustion gas-ion chromatography method. The average number of chlorine atoms and the average number of bromine atoms in one molecule of the pigment are calculated from the average value of the average molecular weight, the chlorine atom content ratio and the bromine atom content ratio. Since the number of sites occupied by chlorine atoms, bromine atoms, and hydrogen atoms in zinc phthalocyanine is 16, the average number of hydrogen atoms can be obtained by calculating the remaining sites not occupied by chlorine atoms and bromine atoms.

Such a halogenated zinc phthalocyanine pigment can be produced by a known method. Further, a commercially available pigment, a green pigment "G59" manufactured by DIC Corporation, can be used.

The copper phthalocyanine pigment can be used without particular limitation. An example of the color index number is as follows.
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 17: 1,
C. I. Pigment Green 7, 36.

The content of the phthalocyanine pigment contained in the pigment dispersion is preferably 8 to 18% by weight, more preferably 10 to 16% by weight.

The pigment dispersion may contain other pigments in addition to the phthalocyanine pigment. As such other organic pigments, when indicated by a color index number, for example, C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 36, 37, 40, 41, 42, 43, 48, 53, 55, 61, 62, 63, 65, 73, 74, 75, 81, 83, 108, 109, 110, 111, 120, 125, 126, 129, 133, 138, 139, 142, 150, 151, 153, 154, 155, 158, 160, 162, 164, 165, 168, 169, 170, 172, 174, 175, 176, 180, 181, 182, 183, 184, 185, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23. In addition, a dye may be added if necessary.

The content of pigments other than the phthalocyanine pigment can be appropriately determined depending on the intended purpose. Generally, it is 1 to 8 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment.

The average particle size (average primary particle size) of the primary particles of the phthalocyanine pigment can be appropriately adjusted within a range that does not affect the contrast or the like. The average primary particle size is preferably 10 to 100 nm, more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. The primary particle size can be measured, for example, from an image of a pigment taken with a transmission electron microscope at a magnification of 100,000. As for the average primary particle size, for example, 100 particles can be measured and the average value thereof can be used as the average primary particle size.

In the embodiment of the present invention, depending on the type of pigment, milling treatment may be performed in advance from the viewpoint of adjusting the average primary particle size. The milling treatment can be carried out according to a standard method according to the type of pigment and the like. Examples of such a milling treatment include a solvent salt milling method and the like.

Examples of the dispersant include a resin-type dispersant and a surfactant-type dispersant. Further, the resin type dispersant is an acid value type dispersant having an amine value of 0 and an acid value greater than 0 due to the difference between the acid value and the amine value of the resin, and an acid value of 0 and an amine value of 0 or more. There are large amine-valued dispersants and dispersants with an acid value and amine value greater than zero.

Examples of the resin type dispersant include polyurethane; polyester; unsaturated polyamide; phosphoric acid ester; polycarboxylic acid and its amine salt, ammonium salt, alkylamine salt; polycarboxylic acid ester; hydroxyl group-containing polycarboxylic acid ester; polysiloxane; Modified polyacrylate; water-soluble polymer compounds such as alginic acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinylpyrrolidone, and gum arabic; styrene-acrylic acid resin, styrene-methacrylate resin, styrene-acrylic Acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene-maleic acid resin, vinyl-ester resin, rosin-modified malein Examples thereof include ethylenic double bond-containing resins such as acid resins; amine-based resins such as polyallylamine, polyvinylamine, and polyethyleneimine; and the like.

Among the resin-type dispersants, those having a tertiary amino group are preferable from the viewpoint of further exerting the effect of suppressing the increase in viscosity of the pigment dispersion and the effect of suppressing the decrease in contrast of the coating film.

As the resin type dispersant, a commercially available one can be used. Specific examples of commercially available products are as follows, but are not limited thereto.
Made by Japan Lubrizol Co., Ltd .: Solspers 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000,
Made by Big Chemie Japan Co., Ltd .: Disperbyk 108, 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2050, 2070, 2150, LPN6919, LPN22101, LPN21116,
Made by BASF: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244,
Ajinomoto Fine Techno Co., Ltd .: Ajispar-PB821 (F), PB822, PB880,
Kawaken Fine Chemical Co., Ltd .: Hinoact T-8000,
Kusumoto Kasei Co., Ltd .: Disparon PW-36, Disparon DA-325, 375, 7301,
Made by Otsuka Chemical Co., Ltd .: TERPLUS D2015, etc.

The molecular weight of the resin-type dispersant is not particularly limited, but the weight average molecular weight is preferably 1000 to 100,000.

The acid value and amine value of the resin-type dispersant are determined by the functional groups contained in the resin constituting the resin-type dispersant and their contents. The acid value (acid value when converted to solid content) can be determined, for example, by a method conforming to DIN EN ISO 2114, and the amine value (amine value when converted to solid content) can be determined, for example, DIN 16945. It can be obtained by a method conforming to. The acid value of the acid value type dispersant is not particularly limited, but is preferably 20 to 150 mgKOH / g, and the amine value of the amine value type dispersant is not particularly limited, but is preferably 5 to 30 mgKOH / g. In the case of a dispersant having an acid value and an amine value greater than 0, the acid value is preferably 5 to 50 mgKOH / g, and the amine value is preferably 5 to 50 mgKOH / g, although there is no particular limitation.

Surfactant-type dispersants include anion activators (anion type) such as naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, and polyoxyethylene, depending on the ionicity. Examples thereof include nonionic activators such as alkyl ethers (nonionic type), cationic activators such as alkylamine salts and quaternary ammonium salts (cationic type). Various surfactant-type dispersants are commercially available, and specific examples thereof are as follows, but the present invention is not limited to these.
Made by Kao Corporation: Demor N, RN, MS, SN-B, Emargen 120, 430, Acetamine 24, 86, Cotamine 24P,
Made by Nikko Chemicals Co., Ltd .: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25,
Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Pricesurf AL, A208F,
Made by Lion Corporation: Alucard C-50, T-28, T-50, etc.

The above-mentioned dispersants may be used alone or in combination of two or more. When combining two or more types, for example, in the case of resin-type dispersants, those with different resins are combined, in the case of surfactant-type dispersants, those with different ionicity are combined. (For example, anion type and nonion type, etc.) can be combined, and the like, but the present invention is not limited to these.

The content (solid content or active ingredient) of the dispersant in the pigment dispersion is 2 to 20 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment (the total of other pigments if included) from the viewpoint of dispersion stability. Is preferable, and 5 to 10 parts by weight is more preferable. However, the optimum amount of the dispersant added may be appropriately adjusted depending on the combination with the type of pigment used. When a pigment derivative described later is used, the content of the phthalocyanine pigment means the total amount including the pigment derivative.

In the embodiment of the present invention, in addition to the above-mentioned dispersant, a pigment derivative may be used as a dispersion aid in order to disperse the phthalocyanine pigment more stably in the pigment dispersion. When a pigment derivative is used, a portion having an affinity with the dispersant or a pigment derivative having a polar group introduced therein is adsorbed on the surface of each pigment, and this can be an adsorption point of the dispersant. In that case, since the dispersant can be present on the pigment surface via the pigment derivative, each pigment can be more stably dispersed in the pigment dispersion as fine particles. In addition, the reaggregation can be prevented more effectively.

Specifically, the pigment derivative is a compound in which a pigment is used as a parent skeleton and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specifically, the pigments that form the parent skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazoles. Ron pigments, dioxazine pigments and the like can be mentioned. The maternal skeleton also includes pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline, which are not generally called pigments.

Examples of the pigment derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-1997. No., JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210 and the like can be used.

From the viewpoint of dispersion stability, the content (solid content) of the pigment derivative in the pigment dispersion is preferably 2 to 15 parts by weight based on 100 parts by weight of the total of the phthalocyanine pigment and the pigment contained as necessary. 10 parts by weight is more preferable. However, the optimum amount of the pigment derivative added may be appropriately adjusted depending on the combination with the type of pigment and dispersant used. The total amount of 100 parts by weight of "phthalocyanine pigment and pigment contained as needed" means the total amount not containing the pigment derivative.

As the pigment dispersion, a dispersion resin may be used as a dispersion aid in addition to the above-mentioned dispersant from the viewpoint of further improving the dispersibility of the phthalocyanine pigment and the like in the pigment dispersion and the coloring composition. Such a dispersed resin is particularly preferably used when the coating film-forming component used in the coloring composition described later contains a polymerizable component, particularly a photopolymerizable component. Examples of such a dispersed resin include alkali-soluble resins described later. The dispersed resin may be the same type of resin as the alkali-soluble resin used in the coloring composition, or may be a different type of resin. The content of the dispersed resin is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment (the total of other pigments, if any). When a pigment derivative is used, the content of the phthalocyanine pigment (the total amount when other pigments are contained) means the total amount including the pigment derivative.

The solvent can be appropriately selected depending on the type of coating film-forming component described later, and for example, various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic. Examples include solvents. Of these, from the viewpoint of coating film forming property, an organic solvent selected from aromatics, ketones, esters, and glycol ethers is preferable. The organic solvent may be only one kind or a combination of two or more kinds.

Examples of the aromatic organic solvent include aromatic hydrocarbons such as toluene, xylene and ethylbenzene.

Examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, cyclohexanone and the like.

Examples of the ester-based organic solvent include ethyl acetate, -n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate (PMA), and propylene. Glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypro Pionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butylene glycol diacetate and the like can be mentioned.

Examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and ethylene glycol mono-iso-. Propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-Methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl Water-soluble such as ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, etc. Glycol ethers,
Ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, Examples thereof include water-insoluble glycol ethers such as propylene glycol methyl ether propionate.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol and isopropanol.
Ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butane-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene Glycol, polyethylene glycol with a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol , Glycerin, mesoerythritol, pentaerythritol and the like.

Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

When used in the preparation of the coloring composition described later, the amount of the solvent added can be adjusted so that the solid content concentration containing the phthalocyanine pigment or the like is 50 to 85% by weight from the viewpoint of handleability.

The pigment dispersion may contain other additives in addition to the above-mentioned components.

The pigment dispersion can be obtained, for example, by adding each of the above-mentioned components to a known disperser such as a bead mill, a sand mill, or a disper and dispersing the pigment dispersion. That is, the pigment dispersion is a dispersion in which solid contents such as a phthalocyanine pigment are dispersed as particles in a solvent. Here, the particles mean secondary particles formed by agglomeration of the above-mentioned phthalocyanine pigment and primary particles of other pigments contained as needed.

The average particle size of the particles dispersed in the pigment dispersion obtained as described above (hereinafter, may be referred to as “dispersion average particle size”) is not particularly limited, but is approximately 30 to 300 nm. Can be preferably used. Further, from the viewpoint of surface smoothness of the coating film, the dispersed average particle size is more preferably 30 to 150 nm. The dispersed average particle size can be measured by, for example, a particle size measuring machine. Examples of the particle size measuring machine include FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.

<Coloring composition>
Embodiments of the coloring composition according to the present invention include the above-mentioned pigment dispersion and coating film forming component. By including the above-mentioned pigment dispersion in this way, it is possible to suppress a decrease in the contrast of the coating film after preparing the coloring composition. Further, since the increase in viscosity after the preparation of the pigment dispersion is suppressed, the pigment dispersion can be easily handled and the coloring composition can be easily prepared.

The coating film-forming component is not particularly limited as long as it is a component capable of forming a coating film, and may be a polymerizable component, a polymer, or a mixture thereof. As the polymerizable component, a photopolymerizable component is preferable because patterning can be easily performed by development (negative development). Examples of the polymer include thermoplastic urethane resin, (meth) acrylic resin, polyamide resin, polyimide resin, styrene / maleic acid resin, polyester resin, silicone resin, cardo resin and the like. .. The molecular weight of the polymer can be determined as appropriate.

The photopolymerizable component that can be used includes a photopolymerizable compound and a photopolymerization initiator. As such a photopolymerizable compound and a photopolymerization initiator, those described in JP-A-2009-179789 can be used, for example. More specifically, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Is selected from. Such a group of compounds is widely known in the art, and these can be used without particular limitation in the present invention. Photopolymerizable compounds have chemical forms such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

Examples of the monomer and its copolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferable. Is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, and a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of amides with monofunctional or polyfunctional alcohols, amines, thiols, a halogen group, and the like. , An unsaturated carboxylic acid ester having a desorbing substituent such as a tosyloxy group or a substitution reaction product of amides with monofunctional or polyfunctional alcohols, amines and thiols is also suitable. Further, as another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like.

Specific examples of these are generally as described in JP-A-2009-179789, but specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid ester. , Ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propanetri (acryloyl) Oxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate Acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, EO-modified triacrylate of isocyanurate. And so on.

The details of the structure of these addition-polymerizable compounds, whether they are used alone or in combination, and how they are used, such as the amount of addition, can be arbitrarily set according to the performance design of the final coloring composition.
For example, it is selected from the following viewpoints. In terms of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, bifunctionality or higher is preferable. Further, in order to increase the strength of the cured film, a trifunctional or higher functional group is preferable, and further, a different functional number and a different polymerizable group (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) It is also effective to adjust both the sensitivity and the intensity by using the same compound.

In addition, the addition polymerization compound is selected with respect to the compatibility and dispersibility with other components in the coloring composition (for example, a binder polymer such as an alkali-soluble resin, a photopolymerization initiator, and a coloring agent (pigment)). The usage is an important factor, and for example, the compatibility may be improved by using a low-purity compound or by using two or more kinds in combination.

In addition, a specific structure may be selected for the purpose of improving the adhesion to the base material or the like. The photopolymerizable compound is preferably contained in an amount of 5 to 70% by weight, more preferably 10 to 60% by weight, based on the non-volatile component in the coloring composition. In addition, these may be used alone or in combination of two or more. In addition, as for the usage of the photopolymerizable compound, an appropriate structure, composition, and addition amount can be arbitrarily selected from the viewpoints of the magnitude of polymerization inhibition with respect to oxygen, resolution, fog, change in refractive index, surface adhesiveness, and the like.

As the photopolymerization initiator, those described in JP-A-2009-179789 can be used.
For example, acetophenone-based, ketal-based, benzophenone-based, benzoin-based, benzoyl-based, xanthone-based, active halogen compounds (triazine-based, oxadiazole-based, coumarin-based), acridine-based, biimidazole-based, oxime ester-based, and the like.
Specific examples of these specific examples of the benzophenone-based photopolymerization initiator include, for example, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-. Examples thereof include dichlorobenzophenone.

The content of the photopolymerization initiator in the coloring composition is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, based on the total solid content of the coloring composition. Is. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed satisfactorily and a film having good strength can be formed.

When the coloring composition contains a photopolymerizable component as a coating film-forming component, an alkali-soluble resin may be contained in addition to the pigment dispersion and the photopolymerizable component described above.

When an alkali-soluble resin is contained in the coloring composition, the pattern forming property can be further improved when the coloring composition is applied to pattern formation, for example, in a photolithography step.

As such an alkali-soluble resin, those described in JP-A-2009-179789 can be used. Briefly, the alkali-soluble resin is, for example, a linear organic polymer polymer, and at least in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from the alkali-soluble resins having one group that promotes alkali solubility (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Of these, more preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

Suitable alkali-soluble resins include, in particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith. Here, (meth) acrylic acid is a general term for a combination of acrylic acid and methacrylic acid, and similarly, (meth) acrylate is a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Here, the hydrogen atoms of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth). Examples include meta) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer, and CH. ₂ = CR ⁵ R ⁶ , CH ₂ = C (R ⁵ ) (COOR ⁷ ) (where R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ is an aromatic having 6 to 10 carbon atoms. It represents a group hydrocarbon ring, and R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.)

These other copolymerizable monomers may be used alone or in combination of two or more.

The weight average molecular weight of the alkali-soluble resin is preferably 5000 to 50,000 from the viewpoint of developability.

Various alkali-soluble resins are commercially available, and specific examples thereof are as follows, but the present invention is not limited thereto.
Showa High Polymer Co., Ltd .: Lipoxy SPC-2000,
Made by Mitsubishi Rayon Co., Ltd .: Diamond NR series,
Diamond hamlock Co., Ltd. Ltd. , Made by: Photomer 6173 (COOH-containing Polyurethane carboxylic acidomer),
Made by Osaka Organic Chemical Industry Co., Ltd .: Viscort R-264, KS resist 106, SOP-005,
Made by Daicel Chemical Industry Co., Ltd .: Cyclomer P series, Praxel CF200 series,
Daicel UCB Co., Ltd .: Ebeclyl 3800,
Nippon Shokubai Co., Ltd .: Acrycure (registered trademark) RD-Y-503, RD-Y-702-A, etc.

The content of the alkali-soluble resin in the coloring composition is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, and particularly preferably 3 to 3 to 20% by weight, based on the total solid content of the coloring composition. It is 12% by weight. When it is contained as a dispersion resin in the pigment dispersion, it is the total amount.

When the coloring composition contains a photopolymerizable component as a coating film-forming component, a solvent may be contained in addition to the pigment dispersion, the photopolymerizable component, and the alkali-soluble resin described above. It can be suitably prepared by using a solvent.

Examples of such a solvent include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, 3-oxypropionate 3-Oxypropionate alkyl esters such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc .; Heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene; and the like.
The solvent may be used alone or in combination of two or more.

As for the content of the solvent in the coloring composition, the total solid content (nonvolatile component) content in the coloring composition is 15 to 50% by weight in consideration of the type and content of the solvent in the pigment dispersion. It is preferable to be contained in.

When a polymer is used as the coating film-forming component, a solvent may be used in the same manner as when a photopolymerizable component is used. As such a solvent, one that can be used in the above-mentioned pigment dispersion and one that can be used together with a photopolymerizable component can be used.

Also in this case, as the content of the solvent in the coloring composition, the total solid content (nonvolatile component) content in the coloring composition is 15 to 50% by weight in consideration of the type and content of the solvent in the pigment dispersion. It is preferably contained so as to be%.

If necessary, the coloring composition includes a dispersion aid, a sensitizer (sensitizer), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a surfactant, and an adhesion promotion. Various additives such as an agent, an antioxidant, an antioxidant, and a surface conditioner (leveling agent) may be added. When it is contained in the pigment dispersion, the addition amount may be adjusted.

The coloring composition is obtained by adding a coating film-forming component to the pigment dispersion and stirring with a disper or the like.

The coating film formed by using the coloring composition can suppress a decrease in contrast after preparing the coloring composition. Therefore, the coloring composition containing the pigment dispersion described above is suitable for forming a color filter.

Examples, comparative examples, reagents used in the control, etc., which will be described later, are as follows.

(1) Pigments ・ C.I. I. Pigment Green 59
Product name "FASTOGEN GREEN C100" (referred to as "C100" in the table), manufactured by DIC Corporation. It is a chlorinated brominated zinc phthalocyanine pigment, and has an average number of hydrogen atoms contained in one molecule of 2 or more.
・ C. I. Pigment Blue 15: 6
Product name CYANINE BLUE A540, manufactured by DIC Corporation. It is a copper phthalocyanine pigment.

(2) Phthalimide and its derivatives ・ Phthalimide: manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ Phthalimide acetic acid: manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ N-butyl phthalimide: manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ Phthalimide acetone: manufactured by Tokyo Kasei Kogyo Co., Ltd. ・ 3 -Phthalimide propionic acid: manufactured by Accel Pharmatech-Tetrachlorophthalimide acetic acid: see Production Example 3.
-Tetrabromophthalimide acetic acid: See Production Example 4.
-3-Tetrachlorophthalimide propionic acid: See Production Example 1.
-3-Tetrabromophthalimide propionic acid: See Production Example 5.
-N- (2-hydroxyethyl) phthalimide: manufactured by Tokyo Chemical Industry Co., Ltd.-2-tetrachlorophthalimide ethane phosphoric acid: see Production Example 2.

(3) Dispersant ・ Disperbyk-LPN6919, manufactured by Big Chemie Japan Co., Ltd., resin-type dispersant having a tertiary amino group ・ Solsperse 41000, manufactured by Japan Lubrizol Co., Ltd., resin-type dispersant

(4) Solvent-Propylene glycol monomethyl ether acetate (hereinafter referred to as "PMA")
-Propylene glycol monomethyl ether (hereinafter referred to as "PM")

(5) Dispersed resin-Acrycure (registered trademark) RD-Y-702-A, manufactured by Nippon Shokubai Co., Ltd.

(Production Example 1) Production of phthalimide derivative (3-tetrachlorophthalimide propionic acid) A 100 ml eggplant flask is set in an oil bath, 75 g of propylene glycol monomethyl ether (hereinafter referred to as “PM”), tetrachlorophthalic anhydride. 20.02 g (70 mmol) and 6.24 g (70 mmol) of β-alanine were added, a cooling tube was installed at the top, and the temperature of the oil bath was raised while stirring with a magnetic stirrer. Since the target substance began to precipitate when the temperature reached 130 ° C., stirring was continued for 5 minutes as it was. Then, the mixture was cooled to room temperature, 25 g of PM was added, and stirring was continued for 30 minutes. The contents were filtered through Nutche, the residue was washed with pure water, and then dried at 100 ° C. for 18 hours. The yield was 18.7 g (yield 74%). This dried product was used as a phthalimide derivative, 3-tetrachlorophthalimide propionic acid, in the examples described later.
The target object (m / z 355) was added to the negative mode spectrum using 2,5-Dihydroxybenzoic acid (DHBA) in the matrix obtained by the MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation). It was confirmed that there was a peak of.

(Production Example 2) Production of phthalimide derivative (2-tetrachlorophthalimide ethanephosphoric acid) A 500 ml four-necked flask is set in an oil bath, PM 200 g, tetrachlorophthalic anhydride 41.95 g (150 mmol), O-phosphoryl ethanolamine. 20.70 g (150 mmol) and 1,4-diazabicyclo [2,2,2] -octane 33.65 g (300 mmol) were added, a cooling tube was placed at the top, and the mixture was heated under reflux with stirring with a magnetic stirrer for 6 hours. After allowing to cool to room temperature, the contents were filtered through Nutche and the residue was washed with PM. The residue was redispersed in 1.5 L methanol for 30 minutes, 300 g of 35% hydrochloric acid was added, and the mixture was stirred for 30 minutes. The contents were filtered through Nutche and the residue was washed with a small amount of methanol and then dried. The yield was 42 g (yield 69%). This dried product was used as a phthalimide derivative, 2-tetrachlorophthalimide ethane phosphoric acid, in the examples described later.
Negative mode using α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-Dihydroxybenzoic acid (DHBA) in the matrix obtained by MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation). It was confirmed that there was a peak of the target product (m / z 407) in the spectrum of.

(Production Example 3) Production of phthalimide derivative (tetrachlorophthalimide acetic acid) A dried product was obtained by operating under the same conditions as in Production Example 1 except that 70 mmol of β-alanine was 70 mmol of glycine. The yield was 15.12 g (yield 63%). This dried product was used as a phthalimide derivative, tetrachlorophthalimide acetic acid, in the examples described later.
Negative mode using α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-Dihydroxybenzoic acid (DHBA) in the matrix obtained by MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation). It was confirmed that there was a peak of the target product (m / z 341) in the spectrum of.

(Production Example 4) Production of phthalimide derivative (tetrabromophthalimide acetic acid) Drying under the same conditions as in Production Example 1 except that 70 mmol of β-alanine was 70 mmol of glycine and 70 mmol of tetrachlorophthalic anhydride was 70 mmol of tetrabromophthalic anhydride. I got something. The yield was 26.24 g (yield 72%). This dried product was used as a phthalimide derivative, tetrachlorophthalimide acetic acid, in the examples described later.
Negative mode using α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-Dihydroxybenzoic acid (DHBA) in the matrix obtained by MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation). It was confirmed that there was a peak of the target product (m / z 517) in the spectrum of.

(Production Example 5) Production of phthalimide derivative (3-tetrabromophthalimide propionic acid) A dried product was obtained by operating under the same conditions as in Production Example 1 except that 70 mmol of tetrachlorophthalic anhydride was changed to 70 mmol of tetrabromophthalic anhydride. .. The yield was 28.08 g (yield 75%). This dried product was used as a phthalimide derivative, 3-tetrabromophthalimide propionic acid, in the examples described later.
Negative mode using α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-Dihydroxybenzoic acid (DHBA) in the matrix obtained by MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation). It was confirmed that there was a peak of the target product (m / z 531) in the spectrum of.

(Control 1)
<Manufacturing of pigment dispersion>
C.I. as a phthalocyanine pigment on a sand mill. I. Pigment Green 59 (FASTOGEN GREEN C100) 38.40 g, Dispersant (Disperbyk-LPN6919) 22.03 g, Dispersion Resin (Acrycure® RD-Y-702-A) 23.59 g, PMA as solvent 75.98 g was added.
After stirring at 2000 rpm for 10 minutes, 640 g of φ0.8 mm zirconia beads were added, and dispersion treatment was performed at 2000 rpm for 30 minutes.
Further, 30.28 g of PMA and 1.72 g of a dispersant (Solspers 41000, manufactured by Japan Lubrizol) were added to this dispersion treatment liquid, and the dispersion treatment was carried out at 2000 rpm for 10 minutes.
160 g of the dispersion treatment liquid from which the φ0.8 mm zirconia beads were removed was put into another pot together with 640 g of the φ0.1 mm zirconia beads, and the dispersion treatment was performed at 2000 rpm for 60 minutes.
After adding 77.04 g of PMA, dispersion treatment was carried out at 1500 rpm for 10 minutes, and φ0.1 mm zirconia beads were removed to obtain a green pigment dispersion.

<Manufacturing of coloring composition>
As a (meth) acrylic polymer, Acrycure (registered trademark) BX-Y-10 manufactured by Nippon Catalyst Co., Ltd. is 12.0% by weight (pure content), and is a polyfunctional acrylate monomer which is a photopolymerizable component. 26.0% by weight of dipentaerythritol (hexa / penta) acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), 4.0% by weight of Irgacare 369 manufactured by BASF Japan as a photopolymerization initiator, and PMA as a solvent. A coating film-forming component containing 58.0% by weight of
A coating film-forming component was added to the obtained green pigment dispersion and stirred with a disper to obtain a colored composition. The amount of the coating film-forming component added was 4.0 g with respect to 6.0 g of the green pigment dispersion.

(Examples 1 to 9, Comparative Example 1)
<Manufacturing of pigment dispersion>
C. I. Pigment Green 59 (FASTOGEN GREEN C100) and phthalimide or a derivative thereof were added as shown in Table 1, and a green pigment dispersion was obtained in the same manner as in Control 1.

<Manufacturing of coloring composition>
Using the obtained green pigment dispersion, a coloring composition was obtained in the same manner as in Control 1.

(Control 2)
<Manufacturing of pigment dispersion>
C.I. as a phthalocyanine pigment on a sand mill. I. Pigment Blue 15: 6 (FASTGEN BLUE A540) 30.72 g, Dispersant (Disperbyk-LPN6919) 21.28 g, Dispersion Resin (Acrycure® RD-Y-702-A) 42.44 g, Manufactured 1.28 g of the phthalimide derivative of Example 2, 38.68 g of PMA and 25.60 g of PM as a solvent were added.
After stirring at 2000 rpm for 10 minutes, 640 g of φ0.8 mm zirconia beads were added, and dispersion treatment was performed at 2000 rpm for 30 minutes.
Further, 28.24 g of PMA was added to this dispersion treatment liquid, and the dispersion treatment was carried out at 2000 rpm for 10 minutes.
160 g of the dispersion treatment liquid from which the φ0.8 mm zirconia beads were removed was put into another pot together with 640 g of the φ0.05 mm zirconia beads, and the dispersion treatment was performed at 2000 rpm for 60 minutes.
After adding 105.0 g of PMA, dispersion treatment was carried out at 1500 rpm for 10 minutes, and φ0.05 mm zirconia beads were removed to obtain a blue pigment dispersion.

<Manufacturing of coloring composition>
Using the obtained green pigment dispersion, a coloring composition was obtained in the same manner as in Control 1.

(Examples 10 to 12)
<Manufacturing of pigment dispersion>
C. I. A blue pigment dispersion was obtained in the same manner as in Control 2, except that the amounts of Pigment Blue 15: 6 (FASTGEN BLUE A540) and the phthalimide derivative were as shown in Table 1.

<Manufacturing of coloring composition>
Using the obtained green pigment dispersion, a coloring composition was obtained in the same manner as in Control 2.

(Evaluation)
<Changes in viscosity of pigment dispersion over time>
The viscosities of the pigment dispersions obtained in the controls, examples, and comparative examples immediately after production and the viscosities after allowing the pigment dispersion to stand at 40 ° C. for 3 days were determined by the E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd. Was measured using. Table 1 shows the viscosities (mPa · s) measured for the pigment dispersions of each control, example and comparative example.

<Change in contrast of coloring composition over time>
The viscosity of the pigment dispersions obtained in the controls, examples, and comparative examples immediately after production and the contrast after allowing the pigment dispersion to stand at 40 ° C. for 3 days were evaluated by the following method. That is, a spin coater (manufactured by Mikasa Co., Ltd.) adjusted to have a chromaticity of x = 0.550 in the case of a green coloring composition and y = 0.107 in the case of a blue coloring composition. It was applied to a glass plate having a thickness of 1 mm and a size of 100 mm square using a spin coater MS-150A). The coating plate was allowed to stand at room temperature for 5 minutes and then dried (prebaked) at 80 ° C. for 2 minutes by Airbus. Furthermore, using an exposure device (manufactured by Sanaga Denki Seisakusho Co., Ltd., trade name: UVE-1001S type exposure light source device, YSH-100SA type ultra-high pressure mercury lamp), ultraviolet rays (UV) ^{are used to achieve an exposure intensity of 60 mJ / cm 2.} Was applied to the coating plate, and post-baking was carried out at 235 ° C. under the conditions of 60 minutes in the case of green and 30 minutes in the case of blue. The post-baked coating plate was placed on a lamp (trade name: HF-LS-100WLCG) by sandwiching it with a polarizing plate (trade name: POLAX-38S, manufactured by Luceo Co., Ltd.). The brightness when the polarizing plate is in the cross Nicol position and the brightness when the polarizing plate is in the parallel position are measured using a color luminance meter (trade name: LS-100, manufactured by Konica Minolta Sensing Co., Ltd.). , The ratio (%) was calculated as the contrast (CR). Table 1 shows the measurement results for the pigment dispersions of each control, example and comparative example. Values were shown as ratios of each Example and Comparative Example to controls and evaluated according to the following criteria: When the ratio to the control was 140 or more, it was evaluated as ⊚, when the ratio was 100 to 139, it was evaluated as ◯, and when the ratio was 0 to 99, it was evaluated as ×.

Claims (5)

At least one selected from phthalimide acetic acid, 3-phthalimide propionic acid, tetrachlorophthalimide acetic acid, tetrabromophthalimide acetic acid, 3-tetrachlorophthalimide propionic acid, 3-tetrabromophthalimide propionic acid , zinc phthalocyanine pigments, dispersants and organic solvents. A pigment dispersion containing . The zinc phthalocyanine pigment, pigment dispersion according to claim 1, wherein the average number of hydrogen atoms contained in the one molecule is a halogenated zinc phthalocyanine pigment is two or more. The pigment dispersion according to claim 2 , wherein the halogenated zinc phthalocyanine pigment is a chlorinated brominated zinc phthalocyanine pigment. A coloring composition containing the pigment dispersion and the coating film-forming component according to any one of claims 1 to 3. The coloring composition according to claim 4, which contains a photopolymerizable component as the coating film forming component.