WO2014017330A1

WO2014017330A1 - Π-conjugated phthalocyanine pigment, method for producing said π-conjugated phthalocyanine pigment, and colored composition prepared using said π-conjugated phthalocyanine pigment

Info

Publication number: WO2014017330A1
Application number: PCT/JP2013/069260
Authority: WO
Inventors: 卓也小谷; 健太齋藤; 武藤　俊明
Original assignee: 東洋インキＳｃホールディングス株式会社
Priority date: 2012-07-25
Filing date: 2013-07-16
Publication date: 2014-01-30
Also published as: JP2014040567A; CN104105759B; JP5277469B1; CN104105759A; TWI582172B; TW201406869A; KR20150035487A

Abstract

Provided is a π-conjugated phthalocyanine pigment represented by general formula (1), which enables the provision of a color filter having excellent display quality including color performance. A π-conjugated pigment having excellent color performance including brightness can be produced stably on the bounty of a conformational factor caused by selectively introducing a functional group into R¹ to R⁸.

Description

π-type phthalocyanine pigment, method for producing π-type phthalocyanine pigment, and coloring composition using the π-type phthalocyanine pigment

The present invention relates to a π-type phthalocyanine pigment having excellent color characteristics such as brightness and high stability in terms of heat resistance, a method for producing the π-type phthalocyanine pigment, and a coloring composition using the π-type phthalocyanine pigment. More specifically, the present invention relates to the above pigment that can provide a color filter having excellent display quality when used in a color filter used in a color liquid crystal display device, a solid-state imaging device, and the like.

In general, the color filter is a red filter layer (R), green filter layer (G) and blue filter layer (B) formed on the surface of a transparent substrate such as glass, or a complementary color of red, green and blue. The corresponding fine band (striped) filter segments (pixels) composed of a cyan filter layer (C), a magenta filter layer (M), and a yellow filter layer (Y) are divided into “strip arrangement”, “ It is also called “mosaic array”, “delta array”, or the like, and is composed of parallel or crossing arrangements, or arrangements of fine filter segments arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several micrometers to several hundred micrometers, and are regularly arranged in a predetermined arrangement for each hue.

On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

Quality items required for color filters include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, high contrast is indispensable for realizing a high-quality liquid crystal display device.

Also, when a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device is used in a television or a personal computer monitor, there is an increasing demand for a color filter with higher lightness and higher contrast and higher reliability.

Copper phthalocyanine is often used as a blue pigment because it has a clear hue and a high tinting strength and is excellent in various resistances such as weather resistance, heat resistance, and chemical resistance. In addition, copper phthalocyanine shows homogeneous heterocrystals, and crystal types such as α, β, ε, γ, δ, π, ρ, χ, and R have been reported. Among them, for printing inks and color filters, α, β and ε type copper phthalocyanines are often used because they have advantages such as color characteristics and crystal stability.
The blue filter layer of the color filter requires a reddish hue, α is compared to β, and ε type is more reddish than α, so ε type copper phthalocyanine is used. There are many. Furthermore, the ε-type copper phthalocyanine pigment has an excellent property of being highly clear and having high coloring power.
However, even when the ε-type copper phthalocyanine pigment is refined using a known method, the contrast ratio increases with the refinement, but the lightness of the primary particle size of the pigment is several tens of nm. Since it converges when the level is below the level, it is difficult to improve further. Therefore, it is difficult to improve the energy saving performance by further improving the brightness and suppressing the increase in power consumption.

Π-type copper phthalocyanine is preferable for use as a blue filter layer of a color filter because it exhibits a reddish color compared to ε-type copper phthalocyanine. However, the stability is low, and when exposed to a high temperature and / or an organic solvent, the crystal transitions easily and lacks stability.

JP-A-48-725 Japanese Unexamined Patent Publication No. 63-308074 JP 62-48769 A

Patent Document 1 describes a method for producing π-type copper phthalocyanine. However, the obtained π-type phthalocyanine is an unsubstituted product having no substituent on the benzene ring, and is inferior in stability compared to other crystal types, so it can withstand practicality such as color filter applications. It wasn't.

Patent Document 2 describes a method for synthesizing copper phthalocyanine, which is characterized by reacting an aromatic polybasic acid in the presence of copper phthalocyanine by the Weiler method. Although there is no description about the crystal form of the copper phthalocyanine to be produced, as shown in Comparative Example 3 of this specification described later, not the π type but the ε type is produced.

Patent Document 3 describes a method for synthesizing π-type copper phthalocyanine, characterized in that pyromellitic acid is added and reacted during synthesis of copper phthalocyanine by the Weiler method. However, π-type copper phthalocyanine obtained by this method is inferior to ε-type copper phthalocyanine in terms of color characteristics. Furthermore, the stability of the three-dimensional crystal form was inferior.

The present invention was devised in view of the drawbacks of the prior art, and provides a novel π-type phthalocyanine pigment that improves color characteristics such as brightness and is highly stable in terms of heat resistance and the like. Let it be an issue.
Furthermore, an object of the present invention is to provide a color filter having excellent color characteristics and display quality by using the novel π-type phthalocyanine pigment in a color filter used in a color liquid crystal display device and a solid-state imaging device. .

The present invention relates to a π-type phthalocyanine pigment represented by the following general formula (1).
General formula (1)

(R ¹ to R ⁸ are each independently a hydrogen atom, COOH, CONH ₂ , CF ₃ , OC ₆ H ₅ , NH ₂ , NO ₂ , C ₆ H ₅ , or an alkyl group. R ¹ to R ⁸ Are not simultaneously hydrogen atoms, M is a metal atom or 2H, and R ⁹ to R ¹⁶ are each independently a hydrogen atom, aryl group, sulfone group, sulfoamide group, cyano group, hydroxyl group, thiol. A substituent, an acyl group, a halogeno group, a silyl group, or a silyloxy group, and the substituents of R ¹ to R ¹⁶ may be in the form of a metal salt.)

Another aspect of the present invention is a method for producing a π-type phthalocyanine pigment according to the present invention,
Phthalic anhydride, a phthalic acid derivative substituted at least in the α-position, urea, a urea derivative or ammonia, and a metal salt,
The reaction temperature is x (° C.),
The input weight (%) of the phthalic acid derivative substituted at least at the α-position to the total input weight of phthalic anhydride and the phthalic acid derivative substituted at least at the α-position is y,
When z is the amount of solvent input (times) with respect to the total input weight of phthalic anhydride and at least the α-substituted phthalic acid derivative,
Formula (1): x-4.3y-1.8z-145 ≦ 0
(However, 90 ≦ x ≦ 300, 0 <y, 0 ≦ z)
The manufacturing method of (pi) -type phthalocyanine pigment including the process made to react on the conditions represented by these.

Another aspect of the present invention is a method for producing a π-type phthalocyanine pigment according to the present invention,
A phthalonitrile and / or diiminoisoindoline, a phthalonitrile derivative substituted at least in the α-position and / or a diiminoisoindoline derivative substituted in at least the α-position, and a metal salt are reacted at 60 to 300 ° C. The present invention relates to a method for producing a π-type phthalocyanine pigment including a step.

Another present invention relates to a pigment composition containing the π-type phthalocyanine pigment according to the present invention and a π-type unsubstituted phthalocyanine pigment.

Another present invention relates to a coloring composition containing the pigment composition according to the present invention and a pigment carrier.

Still another invention is a color filter comprising at least a substrate and a filter segment formed on the substrate, and a part of the filter segment is obtained using the coloring composition according to the invention. About.

The novel π-type phthalocyanine pigment according to the present invention is excellent in color characteristics and stability, and by using it in a color filter used in a color liquid crystal display device and a solid-state imaging device, brightness and contrast ratio are improved. A color filter with excellent display quality can be provided.

It is an example of the powder X-ray diffraction pattern of the π-type copper phthalocyanine pigment represented by the general formula (1). It is an example of the powder X-ray diffraction pattern of a β-type copper phthalocyanine pigment. It is an example of the powder X-ray diffraction pattern of an epsilon-type copper phthalocyanine pigment. It is an example of the powder X-ray diffraction pattern of the refined | miniaturized pi-type copper phthalocyanine pigment shown by General formula (1). 2 is an example of a TOF-MS chart of a π-type copper phthalocyanine pigment represented by the general formula (1).

Hereinafter, the details of the present invention will be described based on preferred embodiments.
1. π-type phthalocyanine pigments As shown by the following general formula (1), the present inventors include COOH, CONH ₂ , CF _{3 in} at least one of R ¹ to R ⁸ , which is the so-called α-position of phthalocyanine. , OC ₆ H ₅ , NH ₂ , NO ₂ , C ₆ H ₅ , or an alkyl group makes it easy to maintain the π form of the phthalocyanine crystal in a three-dimensional structure. It was found that the stability of the crystal was improved while the formation of was facilitated. Furthermore, the present inventors have provided a color filter excellent in color characteristics such as brightness and contrast ratio and display quality when the π-type phthalocyanine is used in a color filter used in a color liquid crystal display device and a solid-state imaging device. The present invention has been completed.

General formula (1)

(R ¹ to R ⁸ are each independently a hydrogen atom, COOH, CONH ₂ , CF ₃ , OC ₆ H ₅ , NH ₂ , NO ₂ , C ₆ H ₅ , or an alkyl group. R ¹ to R ⁸ are not all hydrogen atoms at the same time, M is a metal atom or 2H, and R ⁹ to R ¹⁶ are independently a hydrogen atom, an aryl group, a sulfone group, a sulfoamide group, a cyano group, a hydroxyl group, (A thiol group, an acyl group, a halogeno group, a silyl group, or a silyloxy group. The substituents of R ¹ to R ¹⁶ may be in the form of a metal salt.)

That is, the phthalocyanine pigment according to the present invention is a π-type crystal of phthalocyanine of the general formula (1) having a substituent at a position corresponding to the α-position of phthalic acid. Here, the phthalocyanine pigment represented by the general formula (1) may be referred to as a substituted (α-substituted) phthalocyanine pigment or α-substituted product.
The functional group introduced into at least one of R ¹ to R ⁸ in the general formula (1) is any one of COOH, CONH ₂ , CF ₃ , OC ₆ H ₅ , NH ₂ , NO ₂ , C ₆ H ₅ , or an alkyl group. Even a functional group is preferable. The alkyl group is preferably a linear or branched alkyl group having about 1 to 12 carbon atoms. Among these, it is particularly desirable to have at least one substituent selected from the group consisting of COOH, CONH ₂ , CF ₃ , and OC ₆ H ₅ .
The number of functional groups to be introduced is not particularly specified, but the increase in the number of functional groups increases the possibility of adversely affecting the color characteristics when used in color filters, so other than hydrogen atoms introduced into one molecule of phthalocyanine The total number of functional groups of R ¹ to R ⁸ (α position) and R ⁹ to R ¹⁶ (β position) is preferably about 1 to 8, preferably 1 to 4, or 1 to 3. More preferably it is. Moreover, multiple types of functional groups may be introduced.

By introducing COOH, CONH ₂ , CF ₃ , OC ₆ H ₅ , NH ₂ , NO ₂ , C ₆ H ₅ , or an alkyl group into at least one of R ¹ to R ⁸ (α position), the so-called β position Compared with the case where it is introduced into R ⁹ to R ¹⁶ , the functional group acts as a steric hindrance factor, and as a result, it is considered that the effect of stabilizing the crystal type to the π type is enhanced. It is important to introduce a functional group into R ¹ to R ⁸ .
The π-type copper phthalocyanine obtained in the above-mentioned Patent Document 3 does not have a substituent introduced at the α-position, and its three-dimensional structural crystal type has a functional group in any of the above R ¹ to R ^8. It is not enough compared to the case of introduction.

Since the functional group introduced into R ⁹ to R ¹⁶ does not significantly affect the crystal type, any functional group may be introduced. However, since the hue of the pigment is affected, a hydrogen atom, an aryl group, a sulfone group (also referred to as a sulfo group, —SO ₃ H), a sulfoamide group (—SO ₂ NRR ′), a cyano group (— CN), hydroxyl group (also referred to as hydroxy group, —OH), thiol group (—SH), acyl group, halogeno group (—F, —Cl, —Br, —I), silyl group, or silyloxy group Is desirable. R and R ′ of the sulfoamide group are each independently a hydrogen atom, a linear or branched alkyl group having about 1 to 5 carbon atoms, an N, N-dimethylaminomethyl group, an N, N-dimethylamino group. An amino-substituted alkyl group such as an ethyl group is desirable. The aryl group is preferably a phenyl group, a benzyl group, a tolyl group, a xylyl group, etc., and the acyl group (—COR) is preferably such that R is methyl, ethyl, phenyl, etc., and a silyl group (—SiRR′R ″) ) Is preferably a trimethylsilyl group, a triethylsilyl group or the like, and the silyloxy group (—OSiRR′R ″) is preferably a trimethylsilyloxy group, a triethylsilyloxy group or the like, but is not limited thereto.
The substituents R ¹ to R ¹⁶ may be in the form of a metal salt. Examples thereof include carboxylate (—COOM), sulfonate (—SO ₃ M), alkoxide or phenoxide (—OM), and examples of metal (M) include alkali metals such as sodium, potassium and lithium.

The central metal M in the general formula (1) represents 2H or a metal. Among these, M is preferably Cu, Zn, Al (OH), or 2H, and more preferably Cu. M may be one kind or plural kinds in one pigment.

The π-type crystal form of phthalocyanine has a powder X-ray diffraction pattern as shown in FIG. In other words, π-type phthalocyanine has a Bragg angle 2θ (± 0.3 degrees) of 4.9, 6.5, 8.5, 9.7, 10.7, 17 when measured using Cu—Kα rays. It is a crystal type having a diffraction peak at 0 degree. FIG. 1 shows data obtained for a phthalocyanine π-type crystal of the general formula (1) having a substituent at the α-position, although the position of each diffraction peak is slightly shifted by the introduced functional group. As long as the mold is π-type, the diffraction pattern shows a pattern similar to FIG. However, when the phthalocyanine or phthalocyanine pigment is further refined, the diffraction peak becomes broad and a part of the peak may disappear. FIG. 4 shows a diffraction pattern of π-type phthalocyanine (α-substituted product) in which the peak is broad and partially disappeared.
The presence of the substituent introduced into the benzene ring can be confirmed by TOF (Time of Flight) -MS (Time of Flight Mass Spectrometer) or the like (see FIG. 5).

2. Next, a typical method for producing a π-type crystal of the α-substituted phthalocyanine pigment represented by the general formula (1) will be described.
The production method of phthalocyanine can be selected from conventionally known methods, and the reaction conditions are not particularly limited, but as described below, in order to stably obtain π-type crystals in the Weiler method, the reaction It is necessary to pay attention to the temperature, the input weight of the phthalic acid raw material, and the input weight of the solvent, and it is preferable to manufacture them under conditions that satisfy the following formula (1).
There are two main methods for producing phthalocyanine which are generally known. The first is a method called the Weiler method, which uses phthalic anhydride or its derivatives (hereinafter these phthalic acid raw materials are collectively referred to as “phthalic acids”) and urea or its derivatives as a raw material, metal source, catalyst. This is the industrially mainstream method of synthesizing by simultaneously adding a solvent and a solvent. The second method is called the phthalonitrile method, which is a highly reactive phthalonitrile or derivative thereof (hereinafter, these phthalonitrile raw materials are collectively referred to as “phthalonitriles”), or instead of phthalonitriles. Method of synthesizing diiminoisoindoline or a derivative thereof (hereinafter, these diiminoisoindoline raw materials are collectively referred to as “diiminoisoindolines”) by adding a metal source and heating. It is.

As will be described in detail below, regardless of whether the Weiler method or the phthalonitrile method is used, the former uses phthalic anhydride and the latter uses phthalonitrile and / or diiminoisoindoline. In addition to the α-substituted phthalocyanine pigment represented by the formula (1), an unsubstituted phthalocyanine pigment is also produced. The ratio of the unsubstituted product in the produced phthalocyanine pigment can be arbitrarily adjusted according to the raw material ratio to be used. At this time, since the phthalocyanine pigment represented by the general formula (1) is formed in a π-type crystal type, the presence of this π-type crystal causes the unsubstituted phthalocyanine pigment to have the same crystal type, and the same crystal type (π-type). The composition can be obtained. In addition, as the α-substituted phthalocyanine pigment of the general formula (1), a plurality of compounds having different substitution positions, the number of substituents, and the like can be obtained.

(1) Weiler Method The present inventors have used a Weiler method to convert phthalic anhydride and a phthalic acid derivative substituted at least at the α-position (such as (phthalic anhydride) substituted at least at the α-position) to urea. In order to obtain a π-type crystal stably by reacting with a urea derivative or ammonia and a metal salt,
The reaction temperature is x (° C.),
The input weight (%) of the phthalic acid derivative with respect to the total input weight of the phthalic anhydride and the phthalic acid derivative substituted at least at the α-position is y,
When the amount of solvent input (times) with respect to the total input weight of phthalic anhydride and phthalic acid derivative is z,
Experiment that it is desirable to carry out the reaction under the conditions represented by Formula (1): x-4.3y-1.8z-145 ≦ 0 (where 90 ≦ x ≦ 300, 0 <y, 0 ≦ z) I found it. When the value of Equation (1) is greater than 0, not a π-type, but a β-type, an ε-type, or a mixed crystal of various types of crystals is obtained (see Patent Document 2 above). A crystal form with low brightness.
In order for Formula (1) to be less than or equal to zero, that is, in order to reliably produce π-type phthalocyanine, the reaction temperature (x) is relatively low and the amount (z) of the reaction solvent is large. It can be seen that the reaction must be carried out under various conditions. For example, when the reaction temperature is relatively high, transition to a thermodynamically stable crystal form is likely to occur. Therefore, the reaction conditions may be moderated by increasing the amount of solvent and / or the phthalic acid derivative. It is considered preferable to increase the stability of the crystal by increasing the blending ratio.

X, which is the reaction temperature (° C.) in Equation (1), is one of the important factors because it greatly affects the crystal form and yield of the pigment. Although it is desirable to adjust the temperature constant to x ° C. from the start of the reaction until the pigment starts to form, the temperature is adjusted to 90 to 300 ° C. during the reaction in order to control the particle size and particle size distribution of the produced pigment particles. You may raise and lower within the range.
In a preferred embodiment, x is not particularly limited as long as Formula (1) is satisfied, but as a general condition, x is 90 to 300 ° C., and more preferably from the viewpoint of reaction time, yield, and the like. 120-250 ° C, most preferably 150-200 ° C.
Further, the reaction may be carried out under a pressure condition of about 0.05 to 1.0 MPa for the purpose of improving yield and / or purity.

In formula (1), y (= phthalic acid derivative input weight × 100) which is the input weight (%) of a phthalic acid derivative substituted at least at the α-position (such as a (phthalic anhydride) phthalic acid derivative substituted at least at the α-position). / ((Phthalic anhydride + phthalic acid derivative) total input weight) is one of the important factors for controlling the crystal form. It is preferable to add an appropriate amount of the phthalic acid derivative so as to satisfy the above mathematical formula (1). As for the timing of adding the phthalic acid derivative, the entire amount may be added at the start of the reaction, or may be divided and added until the generation of the pigment particles during the reaction is completed.
In a preferred embodiment, y is not particularly limited as long as the above formula (1) is satisfied. However, from the viewpoint of reaction time, yield, etc., y is preferably about 1 to 20%, more preferably. It is about 1 to 10%, more preferably about 2 to 8%.

In the Weiler method, a solvent may be used for the purpose of controlling the temperature in the system and / or improving the stirring efficiency during synthesis, and it is preferable to use a solvent to obtain a π-type crystal form.
In Formula (1), z (= solvent input weight / (phthalic anhydride + phthalic acid derivative) total input weight), which is the amount of solvent input (times), is an important factor for controlling the reactivity in the system. One. The entire amount of the solvent may be added at the start of the reaction, but may be divided in the middle of the reaction and may be added continuously or stepwise, and the value of z that satisfies the formula (1) is reached before the formation of the pigment is completed. By adjusting, a π-type crystal can be preferably obtained.
In a preferred embodiment, z is not particularly limited as long as Formula (1) is satisfied, but z is more preferably about 2 to 15 times, and 3 to 10 times from the viewpoint of reaction time, yield, and the like. More preferably, it is about.

Examples of phthalic acids used in the synthesis by the Weiler method include those known in various literatures such as phthalic anhydride, phthalic acid and salts thereof, esters thereof, phthalimide, and phthalamide. The phthalic acid ester is preferably a C1-C12 alkyl ester.
In addition, alkyl groups, aryl groups, nitro groups, sulfone groups or their metal bases, sulfoamide groups, cyano groups, amino groups, hydroxyl groups or their metal bases, carboxyl groups or their metal bases, amides on the aromatic rings of these compounds A phthalic acid having a substituent such as a group, a trifluoromethyl group, a phenyloxy group, a thiol group, an acyl group, a silyloxy group, a silyl group, or a halogeno group may be contained.

In order to synthesize the phthalocyanine of the general formula (1), at least phthalic anhydride and a phthalic acid derivative substituted at least at the α-position are used as raw materials. Phthalic acid derivatives substituted with phthalic acid derivatives, phthalic acid derivatives other than anhydrides having no substituent on the benzene ring, etc.) may be used in part.
This “phthalic acid derivative substituted at the α-position” means “an α-substituted phthalic acid having one or more substituents described as R ¹ to R ⁸ at least at one α-position of phthalic acid. Acid or derivative thereof. Examples of the derivative on the carboxy group side of phthalic acid include general carboxylic acid derivatives such as phthalic anhydride, phthalic acid ester, phthalimide, and phthalamide. Representative carboxylic acid derivatives phthalic anhydride and phthalic acid may be collectively expressed as “(anhydrous) phthalic acid” or “(anhydrous) phthalic acid derivative”. As the α-substituted phthalic acid derivative, plural kinds of compounds having different kinds of substituents and / or different substitution positions may be used.

This α-substituted phthalic acid derivative may have any one or more substituents (substituents R ⁹ to R ^{16 in} the above general formula (1)) at the β-position.
Moreover, as an unsubstituted phthalic acid derivative, derivatives (phthalic acid ester, phthalimide, etc.) other than anhydrides may be used in part.
Furthermore, β-substituted phthalic acid having one or more substituents only at the β-position or derivatives thereof may be used in part. The substituent at the β-position in these phthalic acid derivatives is any one or more substituents described as R ⁹ to R ¹⁶ above.
When using phthalic acids other than phthalic anhydride and α-substituted phthalic acid derivatives (β-substituted phthalic acid or its derivatives, phthalic acid derivatives other than unsubstituted anhydride), the total amount of phthalic acids used as raw materials It is preferably about 10% by weight or less.

Examples of urea or a derivative thereof to be reacted with the phthalic acid include urea, biuret, and triuret, and it is also preferable to use ammonia. A plurality of these may be used.
The amount used is preferably in the range of 1 to 10 in molar ratio to the total amount of phthalic acids (phthalic acid or derivatives thereof) as raw materials.

The metal salt constitutes the central metal M of the general formula (1), and is preferably a salt of Cu, Zn, Al or the like. Metal sources for supplying this metal salt include metal powders of metals such as Cu, Zn, Al, chloride, bromide, iodide, sulfate, sulfide, acetate, oxide, hydroxide, carbonate, Phosphate etc. can be used. Although the valence of the metal affects the reaction, it can generally be used for phthalocyanine synthesis without any particular limitation on the valence. Especially, it is preferable that a metal is copper, Preferably copper (I) chloride, copper (II) chloride, copper sulfate, copper hydroxide (I), copper hydroxide (II) etc. are used as a metal source or a metal salt. It can be preferably used. Two or more of these may be used.
The metal salt is preferably used in a molar ratio of 0.15 to 0.40 with respect to the total amount of phthalic acids (phthalic acid or derivatives thereof) as raw materials.

As the catalyst for the reaction, those known by the Weiler method can be used. Examples thereof include molybdate compounds such as ammonium molybdate and phosphomolybdic acid, titanium compounds such as titanium tetrachloride and titanate, antimony oxide, arsenic oxide, and boric acid. Two or more of these may be used.
The amount of the catalyst used is not particularly limited, but it is preferably used in the range of 0.0001 to 0.3 by weight with respect to the total of phthalic acids (phthalic acid or derivatives thereof) as raw materials.
In addition, orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide and the like for the purpose of improving the reactivity, improving the reactivity, improving the purity of the product, and improving the clarity. The metal salt or ammonium salt may be optionally used with respect to the phthalic acid (phthalic acid or derivative thereof) as a raw material, and in that case, it can be added in a range of 0.05 to 1 by weight.

As the reaction solvent, a known organic solvent can be used as a synthetic solvent for the Weiler method. For example, aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin; alicyclic hydrocarbons such as alkylcyclohexane, decalin and alkyldecalin; aliphatic hydrocarbons such as decane and dodecane; nitro compounds such as nitrobenzene and o-nitrotoluene; Halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene and hexachlorobutadiene; sulfur compounds such as sulfolane, dimethylsulfolane and dimethyl sulfoxide; heterocyclic compounds such as quinoline and the like can be used. These organic solvents may be a mixture of two or more. Among them, in order to stably control the crystal form, aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, sulfolane and the like are used. It is particularly preferred to use it.

(2) Phthalonitrile Method As described above, the phthalonitrile method is a method for synthesizing phthalocyanines in which phthalonitriles and / or diiminoisoindolines are reacted with metal salts in the presence of a base serving as a catalyst.
In a preferred embodiment, phthalonitrile and / or diiminoisoindoline, a phthalonitrile derivative substituted at least at the α-position and / or a diiminoisoindoline derivative substituted at least at the α-position, and a metal salt, A step of reacting at 300 ° C.
In the synthesis, a solvent may be used for the purpose of controlling the temperature in the system and / or improving the stirring efficiency. In addition, the reaction may be performed under a pressure condition of about 0.05 to 1.0 MPa for the purpose of improving the yield and purity.

As the phthalonitriles, phthalonitrile and / or derivatives thereof can be used. As the diiminoisoindoline, 1,3-diiminoisoindoline and / or a derivative thereof can be used. A plurality of types of compounds may be used as the phthalonitrile derivative or diiminoisoindoline derivative, respectively.
These derivatives are compounds having one or more substituents of R ¹ to R ⁸ or R ⁹ to R ¹⁶ of the above general formula (1) on the aromatic ring of phthalonitrile or diiminoisoindoline. means. Moreover, the compound of the state of the above metal salts can also be used.
In order to synthesize the phthalocyanine of the general formula (1), a derivative having at least one of the substituents R ¹ to R ^{8 in} the α position is used as at least one of phthalonitriles and diiminoisoindolines.

As the metal source that can be used in the phthalonitrile method, the same sources as described in the above-mentioned Weiler method can be preferably used. That is, metal powders of metals such as Cu, Zn, and Al, chlorides, bromides, iodides, sulfates, sulfides, acetates, oxides, hydroxides, carbonates, phosphates, and the like. Also in the phthalonitrile method, the valence of the metal affects the reaction, but in general, the valence can be used for phthalocyanine synthesis without any particular limitation. Two or more of these may be used.
The amount of the metal source used is in the range of 0.15 to 0.40 in molar ratio to the total of phthalonitriles and diiminoisoindolines (total of either one when only one is included). Is preferred.

The catalyst base is not particularly limited, but is a cyclic amine such as ammonia, morpholine, or piperidine; an amine having nitrogen introduced into an aromatic ring such as pyridine, picoline, or quinoline; 1,5-diazabicyclo [4.3 .0] -5-nonene (DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [5.4.0] undec-5-ene, Preferred are amines having an amidine moiety such as 1,4-diazabicyclo [2.2.2] octane; alkoxides having 1 to 12 carbon atoms; or a mixture thereof. Two or more of these may be used.
The amount of the base is preferably 0.001 to 2 in terms of molar ratio with respect to the total of phthalonitriles and diiminoisoindolines (when either one is included). . When a base is used as a solvent, it may be further increased.

As a solvent that can be used for the reaction, a known organic solvent can be used as a synthetic solvent for the phthalonitrile method. For example, alcohols such as methanol and ethylene glycol; aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin; alicyclic hydrocarbons such as alkylcyclohexane, decalin and alkyldecalin; aliphatic hydrocarbons such as decane and dodecane Nitro compounds such as nitrobenzene and o-nitrotoluene; halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene and hexachlorobutadiene; sulfur compounds such as sulfolane, dimethyl sulfolane and dimethyl sulfoxide; heterocyclic compounds such as quinoline; Formamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be preferably used. These organic solvents may be a mixture of two or more.

The reaction may be performed in an inert gas atmosphere if necessary, or a compound known to be used in the Weiler method, such as ammonium molybdate and / or urea, may be added if necessary.

(3) Other steps In both the Weiler method and the phthalonitrile method, after completion of the reaction, after separation from the reaction solvent such as solvent filtration and solvent distillation, washing with water and / or organic solvent is performed. Is preferred. An acid or an alkali may be used at the time of washing. If further purification is required, impurities may be removed by a known purification technique such as sublimation, acid paste, acid slurry, reprecipitation, recrystallization, or extraction.

The phthalocyanine pigment synthesized by the production methods typified by the above two methods may be used as it is, but it is refined for the purpose of controlling the particle size, imparting easy dispersibility, etc. The operation of pigmentation or sizing may also be performed.
A well-known refinement method can be used, and a main method includes a solvent method, a solvent milling method, a solvent salt milling method, and the like. At the time of miniaturization, a metal-free or metal phthalocyanine derivative having at least one substituent may be added in order to advance the miniaturization while suppressing crystal growth.
The particle diameter of the pigment (average primary particle diameter) is preferably adjusted to about several nanometers to several tens of nanometers, which is a general pigment particle diameter, but is not limited thereto.

According to the study by the present inventors, the π-type crystal is obtained as a more elongated (high aspect ratio) needle-like crystal as compared with other crystal types such as the ε-type crystal. In addition, there is an advantage that it is not necessary to perform a kneading step using a kneader or the like in the case of miniaturization, and a pigment refined to a desired particle size can be obtained only by a dispersion step without the kneading step. On the other hand, for example, the ε-type crystal that has been generally used for liquid crystal televisions or the like so far is a spherical shape or a needle-like shape, and is difficult to miniaturize unless it is based on a kneading process. It is difficult to omit the kneading step before the dispersing step.

3. Pigment Composition The pigment composition comprises a π-type phthalocyanine pigment of general formula (1) (α-substituted product) and an unsubstituted π-type phthalocyanine pigment having no substituent other than a hydrogen atom on the benzene ring of phthalocyanine, that is, π-type It contains at least an unsubstituted phthalocyanine pigment. As the α-substituted product, a plurality of compounds having different substituents and / or substitution positions can be contained. Further, α-substituted and / or unsubstituted compounds having different types of the central metal M may be mixed and used.
As described above, in the production of the α-substituted π-type phthalocyanine pigment of the general formula (1), phthalic anhydride is used for the Weiler method, phthalonitrile and / or diiminoisoindoline is used for the phthalonitrile method, By using each as a raw material, an unsubstituted π-type phthalocyanine pigment can also be produced and produced as a π-type crystal mixture of an α-substituted product and an unsubstituted product, as described above.

The π-type phthalocyanine pigment may partially contain a β-substituted π-type phthalocyanine pigment (β-substituted product) having no substituent at the α-position. The amount of the β-substituted product that may be optionally contained is preferably about 10% by weight or less in the π-type phthalocyanine pigment in order to further enhance the stability of the π-type crystal type.

In addition to the π-type phthalocyanine pigment and the unsubstituted π-type phthalocyanine pigment, the pigment composition can also contain a solvent, a resin, an additive, and the like as optional components. For example, rosin, metal rosin, rosin ester for various purposes such as inhibition of crystal growth at the time of miniaturization, provision of crystal stability, prevention of aggregation, provision of easy dispersibility when using a pigment as a colorant, and improvement of coloring power. A rosin derivative such as rosin, a resin, an activator, a pigment derivative (pigment derivative), or the like may be mixed with the pigment during or after the refinement step. Furthermore, as a pigment component, a part of another crystal type phthalocyanine pigment other than the π-type or an amorphous phthalocyanine pigment may be included within a range that does not impair the effects of the present invention. Hereinafter, these phthalocyanine pigments that can be used in the pigment composition are collectively referred to simply as “phthalocyanine pigments”.
The form of the pigment composition is not particularly limited, and may take any form such as powder, water-containing press cake, etc., and may be processed in some way, such as a mixture with resin. .

4). Coloring composition The coloring composition contains at least the pigment composition and a pigment carrier, and includes printing inks such as inkjet inks, paints, plastics, water-based colors, printing inks, toning agents, toners, and resists for color filters. A pigment dispersion such as ink is a typical form. Among these, in particular, the color characteristics such as lightness expressed by the π-type phthalocyanine pigment of the general formula (1) are in good agreement with the color characteristics required for the color filter, and therefore are preferably used for color filters. it can.

The phthalocyanine pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the coloring composition (100% by weight). A ratio of 20 to 50% by weight is more preferable.

The pigment carrier contained in the coloring composition is for dispersing a phthalocyanine pigment, and is composed of a resin, a precursor thereof, or a mixture thereof.
As the resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is selected. Resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and their precursors are activated by irradiation with active energy rays such as ultraviolet rays and electron beams to produce resins. An energy ray polymerizable monomer or oligomer is included. These can be used alone or in admixture of two or more.

The pigment carrier is preferably used in an amount of 30 to 700 parts by weight, more preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the phthalocyanine pigment in the coloring composition.
When a mixture of a resin and its precursor is used as a pigment carrier, the resin is preferably used in an amount of 20 to 400 parts by weight, more preferably 50 parts per 100 parts by weight of the phthalocyanine pigment in the coloring composition. It can be used in an amount of up to 250 parts by weight. The resin precursor is preferably used in an amount of 10 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the phthalocyanine pigment in the coloring composition.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, or polyimide resins. One or more of these thermoplastic resins can be preferably used.

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin. One or more of these thermosetting resins can be preferably used.

As the active energy ray-curable resin, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group (meta ) An acrylic compound or a cinnamic acid having the same reactive substituent is reacted to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is used as a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product is also used. One or more kinds of these active energy ray-curable resins can be preferably used.
“(Meth) acryl” represents both “acryl” and “methacryl”.

As polymerizable monomers and polymerizable oligomers (photopolymerizable monomers, photopolymerizable oligomers, etc.) that are resin precursors,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates and cyclic alkyl (meth) acrylates or cyclic alkenyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, and polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) Acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) Acrylate, poly (propylene glycol - tetramethylene glycol) mono (meth) acrylate, and a hydroxyl group, such as glycerol (meth) acrylate (meth) acrylates;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate;
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide modified tri (meth) acrylate phosphate, and glycerol di (meth) acrylate Di (meth) acrylates such as relations;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether- (Meth) acrylic acid adduct, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) Acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic Acid adducts, epichlorohydrin modified phthalic acid- (meth) acrylic acid adducts, epichlorohydrin modified hexahydrophthalic acid- (meth) acrylic acid adducts, ethylene glycol diglycidyl ether- (meth) acrylic acid adducts, polyethylene glycol diglycidyl Ether- (meth) acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid addition , Cresol novolac-type epoxy resin- (meth) acrylic acid adducts, other epoxy resins- (meth) acrylic acid adducts and other epoxy (meth) acrylates;
(Meth) acryloyl modified isocyanurate, (meth) acryloyl modified polyurethane, (meth) acryloyl modified polyester, (meth) acryloyl modified melamine, (meth) acryloyl modified silicone, (meth) acryloyl modified polybutadiene, and (meth) acryloyl modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, and allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-vinylformamide; and acrylonitrile. These may be used alone or in combination of two or more.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition.
As a photopolymerization initiator,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4′-methyldiphenyl sulfide;
A thioxanthone photopolymerization initiator such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl (4′-methoxystyryl) -6 -Triazine photopolymerization initiators such as triazine;
Borate photopolymerization initiator;
A carbazole photopolymerization initiator; or an imidazole photopolymerization initiator is used.
The photopolymerization initiator is preferably used in an amount of 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the phthalocyanine pigment in the coloring composition.

The above photopolymerization initiators can be used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10 -Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, etc. These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

The coloring composition can be prepared in the form of a solvent developing type or alkali developing type colored resist. The colored resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or an active energy ray curable resin and a polymerizable monomer. Disperse one or more organic pigments together with a photopolymerization initiator, if necessary, in a pigment carrier using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor Can be manufactured. Here, the organic pigment is a concept including both the π-type phthalocyanine pigment and an organic pigment other than the π-type phthalocyanine pigment that is optionally added for adjusting the hue as necessary.

The manufacturing method of a coloring composition is not specifically limited, A coloring composition can be obtained by mixing a pigment composition or a phthalocyanine pigment, a pigment simple substance, and the component contained arbitrarily by a well-known arbitrary method. Known methods include the various dispersing means described above.
The colored composition can also be produced by mixing several types of organic pigments separately dispersed in a pigment carrier.

When the phthalocyanine pigment is dispersed in the pigment carrier, a dispersion aid (dispersant) such as a resin-type pigment dispersant, a surfactant, and a pigment derivative (pigment derivative) can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the dispersion aid is obtained by using a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid. The colored film is excellent in transparency.
The dispersion aid is preferably used in an amount of 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the phthalocyanine pigment in the coloring composition. it can.

Among these, a pigment derivative (pigment derivative) is excellent in the function of preventing aggregation of organic pigments and maintaining a finely dispersed state of organic pigments. By using a coloring composition containing these derivatives, a high contrast ratio can be obtained. Since a colored film with high color purity can be produced, it is preferable as a dispersion aid.
As a pigment derivative used as a pigment dispersant, known ones generally used (for example, JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, JP-B 63- 17102, JP-B-5-9469, etc.) can be used without particular limitation. Specifically, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, Anthraquinone pigments such as flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone Pigments such as pigments, selenium pigments, metal complex pigments and the like, and those having basic substituents (amino groups, etc.) or acidic substituents (phosphoric acid groups, sulfonic acid groups, carboxyl groups, etc.). . These can be used alone or in admixture of two or more.

The blending amount in the case of using the pigment derivative is not particularly limited, but is preferably 0.1 part by weight or more in order to sufficiently exhibit the blending effect with respect to 100 parts by weight of the pigment, From the viewpoint of maintaining good light resistance, it is preferably 30 parts by weight or less, and more preferably about 0.5 to 25 parts by weight.

The resin-type pigment dispersant added in the coloring composition has a pigment-affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to give the pigment to the pigment carrier. It works to stabilize dispersion.

Examples of the resin-type pigment dispersant include polyvinyl, polyurethane, polyester, polyether, formalin condensation, silicone, and composite polymers thereof. Examples of the pigment affinity site include a carboxyl group, a hydroxyl group, Polar groups such as phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, hydroxyl groups, amino groups, quaternary ammonium bases, or amide groups, and hydrophilic polymers such as polyethylene oxide, polypropylene oxide, or composites thereof Examples of the site compatible with the dye carrier include a long-chain alkyl chain, a polyvinyl chain, a polyether chain, or a polyester chain.

Specifically, as a resin-type pigment dispersant,
Styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester Copolymer, (meth) acrylic acid-polyvinyl-based macromer copolymer, phosphoric ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxy Anionic resin type pigment dispersants such as methylcellulose, polyurethane having a carboxyl group, formalin condensate of naphthalenesulfonate, or sodium alginate;
Nonionic resin-type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or
Preferred examples include cationic resin-type pigment dispersants such as polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane having an amino group, and a reaction product of polyalkyleneimine and polyester having a free carboxyl group. . These can be used alone or in admixture of two or more.

In particular, the colored composition preferably contains an acidic resin-type pigment dispersant from the viewpoint of the stability of the colored composition. Furthermore, by using an acidic resin-type pigment dispersant and a basic dye derivative in combination, not only the fluidity and stability of the colored composition, but also a filter segment with excellent brightness and high contrast ratio can be obtained. preferable.
Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165 manufactured by Big Chemie Japan. 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204 Or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc .;
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Nippon Lubrizol 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc .;
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by Ciba Japan 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc .;
DISPARLON 3600N, DISPARLON 1850, etc. manufactured by Enomoto Kasei Co., Ltd .;
Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. are mentioned, but it is not limited to these. These can be used alone or in admixture of two or more.
Among these, a resin-type pigment dispersant having an acidic functional group, Disperbyk-108, 110, 111, 112, 116, 142, 180, 2000, 2001, manufactured by Big Chemie Japan, or manufactured by Nippon Lubrizol, Inc. SOLPERSE-3000, 21000, 26000, 36600, 41000, or EFKA-4401, 4550 manufactured by Ciba Japan, or DISPARLON 3600N, DISPARLON 1850 manufactured by Enomoto Kasei Co., or Ajimoto Fine Techno Co., Ltd. However, it is not limited to these.

The surfactant is not particularly limited, but for example,
Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate tri Anionic surfactants such as ethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Examples thereof include chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines. These can be used alone or in admixture of two or more.

In the coloring composition, a phthalocyanine pigment is sufficiently dispersed in a pigment carrier and coated on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a colored film. For ease, any non-aqueous solvent can be included.

The non-aqueous solvent is not particularly limited. For example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4 -Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m- Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethyl Formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol Monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Butyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol No ethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether , Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzine Alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate or dibasic acid esters and the like, may preferably be mentioned. These are used alone or in combination.
The solvent is preferably used in an amount of 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment in the coloring composition or pigment dispersion.

Further, the coloring composition may contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include commonly used ones such as benzyltrimethylammonium chloride or quaternary ammonium chlorides such as diethylhydroxyamine; lactic acid or organic acids such as oxalic acid; methyl esters of the organic acids Catechols such as t-butylpyrocatechol; organic phosphines such as triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; or phosphites, but not limited thereto.
The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the phthalocyanine pigment in the coloring composition.

In addition, the coloring composition may contain a dye within a range that does not reduce heat resistance for color matching. The dye used is not particularly limited, but azo dye, anthraquinone dye, indigoid dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dye, quinoline dye, nitro dye, nitroso dye, benzoquinone and naphthoquinone dye, Naphthalimide dyes, perinone dyes and the like can be preferably used, and two or more kinds may be arbitrarily used in combination.

The use of the coloring composition is not particularly limited, but in a preferred embodiment, it is prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type coloring resist. be able to.
As described above, the colored resist is a pigment (dye) dispersed in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a polymerizable monomer, a photopolymerization initiator, and an organic solvent. It has been made.

The coloring composition preferably does not contain coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more, and by means such as centrifugation, sintered filter, membrane filter, It is preferable to remove these coarse particles and mixed dust. In particular, when a colored composition is used for a color filter, it is preferable that substantially no particles of 0.5 μm or more are contained, and more preferably no particles larger than 0.3 μm.

5. Color filter The color filter includes at least a substrate and a filter segment formed on the substrate, and the filter segment includes a filter segment obtained using the colored composition. That is, the color filter includes, on the substrate, at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the blue filter segment includes the phthalocyanine pigment. Formed from the composition. Red filter layer (R) and green filter layer (G) other than blue, or cyan filter layer (C), magenta filter layer (M), and yellow filter layer corresponding to complementary colors of red, green, and blue (Y) can be formed using arbitrary coloring compositions, and is not limited at all. In addition to the red pigment, an orange pigment and / or a yellow pigment can be used in combination with the red coloring composition for forming the red filter segment, so that the green coloring composition for forming the green filter segment can be used. In addition to the green pigment, a yellow pigment can be used in combination.

The manufacturing method of a color filter is not specifically limited, A well-known method can be used.
The filter segment can be formed by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

When forming a filter segment by photolithography, for example, it can be performed as follows, but is not limited thereto. The colored composition prepared as the solvent developing type or alkali developing type colored resist is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Apply as follows. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the film. Thereafter, the film is immersed in a solvent or an alkali developer, or the developer is sprayed by spraying or the like to remove uncured portions, thereby forming a desired pattern. Similar operations can be repeated for other colors to form filter segments for each color. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.
In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, the colored resist is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

The filter segment may be manufactured by an electrodeposition method, a transfer method or the like in addition to the above method. The electrodeposition method is a method in which each color filter segment is electrodeposited on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

The arrangement of the sub-pixels or filter segments (pixels) is not particularly limited, and may be a known pattern such as a “stripe arrangement”, “mosaic arrangement”, “delta arrangement”, or the like. The size of the filter segment can be arbitrarily formed in the range of several micrometers to several hundred micrometers.

The substrate of the color filter is a transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali alumino borosilicate glass, which have high transmittance for visible light, polycarbonate, polymethyl methacrylate, A resin plate such as polyethylene terephthalate is used.
The color filter further includes a transparent electrode for driving the liquid crystal. The transparent electrode is made of indium oxide, tin oxide, or the like, and can be formed by vapor deposition or sputtering.

If a black matrix is formed in advance before forming the filter segment on the substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, a multilayer film of chromium, chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed on a substrate in advance, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

6). Liquid crystal panel A color filter is attached to the opposite substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or retardation film is attached to the substrate. A liquid crystal display panel is manufactured by sticking to the outside.
LCD panels include Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Convencend Bend (OCB), etc. The liquid crystal display mode can be used for colorization using a color filter.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

1. Measurement Method (1) Color Characteristics Each phthalocyanine pigment coloring composition (blue resist material) was applied on a glass substrate to a thickness such that y = 0.1500 in a C light source, and the substrate was heated at 230 ° C. Heated for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(2) Contrast ratio The contrast ratio was measured using the coating film used for color characteristic measurement. Below, the measuring method of the contrast ratio of a coating film is demonstrated.
(Measurement method of contrast ratio of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the first polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the second polarizing plate. . When there is nothing between the first polarizing plate and the second polarizing plate, if the polarization planes of both polarizing plates are parallel to each other, the light is transmitted through the second polarizing plate, but the polarization planes are orthogonal to each other. If so, the light is blocked by the second polarizing plate. However, if there is a dried coating film of the colored composition between both polarizing plates, the light polarized by the first polarizing plate passes through the dried coating film of the colored composition, causing scattering by pigment particles, etc. When a deviation occurs in part of the surface (polarization direction), the amount of light transmitted through the second polarizing plate decreases when both polarizing plates are parallel, and part of the second polarizing plate when both polarizing plates are orthogonal to each other. Light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the two polarizing plates were parallel and the luminance when they were orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)
That is, when scattering occurs due to the pigment in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, the contrast ratio is lowered.

In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. The first and second polarizing plates are overlapped on both surfaces of the substrate on which the colored film is formed so that the polarizing axes of both polarizing plates are parallel to each other, and the backlight from one polarizing plate (first polarizing plate) side. And the luminance (Lp) of the light transmitted through the other polarizing plate (second polarizing plate) was measured with a luminance meter. Next, both polarizing plates stacked on both sides of the substrate are arranged so that the polarization axes of both polarizing plates are orthogonal to each other, the backlight is incident from one polarizing plate side, and the light transmitted through the other polarizing plate The luminance (Lc) was measured with a luminance meter. The contrast ratio Lp / Lc was calculated using the measured luminance value obtained. The measurement was performed in the normal direction of the substrate. As the two polarizing plates, “NPF-SEG1224DU” (manufactured by Nitto Denko Corporation) was used. As a luminance meter, “BM-5A” (manufactured by Topcon Corporation) was used, and the luminance was measured under the condition of a 2 ° visual field.

(3) Powder X-ray diffraction The dried pigment was pulverized on an 80-mesh wire mesh to obtain a particle size of 80 mesh or less, and then X-ray measurement was performed. The X-ray diffraction spectrum was measured under the following conditions.
Equipment: X'pert-Pro Fully automatic multipurpose X-ray diffractometer (manufactured by Philips)
X-ray source: Cu2kW tube Voltage: 30kV
Current: 40 mA
Measurement range: 3.0 ° to 35.0 °
Step angle: 0.01 °

2. Example Example 1
A π-type copper phthalocyanine pigment was produced by the Weiler method using the following raw materials.
Phthalic anhydride 56 parts Urea 97 parts Cuprous chloride 15.4 parts Ammonium molybdate 1.5 parts Hemimellitic acid 3.6 parts Dimethylformamide 420 parts Each raw material is placed in a synthesizer and stirred at 180 ° C for 5 minutes. By maintaining the time, a copper phthalocyanine pigment was produced. The obtained reaction liquid containing a copper phthalocyanine pigment was filtered under reduced pressure while washing with warm water at 60 ° C. to remove the solvent and ungenerated products from the reaction liquid.
The crude pigment from which the solvent and the like were removed was subjected to the following filtration and purification. First, the crude pigment was added to 500 parts of 3% sulfuric acid heated to 80 ° C., stirred for 30 minutes, and then filtered under reduced pressure while washing with warm water at 60 ° C. Next, the mixture was added to 500 parts of 3% sodium hydroxide heated to 80 ° C., stirred for 30 minutes, and then filtered under reduced pressure while washing with hot water at 60 ° C. Finally, it was added to 500 parts of warm water heated to 60 ° C., stirred for 30 minutes, and then filtered under reduced pressure while washing with warm water at 60 ° C.
A copper phthalocyanine pigment 1 was obtained by drying the pigment cake obtained through the filtration and purification steps in an oven at 90 ° C. for 15 hours. As a result of measuring the obtained copper phthalocyanine pigment 1 by X-ray diffraction, the Bragg angle 2θ has diffraction peaks at 4.9, 6.5, 8.5, 9.7, 10.7, 17.0 degrees. The diffraction pattern of π-type copper phthalocyanine pigment was shown. The diffraction pattern is shown in FIG.
Further, the obtained copper phthalocyanine pigment 1 was analyzed by TOF-MS. As a result, one or two CONH ₂ groups (generated by reaction of carboxy group at the α-position of hemimellitic acid with ammonia and isocyanate) were substituted. The presence of the compound having the number was confirmed (FIG. 5).

Next, after uniformly stirring a mixture of the following composition containing the obtained π-type copper phthalocyanine pigment 1, using a zirconia bead having a diameter of 0.5 mm, it was filtered with a 2 μm filter dispersed in a bead mill for 3 hours, A pigment composition (organic pigment composition) 1 was prepared.
Copper phthalocyanine pigment 1 9.0 parts Copper phthalocyanine dye derivative 1.0 part Acrylic resin solution 40.0 parts Methoxypropyl acetate (PGMAc) 50.0 parts Copper phthalocyanine dye derivative is copper phthalocyanine dimethylaminopentylsulfonamide The acrylic resin solution is a cyclohexanone solution having a solid content of 20% and containing a 2: 8 (weight ratio) copolymer of methacrylic acid and n-butyl methacrylate (weight average molecular weight 40000).

Further, a mixture of the following composition including the obtained pigment composition 1 was stirred and mixed so as to be uniform, and then filtered through a 2 μm filter to prepare a colored composition (alkali development resist material) 1.
Pigment composition 1 45.0 parts Acrylic resin solution (same as above) 15.0 parts Trimethylolpropane triacrylate 9.0 parts (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.0 parts of photopolymerization initiator (2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (“Irgacure 907” manufactured by BASF)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Cyclohexanone 28.8 parts

Examples 2 to 27
As in Example 1, as shown in Table 1, solvent species, catalyst species, α-substituted phthalic acid (phthalic acid derivative) species, synthesis temperature, phthalic anhydride input amount, α-substituted phthalic acid The π-type copper phthalocyanine pigments 2 to 27 of Examples 2 to 27 were produced by changing the input amount and the solvent amount and synthesizing by the same operation. It was confirmed by powder X-ray diffraction that both of these crystal types were π-type.
Similarly, pigment compositions 2 to 27 and colored compositions 2 to 27 were prepared using π-type copper phthalocyanine pigments 2 to 27.

Example 28
A π-type copper phthalocyanine pigment was produced by the phthalonitrile method using the following raw materials.
12.8 parts of phthalonitrile 3.3 parts of cuprous chloride 0.79 parts of 3-phenoxyphthalonitrile 230 parts of n-amyl alcohol Each raw material was charged into a synthesizer and heated to 130 ° C. with stirring. Copper phthalocyanine pigment 28 was made by adding 15.2 parts of diazabicycloundecene and maintaining for 3 hours. Further, filtration purification after the synthesis, dispersion, and stirring and mixing were processed in the same manner as in Example 1 to prepare a pigment composition 28 and a colored composition 28. The obtained crystal type was π type.

Example 29
A copper phthalocyanine pigment 29 was prepared in the same manner by changing 3-phenoxyphthalonitrile of Example 28 to 3-nitrophthalonitrile. Further, filtration purification after the synthesis, dispersion, and stirring and mixing were processed in the same manner as in Example 1 to prepare a pigment composition 29 and a colored composition 29. The obtained crystal type was π type.

Comparative Examples 1 to 3
As in Example 1, as shown in Table 1, solvent species, catalyst species, α-substituted phthalic acid (phthalic acid derivative) species, synthesis temperature, phthalic anhydride input amount, α-position substituted The copper phthalocyanine pigments of Comparative Examples 1 to 3 were prepared by changing the amount of phthalic acid and the amount of the solvent, and synthesizing by the same operation. Further, filtration purification after the synthesis, dispersion, and stirring and mixing were similarly processed to prepare a pigment composition and a colored composition.

Comparative Example 4
After kneading 76 parts of LIONOL BLUE E manufactured by Toyocolor Co., 4 parts of copper phthalocyanine dimethylaminopentylsulfonamide, 600 parts of sodium chloride, and 100 parts of diethylene glycol at 70 ° C. for 6 hours in a stainless steel kneader (manufactured by Inoue Seisakusho) Then, washing with water and drying and grinding were performed to prepare a copper phthalocyanine pigment.
Using the obtained pigment, a pigment composition and a colored composition were obtained in the same manner as in Example 1.

The pigment crystal types produced by the methods of the above Examples and Comparative Examples, and the hue (Y value: C light source) and contrast ratio of the coatings produced using the respective colored compositions were measured.
The results are shown in Table 2.

As a result of measuring the pigment synthesized without adding hemimellitic acid as in Comparative Example 1 by X-ray diffraction, the Bragg angle 2θ was 6.9, 9.0, 10.2, 12.3, 18 The diffraction pattern of a β-type copper phthalocyanine pigment as shown in FIG. Further, even when hemimellitic acid was added as in Comparative Examples 2 and 3, pigments that did not select appropriate synthesis conditions such that (Equation 1) ≦ 0 were measured by X-ray diffraction, A diffraction pattern of an ε-type copper phthalocyanine pigment as shown in FIG. 3 having diffraction peaks at Bragg angles 2θ of 7.5, 9.0, and 14.2 degrees was shown.
The pigment used in Comparative Example 4 was measured by X-ray diffraction. As a result, the diffraction pattern of an ε-type copper phthalocyanine pigment having diffraction peaks at Bragg angles 2θ of 7.5, 9.0, and 14.2 degrees was shown.

The copper phthalocyanine pigments 1 to 29 from which the π type was obtained showed excellent results with high brightness as compared with the copper phthalocyanine pigments prepared in Comparative Examples 1 to 4 having the β or ε crystal type. As for the contrast ratio, in many Examples, it was confirmed that the obtained π-type phthalocyanine pigment had higher brightness than the ε-type or β-type and had excellent color characteristics. The high brightness means that the transmitted light has a high transmittance, so that it is possible to show the same luminance with a smaller amount of light. For example, in an image display device such as a liquid crystal television, it leads to further energy saving. Furthermore, since the contrast ratio is high, it is possible to provide an image display device such as a colorful liquid crystal television.
From these results, a π-type crystal of a phthalocyanine pigment having a substituent at least at the α-position can be produced by the phthalonitrile method or the Weiler method satisfying the mathematical formula (1), unlike the prior art, and the obtained π It was confirmed that the type pigment was superior in color characteristics and display characteristics as compared with the prior art.

It should be noted that various modifications and changes may be made to the above-described embodiments without departing from the novel and advantageous features of the present invention other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

Claims

A π-type phthalocyanine pigment represented by the following general formula (1).
General formula (1)

(R 1 to R 8 are each independently a hydrogen atom, COOH, CONH 2 , CF 3 , OC 6 H 5 , NH 2 , NO 2 , C 6 H 5 , or an alkyl group. R 1 to R 8 Are not simultaneously hydrogen atoms, M is a metal atom or 2H, and R 9 to R 16 are each independently a hydrogen atom, aryl group, sulfone group, sulfoamide group, cyano group, hydroxyl group, thiol. A substituent, an acyl group, a halogeno group, a silyl group, or a silyloxy group, and the substituents of R 1 to R 16 may be in the form of a metal salt.)
The π-type phthalocyanine pigment according to claim 1, wherein M is Cu.
A method for producing a π-type phthalocyanine pigment according to claim 1,
Phthalic anhydride, a phthalic acid derivative substituted at least in the α-position, urea, a urea derivative or ammonia, and a metal salt,
The reaction temperature is x (° C.),
The input weight (%) of the phthalic acid derivative to the total input weight of phthalic anhydride and the phthalic acid derivative is y,
When the amount of solvent input (times) relative to the total input weight of phthalic anhydride and the phthalic acid derivative is z,
Formula (1): x-4.3y-1.8z-145 ≦ 0
(However, 90 ≦ x ≦ 300, 0 <y, 0 ≦ z)
The manufacturing method of (pi) -type phthalocyanine pigment including the process made to react on the conditions represented by these.
A method for producing a π-type phthalocyanine pigment according to claim 1,
A phthalonitrile and / or diiminoisoindoline, a phthalonitrile derivative substituted at least in the α-position and / or a diiminoisoindoline derivative substituted in at least the α-position, and a metal salt are reacted at 60 to 300 ° C. A method for producing a π-type phthalocyanine pigment, comprising a step.
A pigment composition comprising the π-type phthalocyanine pigment according to claim 1 and a π-type unsubstituted phthalocyanine pigment.
A coloring composition comprising the pigment composition according to claim 5 and a pigment carrier.
The coloring composition according to claim 6, further comprising a resin-type pigment dispersant and / or a pigment derivative.
The colored composition according to claim 6, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.
Comprising at least a substrate and a filter segment formed on the substrate, and a part of the filter segment is obtained by using the coloring composition according to any one of claims 6 to 8. Color filter.