JP2007291232A - Composition of compound containing chlorinated and brominated phthalocyanine skeleton, method of preparing the composition and pigment-dispersed ink and color filter using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green pigment which is more yellowish and has a high color value. <P>SOLUTION: A composition of a compound containing a chlorinated and brominated phthalocyanine skeleton is obtained by first chlorinating a phthalocyanine skeleton and second brominating the chlorinated phthalocyanine skeleton. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition of a chlorinated brominated phthalocyanine skeleton-containing compound, a method for producing the composition, a pigment-dispersed ink and a color filter using the composition. More specifically, the present invention relates to a composition of a chlorinated brominated phthalocyanine skeleton-containing compound that is obtained by controlling the position of chlorine substitution on the phthalocyanine skeleton, which is more yellowish green.

  Halogenated phthalocyanine pigments are widely used as green pigments in the color material industry because of their beautiful color tone, high tinting strength, and good performance such as heat resistance and weather resistance.

  As an industrial method for producing a halogenated phthalocyanine pigment, a method in which a blue phthalocyanine compound is produced and then halogenated is common. The phthalocyanine compound is a cyclic compound having four isoindoles around a central metal (or metal free), and is a blue compound having four aromatic rings in one molecule. Each of the aromatic rings has 4 hydrogen atoms, and a total of 16 hydrogen atoms are substituted with halogen atoms such as chlorine and bromine, whereby a green halogenated phthalocyanine pigment is obtained.

  As a general method for halogenating a phthalocyanine compound, there is a method in which a phthalocyanine compound is dissolved in an eutectic salt of aluminum chloride and sodium chloride and halogenated (see Patent Document 1 below). In addition, as other methods, a method in which an adduct of a phthalocyanine compound and aluminum chloride is formed in a titanium tetrachloride solvent and halogenated (see Patent Document 2 below), a phthalocyanine compound is dissolved in chlorosulfonic acid. And a halogenation method (see Patent Document 3 below).

  As the halogenated phthalocyanine pigment produced in this manner, many structures having copper, zinc, nickel, cobalt, aluminum and the like as a central metal, and metal-free structures are known. Among these structures, in particular, a copper halide phthalocyanine pigment whose central metal is copper is most often used because of its clearest color tone (see Patent Document 4 below).

  Examples of the halogenated copper phthalocyanine pigment include chlorinated brominated copper phthalocyanine pigment (CI Pigment Green 36) and chlorinated copper phthalocyanine (CI Pigment Green 7). Widely used as electronic materials and color materials such as filters.

  A color filter used in a liquid crystal display device is formed by forming pixels of three colors of red, green, and blue on a transparent substrate such as glass. Of these, a green pigment is generally used to form a green pixel, and as this green pigment, a pigment having a strong yellowness and a high brightness is usually required. Among the above-mentioned halogenated copper phthalocyanine pigments, chlorinated brominated copper phthalocyanine pigments are particularly strong yellowish green pigments, and are therefore often used as pigments for green pixels of color filters.

  In the conventional literature on halogenation of phthalocyanine compounds, copper phthalocyanine is substituted with 3 to 9 bromine atoms and 6 to 13 chlorine atoms, or the bromine atom is substituted at the α-position as the substitution position. In addition, there is a description that yellowness as a pigment is increased by substitution of a chlorine atom at the β-position (see Patent Document 5 below).

  However, in recent years, with regard to the color tone of the halogenated phthalocyanine pigment, many studies have applied that the degree of halogenation is increased and that the halogen to be substituted is more yellow than chlorine. For example, a strong yellowish chlorinated brominated copper phthalocyanine pigment having 14 or more bromine atoms is often used as a green pixel of a color filter (see Patent Document 6 below).

  As for the method for producing such a chlorinated brominated copper phthalocyanine pigment, most of the methods for introducing chlorine and bromine into the phthalocyanine compound are to first introduce bromine and then introduce chlorine. As another method, there is a production method in which a chlorine source and a bromine source are simultaneously present in the reaction system (see Patent Document 7 below).

JP 52-155625 A JP-A-1-279975 U.S. Pat. No. 2,662,085 JP 2002-131521 A U.S. Pat. No. 3,332,961 JP 2001-342374 A Japanese Patent Laid-Open No. 51-64534 JP 63-123004 A Japanese Patent Laid-Open No. 10-160928

  However, even a strong yellowish chlorinated brominated copper phthalocyanine pigment having 14 or more bromine atoms is often not sufficient for a strong yellowish demand. Therefore, instead of using a chlorinated brominated copper phthalocyanine pigment alone for the purpose of enhancing the yellowness as a green pixel of the color filter, for example, C.I. I. Adjustment to a desired color is performed by mixing colors with yellow pigments such as Pigment YELLOW 150 and 185 (see Patent Documents 8 and 9 above).

  It is also known that by mixing a yellow pigment with a green pigment in this way, the color becomes more yellowish, but at the same time, there is a risk of causing a decrease in brightness. In general, yellow pigments have low light resistance and may reduce the lifetime of the display device. Therefore, in order to reduce the addition amount of the yellow pigment and to eliminate the need for further addition, a high brightness green pigment having a stronger yellowishness is desired.

  [1] A composition of a chlorinated brominated phthalocyanine skeleton-containing compound obtained by first chlorinating a phthalocyanine skeleton and secondly brominating the chlorinated phthalocyanine skeleton.

  [2] Third, the chlorinated brominated phthalocyanine skeleton-containing compound composition according to [1], which is obtained by chlorinating the chlorinated and brominated phthalocyanine skeleton.

  [3] The number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton in the chlorinated brominated phthalocyanine skeleton-containing compound is 0.15 to 3.0 on average per phthalocyanine skeleton, and the phthalocyanine A chlorination containing a chlorinated brominated phthalocyanine skeleton-containing compound group (A) in which the average number of bromine atoms substituted on the four aromatic rings of the skeleton is 10.0 to 15.7 on average per phthalocyanine skeleton A composition of a brominated phthalocyanine skeleton-containing compound.

  [4] Furthermore, the average number of chlorine atoms substituted at the β-position in the four aromatic rings of the phthalocyanine skeleton in the chlorinated brominated phthalocyanine skeleton-containing compound is 0.15 to 4.0 per phthalocyanine skeleton, Chlorinated brominated phthalocyanine skeleton-containing compounds other than the compound group (A), wherein the number of bromine atoms substituted on the four aromatic rings of the phthalocyanine skeleton is 10.0 to 15.7 on average per one phthalocyanine skeleton The composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to [3], which contains (B).

  [5] The chlorinated bromine according to [3] or [4], further comprising a brominated phthalocyanine skeleton-containing compound (C) having 16 bromine atoms substituted on four aromatic rings of the phthalocyanine skeleton A composition of a phthalocyanine skeleton-containing compound.

  [6] The content ratio of compound group (A), compound group (B) and compound (C) in the composition is the number of phthalocyanine skeletons derived from compound group (A): phthalocyanine skeletons derived from compound group (B) The composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to [5], wherein the content ratio is such that the number of phthalocyanine skeletons derived from the compound (C) is 20 to 150: 100: 1 to 150.

[7] When the central metal in the phthalocyanine skeleton is copper, the hue h ° value of the composition is 140.00 to 158.00,
When the central metal in the phthalocyanine skeleton is aluminum, the hue h ° value of the composition is 140.00 to 156.00,
When the central metal in the phthalocyanine skeleton is zinc, nickel, cobalt or metal free, the hue h ° value of the composition is 140.00 to 154.00.
[3] A composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to any one of [3] to [6].

  [8] The composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to any one of [1] to [7], wherein the composition of the chlorinated brominated phthalocyanine skeleton-containing compound is a pigment.

  [9] A pigment-dispersed ink comprising the composition of the chlorinated brominated phthalocyanine skeleton-containing compound described in [8] and a pigment carrier.

  [10] A color filter having pixels formed on the substrate with the pigment-dispersed ink according to [9].

  [11] A method for producing a composition of a chlorinated brominated phthalocyanine skeleton-containing compound, comprising a first halogenation step of chlorinating a phthalocyanine skeleton and a second halogenation step of brominating the chlorinated phthalocyanine skeleton .

  [12] The chlorine according to [11], wherein the first halogenation step chlorinates the phthalocyanine skeleton so that the average number of substituents is 0.3 to 6.0 per phthalocyanine skeleton. Of the composition of a brominated phthalocyanine skeleton-containing compound.

  [13] Bromination of the chlorinated phthalocyanine skeleton wherein the average number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton is 0.15 to 3.0 per phthalocyanine skeleton. A method for producing a composition of a chlorinated brominated phthalocyanine skeleton-containing compound, comprising a bromination step.

  [14] The chlorinated brominated phthalocyanine skeleton-containing compound composition according to any one of [11] to [13], further comprising a chlorination step of chlorinating the chlorinated and brominated phthalocyanine skeleton. Production method.

  [15] The step of brominating comprises brominating the phthalocyanine skeleton so that the average number of substituents is 10.0 to 15.7 per phthalocyanine skeleton. The manufacturing method of the composition of the chlorinated brominated phthalocyanine skeleton containing compound described in any one.

  [16] The chlorination step or the bromination step is independently performed by dissolving phthalocyanine in an eutectic salt of aluminum chloride and sodium chloride to chlorinate or bromine, in a titanium tetrachloride solvent. The chlorinated brominated phthalocyanine according to any one of [11] to [15], which is a step of chlorinating or brominating phthalocyanine, or a step of dissolving and chlorinating phthalocyanine in chlorosulfonic acid A method for producing a composition of a skeleton-containing compound.

  According to a preferred embodiment of the present invention, it is possible to provide a high brightness green pigment with stronger yellowness. Therefore, basically, since this green pigment alone can provide a strong yellowish green color, the amount of yellow pigment added as a complementary color can be reduced or not added. As a result, it is possible to eliminate the possibility of a decrease in light resistance and lightness that occurs when a yellow pigment is added. When this green pigment is used, for example, in a color filter, the lifetime of the display device can be improved.

<Chlorinated brominated phthalocyanine skeleton-containing compound group (A)>
The composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to the present invention is a composition described below.
That is, the average number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton in the chlorinated brominated phthalocyanine skeleton-containing compound is 0.15 to 3.0 per phthalocyanine skeleton, The chlorinated bromine containing the chlorinated brominated phthalocyanine skeleton-containing compound group (A) in which the number of bromine atoms substituted on the four aromatic rings is an average of 10.0 to 15.7 per phthalocyanine skeleton This is a composition of a compound containing a fluorinated phthalocyanine skeleton.

  Here, the “chlorinated brominated phthalocyanine skeleton-containing compound” is a compound containing in its molecule a chlorinated and brominated phthalocyanine skeleton. Further, the “compound group (A)” and “composition of a chlorinated brominated phthalocyanine skeleton-containing compound” (hereinafter, also simply referred to as “composition”) mean that the aromatic ring hydrogen atoms are bromine atoms and / or Alternatively, it is a mixture of a plurality of chlorinated brominated phthalocyanine skeleton-containing compounds substituted with chlorine atoms.

  In the composition according to the present invention, the average number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton is 0.15 to 3.0 per phthalocyanine skeleton, and the four aromatic rings of the phthalocyanine skeleton A compound group (A) containing a chlorinated brominated phthalocyanine skeleton having an average of 10.0 to 15.7 bromine atoms per phthalocyanine skeleton.

  In order to make the color more yellowish, the average number of chlorine atoms substituted at the α-position of the compound group (A) is preferably 0.20 to 2.5, and preferably 0.25 to 2.0 Is more preferably 0.30 to 1.5, and most preferably 0.35 to 1.0. When the average number of chlorine atoms substituted at the α-position is less than 0.15, the yellowing effect is small, and when it exceeds 3.0, the bromine atom decreases and the tendency to become bluish becomes strong.

  The average number of chlorine atoms substituted at the α-position of the compound group (A) is as described above, but the number of chlorine atoms substituted at the α-position of the compound group (A) is 0, 1, 2 It is preferable that the number is 3 or 4. More preferably, it is 0-3, More preferably, it is 0-2, Most preferably, it is 0 or 1.

  The compound group (A) is a chlorinated brominated phthalocyanine skeleton-containing compound group in which chlorine is substituted at the α-position, but β-position chlorine may be present at the same time.

  Moreover, in order to obtain a chlorinated brominated phthalocyanine having a strong yellowish taste, the average number of bromine atoms substituted on the four aromatic rings of the phthalocyanine skeleton of the compound group (A) is 10.0 to 15.7. Is more preferable, 11.5 to 15.4 is more preferable, 13.0 to 15.2 is further preferable, and 14.0 to 15.0 is most preferable. When the average number of bromine atoms is less than 10.0, the bluish color becomes strong. When chlorine is substituted at the α-position by 0.15 or more, chlorine is also substituted at the β-position by 0.15 or more. No more than 15.7 can be replaced.

  The average number of bromine atoms substituted on the four aromatic rings of the compound group (A) is as described above, but the number of bromine atoms substituted on the four aromatic rings of the compound group (A) is four aromatic rings. In the substitution positions other than the place where the chlorine is substituted, the number is 9, 10, 11, 12, 13, 14, 15, 15 or 16. The preferred number of bromine atoms is selected in relation to the number of chlorine atoms, and is selected so that the sum of chlorine atoms and bromine atoms substituted on four aromatic rings is 14, 15, or 16. More preferably, the sum is selected to be 15 or 16, and still more preferably, the sum is selected to be 16.

<Chlorinated brominated phthalocyanine skeleton-containing compound group (B)>
The composition according to the present invention further has an average number of chlorine atoms substituted at the β-position of 0.15 to 4.0 per phthalocyanine skeleton, and bromine substituted on four aromatic rings of the phthalocyanine skeleton. It is preferable to contain the chlorinated brominated phthalocyanine skeleton-containing compound group (B) other than the compound group (A), which has an average number of atoms of 10.0 to 15.7 per phthalocyanine skeleton. By containing the compound group (B) in the composition, the crystallinity of the composition can be suppressed, and the composition can be adjusted to a desired color.

  The average number of chlorine atoms substituted at the β-position of the compound group (B) is preferably 0.20 to 3.0, more preferably 0.25 to 2.5, and 0.30. More preferably, it is -2.0, and most preferably is 0.35-1.5.

  The average number of chlorine atoms substituted at the β-position of the compound group (B) is as described above, but the number of chlorine atoms substituted at the β-position of the compound group (B) is 0, 1, 2 Three, four or five are preferable. More preferably, it is 0-4, More preferably, it is 0-3, Most preferably, it is 0-2.

  The number of bromine atoms substituted on the four aromatic rings of the compound group (B) is 9 or 10 at the substitution positions other than the place where the chlorine is substituted among the 16 substitution positions on the four aromatic rings. 11, 12, 13, 14, 15 or 16. The preferred number of bromine atoms is selected in relation to the number of chlorine atoms, and is selected so that the sum of chlorine atoms and bromine atoms substituted on four aromatic rings is 14, 15, or 16. More preferably, the sum is selected to be 15 or 16, and still more preferably, the sum is selected to be 16.

<Chlorinated brominated phthalocyanine skeleton-containing compound (C)>
The composition according to the present invention preferably further contains a brominated phthalocyanine skeleton-containing compound (C) having 16 bromine atoms substituted on four aromatic rings. By containing the compound (C) in the composition, the composition can be adjusted to a desired color.

<Content Ratio of Compound Group (A), Compound Group (B) and Compound (C)>
When the composition described above contains the compound group (A), the compound group (B), and the compound (C), the compound group (A), the compound group (B), and the compound (C) in the composition The content ratio is such that the number of phthalocyanine skeletons derived from the compound group (A): the number of phthalocyanine skeletons derived from the compound group (B): the number of phthalocyanine skeletons derived from the compound (C) is 20 to 150: 100: 1 to 150. It is a content ratio.

  Here, the reason based on “the number of phthalocyanine skeletons derived from the compound” is that each compound contains not only one phthalocyanine skeleton but also a plurality of phthalocyanine skeletons (for example, a dimer). This is because the content ratio of each compound is defined in consideration of the number of phthalocyanine skeletons contained in the molecule.

  The content ratio of the compound group (A), the compound group (B), and the compound (C) is a content ratio such that the number of phthalocyanine skeletons derived from each compound is 50 to 120: 100: 15 to 120. It is more preferable that the content ratio be 70 to 100: 100: 30 to 100. The effect of making the color yellow is because it is important that the compound group (A), the compound group (B) and the compound (C) are contained almost equally in the composition.

<Color of composition>
The composition according to the present invention has a strong yellowish green color, and the hue h ° value of the composition is influenced by the degree of chlorination and bromination and the substitution position, as well as the central metal (or metal free) of the phthalocyanine skeleton. Also affected by.

For example, in the case of copper phthalocyanine whose central metal is Cu, the hue h ° value of the composition is preferably 140.00 to 158.00, more preferably 142.00 to 157.00, It is preferably 144.000 to 156.00, and most preferably 146.000 to 155.00.
In the case of phthalocyanine whose central metal is Al, Ga, In, Si, the hue h ° value of the composition is preferably 140.00 to 156.00, more preferably 142.00 to 155. 0.00, more preferably 144.00 to 153.00, and most preferably 146.000 to 152.00.
In the case where the central metal is Zn, Co, Ni, or metal-free phthalocyanine, the hue h ° value of the composition is preferably 140.00 to 154.00, more preferably 141.00. It is -153.00, More preferably, it is 142.00-151.00, Most preferably, it is 143.000-150.00.

  When the composition is a mixture of these various phthalocyanines, a hue h ° value is expected with a degree of contribution according to each content. The “hue h °” is an element in the color system, along with “lightness L *” and “saturation C *”, and the smaller the hue h ° value is, the stronger yellow Yes, it means that the larger one is greener with more bluish tint.

<Substituents other than halogen to the phthalocyanine skeleton>
Substituents other than halogen atoms may be bonded to the aromatic ring of the phthalocyanine skeleton. Examples of substituents other than halogen atoms that may be substituted on the aromatic ring of the phthalocyanine skeleton include hydrogen, hydroxyl group, nitro group, amino group, cyano group, alkyl group, cyclic alkyl group, alkoxy group, cyclic alkoxy group, alkoxyalkyl Group, alkylthio group, cyclic alkylthio group, alkenyl group, cyclic alkenyl group, alkenyloxy group, alkylamino group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, alkylaminocarbonyl group, fluoroalkyl group, fluoroalkoxy group, Fluoroalkylthio group, carboxyl group, formyl group, sulfonic acid group, alkylsulfonyl group, alkylaminosulfonyl group, alkylaminosulfonic acid group, chlorosulfone group, carbamide group, sulfonamido group, aryl group, ant Aryloxy group, an arylthio group, an aliphatic heterocyclic group or an aromatic heterocyclic group.

  Examples of the alkyl group include straight-chain or branched alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group. Of the alkyl group. Examples of the cyclic alkyl group include cyclic alkyl groups having 3 to 6 carbon atoms, such as a cyclopropyl group and a cyclobutyl group.

  Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, for example, a straight chain such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, and a sec-butoxy group. Examples include branched alkoxy groups. Examples of the cyclic alkoxy group include a C3-C6 cyclic alkoxy group such as a cyclopropyloxy group and a cyclobutyloxy group.

  Examples of the alkoxyalkyl group include an alkoxyalkyl group having 2 to 5 carbon atoms, for example, a linear or branched alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

  As the alkylthio group, an alkylthio group having 1 to 4 carbon atoms, for example, a straight chain such as methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, tert-butylthio group, sec-butylthio group or the like Examples include branched alkylthio groups. Examples of the cyclic alkylthio group include a cyclic alkylthio group having 3 to 6 carbon atoms, such as a cyclopropylthio group and a cyclobutylthio group.

  Examples of the alkenyl group include alkenyl groups having 2 to 5 carbon atoms, for example, linear or branched alkenyl groups such as vinyl group, propenyl group, butenyl group, and pentenyl group. Examples of the cyclic alkenyl group include C3-C6 cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl. Examples of the alkenyloxy group include alkenyloxy groups having 2 to 5 carbon atoms, for example, linear or branched alkenyloxy groups such as a propenyloxy group, a butenyloxy group, and a pentenyloxy group.

  Examples of the alkylamino group include C1-C10 alkylamino groups, for example, linear or branched alkylamino groups such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group.

  Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 5 carbon atoms, for example, a linear or branched alkylcarbonyl group such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group. Examples of the alkoxycarbonyl group include those having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, sec. -Linear or branched alkoxycarbonyl groups such as butoxycarbonyl group.

  Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 5 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, tert Examples thereof include linear or branched alkylcarbonyloxy groups such as -butylcarbonyloxy group and sec-butylcarbonyloxy group.

  Examples of the alkylaminocarbonyl group include an alkylaminocarbonyl group having 1 to 6 carbon atoms, such as a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group. Examples of the fluoroalkyl group include C1-C4 fluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, perfluoro-n-butyl group, perfluoro group. Examples thereof include linear or branched fluoroalkyl groups such as a fluoro-tert-butyl group and a perfluoro-sec-butyl group.

  As the fluoroalkoxy group, a fluoroalkoxy group having 1 to 4 carbon atoms, such as a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoro-n-propoxy group, a heptafluoroisopropoxy group, a perfluoro-n-butoxy group, Examples thereof include linear or branched fluoroalkoxy groups such as a perfluoro-tert-butoxy group and a perfluoro-sec-butoxy group.

  As the fluoroalkylthio group, a fluoroalkylthio group having 1 to 4 carbon atoms, such as a trifluoromethylthio group, a pentafluoroethylthio group, a heptafluoro-n-propylthio group, a heptafluoroisopropylthio group, a perfluoro-n-butylthio group And a linear or branched fluoroalkylthio group such as perfluoro-tert-butylthio group and perfluoro-sec-butylthio group.

  Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 4 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, tert-butylsulfonyl group, sec- Examples thereof include linear or branched alkylsulfonyl groups such as a butylsulfonyl group. Examples of the alkylaminosulfonyl group include alkylaminosulfonyl groups having 1 to 6 carbon atoms, such as a methylaminosulfonyl group, an ethylaminosulfonyl group, a dimethylaminosulfonyl group, and a diethylaminosulfonyl group.

  Examples of the alkylaminosulfonate group include C1-C6 alkylaminosulfonate groups such as methylaminosulfonate group, ethylaminosulfonate group, dimethylaminosulfonate group, and diethylaminosulfonate group.

  The number of substituents other than the halogen atom and the hydrogen atom depends on the size of the substituent, but is preferably 2 or less in order to maintain the properties as a pigment. More preferably, it is 1 or less, most preferably 0.

<Central metal of phthalocyanine skeleton and substituent to central metal>
As the central metal of the phthalocyanine skeleton, Cu, Ni, Co, Zn, Fe, Pd, Mg, Ru, Rh, Pt, Mn, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, Ag, Au, etc. Divalent metals (hereinafter also referred to as “L2”), trivalent metals (hereinafter also referred to as “L3”) such as Al, In, Ga, Tl, Mn, Fe, and Ru, Si, Ge, Sn, Ti, Various metals such as a tetravalent metal such as Cr, Zr, Mn, and V (hereinafter also referred to as “L4”) can be given. These central metals may be in the form of an oxy metal or may have one or more substituents Z described later. The central metal of the phthalocyanine skeleton is preferably Cu, Ni, Co, Zn, Al, In, Ga, Si, Sn, Ti, more preferably Cu, Al, Zn, Ni, Co, and more preferably Includes Cu, Al, and Zn. Further, a form having no central metal (that is, two hydrogen atoms) is also preferable.

Specific forms of the central metal include Cu, Ni, Co, Zn, Fe, Pd, Mg, Ru, Rh, Pt, Mn, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, Ag, 1-substitution represented by divalent metal L2 such as Au or L3-Z such as Al-Z, In-Z, Ga-Z, Tl-Z, Mn-Z, Fe-Z, Ru-Z trivalent or _{metal, Si-Z 2, Ge-} Z 2, Sn-Z 2, Ti-Z 2, Cr-Z 2, Zr-Z 2, Mn-Z 2 , such as _{L4-Z 2} (where, L4 The two Z substituted in the above may be different from each other, or may be the same substituent.) A disubstituted tetravalent metal represented by: V = O, Mn = Examples thereof include oxymetals represented by L4 = O such as O and Ti = O, and lanthanides.

  Z is an arbitrary substituent, and among them, a halogen atom, a hydroxyl group, a sulfonic acid group, an alkoxy group or an aryloxy group is preferable. The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but is preferably a fluorine atom, a chlorine atom, or a bromine atom, and particularly preferably a chlorine atom or a bromine atom. As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms in which an alkyl chain portion is linear, branched or cyclic, such as a methoxy group, an ethoxy group, a butoxy group, and a hexyloxy group is preferable, and in particular, an alkoxy group having 1 to 4 carbon atoms. The alkoxy group is preferable. As the aryloxy group, any of 2 or 3 condensed rings in which the aryl moiety is a 5-membered ring, a 6-membered ring, a 5-membered ring and / or a 6-membered ring, such as a phenoxy group, a naphthyloxy group, a pyridyloxy group, or a quinolyloxy group. An aryloxy group. Z is particularly preferably a halogen atom or a hydroxyl group.

  In order to coordinate a hydroxyl group to Al, In, Ga, Si or the like of the central metal, for example, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine or chlorosilane phthalocyanine may be hydrolyzed by a known method. In order to coordinate an alkoxy group to the central metal Al, In, Ga, Si, for example, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine or chlorosilane phthalocyanine, hydroxyaluminum phthalocyanine, hydroxyindium phthalocyanine, hydroxygallium phthalocyanine or A method of heat-treating hydroxysilane phthalocyanine in an alcohol solvent such as methanol or ethanol is used. At this time, a base such as sodium alkoxide or sodium hydride may coexist in the alcohol solvent.

  In order to coordinate an aryloxy group to the central metal Al, In, Ga, Si, etc., for example, chloroaluminum phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine or chlorosilane phthalocyanine, hydroxyaluminum phthalocyanine, hydroxyindium phthalocyanine, hydroxy A method is used in which gallium phthalocyanine or hydroxysilane phthalocyanine is heat-treated in a solvent containing a hydroxy derivative of an aromatic compound. At this time, a base such as sodium alkoxide or sodium hydride may coexist in a solvent containing a hydroxy derivative of an aromatic compound.

<Dimer and multimeric structure of phthalocyanine>
The phthalocyanine skeleton may form a multimer in which the central metal is bonded to the central metal of a plurality of other phthalocyanine skeletons via a polyvalent atomic group. Further, the connection site may be not only the central metal of each phthalocyanine skeleton but also four aromatic rings of the phthalocyanine skeleton. Preferably, the phthalocyanine skeleton has a central metal of another phthalocyanine skeleton via a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO ₂ —). A dimer formed by bonding with. In this case, examples of the trivalent metal L3 as a specific embodiment of the central metal include Al, In, Ga, Tl, Mn, Fe, Ru, and the like, and 1-substituted 4 represented by L4-Z. Examples of the valent metal include Si—Z, Ge—Z, Sn—Z, Ti—Z, Cr—Z, Zr—Z, and Mn—Z.

<Method for producing composition according to the present invention>
The manufacturing method of the composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to the present invention is a manufacturing method described below.
That is, in a method for producing a composition of a chlorinated brominated phthalocyanine skeleton-containing compound, comprising a first halogenation step of chlorinating a phthalocyanine skeleton and a second halogenation step of brominating the chlorinated phthalocyanine skeleton. is there.
Moreover, you may have the 3rd halogenation process which further chlorinates the said chlorinated and brominated phthalocyanine frame | skeleton as needed.

Moreover, the composition which concerns on this invention mentioned above will be a composition demonstrated below if another expression is used.
That is, a chlorinated brominated phthalocyanine skeleton obtained by first chlorinating a phthalocyanine skeleton (first halogenation step) and secondly brominating the chlorinated phthalocyanine skeleton (second halogenation step) It is a composition of a containing compound.
If necessary, thirdly, the chlorinated and brominated phthalocyanine skeleton may be chlorinated (third halogenation step).

  In order to produce the composition according to the present invention, the order of each halogenation is important, and the order of each halogenation cannot be performed by a known method. Thus, the order of halogenation is important, but this order varies slightly depending on the raw materials. That is, when a compound having an unsubstituted phthalocyanine skeleton is used as a raw material, first, a first halogenation step (chlorination) is performed, and then a second halogenation step (bromination) is performed. A halogenation step (chlorination) is performed. On the other hand, when a compound having a chlorine atom at the α-position, for example, a compound having a monochlorophthalocyanine skeleton, a compound having a dichlorophthalocyanine skeleton, or a mixture thereof is used as a raw material, the first halogenation step (chlorination) is eliminated. Alternatively, the amount of chlorine introduced in the first halogenation step (chlorination) is suppressed.

  The present inventors have obtained knowledge shown in the following reaction formula regarding the substitution position of a halogen atom in halogenating phthalocyanine. In addition, although the halogen (X = F, Cl, Br, I) reaction of copper phthalocyanine is shown as an example in the following reaction formula, the present invention is not limited to copper as a central metal, and other central metals can also be used. Can be applied.

According to the above reaction formula, when phthalocyanine is halogenated, the compound (1) in which the α-position of the aromatic ring is first halogenated and the compound (2) in which the β-position is halogenated are formed almost equally (step a). ).
Next, a compound (3) in which two α-positions are halogenated is formed from the compound (1) at a ratio of about 100%, and the α-position and the β-position are formed from the compound (2) at a ratio of about 90%. The halogenated compound (4) and the compound (5) in which the two β-positions are halogenated at a ratio of about 10% are formed (step b).
Next, a compound (6) in which the β-position and the two α-positions are halogenated is formed from the compound (3) and the compound (4) at a ratio of about 100%, and about 100% from the compound (5). The compound (7) in which the α-position and the two β-positions are halogenated is produced at a ratio of (Step c).
Finally, compound (8) in which all substitution sites are halogenated is formed from compound (6) and compound (7) (step d).

  That is, in the initial stage up to step b, phthalocyanine in which at least one α-position is halogenated is formed at a ratio of about 95%. On the other hand, up to step b, the phthalocyanine in which at least one β-position is halogenated remains at a ratio of about 50%. From this, it is understood that when a desired halogen element (chlorine in the present invention) is to be substituted at the α-position of the aromatic ring, first, halogenation with the halogen element may be performed as the first step.

<First halogenation (chlorination) step in the production method>
In order to make the hue of chlorinated brominated phthalocyanine yellowish green, the number of chlorine atoms substituted at the α-position of the aromatic ring is important, but the conventional halogenation sequence (after first supplying the bromine source) Next, when supplying a chlorine source or supplying a bromine source and a chlorine source at the same time), most of the α-position of the aromatic ring was substituted with bromine. Therefore, in the present invention, by supplying a chlorine source in the first halogenation step, the α-position of the aromatic ring is mainly substituted with a chlorine atom.

  In the first halogenation step, the phthalocyanine skeleton is preferably chlorinated so that the average number of substituents is 0.3 to 6.0 per phthalocyanine skeleton. As described above, in the halogenation in the initial stage, the α-position and the β-position are equally introduced, so “so that the average number of substituents is 0.3 to 6.0 per phthalocyanine skeleton” means “phthalocyanine” An average of 0.15 to 3.0 chlorine is introduced into the α-position (total of 8 locations) of the skeleton, and an average of 0.15 to 3.0 chlorine is also introduced into the β-position (total of 8 locations). It is said to be.

  In the first halogenation step, the average number of chlorine atoms substituted at the α-position in the step is 0.20 to 2.5 (a total of 0.40 to 5.0 including the β-position). It is preferable to make it 0.25 to 2.0 (more preferably 0.50 to 4.0 including β position), and 0.30 to 1.5 ( It is more preferable to include a total of 0.60 to 3.0 when the β position is included, and 0.35 to 1.0 (a total of 0.70 to 2.0 when the β position is also included). Most preferably.

  Usually, in the first halogenation step, introduction of halogen is relatively suppressed in order to suppress heat generation in the reaction system. This means that the introduced halogen reacts at a rate of almost 100% and is introduced almost uniformly into the α and β positions. Accordingly, in the first halogenation step, a theoretical amount of chlorine corresponding to the desired number of substituents may be introduced into the reaction system.

<Second halogenation (bromination) step in the production method>

  As described above, in the present invention, since the α-position of the aromatic ring is controlled to be mainly substituted with a chlorine atom, the second halogenation step that is bromination after the first halogenation step that is chlorination. To do. In the second halogenation step, the phthalocyanine skeleton is preferably brominated so that the average number of substituents per phthalocyanine skeleton is 10.0 to 15.7. The reaction rate in the second halogenation step varies depending on the halogenation method and reaction scale. Therefore, it is necessary to determine the reaction temperature, the bromine introduction rate, the introduction amount, etc. for each type of halogenation method.

<Third halogenation (chlorination) step in the production method>
The third halogenation step is a chlorination step and may be performed as necessary. That is, when there is an aromatic ring substitution site (a hydrogen atom is bonded) that is not halogenated in the first and second halogenation steps, and chlorine is to be introduced into this substitution site, the third halogenation is performed. Perform the process. In the first and second halogenation steps, almost all of the α-position of the aromatic ring is substituted with chlorine or bromine, so the chlorine substitution position in the third halogenation step is mainly the β-position. The substituted site to which the hydrogen atom is bonded may be left as it is as a hydrogen atom, or a substituent other than halogen may be bonded.

  The composition obtained through the first and second halogenation steps (the third halogenation step if necessary) contains the compound group (A), the compound group (B) and the compound (C). Is preferred. In this case, the content ratios of the compound group (A), the compound group (B), and the compound (C) in the composition are as described above.

<Production method using chlorinated phthalocyanine skeleton as a starting material>
Moreover, the other manufacturing method of the composition based on this invention is a manufacturing method demonstrated below.
That is, bromination for brominating the chlorinated phthalocyanine skeleton in which the number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton is an average of 0.15 to 3.0 per phthalocyanine skeleton It is a manufacturing method of the composition of a chlorinated brominated phthalocyanine frame | skeleton containing compound which has a process.
Moreover, you may have the chlorination process which further chlorinates the said chlorinated and brominated phthalocyanine frame | skeleton as needed.

  The “bromination step” corresponds to the second halogenation step, and the “chlorination step” corresponds to the third halogenation step.

  In producing chlorinated brominated phthalocyanine, not only unsubstituted phthalocyanine but also phthalocyanine in which the α-position is already substituted with a chlorine atom can be used as a starting material. The phthalocyanine is preferably chlorinated phthalocyanine having an average number of chlorine atoms substituted at the α-position of 0.15 to 3.0 per phthalocyanine skeleton. For example, monochlorophthalocyanine and / or dichlorophthalocyanine And chlorinated phthalocyanines and mixtures thereof.

  The phthalocyanine substituted at the α-position as a raw material with a chlorine atom preferably has an average number of chlorine atoms substituted at the α-position of 0.20 to 2.5, preferably 0.25 to 2. More preferably, it is 0, still more preferably 0.30 to 1.5, and most preferably 0.35 to 1.0. Furthermore, in addition to phthalocyanine substituted at the α-position with chlorine, a raw material containing monochlorophthalocyanine and / or dichlorophthalocyanine substituted at the β-position with chlorine, chlorine in the first and third halogenation steps is used. May be omitted.

<Halogenation method applicable in the first to third halogenation steps>
In the method for producing a composition according to the present invention, as the first to third halogenation steps (chlorination or bromination) described above, phthalocyanine is dissolved independently in a molten salt of aluminum chloride and sodium chloride. Chlorination or bromination step, phthalocyanine and aluminum chloride adducts are produced in a titanium tetrachloride solvent, chlorination or bromination step, or phthalocyanine is dissolved in chlorosulfonic acid to chlorination or bromination step For example, a known halogenation method can be employed.

  Known halogenation methods include, for example, the molten salt method or the chlorosulfonic acid method described in “The Phthalocyanines Volume II Manufacture and Applications” (CRC Press, Inc. 1983).

  Examples of the molten salt method include various halogens such as aluminum halides such as aluminum chloride and aluminum bromide, alkali metal halides or alkaline earth metal halides such as sodium chloride and sodium bromide, and thionyl chloride. A method of halogenating phthalocyanine with a halogenating agent in a melt of about 10 to 170 ° C. composed of one kind or a mixture of two or more kinds of compounds that become a solvent at the time of conversion (Japanese Patent Laid-Open No. 51-64534). (See also U.S. Pat. No. 4,077,974).

  In this method, halogenated phthalocyanines with different halogenation rates and types of halogenation can be obtained by adjusting the ratio of chloride and bromide in the molten salt, or by changing the introduction amount of the halogenating agent and the reaction time. The ratio can be controlled arbitrarily. Although it does not specifically limit as a halogenating agent, A chlorine gas, a bromine, a sulfuryl chloride, a bromine chloride, etc. are mention | raise | lifted.

  Examples of the chlorosulfonic acid method include a method in which phthalocyanine is dissolved in a sulfur oxide solvent such as chlorosulfonic acid, and a halogenating agent is added to the phthalocyanine and halogenated. The reaction at this time is performed, for example, at a temperature of 20 to 120 ° C. and in a range of 1 to 10 hours.

<Specific explanation of molten salt method>
The operating conditions such as the amount of solvent, reaction temperature, and reaction time during halogenation by the molten salt method vary depending on the type of halogenation method, but can be carried out according to known methods. The conditions for the method of halogenating by forming an adduct of phthalocyanine and aluminum chloride in a titanium tetrachloride solvent and the method of halogenating by dissolving phthalocyanine in a eutectic salt of aluminum chloride and sodium chloride are as follows. Etc. will be described in detail.

<Conditions for halogenation in titanium tetrachloride solvent>
The amount of titanium tetrachloride is 4 times or more, preferably 5 to 20 times, more preferably 8 to 12 times the weight of the raw material phthalocyanine. If it is 4 times or less, stirring of the slurry is difficult, and if it is 20 times or more, it is economically disadvantageous.

  The method of adding aluminum chloride as a catalyst to the reaction system is important in order to keep the reaction system stable. That is, it is preferable to produce an adduct or salt of phthalocyanine and aluminum chloride by heating and stirring phthalocyanine and aluminum chloride before halogenation. Appropriate conditions for this include, for example, a method in which 0.4 to 4 times moles of aluminum chloride is added to phthalocyanine before halogenation, and preliminary stirring is performed at 50 ° C. or higher. As a result, a salt of phthalocyanine and aluminum chloride can be generated. After this salt is formed, halogenation is carried out, and it is preferable that aluminum chloride is further added as necessary to make the total addition amount 3 to 8 times mol of phthalocyanine.

  The initial addition amount of aluminum chloride and the stability of the reaction system are also affected by the amount of titanium tetrachloride. That is, in order to keep the reaction system stable, when the amount of titanium tetrachloride is large, the total amount of aluminum chloride required may be added at one time, but when the amount of titanium tetrachloride is small, It is preferable that the initial addition amount of aluminum chloride is also relatively small, and the addition of aluminum chloride is performed little by little. With respect to the timing of adding the additional aluminum chloride, it is preferable that the halogenation reaction becomes slow.

  The pre-stirring temperature for producing an adduct or salt of aluminum chloride and phthalocyanine is 50 ° C. or higher, preferably 80 to 137 ° C., more preferably 120 to 130 ° C. The pre-stirring time varies depending on the initial addition amount of aluminum chloride, the amount of titanium tetrachloride, and the temperature, but the initial addition amount of aluminum chloride is relatively small relative to phthalocyanine and titanium tetrachloride, and the temperature is 100 to 130. In the case of ° C., it is preferably 0.5 to 5 hours, and more preferably 2 to 5 hours. On the other hand, when the initial addition amount of aluminum chloride is relatively large, it is preferably 2 to 10 hours, and more preferably 5 to 10 hours.

  The temperature of the halogenation step is preferably 100 to 137 ° C, more preferably 120 to 135 ° C, and still more preferably 125 to 130 ° C. However, even if the pressure is increased to increase the reaction rate, the reaction temperature may be increased. Good. The time of the halogenation step is preferably that halogen is introduced over 20 to 200 hours, more preferably 30 to 100 hours, and further preferably 40 to 80 hours. If the time of the halogenation step is less than 20 hours, the proportion of the halogen that reacts decreases, and if it exceeds 200 hours, the productivity decreases.

<Conditions for halogenation in molten salt of aluminum chloride and sodium chloride>
The composition ratio of aluminum chloride and sodium chloride in the molten salt is preferably a temperature at which the melting point is as low as possible, for example, the ratio at which the melting point is the lowest, 63:37 in molar ratio, and approximately 4: 1 in weight ratio. This ratio can be adjusted in the range of about ± 10%, more preferably in the range of about ± 5%. If the amount of aluminum chloride is greater than this ratio, the amount of aluminum chloride sublimation may increase, which may be a problem in the process. On the other hand, if the amount is less than the above ratio, the molten salt tends to solidify. There is.

  The amount of the starting phthalocyanine (unsubstituted and chlorinated phthalocyanine) is preferably 10 to 35 parts by weight with respect to 100 parts by weight of the molten salt. More preferably, it is 15-30 weight part with respect to 100 weight part of molten salt, More preferably, it is 20-25 weight part. When the amount is more than 30 parts by weight with respect to 100 parts by weight of the molten salt, the viscosity of the reaction system becomes too high and it is difficult to take out. On the other hand, if it is less than 10 parts by weight with respect to 100 parts by weight of the molten salt, it is disadvantageous in terms of cost.

  In the halogenation step, basically, a molten salt containing phthalocyanine is kept at 120 to 200 ° C., and halogen is introduced over 10 to 160 hours. About reaction temperature, Preferably it is 140-190 degreeC, More preferably, it is 150-180 degreeC. Moreover, about reaction time, Preferably it is 15 to 100 hours, More preferably, it is 20 to 60 hours. If the reaction temperature is higher than 200 ° C, there is a problem in the apparatus of the glass lining kettle, and if it is lower than 120 ° C, the molten salt may solidify. In addition, when the reaction time is less than 10 hours, the proportion of the halogen that reacts decreases, and the heat generated by the reaction heat of the molten salt increases, which may increase the risk. Further, when the reaction time is longer than 160 hours, the productivity is lowered.

  The eutectic salts of other aluminum halides and other alkali (earth) metal halides are the same as the above conditions, or can be inferred from those conditions by those skilled in the art.

<Halogenated phthalonitrile method>
The composition according to the present invention can also be produced by a halogenated phthalonitrile method. As the halogenated phthalonitrile method, for example, as described in “The Phthalocyanines Volume II Manufacture and Applications” (CRC Press, Inc. 1983), for example, a part or all of the aromatic ring hydrogen atoms may be bromine or Examples thereof include a method of synthesizing a corresponding chlorinated brominated phthalocyanine using phthalic acid or phthalodinitrile substituted with chlorine or the like and the above-described central metal species or a metal salt thereof as a starting material as appropriate. In this case, a catalyst such as ammonium molybdate may be used as necessary. The reaction at this time is performed at a temperature of 100 to 300 ° C. and for a range of 1 to 30 hours.

  In any of the above production methods, after completion of the reaction, when the obtained reaction mixture is put into an aqueous acid solution such as water or hydrochloric acid, a composition of a compound containing a halogenated phthalocyanine skeleton (a crude pigment described later) is precipitated. To do. After the composition is filtered, it is washed with water or an aqueous alkali solution such as an aqueous sodium hydrogen sulfate solution, an aqueous sodium hydrogen carbonate solution, or an aqueous sodium hydroxide solution, and if necessary, acetone, toluene, methyl alcohol, ethyl alcohol, dimethylformamide. It is preferable to wash with an organic solvent such as

<Method for producing dimer of chlorinated brominated phthalocyanine>
The dimer of chlorinated brominated phthalocyanine can be produced by a known method. For example, after synthesizing chlorinated brominated aluminum phthalocyanine, chlorinated brominated indium phthalocyanine, etc., it is hydrolyzed by a known method to obtain hydroxyaluminum phthalocyanine and hydroxyindium phthalocyanine, and further obtained by heating and dehydrating in an organic solvent. be able to. As a result, a dimer having two phthalocyanine skeletons in which each central metal is bonded via an oxygen atom (linking group) can be obtained. In addition, dimers via other linking groups such as a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO ₂ —) can also be produced by known methods.

<Pigmentation of the composition according to the present invention>
When the composition according to the present invention obtained as described above is used as a pigment, it is called a so-called crude pigment. Although there are slight differences depending on the production method, coarse particles of about 0.01 μm or less are used. On the contrary, it is a strong aggregate (about 10 to 200 μm) of very fine particles. It is well known that the raw pigments are not adequate in terms of sharpness, transparency, coloring power, etc., and their value as a pigment for coloring such as ink, paint or plastics is very high. Low.

  To obtain a high-value chlorinated brominated phthalocyanine pigment from this crude pigment, it is called pigmentation, which is the process of adjusting the particle size, aspect ratio, crystal type, etc. from the viewpoint of color and dispersibility. A process is required. By this pigmentation, a composition which is further excellent in dispersibility and coloring power and develops a yellowish and light green color can be obtained.

  As a method of pigmentation, for example, the composition according to the present invention is dissolved in a strong acid such as concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, polyphosphoric acid or a mixture thereof, and then poured into a large amount of water to form a fine pigment. And the acid slurry method in which the composition according to the present invention is dispersed in a strong acid and then poured into a large amount of water to form a fine pigment. Further, the composition according to the present invention may be pigmented at the same time as the dispersion.

  Further, as another method, solvent salt milling is performed by using a ball mill or a kneader to add an inorganic salt such as sodium chloride and a solvent to the composition according to the present invention and then grinding and then removing the inorganic salt and the solvent to obtain a fine pigment. There are laws. Further, when the particle size is too small, there is a solvent boiling method in which crystals are grown by heat treatment in an organic solvent. Before performing the solvent salt milling method or the solvent boiling method, the composition according to the present invention may be dry-ground by a pulverizer such as an attritor, a ball mill, a vibration mill, a vibration ball mill or the like, if necessary. Good.

<Pigmentation by solvent salt milling method>
In the present invention, the pigmentation method is not particularly limited, and any known and commonly used methods can be employed, and those pigmented by any of the above methods can also be used. In particular, it is preferable to employ the solvent salt milling method from the viewpoint that the crystal growth can be easily suppressed and pigment particles having a large specific surface area (that is, finer) can be obtained. The solvent salt milling process involves kneading the chlorinated brominated phthalocyanine crude pigment, which has not been pigmented, immediately after manufacturing the composition, or after that, an inorganic salt as a grinding aid, and an organic solvent. Do by grinding. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. Examples of the kneading means at this time include a kneader and a mix muller.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used, and for example, an inorganic salt such as sodium chloride, potassium chloride, or sodium sulfate is preferably used. It is more preferable to use an inorganic salt having an average particle diameter of 1 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  Further, as the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, Liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropy Glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, or the like can be used dipropylene glycol.

  The amount of the water-soluble organic solvent used is not particularly limited, but is preferably 0.5 to 2.5 parts by weight, preferably 0.8 to 1.5 parts by weight based on 1 part by weight of the composition according to the present invention. More preferred are parts by weight. The amount of the inorganic salt used is preferably 5 to 20 parts by weight and more preferably 7 to 15 parts by weight with respect to 1 part by weight of the composition according to the present invention. The temperature of the solvent salt milling treatment is preferably 30 to 190 ° C, more preferably 80 to 140 ° C, and further preferably 90 to 130 ° C. The solvent salt milling time is preferably 5 to 20 hours, more preferably 5 to 15 hours, and even more preferably 6 to 12 hours.

  In this way, a mixture comprising a pigment comprising the composition according to the present invention having an average primary particle size of 0.01 to 0.5 μm, an inorganic salt, and an organic solvent as main components is obtained. It consists of the composition according to the present invention by removing the organic solvent and the inorganic salt, and if necessary, washing, filtering, drying, pulverizing, etc., the solid material mainly composed of the pigment according to the present invention. A pigment (hereinafter also referred to as “the pigment according to the present invention”) can be obtained. As washing for purification of the obtained pigment, neutral, acidic, or alkaline water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

  As the drying after filtration and washing described above, for example, batchwise or continuous drying in which the obtained pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. by a heating source installed in a dryer. Etc. As the dryer, there are generally a box-type dryer, a band dryer, a spray dryer and the like. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, but is obtained as in the case of drying using a box-type dryer or a band dryer. When the obtained pigment becomes a lamp shape or the like, it is performed in order to solve it and turn it into powder. Examples include mortar, hammer mill, disc mill, pin mill, pulverization with a jet mill, and the like.

  In the method of pigmenting the composition according to the present invention, only the composition according to the present invention (crude pigment) may be subjected to solvent salt milling, but the solvent is obtained by using the crude pigment in combination with a dispersant such as a phthalocyanine derivative. Salt milling is also possible. Further, a dispersant such as a phthalocyanine derivative may be added during the synthesis of the crude pigment or after pigmentation, but it is more preferable to add it before the pigmentation step such as solvent salt milling. By adding a dispersing agent such as a phthalocyanine derivative, it is possible to improve the viscosity characteristics and the dispersion stability of the pigment-dispersed ink.

As such dispersants for phthalocyanine derivatives and the like, any known and commonly used dispersants can be used. However, metal-free or metal phthalocyanine derivatives having at least one substituent represented by the following general formula (1) and anthraquinone derivatives, acridone It is preferably selected from the group of derivatives and triazine derivatives.
General formula (1) -XY
(In the formula, X is a direct bond or a divalent bond comprising a chemically reasonable combination composed of 2 to 50 atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. A group, preferably —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, Y is a nitroimido group optionally substituted with a nitro group or a halogen atom, —NR ₁ R ₂ , —SO ₃ · M / m or —COO · M / m, each of R ₁ and R ₂ independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or a substituted An optionally substituted phenyl group or an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom together with R ₁ and R ₂ , M is a hydrogen ion, 1 to 3 valent Metal ion or At least one represents an ammonium ion substituted with an alkyl group, m represents the valence of M.)

  Specific examples of the substituent represented by the general formula (1) include phthalimidomethyl group, 4-nitrophthalimidomethyl group, 4-chlorophthalimidomethyl group, tetrachlorophthalimidomethyl group, carbamoyl group, sulfamoyl group, aminomethyl group, dimethyl group. Aminomethyl group, diethylaminomethyl group, dibutylaminomethyl group, piperidinomethyl group, dimethylaminopropylaminosulfonyl group, diethylaminopropylaminosulfonyl group, dibutylaminopropylaminosulfonyl group, morpholinoethylaminosulfonyl group, dimethylaminopropylaminocarbonyl group, 4 -(Diethylaminopropylaminocarbonyl) phenylaminocarbonyl group, dimethylaminomethylcarbonylaminomethyl group, diethylaminopropylaminomethyl group Bonylaminomethyl group, dibutylaminopropylaminomethylcarbonylaminomethyl group, sulfonic acid group, sodium sulfonate group, calcium sulfonate group, aluminum sulfonate group, dodecylammoniosulfonate group, octadecylammoniosulfonate group, trimethyloctadecyl Ammoniosulfonato group, dimethyldidecylammoniosulfonato group, carboxylic acid group, 2-aluminum carboxylato-5-nitrobenzamidomethyl group, and the like.

  Triazines constituting triazine derivatives are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro groups, hydroxyl groups, alkoxy groups. Group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) 1,3 , 5-triazine.

  The addition amount of a dispersant such as a phthalocyanine derivative is usually 0.01 to 0.3 parts by weight per 1 part by weight of the crude pigment. When using the phthalocyanine derivative, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the amount of the crude pigment used, and the amount of the inorganic salt used is selected from the above range.

<Characteristics of the pigment according to the present invention>
The average particle diameter of the primary particles of the pigment according to the present invention thus obtained is 10 to 500 nm, preferably 20 to 200 nm, more preferably 30 to 100 nm. Any of these pigments can be used for known and commonly used applications. In particular, when the pigment has an average particle size in the above range, the pigment aggregation is relatively weak and the dispersibility to a pigment carrier such as a resin becomes better. The pigment according to the present invention is suitable for coloring paints, plastics, printing inks, rubbers, leathers, textile printing, electronic toners, ink-jet inks, thermal transfer inks, etc., in addition to pigment-dispersed inks for color filters.

  In general, the smaller the particle size of the pigment used in the preparation of the color filter pigment-dispersed ink, the higher the transparency of the color filter pixel portion obtained by using the pigment. Therefore, the average primary particle size of the pigment used for this purpose is preferably in the range of 10 to 100 nm, and particularly preferably in the range of 30 to 50 nm. When the average primary particle size is in this range, a color filter having both high transparency and a high contrast ratio that have been required in recent years can be obtained more easily.

  Here, when the average primary particle diameter of the pigment exceeds 100 nm, the transparency of the color filter pixel portion using this decreases. In addition, when the average primary particle size of the pigment is smaller than 10 nm, the viscosity of the pigment-dispersed ink using the pigment increases with time, thixotropy appears strongly, and the pigment tends to aggregate. In some cases, secondary particles having a larger particle size may be formed. Accordingly, this case is also not preferable because it causes a decrease in the transparency of the color filter pixel portion.

  The average particle diameter of the primary particles of the pigment described above refers to the primary particles of the pigment constituting the aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope (H7650 type, Hitachi High-Technologies). The longer diameter (major diameter) is obtained for each of the 50 and the average is obtained. At this time, the pigment as a sample is ultrasonically dispersed in a solvent and then photographed with a microscope. A scanning electron microscope may be used instead of the transmission electron microscope.

<Yellow pigment that can be used in combination with the pigment according to the present invention>
When using the pigment according to the present invention, the pigment and a yellow pigment may be mixed and used for the purpose of adjusting to a desired hue. By mixing the pigment according to the present invention and the yellow pigment, for example, it is possible to reduce the transmittance of the spectral transmission spectrum at a wavelength of 400 to 500 nm, and the transmittance in the wavelength range is, for example, 50% or less. be able to.

  Hereinafter, specific examples of yellow pigments that may be used together with the pigment according to the present invention are shown by pigment numbers. Terms such as “CI Pigment Yellow 1” mentioned below mean a color index (CI).

  Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62: 1, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 126, 127,127: 1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,156,157,158,159,160,161,162 163,164,165,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,183,184,185,187,188,189, 190,191,191: 1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207 or 208 can be mentioned. Among these, C.I. is preferable because it has high luminance or a small amount of yellow pigment and is suitable for thinning. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 or 185 can be mentioned. These can be used alone or in combination of two or more.

  The combined ratio of the pigment according to the present invention and the yellow pigment can be appropriately selected according to the use, but the yellow pigment is 0 to 30 parts by weight, preferably 0 to 20 parts by weight per 100 parts by weight of the pigment. is there.

  When the pigment according to the present invention is used, a small amount is sufficient even when a yellow pigment is used together for toning. Therefore, when obtaining a color filter of the same color as a conventional green color filter, the same yellow pigment to be used together is used. It can be greatly reduced. Further, when the pigment according to the present invention is used, a small amount is sufficient even when a yellow pigment is used in combination, and reaggregation occurs compared to the conventional case where two or more different color pigments are mixed for toning. It is possible to obtain a color filter having a bright pixel portion that is less turbid and excellent in color purity and has a bright pixel portion. For example, conventional C.I. I. Compared to the case where a mixed pigment using the above-described yellow pigment in combination with a green pigment such as CI Pigment Green 36, the case where the pigment according to the present invention is used in combination with the yellow pigment is, for example, a liquid crystal display. The decrease in brightness is further reduced, and the amount of light transmitted through the green region is also increased.

<Pigs of other colors that can be used in combination with the pigment according to the present invention>
When using the pigment according to the present invention, for the purpose of adjusting to a desired hue, the pigment and a pigment such as a blue pigment, a green pigment, a violet pigment, a red pigment, an orange pigment, a brown pigment, and a black pigment are used. And may be used in combination. Hereinafter, specific examples of pigments that may be used together with the pigment according to the present invention are shown by pigment numbers. Terms such as “CI Pigment Red 1” mentioned below mean a color index (CI).

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

  Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, or 55.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can be used as the pigment.

  The average primary particle size of the yellow pigment and other color pigments described above is preferably 0.5 μm or less, and more preferably 0.2 μm or less.

  When using the pigment according to the present invention, the pigment and the dye may be mixed and used for the purpose of adjusting to a desired hue. Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.

  Other examples of the phthalocyanine dye include C.I. I. Examples of quinoneimine dyes such as Pad Blue 5 include C.I. I. Basic Blue 3, C.I. I. Examples of quinoline dyes such as Basic Blue 9 include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<Pigment dispersion ink containing pigment according to the present invention>
The pigment-dispersed ink contains the pigment according to the present invention described in detail above and a pigment carrier.
<Pigment carrier>
The pigment carrier is constituted by a resin, its precursor or a mixture thereof. When a color filter is produced using the pigment-dispersed ink of the present invention, a transparent resin having a transmittance of 80% or more, particularly 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is used as the resin. Is preferred.

  Examples of the resin include a thermoplastic resin, a thermosetting resin, and a photosensitive resin. Examples of the resin precursor include monomers or oligomers that are cured by irradiation with radiation to form a resin, and these can be used alone or in combination of two or more.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight with respect to 100 parts by weight of the pigment in the pigment-dispersed ink. In the case of producing a pigment dispersion ink for a color filter using a mixture of a resin and a precursor thereof as a pigment carrier, in some cases, the resin is used with respect to 100 parts by weight of the pigment in the pigment dispersion ink. It can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight. The resin precursor can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the pigment in the pigment-dispersed ink.

  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, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Photosensitive resins include (meth) acrylic compounds and silicate polymers having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As monomers and oligomers that are precursors of resins, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β- Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Various acrylates and methacrylates such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Additives>
In order to improve the dispersibility of the pigment in the pigment carrier, the pigment-dispersed ink according to the present invention may appropriately contain a dispersion aid such as a surfactant, a resin-type pigment dispersant, and a dye derivative. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, when using a pigment dispersion ink in which the pigment is dispersed in a pigment carrier using the dispersion aid. A color filter having excellent transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the pigment dispersion ink.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Resin-type pigment dispersant is a resin that has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works to do. Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Examples of commercially available resin-type pigment dispersants include, for example, Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), Florard Fc430 , Fc431 (manufactured by Sumitomo 3M), Solsperse 13240, 20000, 24000, 26000, 28000, etc. Solsperse dispersants (Avisia), Dispersic 111, 161, 162, 163, 164, 182, 2000, 2001, etc. Big Dispersant (made by Big Chemie), Adisper PB711, PB411, PB111, PB814, PB821, PB822, and other Adipar Dispersants (Ajinomoto Fine Techno), Fuka Dispersants such as Fuka 46 and 47 (Fuka Chemicals), etc. Is mentioned.

  The dye derivative is a compound in which a basic or acidic substituent or a phthalimidomethyl group is introduced into an organic dye. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

When the pigment-dispersed ink according to the present invention containing a mixture of a resin and its precursor as a pigment carrier is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4'-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. . The photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the pigment-dispersed ink.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone 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 pigment-dispersed ink.

In the pigment-dispersed ink according to the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a green pixel. In order to facilitate the process, a solvent can be contained. Examples of the solvent include cyclohexanone, propylene glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, n-butyl alcohol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene. Glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether acetate, 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, 1,3-butylene glycol, triacetin, 3,3,5-trimethyl-2-cyclohexen-1-one, ethylene glycol monoethyl ether, γ-butyrolactone, isoamyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, toluene, o-xylene, m-xylene, p-xylene, methyl 3-methoxypropionate, butyl acetate, isobutyl acetate, propyl acetate, etc. Is mentioned. These solvents can be used alone or in combination.
The solvent can be used in a total amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the pigment-dispersed ink.

  The pigment-dispersed ink according to the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the ink. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of the storage stabilizer include hydroquinone such as hydroquinone, methyl hydroquinone, 2,5 di-tert-butyl hydroquinone, tert-butyl hydroquinone, tert-butyl-β benzoquinone, tert-butyl hydroquinone 2,5 diphenyl-p-benzoquinone. Compounds, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, phosphines such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine Compounds, phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide, triphenylphosphite, trisnonyl Examples thereof include phosphite compounds such as phenyl phosphite and t-butylpyrocatechol. 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 pigment in the pigment-dispersed ink.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the pigment in the pigment-dispersed ink.

Further, in the pigment dispersion ink according to the present invention, if necessary, within a range not impairing the effects of the present invention, a thermal polymerization inhibitor, a plasticizer, a surface protective agent, a smoothing agent, a coating aid, an adhesion improver, Additives such as a coatability improver or a development improver can be added.
Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

<Method for producing pigment-dispersed ink>
The pigment-dispersed ink of the present invention is a three-roll mill, a two-roll mill, a sand mill in one or two or more pigments in a pigment carrier and an organic solvent together with the dispersion aid and the photopolymerization initiator as necessary. It can be produced by finely dispersing using various dispersing means such as a kneader and an attritor. In addition, the pigment dispersion ink containing two or more kinds of pigments can be produced by mixing finely dispersed pigments in a pigment carrier and an organic solvent separately.

  The pigment-dispersed ink of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugal separation, sintering filter, membrane filter or the like. It is preferable to remove dust.

<Form of pigment dispersion ink>
The pigment-dispersed ink of the present invention can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent developing type or alkali developing type colored resist material.
The solvent development type or alkali development type colored resist material is a pigment carrier containing a thermoplastic resin, thermosetting resin or photosensitive resin as a pigment carrier, a monomer, a photopolymerization initiator, and a solvent. It is dispersed.

<Color filter>
The pigment-dispersed ink according to the present invention that has been described in detail above can be applied on a substrate by a known method to form a green pixel of a color filter. In general, the color filter has a red pixel and a blue pixel in addition to a green pixel. However, in order to widen a color reproduction region, the color filter may further include a yellow pixel, a cyan pixel, and a magenta pixel. good.

<Production method of color filter>
Generally, a color filter is manufactured through the following manufacturing processes. The pigment dispersion ink prepared as a colored resist material is applied to the entire surface of the color filter substrate provided with a black matrix, heated and dried (pre-baked), then irradiated with ultraviolet rays or visible light through a photomask, and then developed. A photo-cured coating layer of a colored resist material is formed on the part. The same operation is repeated three times for each color, and a color filter having red, green, and blue (or cyan, magenta, and yellow) pixels at predetermined positions is produced. Thereafter, if necessary, the entire color filter may be heat-treated (post-baked) to further thermally cure the photocured coating layer of the colored resist material. Below, the manufacturing method of the color filter which concerns on this invention is demonstrated in detail in order of a process by making the said general manufacturing method into an example, However, This invention is not limited to this.

  The material of the substrate is not particularly limited. Examples of materials include polyesters such as polyethylene terephthalate, polypropylene, polyolefins such as polyethylene, thermoplastic sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins. Examples thereof include thermosetting plastic sheets, and various glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass that have high transmittance to visible light. Among these, a glass plate and a heat resistant plastic sheet are preferable from the viewpoint of heat resistance. In order to improve physical properties such as surface adhesion, the substrate is subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers in advance of the formation of the black matrix. It may be left. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  The black matrix is formed on the substrate using a metal thin film or a black matrix pigment dispersion. The black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide. In this case, first, a thin film of these metals or metal / metal oxide is formed on the substrate by vapor deposition or sputtering. Subsequently, after forming a photosensitive film thereon, the photosensitive film is exposed and developed using a photomask having a repetitive pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, the thin film is etched to form a black matrix.

  When the black matrix pigment dispersion is used, a black matrix is formed using a photosensitive resin composition containing a black color material. For example, carbon black, bone black, graphite, iron black, aniline black, cyanine black, red or the like appropriately selected from the use of a plurality of black color materials such as black, titanium black, or inorganic or organic pigments and dyes, A black matrix is formed using a photosensitive resin composition containing a black color material obtained by mixing green, blue, and the like, in the same manner as the method for forming red, green, and blue pixels described below.

  A colored resist material containing a color material of one of red, green and blue is applied on a substrate provided with a black matrix and dried, and then a photomask is placed on the colored resist material coating film, Pixels are formed through image exposure, development, and thermosetting or photocuring as necessary through a mask. This operation is performed using colored resist materials of other colors to form each color pixel. Among these, the pigment-dispersed ink according to the present invention can be used as a colored resist material for forming a green pixel.

  The coloring resist material can be applied by using a known method such as a spin coating method, a die coating method, a roll coating method, a spray method, a printing method, a bar coating method, or a curtain coating method.

  Drying after applying the colored resist material may be performed using a hot plate, IR oven, convection oven, or the like. The higher the drying temperature, the better the adhesion to the substrate. However, if the drying temperature is too high, the photopolymerization initiator is decomposed and heat polymerization is liable to cause development failure. Therefore, the drying temperature is usually 50 to 200 ° C., preferably 50 to The range is 150 ° C. The drying time is 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes. The thickness of the coating film of the colored resist material after drying is usually 0.5 to 3 μm, and particularly preferably in the range of 1 to 2 μm.

  As light used for photocuring of the colored resist material coating film, it is preferable to use ultraviolet rays or visible light having a wavelength range of 200 to 500 nm. Among them, it is particularly preferable to use ultraviolet rays having a short wavelength and high energy. As a light source for ultraviolet rays or visible light, those widely used in the field of photofabrication can be used.

  Specifically, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, halogen lamp, tungsten lamp, metal halide lamp, chemical lamp, black light lamp, mercury-xenon lamp, excimer lamp, short arc lamp, excimer laser, nitrogen Examples include a laser, helium cadmium laser, a semiconductor laser, a helium / cadmium laser, an argon laser, and a THG or FHG laser using an Nd-YAG laser.

  When only a specific wavelength is used, an optical filter can be used. When a laser is used as the light source, a pixel pattern can be drawn directly on the pigment-dispersed resist coating film without using a photomask. Further, when the pigment dispersion resist has sensitivity to an electron beam, a pixel pattern can be directly drawn on the pigment dispersion resist coating film with an electron beam, as in the case of a laser. In this case, it is not always necessary to add a photopolymerization initiator to the pigment dispersion resist.

The colored resist material can be subjected to image exposure with such a light source, and then developed using an organic solvent or an aqueous solution containing a surfactant and an alkali agent, whereby a pixel can be formed on the substrate. This aqueous solution can further contain an organic solvent and a buffer.
Although there is no restriction | limiting in particular about the image development processing method, Usually, methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, are used at 10-50 degreeC, Preferably it is 15-45 degreeC.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like, both when used alone and when used in combination with an aqueous solution. Can be used alone or in combination of two or more.

  Examples of the developer surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters; amphoteric surfactants such as alkylbetaines and amino acids can be used, These can be used individually by 1 type or in combination of 2 or more types.

  As an alkali agent for the developer, inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc. Or organic amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetraalkylammonium hydroxide, and the like. The above can be used in combination.

  After the development processing described above, it is washed with water and dried. The obtained color filter is heated (post-baked) for a predetermined time at 100 to 280 ° C. with a heating device such as a hot plate or oven to remove volatile components in the coating film, and at the same time, a colored resist material The unreacted monomer remaining in the photocured coating film is thermally cured to complete the color filter. The green pixel of the color filter of the present invention obtained through the above steps is excellent in transparency, color purity, and color density.

  In addition to the above method, the color filter according to the present invention can be manufactured by a method in which a polyimide resin composition containing the pigment according to the present invention is applied and pixels are formed by an etching method. In addition, a method of forming pixels by printing directly on a substrate using a pigment dispersion ink containing the pigment according to the present invention, or a predetermined pattern by immersing the substrate in the electrodeposition liquid containing the pigment according to the present invention It can also be manufactured by a method of forming a pixel by depositing a colored film on the ITO electrode. Further, a film coated with a pigment-dispersed ink containing a pigment according to the present invention is attached to a substrate, peeled off, image-exposed, developed, and a pixel is formed using an ink containing the pigment according to the present invention. It can also be manufactured by a method of forming the film.

A specific example of the color material used for each color coloring resist material is indicated by a pigment number.
Examples of the color material used for the blue coloring resist material include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. . Blue colored resist materials include C.I. I. Pigment violet 1, 1: 1,2,2: 2,3,3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Purple pigments such as 37, 39, 42, 44, 47, 49, and 50 can be used in combination.

  Examples of the color material used for the red coloring resist material include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275 or 276.

  For example, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, Orange pigments such as 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79 and the yellow pigments exemplified above can be used in combination.

[Example 1]
First, 1200 parts by weight of titanium tetrachloride, 60 parts by weight of crude copper phthalocyanine, and 60 parts by weight of aluminum chloride are charged into a reactor, and the temperature is raised with stirring. When the temperature of the reaction system reaches 135 to 137 ° C., reserve for 5 hours. Stir.
To this reaction system, first, in the first halogenation step, chlorine gas was introduced for 2 hours at an introduction rate of 5 parts by weight per hour. Next, in the second halogenation step, bromine was introduced for 80 hours at an introduction rate of 3.5 parts by weight per hour.
After completion of the halogenation, titanium tetrachloride was recovered by distillation to obtain a mixture of aluminum chloride and a chlorinated brominated copper phthalocyanine compound composition. 5 wt% hydrochloric acid was poured into the mixture to make a slurry, and then washed with filtered water to obtain a composition (crude pigment) of a chlorinated brominated copper phthalocyanine compound having a strong yellowish green color.

[Comparative Example 1]
First, 1200 parts by weight of titanium tetrachloride, 60 parts by weight of crude copper phthalocyanine, and 60 parts by weight of aluminum chloride are charged into a reactor, and the temperature is raised with stirring. When the temperature of the reaction system reaches 135 to 137 ° C., reserve for 5 hours. Stir.
For this reaction system, the first halogenation step, which is chlorination, was not performed, but the second halogenation step, which is bromination, was first performed, and then the chlorination step was performed. In this second halogenation step, bromine was introduced at an introduction rate of 3.5 parts by weight per hour for 80 hours. Next, in the chlorination step, chlorine gas was introduced for 2 hours at an introduction rate of 5 parts by weight per hour.
The treatment after completion of the halogenation was carried out in the same manner as in Example 1 to obtain a composition (crude pigment) of a chlorinated brominated copper phthalocyanine compound having a green color.

[Example 2]
After 240 parts by weight of anhydrous aluminum chloride and 60 parts by weight of sodium chloride were charged into a reactor, the temperature was increased while stirring to form a eutectic salt, and then 60 parts by weight of crude copper phthalocyanine was dissolved in this co-dissolved salt. .
First, in the first halogenation step, chlorine gas was introduced into this reaction system at 160 ° C. for 2 hours at an introduction rate of 5 parts by weight per hour. Next, in the second halogenation step, bromine was introduced for 50 hours at an introduction rate of 5 parts by weight per hour. Further, in the third halogenation step, chlorine gas was introduced for 0.5 hour at an introduction rate of 5 parts by weight per hour.
After the halogenation is completed, the reaction solution is slowly poured into 5000 parts by weight of water, heated to 70 ° C., filtered and washed with water, and a composition of a chlorinated brominated copper phthalocyanine compound having a strong yellowish green color (crude product) Pigment) was obtained.

[Comparative Example 2]
After 240 parts by weight of anhydrous aluminum chloride and 60 parts by weight of sodium chloride were charged into a reactor, the temperature was increased while stirring to form a eutectic salt, and then 60 parts by weight of crude copper phthalocyanine was dissolved in this co-dissolved salt. .
For this reaction system, the first halogenation step, which is chlorination, was not performed, but the second halogenation step, which is bromination, was first performed, and then the chlorination step was performed. In this second halogenation step, bromine was introduced at 160 ° C. for 50 hours at an introduction rate of 5 parts by weight per hour. Furthermore, in the third halogenation step, chlorine gas was introduced for 2.5 hours at an introduction rate of 5 parts by weight per hour. The treatment after completion of the halogenation was carried out in the same manner as in Example 2 to obtain a composition (crude pigment) of a chlorinated brominated copper phthalocyanine compound having a green color.

[Example 3]
A composition (crude pigment) of the chlorinated brominated copper phthalocyanine compound of Example 3 was obtained in the same manner except that the crude copper phthalocyanine of Example 2 was changed to crude aluminum phthalocyanine.

[Comparative Example 3]
A composition (crude pigment) of the chlorinated brominated copper phthalocyanine compound of Comparative Example 3 was obtained in the same manner except that the crude copper phthalocyanine of Comparative Example 2 was changed to crude aluminum phthalocyanine.

[Example 4]
A composition (crude pigment) of the chlorinated brominated copper phthalocyanine compound of Example 4 was obtained in the same manner except that the crude copper phthalocyanine of Example 2 was changed to crude zinc phthalocyanine.

[Comparative Example 4]
A composition (crude pigment) of a chlorinated brominated copper phthalocyanine compound of Comparative Example 4 was obtained in the same manner except that the crude copper phthalocyanine of Comparative Example 2 was changed to crude zinc phthalocyanine.

  In the compositions of Examples 1 to 4 and Comparative Examples 1 to 4 obtained as described above, the number of bromine substituents, the number of chlorine substituents, and the position of chlorine substitution were determined from the results of MASS analysis and X-ray fluorescence spectrum analysis. did. This value is shown in Table 1. In addition, the error of each determined value originates from the error of MASS analysis and fluorescent X-ray spectrum analysis.

  In addition, the compositions (crude pigments) of Examples 1 to 4 and Comparative Examples 1 to 4 obtained as described above were prepared according to the pigment test method of JIS K 5101-1991, and the hue was measured. . That is, 0.5 g of the crude pigment according to Example 1 and Comparative Example 1 was kneaded with 1.5 g of resin varnish for offset ink using a Hoover type Mahler to adjust the ink, and these two types of inks were JIS K 5101. -Placed side by side on the white paper defined in 1991, and developed with a steel spatula so that they were in contact with each other to form a very thin layer and a thick layer not affected by the paper color. Three colors of the base color (thin layer) of the color-extended product were measured with a colorimeter (Spectro Color Meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.) (L *, C *, h ° color system). Table 1 shows the average value of these three values as the h ° value. Similarly, test forms for Examples 2 to 4 and Comparative Examples 2 to 4 were prepared, and the measured h ° values are shown in Table 1.

  As shown in Table 1, Examples 1 and 2 had a hue h ° value smaller than those of Comparative Examples 1 and 2, and were green with a stronger yellow. Further, Example 3 and Comparative Example 3 in which the central metal is aluminum, and Example 4 and Comparative Example 4 in which the central metal is zinc have hue h ° values that are higher than those of Examples and Comparative Examples in which the central metal is copper. Smaller green color with a more yellowish color due to changes in the central metal. Further, in the comparison between the central metals of aluminum, Example 3 had a hue h ° value smaller than that of Comparative Example 3 and a green color with stronger yellowness. Further, in the comparison between the central metals of zinc, Example 4 had a hue h ° value smaller than that of Comparative Example 4 and a more yellowish green color.

Claims (16)

  A composition of a chlorinated brominated phthalocyanine skeleton-containing compound obtained by first chlorinating a phthalocyanine skeleton and secondly brominating the chlorinated phthalocyanine skeleton.   Furthermore, the composition of the chlorinated brominated phthalocyanine skeleton containing compound of Claim 1 obtained by chlorinating the said chlorinated and brominated phthalocyanine skeleton 3rdly.   The number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton in the chlorinated brominated phthalocyanine skeleton-containing compound is 0.15 to 3.0 on average per phthalocyanine skeleton, and 4 of the phthalocyanine skeleton A chlorinated brominated phthalocyanine containing the chlorinated brominated phthalocyanine skeleton-containing compound group (A), wherein the average number of bromine atoms substituted on one aromatic ring is 10.0 to 15.7 per phthalocyanine skeleton A composition of a skeleton-containing compound.   Furthermore, the average number of chlorine atoms substituted at the β-position in the four aromatic rings of the phthalocyanine skeleton in the chlorinated brominated phthalocyanine skeleton-containing compound is 0.15 to 4.0 per phthalocyanine skeleton, A group of chlorinated brominated phthalocyanine skeleton-containing compounds (B) other than the compound group (A), wherein the average number of bromine atoms substituted on the four aromatic rings is 10.0 to 15.7 per phthalocyanine skeleton. The composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to claim 3, comprising:   The chlorinated brominated phthalocyanine skeleton-containing compound according to claim 3 or 4, further comprising a brominated phthalocyanine skeleton-containing compound (C) having 16 bromine atoms substituted on four aromatic rings of the phthalocyanine skeleton. Composition.   The content ratio of the compound group (A), the compound group (B), and the compound (C) in the composition is the number of phthalocyanine skeletons derived from the compound group (A): the number of phthalocyanine skeletons derived from the compound group (B): The composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to claim 5, wherein the number of phthalocyanine skeletons derived from the compound (C) is 20 to 150: 100: 1 to 150. When the central metal in the phthalocyanine skeleton is copper, the hue h ° value of the composition is 140.00 to 158.00,
When the central metal in the phthalocyanine skeleton is aluminum, the hue h ° value of the composition is 140.00 to 156.00,
When the central metal in the phthalocyanine skeleton is zinc, nickel, cobalt or metal free, the hue h ° value of the composition is 140.00 to 154.00.
A composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to any one of claims 3 to 6.   The composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to any one of claims 1 to 7, wherein the composition of the chlorinated brominated phthalocyanine skeleton-containing compound is a pigment.   A pigment-dispersed ink comprising the composition of the chlorinated brominated phthalocyanine skeleton-containing compound according to claim 8 and a pigment carrier.   The color filter which has a pixel formed with the pigment dispersion ink of Claim 9 on a board | substrate.   A method for producing a composition of a chlorinated brominated phthalocyanine skeleton-containing compound, comprising a first halogenation step of chlorinating a phthalocyanine skeleton and a second halogenation step of brominating the chlorinated phthalocyanine skeleton.   12. The chlorinated bromination according to claim 11, wherein the first halogenation step chlorinates the phthalocyanine skeleton so that the average number of substituents is 0.3 to 6.0 per phthalocyanine skeleton. A method for producing a composition of a phthalocyanine skeleton-containing compound.   Bromination step of brominating the chlorinated phthalocyanine skeleton, wherein the average number of chlorine atoms substituted at the α-position in the four aromatic rings of the phthalocyanine skeleton is 0.15 to 3.0 per phthalocyanine skeleton The manufacturing method of the composition of a chlorinated brominated phthalocyanine frame | skeleton containing compound which has these.   Furthermore, the manufacturing method of the composition of the chlorinated brominated phthalocyanine frame | skeleton containing compound in any one of Claim 11 thru | or 13 which has a chlorination process which chlorinates the said chlorinated and brominated phthalocyanine frame | skeleton.   15. The bromination step according to claim 11, wherein the bromination step brominates the phthalocyanine skeleton so that the average number of substituents is 10.0 to 15.7 per phthalocyanine skeleton. A method for producing a composition of a chlorinated brominated phthalocyanine skeleton-containing compound.   The chlorination step or the bromination step is independently performed by dissolving phthalocyanine in an eutectic salt of aluminum chloride and sodium chloride and chlorinating or brominating the phthalocyanine in a titanium tetrachloride solvent. The composition of a chlorinated brominated phthalocyanine skeleton-containing compound according to any one of claims 11 to 15, which is a step of chlorination or bromination, or a step of chlorination or bromination by dissolving phthalocyanine in chlorosulfonic acid. Manufacturing method.