CN104105759A

CN104105759A - Pi-CONJUGATED PHTHALOCYANINE PIGMENT, METHOD FOR PRODUCING SAID Pi-CONJUGATED PHTHALOCYANINE PIGMENT, AND COLORED COMPOSITION PREPARED USING SAID Pi-CONJUGATED PHTHALOCYANINE PIGMENT

Info

Publication number: CN104105759A
Application number: CN201380008970.XA
Authority: CN
Inventors: 小谷卓也; 斋藤健太; 武藤俊明
Original assignee: Toyo Ink SC Holdings Co Ltd
Current assignee: Artience Co Ltd
Priority date: 2012-07-25
Filing date: 2013-07-16
Publication date: 2014-10-15
Anticipated expiration: 2033-07-16
Also published as: TWI582172B; JP2014040567A; JP5277469B1; KR20150035487A; CN104105759B; WO2014017330A1; TW201406869A

Abstract

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

Description

The manufacture method of π type phthalocyanine pigments, this π type phthalocyanine pigments and use the coloured composition of this π type phthalocyanine pigments

Technical field

The present invention relates to the colour characteristics excellences such as a kind of brightness and in the manufacture method of the high π type phthalocyanine pigments of the aspect stability such as thermotolerance, this π type phthalocyanine pigments and use the coloured composition of this π type phthalocyanine pigments.While relating in particular to the situation in a kind of colour filter (color filter) using for color liquid crystal display arrangement and solid photographic assembly etc., can provide the above-mentioned pigment of the colour filter of display quality excellence.

Background technology

Generally, colour filter comprises as follows: comprise red colour filter (R) by what form on the surface of the transparency carriers such as glass, green color filter layer (G) and blue colour filter (B), or be equivalent to redness, green, the cyan colour filter (C) of blue complementary color, carmetta colour filter (M), and the colour filter fragment (filter segment) (picture element) of fine band (striped) shape of yellow colour filter (Y) is parallel or cross-over configuration for being called as " striped arrangement ", " mosaic arrangement ", persons such as " rounded projections arranged ", or with the fine colour filter fragment person of forming of certain in length and breadth alignment arrangements.Colour filter fragment is fine to several microns～several 100 microns, and each tone ground with the queueing discipline of regulation configure.

On the colour filter using, be generally formed with to drive the transparency electrode of liquid crystal by evaporation or sputter in color liquid crystal display arrangement, be further formed with thereon with so that the alignment films of liquid crystal aligning on certain orientation.In order to obtain fully the performance of those transparency electrodes and alignment films, must be generally more than 200 DEG C, preferably under more than 230 DEG C high temperature, carry out its formation step.

Can enumerate brightness and contrast gradient (contrast ratio) as the desired quality project of colour filter.If use the low colour filter of contrast gradient, can upset the polarisation degree that liquid crystal is controlled, must interdict light time (OFF state) light leak, seeing through light time (ON state) transmitted light decay, therefore become fuzzy picture.Therefore,, in order to realize high-quality liquid crystal indicator, high-contrast is integral.

And if use the colour filter of low lightness, the penetration coefficient of light is low, therefore becomes dark picture, in order to become bright picture, must make to count increment as the backlight of light source.Therefore, certainly suppress the viewpoint consideration that power consumption increases, the high brightness of colour filter changes into as trend.In addition, as mentioned above, color liquid crystal device becomes for TV or computer screen etc., therefore for colour filter, the requirement of high brightness, high-contrast and high reliability is also increased.

Bright and the tinting strength of copper phthalocyanine is also large, and all tolerance excellences such as weathering resistance, thermotolerance, chemical-resistant, are therefore often used as blue pigments.

And, copper phthalocyanine shows paramorphism, has reported the crystal types such as α, β, ε, γ, δ, π, ρ, χ, R, wherein in printing ink and colour filter etc., the copper phthalocyanine of α, β and ε type has the advantages such as the stability of colour characteristics and crystallization, is therefore often used.

In the blue colour filter of colour filter, necessary general red tone, Comparatively speaking α type is more general red with β type, and Comparatively speaking ε type is more general red with α type, therefore the ε type copper phthalocyanines that use more.In addition, ε type copper phthalocyanine pigments has the character of high distinctness and high-strength excellence.

But, even while carrying out the situation of miniaturization of ε type copper phthalocyanine pigments using known gimmick, contrast gradient increases gradually along with miniaturization, but about brightness, if it is below horizontal that the particle diameter of the primary particle of pigment becomes tens of nm, brightness convergence, therefore becomes and is difficult to make it further to improve.Therefore, be difficult to further to make brightness to improve and the increase that suppresses power consumption to improve energy-efficient performance.

π type copper phthalocyanine and ε type copper phthalocyanine comparatively speaking show general red, are therefore preferably used as the purposes of the blue colour filter of colour filter.But, because its stability is low, be exposed in high temperature and/or organic solvent etc. and easily produce crystallization and shift, poor stability.

Prior art document

Patent documentation

Patent documentation 1: the clear 48-725 communique of Japanese Patent Laid-Open

Patent documentation 2: the clear 63-308074 communique of Japanese Patent Laid-Open

Patent documentation 3: the clear 62-48769 communique of Japanese Patent Laid-Open

Summary of the invention

In patent documentation 1, record the manufacture method of π type copper phthalocyanine.But the π type phthalocyanine of gained is not have the substituent body that do not replace on phenyl ring, with other crystal types poor stability of comparing, therefore not can tolerate the practicality persons such as colour filter purposes.

In patent documentation 2, recorded a kind of synthetic method of copper phthalocyanine, in the copper phthalocyanine of utilizing Wheeler method is synthetic, one side coexists aromatic series polyprotonic acid and simultaneously makes its reaction.There is no the record about the crystal type of generated copper phthalocyanine, but as described later shown in the comparative example 3 of this specification sheets, do not generate π type but generation ε type.

In patent documentation 3, record a kind of synthetic method of π type copper phthalocyanine, in the copper phthalocyanine of utilizing Wheeler method is synthetic, has added Pyromellitic Acid and make its reaction.But the π type copper phthalocyanine of gained is not so good as ε type copper phthalocyanine at aspects such as colour characteristics in the method.In addition, the stability of the crystal type of three-dimensional arrangement is also poor.

The present invention is in view of the shortcoming of above-mentioned prior art and inventor, problem be to provide colour characteristics such as making brightness improve and at the high novel π type phthalocyanine pigments of the aspect stability such as thermotolerance.

In addition, problem is by the colour filter that this novel π type phthalocyanine pigments is used for color liquid crystal display arrangement and solid photographic assembly etc., thereby the colour filter of colour characteristics and display quality excellence is provided.

The invention relates to a kind of π type phthalocyanine pigments, it represents with following general formula (1):

General formula (1)

(R ¹～R ⁸independent is respectively hydrogen atom, COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl; R ¹～R ⁸be not hydrogen atom simultaneously; M is atoms metal or 2H; R ⁹～R ¹⁶independent is respectively hydrogen atom, aryl, sulfuryl, sulfoamido, cyano group, hydroxyl, sulfydryl, acyl group, halogen, silylation or silicon alkoxyl group; R ¹～R ¹⁶substituting group also can be the state of metal-salt).

Other the manufacture method that the invention relates to a kind of π type phthalocyanine pigments, it is the manufacture method of π type phthalocyanine pigments of the present invention, comprises following step:

Temperature of reaction is made as x (DEG C),

With respect to Tetra hydro Phthalic anhydride and total input weight of the substituted phthalic acid derivatives in α position at least, by the input weight (%) of the substituted phthalic acid derivatives in α position be at least made as y,

With respect to Tetra hydro Phthalic anhydride and total input weight of the substituted phthalic acid derivatives in α position at least, when solvent input amount (doubly) is made as to z,

In mathematical expression (1): x-4.3y-1.8z-145≤0

(wherein, 90≤x≤300,0 < y, 0≤z)

Under represented condition, make Tetra hydro Phthalic anhydride and the substituted phthalic acid derivatives in α position at least, with urea, urea derivatives or ammonia, with reacting metal salt.

Make phthalonitrile (phthalonitrile) and/or diiminoisoindole, at least substituted O-phthalic carbonitrile derivatives in α position and/or the substituted diiminoisoindole derivative in α position at least, react at 60 DEG C～300 DEG C with metal-salt.

Other the invention relates to a kind of color compositions, it comprises: π type phthalocyanine pigments of the present invention, the phthalocyanine pigments being unsubstituted with π type.

Other the invention relates to a kind of coloured composition, it contains: color compositions of the present invention and pigment carrier.

In addition, other the invention relates to a kind of colour filter, its at least comprise substrate, with this substrate on the colour filter fragment that forms, a part for this colour filter fragment is to use coloured composition of the present invention and gained person.

[effect of invention]

Colour characteristics and the excellent in stability of the π type phthalocyanine pigments of novelty of the present invention, by using it in the colour filter using in color liquid crystal display arrangement and solid photographic assembly etc., can provide the colour filter of the display quality such as brightness and contrast gradient excellence.

Brief description of the drawings

Fig. 1 is an example of the x-ray diffractogram of powder case of the represented π type copper phthalocyanine pigments of general formula (1).

Fig. 2 is an example of the x-ray diffractogram of powder case of beta type copper phthalocyanine pigments.

Fig. 3 is an example of the x-ray diffractogram of powder case of ε type copper phthalocyanine pigments.

Fig. 4 is an example of the x-ray diffractogram of powder case of the π type copper phthalocyanine pigments of the represented miniaturization of general formula (1).

Fig. 5 is an example of time-of-flight mass spectrometer (Time of Flight Mass Spectrometer, the TOF-MS) figure of the represented π type copper phthalocyanine pigments of general formula (1).

Embodiment

Below, based on preferred embodiment details of the present invention being illustrated.

1. π type phthalocyanine pigments

The people such as present inventor find: as represented in following general formula (1), at the R of the so-called α position as phthalocyanine ¹～R ⁸at least one in import COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl, by this can be easily by the crystallization three-dimensional arrangement of phthalocyanine be maintained π type, therefore become easy generation π type phthalocyanine, and the stability of crystallization improves.In addition, use the situation of this π type phthalocyanine in the colour filter that the people such as present inventor find to use in color liquid crystal display arrangement and solid photographic assembly etc. time, the also colour filter of excellence of the colour characteristics such as brightness and contrast gradient excellence and display quality can be provided, thereby complete the present invention.

General formula (1)

(R ¹～R ⁸independent is respectively hydrogen atom, COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl.R ¹～R ⁸be not hydrogen atom simultaneously.M is atoms metal or 2H.R ⁹～R ¹⁶independent is respectively hydrogen atom, aryl, sulfuryl, sulfoamido, cyano group, hydroxyl, sulfydryl, acyl group, halogen, silylation or silicon alkoxyl group.R ¹～R ¹⁶substituting group also can be the state of metal-salt)

That is phthalocyanine pigments of the present invention is the π type crystallization that is equivalent to α bit position and has the phthalocyanine of substituent general formula (1) at phthalic acid.Sometimes the represented phthalocyanine pigments of general formula (1) is designated as to the phthalocyanine pigments or the α position replacement body that are substituted (replacement of α position) herein.

The R of general formula (1) ¹～R ⁸middle at least one imported functional group is COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl in any functional group all preferred.The preferred carbon number of alkyl is the straight chain of 1～12 left and right or the alkyl of branched chain.Wherein, particularly desirably have and select free COOH, CONH ₂, CF ₃, and OC ₆h ₅at least one substituting group of the group forming.

The sense radix importing there is no and specifies, but the colour characteristics when for colour filter causes dysgenic possibility to improve because sense radix increases, therefore as the sense radix beyond the hydrogen atom importing in 1 molecule phthalocyanine, R ¹～R ⁸(α position) and R ⁹～R ¹⁶preferably 1～8 left and right of the both sides' of (β position) total, more preferably 1～4 or 1～3.And, also can import multiple functional group.

By at R ¹～R ⁸in at least one of (α position), import COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl, with the R that is directed into so-called β position ⁹～R ¹⁶in situation Comparatively speaking, functional group plays a role as the inhibition factor of three-dimensional arrangement, its result improves the stable effect that turns to π type of crystal type, therefore importantly at R ¹～R ⁸middle importing functional group.

In above-mentioned patent documentation 3, the π type copper phthalocyanine of gained not imports the person that has substituting group in α position, with above-mentioned, functional group is directed into R ¹～R ⁸any person in situation Comparatively speaking, the stability of the crystal type of its three-dimensional arrangement is not talkative fully.

Be directed into R ⁹～R ¹⁶in functional group crystal type is not caused to large impact, therefore can import functional group arbitrarily.Wherein, for the tone to pigment exerts an influence, it is desirable to respectively independently for hydrogen atom, aryl, sulfuryl (are also called sulfo group.-SO ₃h), sulfoamido (SO ₂nRR '), cyano group (CN), hydroxyl (is also called hydroxy.-OH), sulfydryl (SH), acyl group, halogen (F ,-Cl ,-Br ,-I), silylation or silicon alkoxyl group.It is desirable to the R of above-mentioned sulfoamido and R ' independent of hydrogen atom, carbon number are the straight chain of 1～5 left and right or the alkyl of branched chain, N respectively, N-dimethylaminomethyl, N, the amino substituted alkyls such as N-dimethyl aminoethyl.The preferred phenyl of aryl, benzyl, tolyl, xylyl etc., acyl group (COR) preferably R is methyl, ethyl, phenyl etc.; (SiRR ' R ") is TMS, triethyl silyl etc. preferably for silylation; (OSiRR ' R ") is trimethyl silicane alcoxyl base, triethyl silicane oxygen base etc. preferably, but is not limited to those for silicon alkoxyl group.

R ¹～R ¹⁶substituting group also can be the state of metal-salt.For example, can enumerate carboxylate salt (COOM), sulfonate (SO ₃m), alkoxide (alkoxide) or phenates (OM), metal (M) can be enumerated the basic metal such as sodium, potassium, lithium.

Central metal M in general formula (1) represents 2H or metal.Wherein, the preferred Cu of M, Zn, Al (OH), 2H, further preferred Cu.M can be a kind in a pigment, also can be multiple.

The π type crystal type of phthalocyanine has x-ray diffractogram of powder case as shown in Figure 1.That is in the time of the situation that uses Cu-K alpha-ray to measure, π type phthalocyanine is the crystal type at 4.9 degree of Bragg angle 2 θ (± 0.3 degree), 6.5 degree, 8.5 degree, 9.7 degree, 10.7 degree, 17.0 degree places with diffraction peak.Fig. 1 is the data about α position with the π type crystallization gained of the phthalocyanine of substituent general formula (1), although due to the functional group who imports, there are some movements the position of each diffraction peak, but as long as crystal type is π type, diffraction pattern shows and the similar pattern of Fig. 1.Wherein, in the time carrying out the situation of miniaturization of phthalocyanine or phthalocyanine pigments, exist diffraction peak to broaden, the phenomenon that the part at peak disappears.Peak is broadened and cause the diffraction pattern of the π type phthalocyanine (α position replaces body) of its part disappearance to be shown in Fig. 4.

The substituent existence that is directed into phenyl ring can be by time-of-flight mass spectrometer (Time ofFlight Mass Spectrometer, TOF-MS) etc. and is confirmed (with reference to Fig. 5).

2. the manufacture method of π type phthalocyanine pigments

Secondly, the representative method for making of the π type crystallization to the represented α position replacement phthalocyanine pigments of above-mentioned general formula (1) is illustrated.

The manufacture method of phthalocyanine can be selected from existing known method, be not particularly limited about its reaction conditions, but as following illustrated as, in Wheeler method in order stably to obtain the crystallization of π type, must be careful the input weight of temperature of reaction, O-phthalic acid starting material, the input weight of solvent, preferably under the condition that meets the mathematical expression of the following stated (1), manufacture.

The main method for making of the phthalocyanine known to general is following 2 kinds.The first is the method that is called as Wheeler method, taking Tetra hydro Phthalic anhydride or derivatives thereof (also those O-phthalic acid starting materials are gathered and are designated as " O-phthalic acids " below) and urea or derivatives thereof as raw material, the gimmick of the present industrial main flow of synthesizing by add source metal, catalyst and solvent etc. simultaneously.The second is the method that is called as phthalonitrile method, use reactive high phthalonitrile or derivatives thereof (also those phthalonitrile raw materials are gathered and are designated as " O-phthalic nitrile " below) or use diiminoisoindole or derivatives thereof (also those diiminoisoindole raw materials are gathered and are designated as " diiminoisoindole class " below) to replace O-phthalic nitrile, by adding source metal etc. and heating and synthetic method.

Below illustrated, in the time using the situation of any means of Wheeler method and phthalonitrile method, by use Tetra hydro Phthalic anhydride in the former, in the latter, use phthalonitrile and/or diiminoisoindole, except the substituted phthalocyanine pigments in α position shown in general formula (1), all can manufacture the phthalocyanine pigments being unsubstituted.The ratio that does not replace body in the phthalocyanine pigments of manufacturing can at random be adjusted according to used feed ratio.Now, generate the represented phthalocyanine pigments of general formula (1) with π type crystal type, therefore due to the existence of this π type crystallization, the phthalocyanine pigments being unsubstituted also becomes identical crystal type, thereby can obtain the composition of identical crystal type (π type).And, as the substituted phthalocyanine pigments in α position of general formula (1), obtain the position of substitution, replace the different multiple compounds such as radix.

(1) Wheeler method

The people such as present inventor are in order to use Wheeler method to make Tetra hydro Phthalic anhydride and the substituted phthalic acid derivatives in α position (at least substituted phthalic acid in α position (acid anhydride) etc.) at least, with urea, urea derivatives or ammonia, and reacting metal salt and stably obtain the crystallization of π type, experimentally is found:

Temperature of reaction is made as x (DEG C),

With respect to Tetra hydro Phthalic anhydride and total input weight of the substituted phthalic acid derivatives in α position at least, by the input weight (%) of this phthalic acid derivatives be made as y,

With respect to total input weight of Tetra hydro Phthalic anhydride and phthalic acid derivatives, when solvent input amount (doubly) is made as to z,

It is desirable in mathematical expression (1): (react under the represented condition in wherein, 90≤x≤300,0 < y, 0≤z) x-4.3y-1.8z-145≤0.In the time that the value of mathematical expression (1) becomes the situation that is greater than 0, obtain not π type, but the mixed crystal of β type, ε type or multiple crystallization etc. (with reference to above-mentioned patent documentation 2) produce and the Comparatively speaking crystal type of low lightness of π type.

Known for mathematical expression (1) is become below zero, that is in order positively to generate π type phthalocyanine, under must amount (z) lower in temperature of reaction (x) and reaction solvent many, gentle condition, react.For example, in the time of the higher situation of temperature of reaction, become the transfer of easy generation to thermodynamically stable crystal type, therefore preferably make quantity of solvent increase etc. and make reaction conditions gentleness, and/or the allotment ratio of phthalic acid derivatives is uprised etc. and the stability of crystallization is uprised.

Temperature of reaction in mathematical expression (1) (DEG C) x is one of important factor in order to crystal type and the productive rate etc. of pigment are caused to large impact.It is desirable to start at autoreaction until start to generate pigment, is x DEG C by temperature fixed adjustment, but in order to control particle diameter and the size-grade distribution of generated pigment particles, also can in the way of reaction, make temperature lifting in the scope of 90 DEG C～300 DEG C.

In a preferred embodiment, as long as meet mathematical expression (1), x is not particularly limited, and general condition is that x is 90 DEG C～300 DEG C, the viewpoint considerations such as autoreaction time, productive rate, and more preferably 120 DEG C～250 DEG C, best is 150 DEG C～200 DEG C.

And, can also improve productive rate and/or raising purity etc. for reacting under the pressurized conditions of object about 0.05MPa～1.0MPa.

The y (=phthalic acid derivatives drops into weight × 100/ (Tetra hydro Phthalic anhydride+phthalic acid derivatives) and always drops into weight) of the input weight (%) of the substituted phthalic acid derivatives at least α position in mathematical expression (1) (at least the substituted phthalic acid in α position (acid anhydride) derivative etc.) is one of important factor in order to crystallization control type.

Preferably drop into the phthalic acid derivatives of sufficient quantity to meet the mode of above-mentioned mathematical expression (1).About the sequential of the input of phthalic acid derivatives, can be in the time that reaction starts otal investment, also can be until the generation of the pigment particles in reaction way be cut apart input between finishing.

In a preferred embodiment, as long as meet above-mentioned mathematical expression (1), y is not particularly limited, but the viewpoints such as autoreaction time, productive rate are considered, y is 1%～20% left and right preferably, more preferably 1%～10% left and right, further 2%～8% left and right more preferably.

In Wheeler method, when synthetic, for the temperature in Controlling System and/or raising stirring efficiency etc., also can use solvent; In order to obtain π type crystal type, preferably use solvent.

The z (=solvent drops into weight/(Tetra hydro Phthalic anhydride+phthalic acid derivatives) and always drops into weight) of the solvent input amount (doubly) in mathematical expression (1) is one of reactive important factor in order in Controlling System.Solvent can total amount drop in the time that reaction starts, and also can divide in the reaction cede territory continuity or interim input, until the generation of pigment finishes, is adjusted into the z that meets mathematical expression (1), can preferably obtain by this crystallization of π type.

In a preferred embodiment, as long as meet mathematical expression (1), z is not particularly limited, and the viewpoint such as autoreaction time, productive rate considers, more preferably z is 2～15 times of left and right, further 3～10 times of left and right more preferably.

The O-phthalic acids using when synthetic by Wheeler method, has known person in various documents, such as Tetra hydro Phthalic anhydride, phthalic acid and salt thereof, its ester, phthalic imidine, phthalic diamide etc.The alkyl ester of the preferred C1～C12 of phthalic ester.

And also can contain on the aromatic ring of those compounds, there is alkyl, the substituent O-phthalic acids such as aryl, nitro, sulfuryl or its metal alkali, sulfoamido, cyano group, amino, hydroxyl or its metal alkali, carboxyl or its metal alkali, amide group, trifluoromethyl, phenoxy group, sulfydryl, acyl group, silicon alkoxyl group, silylation, halogen.

For the phthalocyanine of synthetic general formula (1), at least use Tetra hydro Phthalic anhydride, with the substituted phthalic acid derivatives in α position at least as raw material, but also can partial use O-phthalic acid starting material beyond those (the substituted phthalic acid derivatives in β described later position, do not there is phthalic acid derivatives beyond substituent acid anhydrides etc. on phenyl ring).

Should " the substituted phthalic acid derivatives in α position " be to have as above-mentioned R at least one α position of phthalic acid ¹～R ⁸any one illustrated above substituent " the substituted phthalic acid or derivatives thereof in α position ".The derivative of the carboxyl side of phthalic acid can be enumerated the general carboxylic acid derivative such as Tetra hydro Phthalic anhydride, phthalic ester, phthalic imidine, phthalic diamide.Sometimes also Tetra hydro Phthalic anhydride and phthalic acid summary sheet as representative carboxylic acid derivative are designated as " phthalic acid (acid anhydride) " or " phthalic acid (acid anhydride) derivative ".Replace phthalic acid derivatives as α position, also can use the different multiple compounds of substituent kind and/or the position of substitution.

This substituted phthalic acid derivatives in α position also can have any one above substituting group (R of above-mentioned general formula (1) on β position ⁹～R ¹⁶substituting group).

And, as the phthalic acid derivatives being unsubstituted, also can partially use acid anhydrides derivative (phthalic ester, phthalic imidine etc.) in addition.

In addition, also can partially use and only there is more than one substituent β position replacement phthalic acid or derivatives thereof in β position.The substituting group of the β position in those phthalic acid derivatives is above-mentioned as R ⁹～R ¹⁶and any one above substituting group of explanation.

When the situation of O-phthalic acids beyond using Tetra hydro Phthalic anhydride and the substituted phthalic acid derivatives in α position (phthalic acid derivatives beyond the acid anhydrides that β position replaces phthalic acid or derivatives thereof, be unsubstituted), it in the total of O-phthalic acids that becomes raw material, is preferably left and right below 10 % by weight.

As the urea or derivatives thereof reacting with above-mentioned O-phthalic acids, can enumerate urea, biuret, triuret etc., also preferably use ammonia.Also can use more than those and plant.

Its usage quantity it is desirable to for the total of the O-phthalic acids that becomes raw material (phthalic acid or derivatives thereof), using in 1～10 scope taking molar ratio computing.

Metal-salt is the central metal M person who forms above-mentioned general formula (1), preferably the salt of Cu, Zn, Al etc.As supplying with the source metal of this metal-salt, can use the metal powder, muriate, bromide, iodide, vitriol, sulfide, acetate, oxide compound, oxyhydroxide, carbonate, phosphoric acid salt of the metals such as Cu, Zn, Al etc.The valence mumber of metal impacts reaction, but generally in phthalocyanine is synthetic, can be not particularly limited valence mumber and uses.Wherein, metal preferably copper, preferably can be by cupric chloride (I), cupric chloride (II), copper sulfate, copper hydroxide (I), copper hydroxide (II) etc. preferably as source metal or metal-salt.Also can use those two or more.

The usage quantity of metal-salt is preferably for becoming the total of O-phthalic acids (phthalic acid or derivatives thereof) of raw material, using in 0.15～0.40 scope taking molar ratio computing.

The catalyst of reaction can use known person in Wheeler method.For example can enumerate the molybdic acid compound such as ammonium molybdate, phospho-molybdic acid, the titanium compounds such as titanium tetrachloride, titanic acid ester, weisspiessglanz, arsenic oxide arsenoxide, boric acid etc.Also can use those two or more.

Usage quantity about catalyst is not particularly limited, preferably for becoming the total of O-phthalic acids (phthalic acid or derivatives thereof) of raw material, using in 0.0001～0.3 scope taking weight ratio.

And, can also improve reaction proterties, improve reactive, to improve product purity, raising distinctiveness etc. is object, at random use ortho-phosphoric acid, metaphosphoric acid, Tripyrophosphoric acid, poly-metaphosphoric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide and those metal-salt or ammonium salt for becoming the O-phthalic acids (phthalic acid or derivatives thereof) of raw material, in the time of this situation, can be adding in 0.05～1 scope taking weight ratio.

Reaction solvent can be used as the synthetic of Wheeler method and known organic solvent.For example can use the aromatic hydrocarbonss such as alkylbenzene, alkylnaphthalene, naphthane (tetralin); The ester ring type hydrocarbon such as alkyl cyclohexane, perhydronaphthalene, alkyl perhydronaphthalene; The aliphatic hydrocarbon such as decane, dodecane; The nitro-compound such as oil of mirbane, Ortho Nitro Toluene; The halohydrocarbon such as trichlorobenzene, dichlorobenzene, chloronaphthalene, hexachlorobutadiene; The sulphur compounds such as tetramethylene sulfone, dimethylsulfolane, dimethyl sulfoxide (DMSO); The heterogeneous ring compounds such as quinoline etc.Those organic solvents also can be mixture of more than two kinds.Wherein, for crystallization control type stably, special good is to use the non-proton property polar solvents such as acetonitrile, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-methyl-2-Pyrrolizidine ketone, tetramethylene sulfone.

(2) phthalonitrile method

Phthalonitrile method is as described above under the existence of alkali that becomes catalyst, makes the synthesis method of the phthalocyanine of O-phthalic nitrile and/or diiminoisoindole class and reacting metal salt.

In a preferred embodiment, comprise following steps: make phthalonitrile and/or diiminoisoindole, at least substituted O-phthalic carbonitrile derivatives in α position and/or the substituted diiminoisoindole derivative in α position at least, react at 60 DEG C～300 DEG C with metal-salt.

When synthetic, for the temperature in Controlling System and/or raising stirring efficiency etc., also can use solvent.And, in order to improve productive rate, to improve purity etc., also can under the pressurized conditions of 0.05MPa～1.0MPa left and right, react.

O-phthalic nitrile can use phthalonitrile and/or its derivative.Diiminoisoindole class can be used 1,3-diiminoisoindole and/or its derivative.O-phthalic carbonitrile derivatives or diiminoisoindole derivative can use respectively multiple compounds.

Those derivatives are to be illustrated in the R on the aromatic ring of phthalonitrile or diiminoisoindole with above-mentioned general formula (1) ¹～R ⁸or R ⁹～R ¹⁶any one above substituent compound.And, also can use the compound of the state of metal-salt as above.

For the phthalocyanine of synthetic general formula (1), as at least one party of O-phthalic nitrile and diiminoisoindole class, use and at least there is above-mentioned R in α position ¹～R ⁸any substituent derivative.

As the source metal that can use in phthalonitrile method, can preferably use and the same person of source metal illustrated in above-mentioned Wheeler method.That is, the metal powder of the metals such as Cu, Zn, Al, muriate, bromide, iodide, vitriol, sulfide, acetate, oxide compound, oxyhydroxide, carbonate, phosphoric acid salt etc.In phthalonitrile method, the valence mumber of metal also impacts reaction, but generally in phthalocyanine is synthetic, its valence mumber can there is no particular restriction ground uses.Also can use those two or more.

The usage quantity of source metal is preferably with respect to the total of O-phthalic nitrile and diiminoisoindole class (in the time containing the situation of any one party, be only a side total), using in 0.15～0.40 scope taking molar ratio computing.

There is no particular restriction to become the alkali of catalyst, and suitable is the cyclic amine such as ammonia, morpholine, piperidines; Pyridine, picoline, quinoline etc. import the amine that has nitrogen in aromatic nucleus; 1,5-diazabicyclo [4.3.0]-5-nonene (DBN), 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), 1,5-diazabicyclo [5.4.0] 11 carbon-5-alkene, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane etc. have the amine at amidine position; Carbon number is 1～12 alkoxide; Or those mixture.Also can use those two or more.

The amount of alkali is preferably with respect to the total of O-phthalic nitrile and diiminoisoindole class (in the time containing the situation of any one party, be only a side total), using in 0.001～2 scope taking molar ratio computing.In the time using alkali as the situation of solvent, also can be more.

The solvent that can use in reaction can be used as the synthetic of phthalonitrile method and known organic solvent.For example can preferably use with the alcohols headed by methyl alcohol, ethylene glycol; The aromatic hydrocarbonss such as alkylbenzene, alkylnaphthalene, naphthane; The ester ring type hydrocarbon such as alkyl cyclohexane, perhydronaphthalene, alkyl perhydronaphthalene; The aliphatic hydrocarbon such as decane, dodecane; The nitro-compound such as oil of mirbane, Ortho Nitro Toluene; The halohydrocarbon such as trichlorobenzene, dichlorobenzene, chloronaphthalene, hexachlorobutadiene; The sulphur compounds such as tetramethylene sulfone, dimethylsulfolane, dimethyl sulfoxide (DMSO); The heterogeneous ring compounds such as quinoline etc.; Dimethyl formamide, N-methylpyrrole pyridine ketone, 1,3-dimethyl-2-imidazolidine ketone etc.Those organic solvents also can be mixture of more than two kinds.

Reaction can be carried out at inert gas environment in the time of necessary situation, if desired also can add the known compound in the use of Wheeler method such as ammonium molybdate and/or urea.

(3) other steps

In Wheeler method, phthalonitrile method, all preferably after reaction finishes, carry out the filtration of solvent and solvent distillation remove wait and the separating treatment of reaction solvent after, carry out the cleaning by water and/or organic solvent.In the time cleaning, also can use acid or alkali.In addition, if must purifying, also can be by the distillation as known purification technique, acid paste, acid slurry, the operation such as Shen Dian, recrystallize, extraction and remove impurity again.

By can directly using under synthetic state taking above-mentioned two kinds of methods as the synthetic phthalocyanine pigments of the method for making of representative; but in order to control size of particles, to give easily disperse etc., also can carry out the miniaturization operation of (being also called pigmenting or whole granulation).

Can use known miniaturization method, main method can be enumerated solvent method, solvent polishing, lyonium salt mill method etc.In the time of miniaturization, carry out miniaturization in order to suppress crystal growth, also can add and have that at least one is substituent without metal or metalphthelein cyanine derivative.

The particle diameter (average primary particle diameter) of pigment is preferably prepared as the several nm～number 10nm left and right as the particle diameter of general pigment, but is not limited thereto.

According to the people's such as present inventor research, other crystal types such as the crystallization of π type and such as ε type crystallization comparatively speaking, with the form of the needle crystal of more elongated (aspect ratio is large) and obtain, because be this particle shape, also have advantages of as follows: in the time of miniaturization, without the step of mixing of utilizing kneader etc., can omit and mix step and only obtain the fine pigment that turns to desired granularity by dispersion steps.With respect to this, though the ε type crystal form being for example generally used for up to now in LCD TV etc. be spherical or be needle-like, also equally thick up and down, the step of mixing if do not utilize is difficult to miniaturization, is therefore difficult to omit the step of mixing before dispersion steps.

3. color compositions

Color compositions at least contains the substituent π type phthalocyanine pigments being unsubstituted that is the π type that on the π type phthalocyanine pigments (α position replaces body) of general formula (1) and the phenyl ring of phthalocyanine, do not have beyond hydrogen atom and does not replace phthalocyanine pigments.α position replaces body can comprise substituting group and/or the different multiple compounds of the position of substitution.And diverse α position that also can urban mixed-use center metal M replaces body and/or does not replace body.

As mentioned above, replace in the manufacture of π type phthalocyanine pigments in the α position of general formula (1), if Wheeler rule is used Tetra hydro Phthalic anhydride as raw material, if phthalonitrile rule is used phthalonitrile and/or diiminoisoindole as raw material, also generate by this π type phthalocyanine pigments being unsubstituted, replace body and the π type crystalline mixture that does not replace body thereby can be fabricated to as described above α position.

π type phthalocyanine pigments also can the partial α of being contained in position not be had the substituted π type of a substituting group and β position phthalocyanine pigments (β position replaces body).In order further to improve the stability of π type crystal type, the amount that the β position that can comprise arbitrarily replaces body is preferably left and right below 10 % by weight in π type phthalocyanine pigments.

Color compositions, except π type phthalocyanine pigments and the π type phthalocyanine pigments that is unsubstituted, also can comprise solvent, resin, additive etc. as any composition.

For example, crystal growth when suppressing miniaturization, give crystalline stability, prevent cohesion, easily disperse while giving pigment as tinting material, improve tinting strength etc., also can in miniaturization step or after miniaturization step, the rosin derivatives such as rosin, metal rosin, rosin ester, resin, promoting agent, pigment derivative (pigment derivative) etc. be mixed with pigment.In addition, also can be in the scope that does not hinder effect of the present invention phthalocyanine pigments or the amorphousness phthalocyanine pigments etc. of other crystal types beyond the partial π of comprising type as pigment composition.By those phthalocyanine pigments general names that can be used in color compositions, note by abridging as " phthalocyanine pigments " below.

There is no particular restriction for the form of color compositions, and the arbitrarily form such as the press filtration pie that can adopt powder, contains water also can be made some processing with the mixture of resin etc.

4. coloured composition

The printing inks such as coloured composition at least comprises above-mentioned color compositions and pigment carrier, ink for inkjet, coating, plastics, watercolor, printing and dyeing ink, toning agent (toning agent), carbon dust, colour filter are representative form with pigment dispersions such as resist inks.Wherein, the colour characteristics such as the brightness that particularly the π type phthalocyanine pigments of above-mentioned general formula (1) shows meet the desired colour characteristics of colour filter well, therefore can be aptly for colour filter purposes.

Preferably become component as benchmark (100 % by weight) taking all solids of coloured composition, contain phthalocyanine pigments with the ratio of 5 % by weight～70 % by weight.The more preferably ratio of 20 % by weight～50 % by weight.

In coloured composition, contained pigment carrier is to make phthalocyanine pigments disperse the person of forming, and comprises resin, its precursor or those mixture.

As resin, be chosen in all wavelengths region of 400nm～700nm of visible region, penetration coefficient preferably more than 80%, more than 95% resin more preferably.Resin comprises thermoplastic resin, thermosetting resin and active energy ray hardening resin; Its precursor comprises the active energy ray polymerizable monomer or the oligomer that generate resin by irradiation ultraviolet radiation, electron beam isoreactivity energy line harden.Those compounds can be used alone, or two or more is mixed and is used.

Pigment carrier can be preferably taking for phthalocyanine pigments 100 weight parts in coloured composition as the amount of 30 weight part～700 weight parts is used, more preferably use with the amount of 60 weight part～450 weight parts.

In the time that the mixture of resin and its precursor is used as to the situation of pigment carrier, resin can be preferably taking for phthalocyanine pigments 100 weight parts in coloured composition as the amount of 20 weight part～400 weight parts is used, more preferably use with the amount of 50 weight part～250 weight parts.And, the precursor of resin can be preferably taking for phthalocyanine pigments 100 weight parts in coloured composition as the amount of 10 weight part～300 weight parts is used, more preferably use with the amount of 10 weight part～200 weight parts.

Thermoplastic resin for example can be enumerated butyral resin, styrene-maleic acid copolymer, chlorinatedpolyethylene, Chlorinated Polypropylene III, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, polyurethane(s) is resin, vibrin, acrylic resin, Synolac, polystyrene resin, polyamide resin, natural gum is resin, cyclisation natural gum is resin, cellulose family, polyethylene (high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE)), polyhutadiene, or polyimide resin etc.Can preferably use those a kind of above thermoplastic resin.

Thermosetting resin for example can be enumerated epoxy resin, benzo guanamine (benzoguanamine) resin, rosin upgrading maleic acid resin, rosin upgrading fumaric resin, melamine resin, urea resin or phenol resins etc.Can preferably use those a kind of above thermosetting resin.

Active energy ray hardening resin can use: make to have hydroxyl, carboxyl or the substituent polymer of amino isoreactivity; react with the styracin that there is substituent (methyl) acrylic compound of isocyanato, aldehyde radical or epoxy group(ing) isoreactivity or there is same reaction substituent, import and have the photocrosslinking reaction base persons such as (methyl) acryl or styryl.

And, also can use by (methyl) vinylformic acid hydroxyalkyl acrylate etc. and there is the wire polymer half esterification person of forming that styrene-maleic anhydride copolymer, alpha-olefin-copolymer-maleic anhydride etc. are comprised acid anhydrides by (methyl) acrylic compound of hydroxyl.Can preferably use those a kind above active energy ray hardening resin.

In addition, " (methyl) vinylformic acid " is the both sides that represent " vinylformic acid " and " methacrylic acid ".

As polymerizable monomer and the polymerizability oligomer (photopolymerization monomer, optical polymerism oligomer etc.) of the precursor of resin, can enumerate:

(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl ester, (methyl) vinylformic acid tri-n-butyl, (methyl) vinylformic acid isopentyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) ethyl acrylate, (methyl) aliphatic acrylate, (methyl) vinylformic acid decyl ester, (methyl) vinylformic acid isodecyl ester, (methyl) vinylformic acid Lauryl Ester, (methyl) tridecyl acrylate, the different myristyl ester of (methyl) vinylformic acid, (methyl) stearyl acrylate base ester, and (methyl) vinylformic acid straight chain or branch's alkyl esters such as (methyl) vinylformic acid iso stearyl ester,

(methyl) vinylformic acid cyclic alkyl ester class or (methyl) vinylformic acid ring-type alkenyl esters classes such as (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid tributyl cyclohexyl ester, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid two cyclopentyloxy ethyl esters, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester and (methyl) isobornyl acrylate;

(methyl) vinylformic acid fluoroalkyl ester classes such as (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester and (methyl) vinylformic acid tetrafluoro propyl ester;

(methyl) acryloxy upgrading polydimethylsiloxane (silicone macromonomer) class;

(methyl) vinylformic acid tetrahydrofuran methyl ester and (methyl) vinylformic acid-3-methyl-3-oxa-cyclobutyl ester etc. have (methyl) esters of acrylic acid of heterocycle;

(methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy ethyl, phenoxy group polyoxyethylene glycol (methyl) acrylate, (methyl) vinylformic acid to cumyl phenoxy ethyl, cumyl phenoxy group polyoxyethylene glycol (methyl) acrylate and Nonylphenoxy polyoxyethylene glycol (methyl) acrylate etc. are there is to (methyl) esters of acrylic acid of aromatic ring;

(methyl) vinylformic acid-2-methoxyl group ethyl ester, (methyl) vinylformic acid-2-ethoxy ethyl ester, (methyl) vinylformic acid-3-methoxyl group butyl ester, (methyl) vinylformic acid-2-methoxyl group propyl ester, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, Triethylene glycol ethyl ether (methyl) acrylate, Diethylene Glycol list-2-ethylhexyl ether (methyl) acrylate, dipropylene glycol monomethyl ether (methyl) acrylate, tripropylene glycol list (methyl) acrylate, polyethyleneglycol lauryl ether (methyl) acrylate, and (gathering) alkane glycol monoalkyl ether (methyl) esters of acrylic acid such as polyethyleneglycol stearyl ether (methyl) acrylate,

(methyl) vinylformic acid, acrylic acid dimer, phthalic acid-2-(methyl) acryloxy ethyl ester, phthalic acid-2-(methyl) acryloxy propyl ester, hexahydrophthalic acid-2-(methyl) acryloxy ethyl ester, hexahydrophthalic acid-2-(methyl) acryloxy propyl ester, oxyethane upgrading succsinic acid (methyl) acrylate, (methyl) senecioate-carboxyl ethyl ester, and ω-carboxyl polycaprolactone (methyl) acrylate etc. has (methyl) esters of acrylic acid of carboxyl,

(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) phthalic acid-2-acryloxy ethyl-2-hydroxy methacrylate, Diethylene Glycol list (methyl) acrylate, dipropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, propylene glycol list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, poly-1, 4-butyleneglycol list (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate, poly-(ethylene glycol-1, 4-butyleneglycol) single (methyl) acrylate, poly-(propylene glycol-1, 4-butyleneglycol) single (methyl) acrylate, and glycerol (methyl) acrylate etc. has (methyl) esters of acrylic acid of hydroxyl,

Ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) two (methyl) acrylate, poly-(ethylene glycol-BDO) two (methyl) acrylate, poly-(propylene glycol-BDO) two (methyl) acrylate, poly-BDO two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, and 2-ethyl, (gathering) alkane glycol two (methyl) esters of acrylic acids such as 2-butyl-propylene glycol two (methyl) acrylate,

Dihydroxymethyl two pentamethylene two (methyl) acrylate, hydroxypivalic acid neopentyl glycol two (methyl) acrylate, stearic acid upgrading tetramethylolmethane two (methyl) acrylate, oxyethane upgrading dihydroxyphenyl propane two (methyl) acrylate, propylene oxide upgrading dihydroxyphenyl propane two (methyl) acrylate, tetrahydrofuran (THF) (tetramethylene oxide) upgrading dihydroxyphenyl propane two (methyl) acrylate, oxyethane upgrading Bisphenol F two (methyl) acrylate, propylene oxide upgrading Bisphenol F two (methyl) acrylate, tetrahydrofuran (THF) upgrading Bisphenol F two (methyl) acrylate, dizinc acrylate resin, oxyethane upgrading tricresyl phosphate (methyl) acrylate, and two (methyl) esters of acrylic acid such as glycerol two (methyl) acrylate,

(methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid diethylamino propyl ester etc. have (methyl) esters of acrylic acid of tertiary amine base;

Multifunctional (methyl) acrylate more than trifunctional such as glycerol three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate;

Glycerin triglycidyl ether-(methyl) vinylformic acid affixture, glycerol diglycidylether-(methyl) vinylformic acid affixture, polyglycerol polyglycidyl ether-(methyl) vinylformic acid affixture, 1,6-butanediol diglycidyl ether-(methyl) vinylformic acid affixture, alkyl glycidyl ether-(methyl) vinylformic acid affixture, glycidyl allyl ether-(methyl) vinylformic acid affixture, phenyl glycidyl ether-(methyl) vinylformic acid affixture, Styrene oxide 98min.-(methyl) vinylformic acid affixture, bisphenol A diglycidyl ether-(methyl) vinylformic acid affixture, propylene oxide upgrading bisphenol A diglycidyl ether-(methyl) vinylformic acid affixture, Bisphenol F diglycidylether-(methyl) vinylformic acid affixture, Epicholorohydrin upgrading phthalic acid-(methyl) vinylformic acid affixture, Epicholorohydrin upgrading hexahydrophthalic acid-(methyl) vinylformic acid affixture, ethylene glycol diglycidylether-(methyl) vinylformic acid affixture, polyethyleneglycol diglycidylether-(methyl) vinylformic acid affixture, propylene glycol diglycidylether-(methyl) vinylformic acid affixture, polypropylene glycol diglycidyl ether-(methyl) vinylformic acid affixture, phenols phenolic resin varnish type epoxy resin-(methyl) vinylformic acid affixture, cresols phenolic resin varnish type epoxy resin-(methyl) vinylformic acid affixture, epoxy (methyl) esters of acrylic acids such as other epoxy resin-(methyl) vinylformic acid affixture,

(methyl) acryl upgrading resin oligomer classes such as (methyl) acryl upgrading isocyanuric acid ester, (methyl) acryl upgrading polyurethane(s), (methyl) acryl upgrading polyester, (methyl) acryl upgrading trimeric cyanamide, (methyl) acryl upgrading silicone, (methyl) acryl upgrading polyhutadiene and (methyl) acryl upgrading rosin;

The vinyl such as vinylbenzene, alpha-methyl styrene, vinyl-acetic ester, (methyl) vinyl acrylate and (methyl) allyl acrylate;

The ethene ethers such as hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether and tetramethylolmethane trivinyl ether;

The amidess such as (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide and N-vinyl formamide; And vinyl cyanide etc.Those compounds can be used alone or two or more is mixed and is used.

In coloured composition, in the time said composition being hardened by uviolizing, add photopolymerization initiator etc.

As photopolymerization initiator, can use:

4-phenoxy group dichloroacetophenone, 4-tributyl dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone or 2-methyl isophthalic acid-methyl phenyl ketones such as [4-(methylthio group) phenyl]-2-morpholine propane-1-ketone are photopolymerization initiator;

The st-yraxes such as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether or benzil dimethyl ketal are photopolymerization initiator;

Benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl esters, 4-phenyl benzophenone, dihydroxy benaophenonel, acrylated benzophenone or 4-benzoyl-4 '-benzophenone series photopolymerization initiators such as methyldiphenyl thioether;

The thioxanthones such as thioxanthone (thioxanthone), 2-chlorothiaxanthenone, 2-methyl thioxanthone, isopropyl thioxanthone or 2,4-di-isopropyl thioxanthone are photopolymerization initiator;

2, 4, 6-trichloro-triazine, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-piperonyl-4, two (the trichloromethyl)-s-triazine of 6-, 2, two (the trichloromethyl)-6-styryl-s-triazine of 4-, 2-(naphthalene-1-yl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyl group-naphthalene-1-yl)-4, two (the trichloromethyl)-s-triazine of 6-, 2, 4-trichloromethyl-(piperonyl)-6-triazine, or 2, 4-trichloromethyl (4 '-the methoxyl-styrene)-triazines such as 6-triazine are photopolymerization initiator,

Boric acid ester is photopolymerization initiator;

Carbazole is photopolymerization initiator; Or imidazoles is photopolymerization initiator etc.

Photopolymerization initiator preferably taking for phthalocyanine pigments 100 weight parts in coloured composition as the amount of 5 weight part～200 weight parts is used, amount that more preferably can 10 weight part～150 weight parts and using.

Above-mentioned photopolymerization initiator can be used alone or two or more is mixed and is used; also can and use alpha-acyloxy ester, acylphosphine oxide, methyl benzoylformate (methyl phenyl glyoxylate), benzyl-9 as sensitizing agent in addition; 10-phenanthrenequione, camphorquinone, EAQ, 4; the different phthal.ophenone of 4 '-diethyl, 3; 3 '; 4,4 '-tetra-(tributyl peroxy carbonyl) benzophenone or 4,4 '-compounds such as diethylamino benzophenone.Sensitizing agent can be that the amount of 0.1 weight part～60 weight part is used for photopolymerization initiator 100 weight parts in coloured composition.

Coloured composition can solvent develop type or the form of the painted resist of alkali developable and preparing.Painted resist is the person that is dispersed with pigment in the pigment carrier that comprises thermoplastic resin, thermosetting resin or active energy ray hardening resin and polymerizable monomer.Can use the various decentralized institutions such as three-roll grinder, two roller mills, sand mill, kneader or masher, one kind or two or more pigment dyestuff and photopolymerization initiator optionally are together scattered in pigment carrier and manufacture.Herein, pigment dyestuff be comprise above-mentioned π type phthalocyanine pigments, with the above-mentioned π type phthalocyanine pigments optionally adding arbitrarily in order to regulate tone beyond both sides' the concept of pigment dyestuff.

The manufacture method of coloured composition is not particularly limited, and can color compositions or phthalocyanine pigments and pigment simple substance and the composition that at random comprises be mixed and obtain coloured composition by known any means.Known method comprises above-mentioned various decentralized institution.

And coloured composition also can be scattered in multiple pigment dyestuff respectively the person of forming in pigment carrier to be mixed and is manufactured.

In phthalocyanine pigments is scattered in to pigment carrier time, can suitable use resin type pigment dispersing agent, the dispersing auxiliary (dispersion agent) such as interfacial agent and pigment derivative (pigment derivative).Dispersing auxiliary due to the dispersion excellence to pigment, prevent that the pigment effect of condensing again after disperseing is large, therefore use coloured composition (described coloured composition is the coloured composition that uses dispersing auxiliary that colo(u)rant dispersion is formed in pigment carrier) and the transparency excellence of the coloring film of gained.

Dispersing auxiliary preferably taking for phthalocyanine pigments 100 weight parts in coloured composition as the amount of 0.1 weight part～40 weight part is used, more preferably use with the amount of 0.1 weight part～30 weight part.

Wherein, pigment derivative (pigment derivative) prevents pigment dyestuff cohesion, maintain the effect excellence of the state that pigment dyestuff disperses imperceptibly, and the coloured composition that contains those derivatives by use can be manufactured the coloring film that contrast gradient is high and purity of color is high, therefore preferred as dispersing auxiliary.

As the pigment derivative as pigment dispersing agent, can use with no particular limitation the known pigment derivative (such as, in the clear 63-305173 communique of Japanese Patent Laid-Open, Japanese Patent examined patent publication 57-15620 communique, Japanese Patent examined patent publication 59-40172 communique, Japanese Patent examined patent publication 63-17102 communique, Japanese Patent JP 5-9469 communique etc. record person) generally using.Particularly can enumerate diketopyrrolopyrrolecocrystals series pigments; The azo pigments such as azo, tetrazo, polyazo; The phthalocyanine series pigments such as copper phthalocyanine, copper halide phthalocyanine, metal-free phthalocyanine; The anthraquione pigmentss such as aminoanthraquinone, diamino DIANTHRAQUINONE, anthracene pyrimidine, yellow scholar's ketone, anthanthrone (anthanthrone), indanthrone, pyranthrone, violanthrone; Quinacridone pigment, dioxazine pigment, purple cyclic ketones series pigments, perylene pigments, the indigo series pigments of sulfo-, isoindoline series pigments, isoindolinone pigment, quinoline yellow series pigments, intellectual circle's series pigments, metal complex series pigments etc. have pigment residue and alkali subtituent (amino etc.) or acidic substituent (phosphate, sulfonic group, carboxyl etc.) person.Those compounds can be used alone or two or more is mixed and is used.

Allotment amount when using the situation of pigment derivative, also limit without special, in order to give full play to its allotment effect, for pigment 100 weight parts, be preferably more than 0.1 weight part, consider from maintaining thermotolerance and sunproof viewpoint well, for pigment 100 weight parts, be preferably below 30 weight parts, be more preferably 0.5 weight part left and right, weight part～25 for pigment 100 weight parts.

The resin type pigment dispersing agent adding in coloured composition is to comprise to have the pigment affinity position of the character being adsorbed on pigment and have compatible position with pigment carrier, and plays and be adsorbed on pigment and make the compound of the effect of the decentralized stabilization of pigment in pigment carrier.

That resin type pigment dispersing agent can be enumerated is polyethylene-based, polyurethane(s) system, polyester system, polyethers system, formalin condensation system, silicone-based or those compound based polymer, carboxyl, hydroxyl, phosphate, phosphate-based, sulfonic group, hydroxyl, amino, quarternary ammonium salt base or amide group isopolarity base can be enumerated in pigment affinity position, and the hydrophilic polymer chain such as polyethylene oxide, poly(propylene oxide) or those compound system etc.; There is compatible position with pigment carrier and can enumerate chain alkyl chain, Polyethylene Chain, polyether chain or polyester chain etc.

Resin type pigment dispersing agent particularly can preferably be enumerated:

Styrene-maleic anhydride copolymer, alkene-copolymer-maleic anhydride, poly-(methyl) acrylate, vinylbenzene-(methyl) acrylic copolymer, (methyl) vinylformic acid-(methyl) alkyl acrylate copolymer, (methyl) vinylformic acid-polyethylene-based macromonomer multipolymer, contain phosphate-based acrylic resin, the acrylic resin that contains aromatic carboxyl, poly styrene sulfonate, acrylamide-(methyl) acrylic copolymer, carboxymethyl cellulose, there is the polyurethane(s) of carboxyl, the formalin condenses of naphthalenesulfonate, or the negatively charged ion such as sodium alginate is resin type pigment dispersing agent,

Polyvinyl alcohol, poly-to stretch the nonionics such as alkyl polyamine, polyacrylamide or polymkeric substance starch be resin type pigment dispersing agent; Or

Polymine, (methyl) acrylic-amino alkyl ester copolymer, polyvinyl imidazol quinoline, there is amino polyurethane(s), the poly-alkyl imines of stretching is resin type pigment dispersing agent with the positively charged ion such as reactant of the polyester with free carboxyl.Those compounds can be used alone or two or more is mixed and is used.

Particularly, aspect the stability of coloured composition, preferably coloured composition comprises acidic resins type pigment dispersing agent.In addition, by by acidic resins type pigment dispersing agent and alkaline pigment derivative use, can obtain not only mobility, the excellent in stability of coloured composition, and the excellent colour filter fragment of high brightness, high-contrast, therefore preferred.

Commercially available resin type dispersion agent can be enumerated (Di Shipabike-101) Disperbyk-101 that Japanese Bi Ke chemical company (BYK-CHEMIE JAPAN K.K.) manufactures, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or An Di-Tai La-U (Anti-Terra-U), 203, 204, or BYK-P104, P104S, 220S, 6919, or draw and play illiteracy (Lactimon), Lactimon-WS or Bi Kumen (Bykumen) etc.,

George Soros Paasche-3000 (SOLSPERSE-3000) that Lu Borun (Lubrizol) company of Japan manufactures, 9000,13000,13240,13650,13940,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,38500,41000,41090,53095,55000,76500 etc.;

Ai Fuka-46 (EFKA-46) that vapour Bagong department of Japan (Ciba Japan K.K.) manufactures, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503 etc.,

Nanmu originally changes into Di Shipalong 3600N (DISPARLON3600N), the DISPARLON1850 etc. that company manufactures;

A Jishipa-PA111 (Ajisper-PA111), PB711, PB821, PB822, PB824 etc. that aginomoto fine chemistry company (Ajinomoto Fine-Techno.Co.Inc.) manufactures, but be not limited to those commercially available products.Those commercially available products can be used alone or two or more is mixed and is used.

In those, can preferably enumerate the Disperbyk-108 manufacturing as the Japanese Bi Ke chemical company of resin type pigment dispersing agent with acid functional groups, 110, 111, 112, 116, 142, 180, 2000, 2001, or the SOLSPERSE-3000 of Japanese Lubrizol Corp. manufacture, 21000, 26000, 36600, 41000, or the EFKA-4401 of Japanese vapour Bagong department manufacture, 4550, or nanmu originally changes into the DISPARLON3600N that company manufactures, DISPARLON1850, or the Ajisper PA111 of aginomoto fine chemistry company manufacture etc., but be not limited to those commercially available products.

Interfacial agent is not particularly limited, for example, can enumerate:

The anionic property interfacial agent such as monoethanolamine, Voranol EP 2001 phosphoric acid ester of the alkali salt of polyoxyethylene alkyl ether sulfate salt, Sodium dodecylbenzene sulfonate, styrene-propene acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, sodium stearate, Sodium Lauryl Sulphate BP/USP, styrene-propene acid copolymer;

The non-ionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, Voranol EP 2001 phosphoric acid ester, Tween-60, polyethylene glycol monolaurate;

The cationic interfacial agents such as alkyl quarternary ammonium salt and those ethylene oxide adduct; And the zwitterionic surfactant such as alkyl betaine and alkyl imidazoline such as alkyl-dimethyl oxyneurine.The a little compounds of The can use or 2 Seed are mixed to use above by Single Independence.

For phthalocyanine pigments is scattered in pigment carrier fully, the mode that becomes 0.2 μ m～5 μ m with dry film thickness is coated on the transparency carriers such as glass substrate and the operation that forms coloring film becomes easily, can in coloured composition, contain non-water solvent arbitrarily.

Non-water solvent is not particularly limited, for example, can preferably enumerate glyceryl trichloride, 1,3 butylene glycol, 1,3 butylene glycol, 1,3 butylene glycol diacetate esters, Isosorbide-5-Nitrae-dioxan, 2-heptanone, 2-methyl isophthalic acid, ammediol, 3，5，5-trimethylcyclohexen-2-one-1, 3,3,5-trimethylcyclohexanone, 3-ethoxyl ethyl propionate, 3-methyl isophthalic acid, 3-butyleneglycol, MMB, acetic acid-3-methoxyl group-3-methyl butyl ester, 3-methoxybutanol, acetic acid-3-methoxyl group butyl ester, dipropyl ketone, m-xylene, between diethylbenzene, Meta Dichlorobenzene, N,N-dimethylacetamide, DMF, propyl carbinol, n-butylbenzene, n-propyl acetate, N-methylpyrrole pyridine ketone, o-Xylol, ortho-chlorotolu'ene, adjacent diethylbenzene, orthodichlorobenzene, parachlorotoluene, p-diethylbenzene, the second butylbenzene, tributyl benzene, gamma-butyrolactone, isopropylcarbinol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol list isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol list the 3rd butyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Diethylene Glycol list isopropyl ether, diethylene glycol monoethyl ether acetic ester, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol monomethyl ether, hexalin, adnoral acetate, pimelinketone, dipropylene glycol dme, dipropylene glycol methyl ether acetic ester, DPE, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol list propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, vanay, Tri(propylene glycol)butyl ether,mixture of isomers, Tripropylene glycol monomethyl Ether, propylene-glycol diacetate, propylene glycol phenylate, dihydroxypropane single-ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether propionate, phenylcarbinol, methyl iso-butyl ketone (MIBK), methyl-cyclohexanol, n-amyl acetate, n-butyl acetate, Isoamyl Acetate FCC, isobutyl acetate, propyl acetate, or diester etc.Those non-water solvents can be used alone or as a mixture.

Solvent preferably taking for phthalocyanine pigments 100 weight parts in coloured composition or pigment dispersion as the amount of 800 weight part～4000 weight parts is used, amount that more preferably can 1000 weight part～2500 weight parts and using.

In addition, for make composition through time viscosity stabilization, also can in coloured composition, contain storage stabilizing agent.Storage stabilizing agent is the known storage stabilizing agent generally using, for example, can enumerate the aliquat class such as benzyl trimethyl ammonium chloride or diethyl oxyamine; The organic acid such as lactic acid or oxalic acid; Described organic acid methyl esters class; The pyrocatechols such as tributyl pyrocatechol; The organic phosphine classes such as triphenylphosphine, tetraethyl-phosphine or tetraphenyl phosphine; Or phosphorous acid salt etc., but be not limited to those compounds.

Storage stabilizing agent can be that the amount of 0.1 weight part～10 weight part is used for phthalocyanine pigments 100 weight parts in coloured composition.

And, in order to mix colours, also can, in the scope that does not make thermotolerance reduce, in coloured composition, contain dyestuff.The dyestuff using is not particularly limited, can preferably use azoic dyestuff, anthraquinone dye, indigoide colors, phthalocyanine dye, carbon ion dyestuff, quinonimine dye, methine dyes, quinoline dye, nitro-dye, nitroso-dye, benzoquinones and naphthoquinone dyestuff, naphthalimide dyestuff, purple cyclic ketones dyestuff etc., also can at random combine two or more and use.

The purposes of coloured composition is not particularly limited, in a preferred embodiment, can be for Offset gravure (gravure offset) printing ink, waterless planographic printing ink, for silk screen printing ink, solvent develop type or the painted resist of alkali developable form and prepare.

Painted resist be as described above contain thermoplastic resin, thermosetting resin or photoresist, with the composition of polymerizable monomer, photopolymerization initiator, organic solvent in be dispersed with pigment (pigment) person.

Preferably coloured composition is containing oversize particles more than 5 μ m, preferably oversize particle more than 1 μ m, oversize particle more than 0.5 μ m more preferably, preferably carries out those oversize particles by mechanisms such as centrifugation, sintered filter, membrane filters and the removing of the dust of sneaking into.While particularly coloured composition being used as to the situation of colour filter purposes, preferably in fact containing particle more than 0.5 μ m, more preferably containing the particle that is greater than 0.3 μ m.

5. colour filter

Colour filter at least comprises the colour filter fragment forming on substrate, this substrate, and this colour filter fragment comprises the above-mentioned coloured composition of use and gained person.That is colour filter comprises at least one red color filter section, at least one green color filter section, at least one blue color filter section on substrate, blue color filter section is formed by the above-mentioned coloured composition that comprises phthalocyanine pigments.Red colour filter (R) and green color filter layer (G) beyond blue or the cyan colour filter (C), carmetta colour filter (M) and the yellow colour filter (Y) that are equivalent to redness, green, blue complementary color can use arbitrarily coloured composition and form, and there is no any restriction.And, in order to form in the red colored composition of red color filter section, except red pigment, also can and use orange pigments and/or yellow ultramarine; In the green coloring composition in order to form green color filter section, except veridian, also can and use yellow ultramarine.

The manufacture method of colour filter is not particularly limited, and can use known gimmick.

The formation of colour filter fragment can be by print process or photolithography and is carried out.Utilize the formation of the colour filter fragment of print process to be only repeatedly prepared as the printing of the coloured composition of printing ink and can carry out patterning with dry, therefore, as the manufacturing process of colour filter, cost is low and production is excellent.In addition, can there is the printing of the fine pattern of high dimensional accuracy and smoothness due to the development of printing technology.In order to print, be preferably made as ink in press plate or on clad can and moist, curing composition.And the control of the mobility of the ink on printing press is also important, also can utilize the adjustment of the ink viscosity of dispersion agent or pigment extender.

When form the situation of colour filter fragment by photolithography, for example, can carry out as shown below, but be not limited thereto.By coating processes such as spraying, spin coating, slot coated, roller coat, the mode that becomes 0.2 μ m～5 μ m with dry film thickness is coated the coloured composition that is prepared as above-mentioned solvent develop type or the painted resist of alkali developable on transparency carrier.For optionally and the film of drying, by with the mask with predetermined pattern contacting with this film or non-contacting state is established, carries out ultraviolet exposure., impregnated in solvent or alkaline-based developer thereafter, or by spray etc. and carry out developing solution spraying, unhardened portion is removed, thereby forms desired pattern.Also repeatedly carry out same operation about other colors, thereby can form colour filter fragment of all kinds.In addition, in order to promote the polymerization of painted resist, also can optionally implement heating.By photolithography, can the higher colour filter of more above-mentioned print process manufacturing accuracy.

In the time developing, alkaline-based developer uses the aqueous solution of sodium carbonate, sodium hydroxide etc., also can use the organic bases such as dimethyl benzyl amine, trolamine.And, in developing solution, also can add defoamer or interfacial agent.In addition, in order to improve ultraviolet exposure sensitivity, also after can and being dried at the above-mentioned painted resist of coating, be coated with water-soluble or alkaline water soluble resin, such as polyvinyl alcohol or water soluble acrylic resin etc. and be dried, formation prevents from, after the film of the polymerization obstruction causing due to oxygen, carrying out ultraviolet exposure.

Except aforesaid method, also can manufacture by electrochemical plating, transfer printing etc. colour filter fragment.Electrochemical plating are to utilize the nesa coating forming on substrate, by the electrophoresis of colloidal particle, colour filter fragment of all kinds are electroplated to the method being formed on nesa coating.Transfer printing is to be pre-formed colour filter fragment on the surface of the transfer printing base sheet of separability, makes this colour filter fragment be needed on the method on desired substrate.

The configuration of sub-pixel or colour filter fragment (picture element) is not particularly limited, and can be made as the known patterns such as " striped arrangement ", " mosaic arrangement ", " rounded projections arranged ".As the size of colour filter fragment, can in the scope of several microns～several 100 microns, at random make.

The substrate of colour filter is transparency carrier, except the high soda-lime glass of penetration coefficient for visible ray, low alkali borosilicate glass, sheet glass without soda alumina borosilicate glass etc., also can use the resin board of polycarbonate, polymethylmethacrylate, polyethylene terephthalate etc.

Colour filter further comprises to drive the transparency electrode of liquid crystal.Transparency electrode comprises Indium sesquioxide, stannic oxide etc., can be by evaporation or sputter and form.

If be pre-formed black matrix" form colour filter fragment on substrate before, can further improve the contrast gradient of display panels.As black matrix", use the mineral membrane such as multilayer film, titanium nitride of chromium or chromium/chromic oxide or be dispersed with the resin molding of opalizer, but be not limited to those.And, also can on substrate, be pre-formed thin film transistor (thin-film transistor, TFT), form thereafter colour filter fragment.By form colour filter fragment on TFT substrate, can improve the percentage of open area of display panels, brightness is improved.

On colour filter, optionally form protection tunic, column spacer, nesa coating, liquid crystal orientation film etc.

6. liquid crystal panel

Use sealing agent by colour filter and subtend baseplate-laminating, the inlet that is certainly located at sealing injects after liquid crystal inlet sealing, optionally light polarizing film or phase retardation film is fitted in to the outside of substrate, by this and manufacture display panels.

Display panels can be at twisted nematic (Twisted Nematic, TN) pattern, STN Super TN (Super Twisted Nematic, STN) pattern, coplanar switching (In plane switching, IPS) pattern, vertical orientated (Vertical Alignment, VA) the use colour filter such as pattern, optical compensation curved (optically compensated bend, OCB) pattern and carry out using in the liquid-crystal display pattern of colorize.

Embodiment

Below, by embodiment, the present invention is described in more detail, following embodiment does not do any restriction to interest field of the present invention.In addition, " part " in embodiment and " % " represent respectively " weight part " and " % by weight ".

1. assay method

(1) colour characteristics

On glass substrate, be coated with the thickness that each phthalocyanine pigments coloured composition (blue anticorrosive additive material) becomes y=0.1500 under illuminant-C, this substrate carried out at 230 DEG C to the heating of 20 minutes.,, measure the brightness of the substrate of gained by micro-spectral luminance meter (" OSP-SP200 " that Olympus Optical Co Ltd. manufactures) thereafter.

(2) contrast gradient

Use the coated film using in colour characteristics mensuration to measure contrast gradient.Measuring method in the following contrast gradient to film is illustrated.

(assay method of the contrast gradient of film)

The light penetrating with back light unit from liquid-crystal display is by the 1st Polarizer and polarisation, by the dry coating of the coloured composition that is coated with on glass substrate, arrives the 2nd Polarizer.Between the 1st Polarizer and the 2nd Polarizer, do not exist and appoint when whichever, if the plane of polarization of two Polarizers is parallel to each other, light transmission the 2nd Polarizer, but in the time of the orthogonal situation of two plane of polarization, light is interdicted by the 2nd Polarizer.But, if there is the dry coating of coloured composition between two Polarizers, while being passed through the dry coating of coloured composition by the light of the 1st Polarizer institute polarisation, if because pigment particles generation scattering etc. produces difference in a part (polarization direction) for plane of polarization, the light quantity that sees through the 2nd Polarizer in the time that two Polarizers are parallel reduces, part light transmission the 2nd Polarizer in the time that two Polarizers are orthogonal.Measure this transmitted light as the brightness on Polarizer, calculate the ratio (contrast gradient) of the brightness of the brightness of two Polarizers when parallel when orthogonal.

(contrast gradient)=when parallel (brightness)/when orthogonal (brightness)

That is if because the pigment in film produces scattering, the brightness when parallel reduces and brightness when orthogonal increases, therefore contrast gradient step-down.

In addition, in the time measuring, in order to interdict unwanted light, be arranged with the black mask that has the square hole of 1cm at determination part.Be formed with two faces of substrate of coloring film, become overlap each Polarizer of the 1st and the 2nd of mode parallel to each other with the axis of deflection of two Polarizers, inject backlight from one of them Polarizer (the 1st Polarizer) side, measure the brightness (Lp) of the light that sees through another Polarizer (the 2nd Polarizer) by luminance meter.Secondly, two Polarizers that overlap on two faces of substrate are configured in the mutually orthogonal mode of the axis of deflection of two Polarizers, inject backlight from one of them Polarizer side, measure the brightness (Lc) of the light that sees through another Polarizer by luminance meter.The mensuration brightness value that uses gained, calculates contrast gradient Lp/Lc.In the normal direction of substrate, measure.And two Polarizers all use " NPF-SEG1224DU " (manufacture of Dong electrician company).Luminance meter uses " BM-5A " (opening up Pu Kang (TOPCON) company manufactures), under the condition in 2 ° of visuals field, measures brightness.

(3) powder x-ray diffraction

Dry pigment is pulverized on 80 object wire cloths, become after the particle diameter below 80 orders, implement X ray and measure.Implement under the following conditions the mensuration of X-ray diffraction spectrum.

Device: the full-automatic many objects X-ray diffraction of X ' pert-Pro device (manufacture of Philip (Philips) company)

X-ray source: Cu2kW pipe ball

Voltage: 30kV

Electric current: 40mA

Measurement range: 3.0 °～35.0 °

Step angle: 0.01 °

2. embodiment

Embodiment 1

Use following each raw material, make π type copper phthalocyanine pigments by Wheeler legal system.

Each raw material is loaded in synthesizer, and one side stirs one side and at 180 DEG C, maintains 5 hours, generates by this copper phthalocyanine pigments.For the reaction solution that contains copper phthalocyanine pigments of gained, one side is cleaned one side with the warm water of 60 DEG C and is carried out filtration under diminished pressure, removes desolventizing and unreacted product etc. in autoreaction liquid.

For the thick pigment of having removed solvent etc., carry out following filtration and purifying.First, thick pigment is added in 500 parts, 3% sulfuric acid that is heated to be 80 DEG C and carries out the stirring of 30 minutes, then one side is cleaned and is simultaneously carried out filtration under diminished pressure with the warm water of 60 DEG C.Secondly, be added in 500 parts, 3% sodium hydroxide that is heated to be 80 DEG C and carry out the stirring of 30 minutes, then one side is cleaned and is simultaneously carried out filtration under diminished pressure with the warm water of 60 DEG C.Finally, be added in 500 parts, the warm water that is heated to be 60 DEG C and carry out the stirring of 30 minutes, then one side is cleaned and is simultaneously carried out filtration under diminished pressure with the warm water of 60 DEG C.

By through filtration, purification step and the pigment filter cake of gained is carried out 15 hours dry in the baking oven of 90 DEG C, obtain by this copper phthalocyanine pigments 1.Measure the copper phthalocyanine pigments 1 of gained by X-ray diffraction, the diffraction pattern that the results are shown in Bragg angle 2 θ is 4.9 degree, 6.5 degree, 8.5 are spent, 9.7 degree, 10.7 are spent, 17.0 degree places have the π type copper phthalocyanine pigments of diffraction peak.Diffraction pattern is shown in Fig. 1.

Further by TOF-MS, the copper phthalocyanine pigments 1 of gained is analyzed, results verification is to having 1 or 2 CONH ₂the existing of the compound of base (by carboxyl and the ammonia of the α position of half sweet cured acid, reacting of isocyanic acid and generate) (Fig. 5).

Secondly, by after the mixture uniform stirring of the following composition of the π type copper phthalocyanine pigments 1 that comprises gained, use the zirconia particles that diameter is 0.5mm, carry out the dispersion of 3 hours by ball mill, make color compositions (pigment dyestuff composition) 1 by the strainer of 2 μ m filters.

Copper phthalocyanine is that pigment derivative is copper phthalocyanine dimethylamino amyl group sulphonamide, and acrylic resin soln is the pimelinketone solution that the solids component of 2: 8 (weight ratio) multipolymers (weight average molecular weight is 40000) of comprising methacrylic acid and n-BMA is 20%.

In addition, the mixture of the following composition of the color compositions that comprises gained 1 is uniformly mixed to after evenly, filters by the strainer of 2 μ m, make coloured composition (alkali developable anticorrosive additive material) 1.

Embodiment 2～embodiment 27

Carry out similarly to Example 1, change solvent species, catalyst kind, the substituted phthalic acid in α position (phthalic acid derivatives) kind, synthesis temperature, Tetra hydro Phthalic anhydride input amount, α position replacement phthalic acid input amount and quantity of solvent as shown in table 1ly, synthesize by same operation, make by this π type copper phthalocyanine pigments 2～π type copper phthalocyanine pigments 27 of embodiment 2～embodiment 27.Confirm that by powder x-ray diffraction those crystal types are π type.

Similarly use π type copper phthalocyanine pigments 2～π type copper phthalocyanine pigments 27 and make color compositions 2～color compositions 27 and coloured composition 2～coloured composition 27.

[table 1]

Embodiment 28

Use following each raw material, manufacture π type copper phthalocyanine pigments by phthalonitrile method.

Each raw material is loaded in synthesizer, and one side stirs one side and is warming up to after 130 DEG C, appends 15.2 parts of diazabicyclo undecylenes and maintains 3 hours, makes by this copper phthalocyanine pigments 28.And, about the filtration purifying after synthetic, disperse and be uniformly mixed, process similarly to Example 1, make color compositions 28 and coloured composition 28.The crystal type of gained is π type.

Embodiment 29

The 3-phenoxy group phthalonitrile of embodiment 28 is changed to 3-nitrophthalonitrile and similarly makes copper phthalocyanine pigments 29.And, about the filtration purifying after synthetic, disperse and be uniformly mixed, process similarly to Example 1, make color compositions 29 and coloured composition 29.The crystal type of gained is π type.

Comparative example 1～comparative example 3

As shown in table 1 similarly to Example 1, change solvent species, catalyst kind, the substituted phthalic acid in α position (phthalic acid derivatives) kind, synthesis temperature, Tetra hydro Phthalic anhydride input amount, the substituted phthalic acid input amount in α position and quantity of solvent, synthesize by same operation, by this and the copper phthalocyanine pigments of comparison example 1～comparative example 3.And, about the filtration purifying after synthetic, disperse and be uniformly mixed, also similarly process, make color compositions and coloured composition.

Comparative example 4

100 parts of (Leo promise blue E) LIONOL BLUE E76 part that company of Japan look material (TOYOCOLOR) is manufactured, 4 parts of copper phthalocyanine dimethylamino amyl group sulphonamide, 600 parts, sodium-chlor and Diethylene Glycols carry out after 6 hours mixing in stainless steel kneader (aboveground manufacturing company manufactures), at 70 DEG C, carry out washing filtering and drying and crushing, make copper phthalocyanine pigments.

Use the pigment of gained, carry out similarly to Example 1 and obtain color compositions and coloured composition.

Measure the crystal type of the pigment made by the method for above-described embodiment and comparative example and use each coloured composition and tone (Y value: illuminant-C) and the contrast gradient of the film made.

Show the result in table 2.

[table 2]

By X-ray diffraction measure as comparative example 1 as do not add half sweet cured acid and carry out synthetic pigment, the results are shown in Bragg angle 2 θ and be 6.9 degree, 9.0 degree, 10.2 degree, 12.3 are spent, 18.2 degree places have the beta type copper phthalocyanine pigments as shown in Figure 2 of diffraction peak diffraction pattern.And, even as add half sweet cured acid as comparative example 2, comparative example 3, but be not selected to the pigment of the suitable synthesis condition of (mathematical expression 1)≤0, the result of measuring by X-ray diffraction is that to be shown in Bragg angle 2 θ be that 7.5 degree, 9.0 degree, 14.2 degree places have the diffraction pattern of the ε type copper phthalocyanine pigments as shown in Figure 3 of diffraction peak.

Measure the pigment using in comparative example 4 by X-ray diffraction, the results are shown in Bragg angle 2 θ is the diffraction pattern that 7.5 degree, 9.0 are spent, 14.2 degree places have the ε type copper phthalocyanine pigments of diffraction peak.

As the copper phthalocyanine pigments 1～copper phthalocyanine pigments 29 that obtains π type, with the copper phthalocyanine pigments with made in the comparative example 1～comparative example 4 of crystal type of β type or ε type comparatively speaking, brightness is high and show excellent result.And, about contrast gradient, in most embodiment, also confirm the brightness of comparing of the π type phthalocyanine pigments of gained and ε type or β type high, colour characteristics excellence.Because the permeability of the light that brightness is high that is irradiate is large, therefore can be by light quantity still less and show equal brightness, for example, in the image displays such as LCD TV, with further energy-saving is relevant.In addition, because contrast gradient is high, therefore for example can provide the image displays such as bright LCD TV.

Can confirm according to those results: by phthalonitrile method or meet the Wheeler method of mathematical expression (1), can manufacture unlike the prior art the π type crystallization at least in α position with substituent phthalocyanine pigments, compare with prior art, colour characteristics and the display characteristic excellence of the π type pigment of gained.

Should note except narrator, also can not depart from novelty of the present invention and favourable feature to various corrections and the change in addition of above-mentioned embodiment.Therefore, this kind of all correction and change are contained in the claims of enclosing.

Claims

1. a π type phthalocyanine pigments, it represents with following general formula (1):

General formula (1)

2. π type phthalocyanine pigments according to claim 1, wherein M is Cu.

3. a manufacture method for π type phthalocyanine pigments, it is the manufacture method of π type phthalocyanine pigments as claimed in claim 1, comprises:

Temperature of reaction is made as x (DEG C),

With respect to total input weight of Tetra hydro Phthalic anhydride and phthalic acid derivatives and by the input weight (%) of described phthalic acid derivatives be made as y,

With respect to total input weight of described Tetra hydro Phthalic anhydride and described phthalic acid derivatives and when solvent input amount (doubly) is made as to z,

In mathematical expression (1): x-4.3y-1.8z-145≤0

(wherein, 90≤x≤300,0 < y, 0≤z)

Under represented condition, make described Tetra hydro Phthalic anhydride and the substituted described phthalic acid derivatives in α position at least, with urea, urea derivatives or ammonia, with the step of reacting metal salt.

4. a manufacture method for π type phthalocyanine pigments, it is the manufacture method of π type phthalocyanine pigments claimed in claim 1, comprises:

Make phthalonitrile and/or diiminoisoindole, at least substituted O-phthalic carbonitrile derivatives in α position and/or the substituted diiminoisoindole derivative in α position at least, the step of reacting with metal-salt at 60 DEG C～300 DEG C.

5. a color compositions, it comprises: π type phthalocyanine pigments as claimed in claim 1, the phthalocyanine pigments being unsubstituted with π type.

6. a coloured composition, it contains: color compositions as claimed in claim 5 and pigment carrier.

7. coloured composition according to claim 6, it also contains resin type pigment dispersing agent and/or pigment derivative.

8. coloured composition according to claim 6, it also contains photopolymerization monomer and/or photopolymerization initiator.

9. a colour filter, its at least comprise substrate, with described substrate on the colour filter fragment that forms, a part for described colour filter fragment is to use coloured composition as described in any one in claim 6-8 and gained person.