CN104105759B

CN104105759B - π type phthalocyanine pigments and its manufacture method, color compositions, coloured composition and colour filter

Info

Publication number: CN104105759B
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: 2016-01-13
Anticipated expiration: 2033-07-16
Also published as: TWI582172B; CN104105759A; JP2014040567A; JP5277469B1; KR20150035487A; WO2014017330A1; TW201406869A

Abstract

The invention provides a kind of π type phthalocyanine pigments and its manufacture method, color compositions, coloured composition and colour filter.By providing the phthalocyanine pigments of the π type represented by following general formula (1), the colour filter of the display quality excellences such as colour characteristics can be provided.By at R ¹~ R ⁸in optionally import functional group, Absorbable organic halogens ground generates the π type pigment of the colour characteristics excellence such as brightness due to the factor of three-dimensional arrangement.General formula (1)

Description

π type phthalocyanine pigments and its manufacture method, color compositions, coloured composition and colour filter

Technical field

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

Background technology

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

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

Brightness and contrast gradient (contrastratio) can be enumerated as the quality project required by colour filter.If use the colour filter that contrast gradient is low, then can upset the polarization degree that liquid crystal controls, (OFF state) light leak when interdicting light, when must be transmitted through light, the decay of (ON state) transmitted light, therefore becomes 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, then the penetration coefficient of light is low, therefore becomes dark picture, in order to become bright picture, must make the backlight number increment as light source.Therefore, consider from the viewpoint suppressing power consumption to increase, the high brightness of colour filter becomes trend.In addition, as mentioned above, color liquid crystal device becomes in TV or computer screen etc., therefore for colour filter, also increases the requirement of high brightness, high-contrast and high reliability.

Copper phthalocyanine bright and tinting strength is also large, all tolerances such as weathering resistance, thermotolerance, chemical-resistant are excellent, are therefore often used as blue pigments.

And, copper phthalocyanine shows paramorphism, reports 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 color filter layer 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 many use ε type copper phthalocyanines.In addition, ε type copper phthalocyanine pigments has high distinctness and the character of high-strength excellence.

But, even if when carrying out the situation of the 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, then brightness convergence, therefore becomes and is difficult to make it further improve.Therefore, be difficult to further make brightness improve and suppress the increase of 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 color filter layer of colour filter.But, because its stability is low, is exposed in high temperature and/or organic solvent etc. and easily produces crystallization transfer, poor stability.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open No. Sho 48-725 publication

Patent documentation 2: Japanese Patent Laid-Open No. Sho 63-308074 publication

Patent documentation 3: Japanese Patent Laid-Open No. Sho 62-48769 publication

Summary of the invention

The manufacture method of π type copper phthalocyanine is described in patent documentation 1.But the π type phthalocyanine of gained does not have substituently not replace body on phenyl ring, to compare poor stability with other crystal types, therefore not can tolerate the practicality persons such as colour filter purposes.

In patent documentation 2, describe a kind of synthetic method of copper phthalocyanine, in the copper phthalocyanine synthesis utilizing Wheeler method, simultaneously make aromatic polyvalent acid coexist and simultaneously make it react.There is no the record of the crystal type about generated copper phthalocyanine, but as shown in the comparative example 3 of described later specification sheets, do not generate π type but generate ε type.

In patent documentation 3, describe a kind of synthetic method of π type copper phthalocyanine, in the copper phthalocyanine synthesis utilizing Wheeler method, add Pyromellitic Acid and make it react.But, in the method the π type copper phthalocyanine of gained in colour characteristics etc. not as ε type copper phthalocyanine.In addition, the stability of the crystal type of three-dimensional arrangement is also poor.

The present invention is shortcoming in view of above-mentioned prior art and inventor, problem be to provide the colour characteristics such as brightness are improved and in thermotolerance etc. the π type phthalocyanine pigments of the novelty that stability is high.

In addition, problem is to be used in the colour filter used in color liquid crystal display arrangement and solid photographic assembly etc. by by the π type phthalocyanine pigments of this novelty, thus provides the colour filter of colour characteristics and display quality excellence.

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

General formula (1)

(R ¹~ R ⁸be independently 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 ¹⁶be independently 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 set to x (DEG C),

Relative to Tetra hydro Phthalic anhydride and at least total input weight of phthalic acid derivatives of being substituted of α position, the input weight (%) of the phthalic acid derivatives that at least α position is substituted be set to y,

Relative to Tetra hydro Phthalic anhydride and at least total input weight of phthalic acid derivatives of being substituted of α position, when solvent input amount (doubly) is set to z,

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

(wherein, 90≤x≤300,0 < y, 0≤z)

Tetra hydro Phthalic anhydride and at least phthalic acid derivatives that is substituted of α position is made, with urea, urea derivatives or ammonia, with reacting metal salt under represented condition.

The diiminoisoindole derivative that the phthalonitrile derivatives that phthalonitrile (phthalonitrile) and/or diiminoisoindole, at least α position are substituted and/or at least α position are substituted, reacts 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 be 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 the colour filter fragment that formed on this substrate, a part for this colour filter fragment uses coloured composition of the present invention and gained person.

[effect of invention]

The colour characteristics of the π type phthalocyanine pigments of novelty of the present invention and excellent in stability, by using it in the colour filter that uses 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.

Accompanying drawing explanation

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

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

Embodiment

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

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, easily the crystallization three-dimensional arrangement of phthalocyanine can be maintained π type by this, therefore become and easily generate π type phthalocyanine, and the stability of crystallization improve.In addition, when the people such as present inventor find to use the situation of this π type phthalocyanine in the colour filter used in color liquid crystal display arrangement and solid photographic assembly etc., the colour filter that the colour characteristics such as brightness and contrast gradient is excellent and display quality is also excellent can be provided, thus complete the present invention.

General formula (1)

(R ¹~ R ⁸be independently 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 ¹⁶be independently 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 in the position being equivalent to α position of phthalic acid with the phthalocyanine of substituent general formula (1).Herein, sometimes the phthalocyanine pigments represented by general formula (1) is designated as the phthalocyanine pigments being substituted (replacement of α position) or α position replacement body.

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 about 1 ~ 12 or the alkyl of branched chain.Wherein, particularly desirably have and be selected from by COOH, CONH ₂, CF ₃, and OC ₆h ₅at least one substituting group of the group formed.

The sense radix imported there is no and specifies, but due to sense radix increase and to in colour filter time colour characteristics cause dysgenic possibility to improve, therefore as the sense radix beyond the hydrogen atom imported in 1 molecule phthalocyanine, R ¹~ R ⁸(α position) and R ⁹~ R ¹⁶the total of the both sides of (β position) preferably about 1 ~ 8, more preferably 1 ~ 4 or 1 ~ 3.And, also can import multiple functional group.

By at R ¹~ R ⁸cOOH, CONH is imported at least one of (α position) ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅, or alkyl, with the R being directed into so-called β position ⁹~ R ¹⁶in situation Comparatively speaking, functional group as three-dimensional arrangement restraining factors and play a role, its result makes crystal type stablize to turn to the effect of π type to improve, therefore importantly at R ¹~ R ⁸middle importing functional group.

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

Be directed into R ⁹~ R ¹⁶in functional group large impact is not caused on crystal type, therefore can import arbitrary functional group.Wherein, in order to have an impact to the tone of pigment, it is desirable to independently for hydrogen atom, aryl, sulfuryl (are also called sulfo group.-SO ₃h), sulfoamido (-SO ₂nRR '), cyano group (-CN), hydroxyl (be also called hydroxy.-OH), sulfydryl (-SH), acyl group, halogen (-F ,-Cl ,-Br ,-I), silylation or silicon alkoxyl group.It is desirable to R and R ' of above-mentioned sulfoamido independently for hydrogen atom, carbon number are the straight chain of about 1 ~ 5 or alkyl, the N of branched chain, 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.Such as, carboxylate salt (-COOM), sulfonate (-SO can be enumerated ₃m), alkoxide (alkoxide) or phenates (-OM), metal (M) can enumerate the basic metal such as sodium, potassium, lithium.

Central metal M in general formula (1) represents 2H or metal.Wherein, M preferred Cu, 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, when the situation using Cu-K alpha-ray to measure, π type phthalocyanine be 4.9 degree, 6.5 degree, 8.5 degree, 9.7 degree, 10.7 degree of Bragg angle 2 θ (± 0.3 degree), 17.0 degree of places have the crystal type of diffraction peak.Fig. 1 is the data of the π type crystallization gained about α position with the phthalocyanine of substituent general formula (1), although due to the functional group imported, there are some movements the position of each diffraction peak, as long as but crystal type is π type, then the pattern that diffraction pattern display is similar with Fig. 1.Wherein, when carrying out the situation of miniaturization of phthalocyanine or phthalocyanine pigments, there is diffraction peak and broadening, the phenomenon of the part disappearance at peak.Peak is broadened and causes the diffraction pattern of the π type phthalocyanine of one partial disappearance (α position replaces body) shown in Figure 4.

The substituent existence being directed into phenyl ring can confirm by time-of-flight mass spectrometer (TimeofFlightMassSpectrometer, TOF-MS) etc. (with reference to Fig. 5).

2. the manufacture method of π type phthalocyanine pigments

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

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

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

Below illustrated, when using the situation of any means of Wheeler method and phthalonitrile method, Tetra hydro Phthalic anhydride is used by the former, phthalonitrile and/or diiminoisoindole is used in the latter, except the phthalocyanine pigments that the α position shown in general formula (1) is substituted, all can manufacture the phthalocyanine pigments be unsubstituted.The ratio not replacing body in manufactured phthalocyanine pigments at random can adjust according to used feed ratio.Now, the phthalocyanine pigments represented by general formula (1) is generated with π type crystal type, therefore due to the existence of this π type crystallization, the phthalocyanine pigments be unsubstituted also becomes identical crystal type, thus can obtain the composition of identical crystal type (π type).And the phthalocyanine pigments that the α position as general formula (1) is substituted, obtains the multiple compounds that the position of substitution, replacement radix etc. are different.

(1) Wheeler method

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

Temperature of reaction is set to x (DEG C),

Relative to Tetra hydro Phthalic anhydride and at least total input weight of phthalic acid derivatives of being substituted of α position, the input weight (%) of this phthalic acid derivatives is set to y,

Relative to total input weight of Tetra hydro Phthalic anhydride and phthalic acid derivatives, when solvent input amount (doubly) is set to z,

It is desirable in mathematical expression (1): react under the condition represented by x-4.3y-1.8z-145≤0 (wherein, 90≤x≤300,0 < y, 0≤z).When the value of mathematical expression (1) becomes the situation being 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 the crystal type with π type Comparatively speaking low lightness.

Known in order to make mathematical expression (1) become less than zero, that is in order to positively generate π type phthalocyanine, must temperature of reaction (x) be lower and the amount (z) of reaction solvent is many, react under gentle condition.Such as, when the situation that temperature of reaction is higher, become the transfer easily produced to thermodynamically stable crystal type, therefore preferably make quantity of solvent increase etc. and make reaction conditions gentle, and/or the allotment ratio of phthalic acid derivatives is uprised etc. and the stability of crystallization is uprised.

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

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

And, can also improve for the purpose of productive rate and/or raising purity etc. and react under the pressurized conditions of 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 phthalic acid derivatives that at least α position in mathematical expression (1) is substituted (at least α position be substituted phthalic acid (acid anhydride) derivative etc.) is one of the important factor in order to crystallization control type.

The phthalic acid derivatives of sufficient quantity is preferably dropped in the mode meeting above-mentioned mathematical expression (1).About the sequential of the input of phthalic acid derivatives, can react start time otal investment, also can until the generation of pigment particles in reaction way terminate between segmentation drop into.

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

In Wheeler method, when synthesizing in order to 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 in order to one of reactive important factor in Controlling System.Solvent total amount can drop into when reacting beginning, also can divide cede territory continuity or interim input in the reaction, till the generation of pigment terminates, be adjusted to the z meeting mathematical expression (1), preferably can obtain the crystallization of π type by this.

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

As the O-phthalic acids used when synthesizing by Wheeler method, have known person in various document, 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 containing having the substituent O-phthalic acids such as alkyl, 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 on the aromatic ring of those compounds.

In order to synthesize the phthalocyanine of general formula (1), the phthalic acid derivatives at least use Tetra hydro Phthalic anhydride, being substituted with at least α position, but also can the O-phthalic acid starting material of partial use beyond those (phthalic acid derivatives that β position described later is substituted, phenyl ring does not have phthalic acid derivatives etc. beyond substituent acid anhydrides) as raw material.

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

The phthalic acid derivatives that this α position is substituted 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 be unsubstituted, the derivative (phthalic ester, phthalic imidine etc.) beyond acid anhydrides also partially can be used.

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

During the situation of O-phthalic acids beyond the phthalic acid derivatives using Tetra hydro Phthalic anhydride and α position to be substituted (β position replaces the phthalic acid derivatives beyond phthalic acid or derivatives thereof, the acid anhydrides that is unsubstituted), be preferably about less than 10 % by weight in the total of O-phthalic acids becoming raw material.

As the urea or derivatives thereof reacted with above-mentioned O-phthalic acids, urea, biuret, triuret etc. can be enumerated, also preferably use ammonia.Also the multiple of those can be used.

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

Metal-salt is the central metal M person forming above-mentioned general formula (1), the salt of preferred Cu, Zn, Al etc.The supply source metal of this metal-salt, can use 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.The valence mumber of metal impacts reaction, but generally in phthalocyanine synthesis, uses with can being not particularly limited valence mumber.Wherein, cupric chloride (I), cupric chloride (II), copper sulfate, copper hydroxide (I), copper hydroxide (II) etc. preferably preferably can be used as source metal or metal-salt by metal preferably copper.Also those two or more can be used.

The usage quantity of metal-salt preferably relative to become raw material O-phthalic acids (phthalic acid or derivatives thereof) total for, with molar ratio computing be 0.15 ~ 0.40 scope in use.

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

Usage quantity about catalyst is not particularly limited, preferably relative to become raw material O-phthalic acids (phthalic acid or derivatives thereof) total for, with mass ratio range be 0.0001 ~ 0.3 scope in use.

And, reaction proterties can also be improved, improve for the purpose of reactive, to improve product purity, raising distinctiveness etc., 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 are at random used for the O-phthalic acids (phthalic acid or derivatives thereof) becoming raw material, when this situation, can with mass ratio range be 0.05 ~ 1 scope in add.

Reaction solvent can be used as the synthetic of Wheeler method and known organic solvent.Such as 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 etc. such as quinoline.Those organic solvents also can be mixture of more than two kinds.Wherein, in order to stably crystallization control type, special good is use the aprotic polar solvent 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 becoming 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: the diiminoisoindole derivative that the phthalonitrile derivatives that phthalonitrile and/or diiminoisoindole, at least α position are substituted and/or at least α position are substituted, react at 60 DEG C ~ 300 DEG C with metal-salt.

When synthesizing, in order to the temperature in Controlling System and/or raising stirring efficiency etc., also solvent can be used.And, in order to improve productive rate, improve purity etc., also can react under the pressurized conditions of about 0.05MPa ~ 1.0MPa.

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

Those derivatives represent 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.

In order to synthesize the phthalocyanine of general formula (1), as at least one party of O-phthalic nitrile and diiminoisoindole class, using and at least in α position, there is above-mentioned R 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, muriate, bromide, iodide, vitriol, sulfide, acetate, oxide compound, oxyhydroxide, carbonate, phosphoric acid salt etc. of the metals such as Cu, Zn, Al.In phthalonitrile method, the valence mumber of metal also impacts reaction, but generally phthalocyanine synthesis in, its valence mumber can there is no particular restriction ground use.Also those two or more can be used.

The usage quantity of source metal preferably relative to the total (when the situation containing any one party, being the total of an only side) of O-phthalic nitrile and diiminoisoindole class, with molar ratio computing be 0.15 ~ 0.40 scope in use.

There is no particular restriction to become the alkali of catalyst, the desirably cyclic amine such as ammonia, morpholine, piperidines; Pyridine, picoline, quinoline etc. are imported with the amine of 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 the alkoxide of 1 ~ 12; Or those mixture.Also those two or more can be used.

The amount of alkali preferably relative to the total (when the situation containing any one party, being the total of an only side) of O-phthalic nitrile and diiminoisoindole class, with molar ratio computing be 0.001 ~ 2 scope in use.When the situation using alkali as solvent, also can be more.

The solvent that can use in the reaction can be used as the synthetic of phthalonitrile method and known organic solvent.Such as preferably can use 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 etc. such as quinoline; 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 in an inert atmosphere when the situation of necessity, if desired then also can add the compound known in the use of Wheeler method such as ammonium molybdate and/or urea.

(3) other steps

In Wheeler method, phthalonitrile method, all preferably after the completion of reaction, the filtration of solvent is carried out and solvent distillation removing waits and after the separating treatment of reaction solvent, carry out the cleaning by water and/or organic solvent.When cleaning, also acid or alkali can be used.In addition, if necessary purifying, then also can remove impurity by as the operation such as the distillation of known purification technique, acid paste, Acid Slurry, again Shen Dian, recrystallize, extraction.

By with above-mentioned two kinds of methods for the method for making of representative and the phthalocyanine pigments that synthesizes directly can use under the state of synthesis; but in order to control size of particles, give easily disperse etc., the operation of miniaturization (being also called pigmenting or whole granulation) also can be carried out.

Can use known miniaturization method, main method can enumerate solvent method, solvent polishing, lyonium salt mill method etc.When miniaturization, in order to suppress crystal growth to carry out miniaturization, also can add and having that at least one is substituent without metal or metalphthelein Cyanine derivative thing.

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

According to the research of the people such as present inventor, other crystal types such as the crystallization of π type and such as ε type crystallization comparatively speaking, obtain with the form of the needle crystal of more elongated (aspect ratio is large), because be this particle shape, also there is following advantage: when miniaturization without the need to carrying out utilizing the step of mixing of kneader etc., can omit and mix step and only obtain the fine pigment turning to desired granularity by dispersion steps.In contrast, even if the ε type crystal form in being such as generally used for LCD TV etc. is up to now spherical or is needle-like, also equally thick up and down, if do not utilize step of mixing, be difficult to miniaturization, be therefore difficult to the step of mixing before omitting dispersion steps.

3. color compositions

The π type phthalocyanine pigments that the π type phthalocyanine pigments (α position replace body) of color compositions at least containing general formula (1) and the phenyl ring of phthalocyanine not to have beyond hydrogen atom substituent is unsubstituted that is π type do not replace phthalocyanine pigments.α position replaces body can comprise substituting group and/or the different multiple compounds of the position of substitution.And, also the diverse α position of urban mixed-use center metal M can replace body and/or do 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 uses Tetra hydro Phthalic anhydride as raw material, if phthalonitrile rule uses phthalonitrile and/or diiminoisoindole as raw material, also generate the π type phthalocyanine pigments be unsubstituted by this, thus α position replacement body and the π type crystalline mixture not replacing body can be fabricated to as described above.

π type phthalocyanine pigments also can not have a π type phthalocyanine pigments (β position replaces body) that substituting group and β position be substituted in the partial α of being contained in position.In order to improve the stability of π type crystal type further, the amount that the β position that can comprise arbitrarily replaces body is preferably about less than 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.

Such as, in order to crystal growth when suppressing miniaturization, give crystalline stability, prevent from condensing, give easily disperse when pigment being used as tinting material, improve tinting strength etc., also 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. can be mixed with pigment.In addition, also can in the scope not hindering effect of the present invention the partial phthalocyanine pigments or amorphousness phthalocyanine pigments etc. comprising other crystal types beyond π type as pigment composition.To those phthalocyanine pigments general names in color compositions be can be used for, referred to as " phthalocyanine pigments " below.

There is no particular restriction for the form of color compositions, can adopt the form arbitrarily such as powder, press filtration pie containing water, also can carry out making and process with some of the mixture of resin etc.

4. coloured composition

The pigment dispersions such as 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 (toningagent), carbon dust, colour filter resist ink are representative form.Wherein, particularly the colour characteristics such as brightness of showing of the π type phthalocyanine pigments of above-mentioned general formula (1) meets the colour characteristics required by colour filter well, therefore can be suitably used in colour filter purposes.

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

Pigment carrier contained in coloured composition makes phthalocyanine pigments disperse the person of forming, and comprises resin, its precursor or those mixture.

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

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

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

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

Thermosetting resin include, for example epoxy resin, benzo guanamine (benzoguanamine) resin, rosin upgrading maleic acid resin, rosin upgrading fumaric resin, melamine resin, urea resin or phenol resins etc.Preferably can use the thermosetting resin of those more than a kind.

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

And, (methyl) acrylic compound having a hydroxyl by (methyl) hydroxyalkyl acrylates etc. also can be used styrene-maleic anhydride copolymer, alpha-olefin-copolymer-maleic anhydride etc. to be comprised the half-esterification person of forming of wire polymer of acid anhydrides.Preferably can use those active energy ray hardening resins of more than a kind.

In addition, " (methyl) vinylformic acid " is the both sides representing " 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 acrylate, (methyl) vinylformic acid tri-n-butyl, (methyl) isoamyl acrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) ethyl acrylate, (methyl) aliphatic acrylate, (methyl) decyl acrylate, (methyl) Isodecyl base ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristyl ester of (methyl) vinylformic acid, (methyl) stearyl acrylate base ester, and (methyl) vinylformic acid straight chain or the branched alkyl groups ester class such as (methyl) vinylformic acid iso stearyl ester,

(methyl) vinylformic acid cyclic alkyl ester class or (methyl) vinylformic acid cyclic alkenyl radical ester classes such as (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tributyl cyclohexyl ester, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid bicyclopentyl oxygen base ethyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester and (methyl) isobornyl acrylate;

(methyl) fluoroalkyl base ester classes such as (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) perfluoroethyl octyl group ethyl ester and (methyl) vinylformic acid tetrafluoro propyl ester;

(methyl) acryloxy upgrading polydimethylsiloxane (silicone-macromers) class;

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

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

(methyl) vinylformic acid-2-methoxy acrylate, (methyl) vinylformic acid-2-ethoxy ethyl ester, (methyl) vinylformic acid-3-methoxybutyl, (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) acryloyloxyethyl ester, phthalic acid-2-(methyl) acryloxy propyl ester, hexahydrophthalic acid-2-(methyl) acryloyloxyethyl ester, hexahydrophthalic acid-2-(methyl) acryloxy propyl ester, oxyethane upgrading succsinic acid (methyl) acrylate, (methyl) senecioate-carboxyethyl, and ω-carboxy-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-hydroxybutyl, (methyl) vinylformic acid-4-hydroxybutyl, (methyl) phthalic acid-2-acryloyl-oxyethyl-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 (gathering) alkane glycol two (methyl) esters of acrylic acid such as 2-ethyl-2-butyl-propylene glycol two (methyl) acrylate,

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

Multifunctional (methyl) acrylate more than trifunctionals 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) acrylic acid adduct, glycerin diglycidyl ether-(methyl) acrylic acid adduct, polyglycerol polyglycidyl ether-(methyl) acrylic acid adduct, 1,6-butanediol diglycidyl ether-(methyl) acrylic acid adduct, alkyl glycidyl ether-(methyl) acrylic acid adduct, glycidyl allyl ether-(methyl) acrylic acid adduct, phenyl glycidyl ether-(methyl) acrylic acid adduct, Styrene oxide 98min.-(methyl) acrylic acid adduct, bisphenol A diglycidyl ether-(methyl) acrylic acid adduct, propylene oxide upgrading bisphenol A diglycidyl ether-(methyl) acrylic acid adduct, Bisphenol F diglycidylether-(methyl) acrylic acid adduct, Epicholorohydrin upgrading phthalic acid-(methyl) acrylic acid adduct, Epicholorohydrin upgrading hexahydrophthalic acid-(methyl) acrylic acid adduct, ethylene glycol diglycidylether-(methyl) acrylic acid adduct, polyethyleneglycol diglycidylether-(methyl) acrylic acid adduct, propylene glycol diglycidylether-(methyl) acrylic acid adduct, polypropylene glycol diglycidyl ether-(methyl) acrylic acid adduct, phenolic novolac type epoxy resin-(methyl) acrylic acid adduct, cresol novolak type epoxy resin-(methyl) acrylic acid adduct, epoxy (methyl) esters of acrylic acids such as other epoxy resin-(methyl) acrylic acid adduct,

(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 divinyl 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 used in combination.

In coloured composition, when hardening to said composition by uviolizing, add photopolymerization initiator etc.

As photopolymerization initiator, can use:

The methyl phenyl ketone system photopolymerization initiators such as 4-phenoxydichloroacetophenone, 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-[4-(methylthio group) phenyl]-2-morpholine propane-1-ketone;

The st-yrax system photopolymerization initiators such as st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether or benzil dimethyl ketal;

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

The thioxanthone system photopolymerization initiators such as thioxanthone (thioxanthone), 2-chlorothiaxanthenone, 2-methyl thioxanthone, isopropyl thioxanthone or 2,4-di-isopropyl thioxanthone;

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-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyl group-naphthalene-1-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2, 4-trichloromethyl-(piperonyl)-6-triazine, or 2, the triazine system photopolymerization initiators such as 4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine,

Boric acid ester system photopolymerization initiator;

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

Photopolymerization initiator preferably to be that the amount of 5 weight part ~ 200 weight parts uses for phthalocyanine pigments 100 weight part in coloured composition, more preferably can 10 weight part ~ 150 weight parts amount and use.

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

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

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

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

When phthalocyanine pigments is scattered in pigment carrier, can be suitable for using the dispersing auxiliaries (dispersion agent) such as resin-bonded pigment dispersion agent, interfacial agent and pigment derivative (pigment derivative).Dispersing auxiliary due to the excellent dispersion to pigment, prevent the effect that re-unites of pigment after disperseing large, therefore use coloured composition (described coloured composition uses dispersing auxiliary by the coloured composition of colo(u)rant dispersion in pigment carrier) and the transparency of the coloring film of gained is excellent.

Dispersing auxiliary preferably to be that the amount of 0.1 weight part ~ 40 weight part uses for phthalocyanine pigments 100 weight part in coloured composition, more preferably uses with the amount of 0.1 weight part ~ 30 weight part.

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

As the pigment derivative being used as pigment dispersing agent, the known pigment derivative (in such as Japanese Patent Laid-Open No. Sho 63-305173 publication, Japanese Patent examined patent publication 57-15620 publication, Japanese Patent examined patent publication 59-40172 publication, Japanese Patent examined patent publication 63-17102 publication, Japanese Patent Laid-fair 5-9469 publication etc. described person) generally used can be used with no particular limitation.Specifically 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, thioindigo series pigments, 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 used in combination.

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

The resin-bonded pigment dispersion agent added in coloured composition comprises the pigment affinity position with the character be adsorbed on pigment and has compatible position with pigment carrier, and play the compound of the effect being adsorbed in the decentralized stabilization that pigment makes pigment in pigment carrier.

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

Resin-bonded pigment dispersion agent specifically 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, containing phosphate-based acrylic resin, acrylic resin containing aromatic carboxyl, poly styrene sulfonate, acrylamide-(methyl) acrylic copolymer, carboxymethyl cellulose, there is the polyurethane(s) of carboxyl, the formaline condensates of naphthalenesulfonate, or the negatively charged ion system resin-bonded pigment dispersion agent such as sodium alginate,

Polyvinyl alcohol, poly-stretch the nonionic system resin-bonded pigment dispersion agents such as alkyl polyamine, polyacrylamide or polymkeric substance starch; Or

Polymine, (methyl) acrylate multipolymer, polyvinyl imidazol quinoline, there is amino polyurethane(s), poly-ly stretch alkyl imino and the positively charged ion system resin-bonded pigment dispersion agent such as reactant of polyester with free carboxyl.Those compounds can be used alone or two or more is used in combination.

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

Commercially available resin type dispersion agent can enumerate (Di Shipabike-101) Disperbyk-101 that Japanese Bi Ke chemical company (BYK-CHEMIEJAPANK.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's 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.;

The Ai Fuka-46 (EFKA-46) that vapour Bagong department of Japan (CibaJapanK.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-the PA111 (Ajisper-PA111) that aginomoto fine chemistry company (AjinomotoFine-Techno.Co.Inc.) manufactures, PB711, PB821, PB822, PB824 etc., but be not limited to those commercially available products.Those commercially available products can be used alone or two or more is used in combination.

The Disperbyk-108 that the Japanese Bi Ke chemistry Inc. as the resin-bonded pigment dispersion agent with acid functional groups makes preferably can be enumerated in those, 110, 111, 112, 116, 142, 180, 2000, 2001, or the SOLSPERSE-3000 that Japanese Lubrizol Corp. manufactures, 21000, 26000, 36600, 41000, or the EFKA-4401 that Japanese vapour Bagong department manufactures, 4550, or nanmu originally changes into the DISPARLON3600N of company's manufacture, DISPARLON1850, or the AjisperPA111 etc. that aginomoto fine chemistry company manufactures, but be not limited to those commercially available products.

Interfacial agent is not particularly limited, and include, for example:

The anionic surfactant such as monoethanolamine, Voranol EP 2001 phosphoric acid ester of the alkali salt of polyoxyethylene alkyl ether sulfate salt, Sodium dodecylbenzene sulfonate, Styrene-acrylic 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-acrylic copolymer;

The non-ionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, ethylene nonyl phenyl 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 compound of The can Single Independence use or by used in combination for 2 more than Seed.

Be scattered in fully in pigment carrier to make phthalocyanine pigments, the mode becoming 0.2 μm ~ 5 μm with dry film thickness is coated the operation transparency carriers such as glass substrate being formed coloring film and is become easy, can contain arbitrary non-water solvent in coloured composition.

Non-water solvent is not particularly limited, such as, preferably can enumerate glyceryl trichloride, 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-methylbutyl butenoate, 3-methoxybutanol, acetic acid-3-methoxybutyl, 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, second butylbenzene, tributyl benzene, gamma-butyrolactone, isopropylcarbinol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyleneglycol monopropylether, 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, dimethyl ether, dipropylene glycol methyl ether acetic ester, DPE, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol monopropyl 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 to be that the amount of 800 weight part ~ 4000 weight parts uses for phthalocyanine pigments 100 weight part in coloured composition or pigment dispersion, more preferably can 1000 weight part ~ 2500 weight parts amount and use.

In addition, in order to make composition through time viscosity stablization, also can contain storage stabilizing agent in coloured composition.Storage stabilizing agent is the known storage stabilizing agent generally used, and include, for example the aliquat such as benzyl trimethyl ammonium chloride or diethylhydroxylamine class; 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 uses for phthalocyanine pigments 100 weight part in coloured composition.

And, in order to mix colours, also in the scope not making thermotolerance reduce, dyestuff can be contained in coloured composition.The dyestuff used is not particularly limited, preferably can 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 dye, 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 Offset gravure (gravureoffset) printing ink, waterless planographic printing ink, silk screen printing ink, solvent developable or the painted resist of alkali developable form and prepare.

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

Preferred coloured composition containing the oversize particle of more than 5 μm, preferably oversize particle, the more preferably oversize particle of more than 0.5 μm of more than 1 μm, preferably by the removing of dust that the mechanisms such as centrifugation, sintered filter, membrane filter carry out those oversize particles and are mixed into.When particularly coloured composition being used as the situation of colour filter purposes, preferably in fact not containing the particle of more than 0.5 μm, more preferably not containing the particle being greater than 0.3 μm.

5. colour filter

Colour filter at least comprises the colour filter fragment that substrate, this substrate are formed, and this colour filter fragment comprises and uses above-mentioned coloured composition and gained person.That is colour filter comprises at least one red color filter fragment, at least one green color fragment, at least one blue color fragment on substrate, and blue color fragment is formed by the above-mentioned coloured composition comprising phthalocyanine pigments.Red color filter layer (R) beyond blueness and green color filter layer (G) or be equivalent to redness, green, the cyan colour filter (C) of blue complementary color, carmetta colour filter (M) and yellow colour filter (Y) and can use arbitrary coloured composition and be formed, there is no any restriction.And, in order to form in the red colored composition of red color filter fragment, except red pigment, also can also with orange pigments and/or yellow ultramarine; In the green coloring composition in order to form green color fragment, 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 undertaken by print process or photolithography.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 drying can carry out patterning, therefore as the manufacturing process of colour filter, cost is low and production excellent.In addition, the printing of the fine pattern with high dimensional accuracy and smoothness can be carried out due to the development of printing technology.In order to print, be preferably set to ink in press plate or on clad can and moist, solidification composition.And the control of the mobility of ink is on the printer also important, the adjustment of the ink viscosity utilizing dispersion agent or pigment extender also can be carried out.

When forming the situation of colour filter fragment by photolithography, such as, can carry out as shown below, but be not limited thereto.By coating processes such as spraying, spin coating, slot coated, roller coat, the coloured composition being prepared as above-mentioned solvent developable or the painted resist of alkali developable is coated on transparency carrier by the mode becoming 0.2 μm ~ 5 μm with dry film thickness.For the optionally film of drying, by contact with this film or non-contacting state and the mask with predetermined pattern established, carry out ultraviolet exposure.Thereafter, impregnated in solvent or alkaline-based developer, or by injection wait and carry out developing solution spraying, unhardened portion is removed, thus formation desired by pattern.Also repeatedly carry out same operation about other colors, thus assorted colour filter fragment can be formed.In addition, in order to promote the polymerization of painted resist, heating also optionally can be implemented.By photolithography, can the higher colour filter of more above-mentioned print process manufacturing accuracy.

When 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 can at the above-mentioned painted resist of coating and in addition after drying, be coated with water-soluble or alkali water-soluble resin, such as polyvinyl alcohol or water soluble acrylic resin etc. and in addition dry, after forming the film preventing the polymerization caused due to oxygen from hindering, carry out ultraviolet exposure.

In addition to the method described above, also colour filter fragment can be manufactured by electrochemical plating, transfer printing etc.Electrochemical plating utilize the nesa coating that substrate is formed, and by the electrophoresis of colloidal particle, assorted colour filter fragment electroplated the method be formed on nesa coating.Transfer printing is pre-formed colour filter fragment on the surface of the transfer printing base sheet of separability, makes this colour filter fragment be needed on method on desired substrate.

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

The substrate of colour filter is transparency carrier, except the sheet glass of the high soda-lime glass, low alkali borosilicate glass, alkali-free alumina borosilicate glass etc. of penetration coefficient for visible ray, also can use the resin board of polycarbonate, polymethylmethacrylate, polyethylene terephthalate etc.

Colour filter comprises the transparency electrode driving liquid crystal further.Transparency electrode comprises Indium sesquioxide, stannic oxide etc., can be formed by evaporation or sputter.

If be pre-formed black matrix" form colour filter fragment on substrate before, then 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 being not limited to those.And, also can be pre-formed thin film transistor (thin-filmtransistor, TFT) on substrate, form colour filter fragment thereafter.By forming colour filter fragment on the tft substrate, the percentage of open area of display panels can be improved, brightness is improved.

Colour filter optionally forms 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, after being certainly located at the inlet injection liquid crystal of sealing, inlet is sealed, optionally light polarizing film or phase retardation film are fitted in the outside of substrate, manufacture display panels by this.

Display panels can at twisted nematic (TwistedNematic, TN) pattern, STN Super TN (SuperTwistedNematic, STN) pattern, coplanar switching (Inplaneswitching, IPS) pattern, vertical orientated (VerticalAlignment, VA) pattern, optical compensation curved (opticallycompensatedbend, OCB) pattern etc. use colour filter and carry out using in the liquid crystal display mode of colorize.

Embodiment

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

1. assay method

(1) colour characteristics

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

(2) contrast gradient

The coated film used in using colour characteristics to measure measures contrast gradient.Be illustrated at the measuring method of the following contrast gradient to film.

(assay method of the contrast gradient of film)

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

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

That is, if produce scattering due to the pigment in film, then brightness time parallel reduce and orthogonal time brightness increase, therefore contrast gradient step-down.

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

(3) powder x-ray diffraction

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

Device: X ' pert-Pro full-automatic many objects X-ray diffraction 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.

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

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

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

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

Secondly, by comprise the following composition of the π type copper phthalocyanine pigments 1 of gained mixture uniform stirring after, use the zirconia particles that diameter is 0.5mm, carry out the dispersion of 3 hours by ball mill, make color compositions (organic pigment compositions) 1 by the strainers of 2 μm carry out filtering.

Copper phthalocyanine system pigment derivative is copper phthalocyanine dimethylaminopentyl sulphonamide, and acrylic resin soln be the solids component of 2: 8 (weight ratio) multipolymer (weight average molecular weight is 40000) comprising methacrylic acid and n-BMA is the cyclohexanone solution of 20%.

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

Embodiment 2 ~ embodiment 27

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

Be loaded in synthesizer by each raw material, one side adds diazabicyclo undecylene 15.2 parts and maintains 3 hours after stirring and being simultaneously warming up to 130 DEG C, makes copper phthalocyanine pigments 28 by this.And, about the Purification by filtration after synthesis, disperse and be uniformly mixed, processing similarly to Example 1, making 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 Purification by filtration after synthesis, disperse and be uniformly mixed, processing similarly to Example 1, making color compositions 29 and coloured composition 29.The crystal type of gained is π type.

Comparative example 1 ~ comparative example 3

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

Comparative example 4

After (Leo promise blue E) LIONOLBLUEE76 part Japan look material (TOYOCOLOR) company manufactured, copper phthalocyanine dimethylaminopentyl sulphonamide 4 parts, 600 parts, sodium-chlor and Diethylene Glycol 100 parts carry out 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 method for above embodiment and comparative example and the crystal type of pigment that makes and the tone (Y value: illuminant-C) of film using each coloured composition and make and contrast gradient.

Show the result in table 2.

[table 2]

Measure by X-ray diffraction and as comparative example 1, do not add half sweet cured acid and carry out the pigment that synthesizes, the results are shown in Bragg angle 2 θ is the diffraction pattern that 6.9 degree, 9.0 degree, 10.2 degree, 12.3 degree, 18.2 degree places have the beta type copper phthalocyanine pigments as shown in Figure 2 of diffraction peak.And, even if as such as adding 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 being undertaken measuring by X-ray diffraction is that to be shown in Bragg angle 2 θ be the diffraction pattern that 7.5 degree, 9.0 degree, 14.2 degree places have the ε type copper phthalocyanine pigments as shown in Figure 3 of diffraction peak.

Measure the pigment used 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 degree, 14.2 degree places have the ε type copper phthalocyanine pigments of diffraction peak.

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

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

Should note except narrator, also can not depart from novelty of the present invention and favourable characteristically to various correction 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)

R ¹~ R ⁸be independently hydrogen atom, COOH, CONH ₂, CF ₃, OC ₆h ₅, NH ₂, NO ₂, C ₆h ₅or alkyl; R ¹~ R ⁸be not hydrogen atom simultaneously; M is atoms metal or 2H; R ⁹~ R ¹⁶be independently 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.

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 set to x DEG C,

Relative to Tetra hydro Phthalic anhydride and phthalic acid derivatives total input weight and the input weight of described phthalic acid derivatives is set to y%,

Relative to described Tetra hydro Phthalic anhydride and described phthalic acid derivatives total input weight and when solvent input amount is set to z times,

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

Described Tetra hydro Phthalic anhydride and at least described phthalic acid derivatives that is substituted of α position is made under represented condition, with urea, urea derivatives or ammonia, with the step of reacting metal salt, wherein, 90≤x≤300,0 < y, 0≤z.

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

The diiminoisoindole derivative that the phthalonitrile derivatives that phthalonitrile and/or diiminoisoindole, at least α position are substituted and/or at least α position are substituted, carries out 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 be 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 is also containing resin-bonded pigment dispersion agent and/or pigment derivative.

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

9. a colour filter, it at least comprises the colour filter fragment that substrate and described substrate are formed, and the part of described colour filter fragment uses coloured composition according to any one of claim 6-8 and gained person.