CN102947733A - Colored resin composition, color filter, liquid crystal display device, and organic EL display - Google Patents

Abstract

Provided is a colored resin composition that satisfies the heat resistance required for the steps involved in color display production. Also provided are, as a result of using such a colored resin composition, a color filter having excellent color purity and transmittance of blue pixels, and an organic EL display and a liquid crystal display device having good blue color purity. The colored resin composition comprises (A) a dye, (B) a solvent, and (C) a binder resin, and the dye (A) comprises a compound that is a counterion of disulfonylimide anionic and cationic dyes.

Description

Colored resin composition, colored filter, liquid crystal indicator and OLED display

Technical field

The invention reside in colored resin composition, colored filter, liquid crystal indicator and OLED display.

Background technology

In recent years, colored liquid crystal indicator or organic EL(Organic Electro Luminescence) display attracted attention as flat-panel screens, uses colored filter in these displays.

In the color liquid crystal display arrangement, as an example, for example have roughly by the transmissive liquid crystal display device that consists of such as lower member: possess black matrix" (black matrix), multiple color (is generally red (R), green (G), blue (B) 3 primary colors) dyed layer that consists of, the colored filter substrate of transparency electrode and oriented layer, possesses thin film transistor (TFT) (TFT element), pixel electrode and oriented layer to electrode base board, and these two substrates are faced mutually with the gap of regulation, with containment member sealing, inject liquid crystal material in the above-mentioned gap and the liquid crystal layer that forms.In addition, also has the reflection-type liquid-crystal display device that is provided with the reflection horizon between the substrate of above-mentioned colored filter and the dyed layer.

OLED display is on principle, to have the device that clips the organic EL of organic EL luminous layer structure between anode and the negative electrode, in the reality, manufacturing can display color the OLED display of use organic EL following mode is arranged: (1) will send respectively the mode that the organic EL of each coloured light is arranged in the three primary colors, (2) will the turn white mode of the organic EL of coloured light and trichromatic colored filter combination, and (3) will turn blue the organic EL of coloured light with realize respectively blue → CCM mode that green and blue → red versicolor color conversion layer (CCM layer) makes up etc.

Mode (1) much less because use organic EL of all kinds, so it is characterized in that embodying high color reprodubility.Therefore, by the colored filter corresponding to organic EL of all kinds is installed, can expect the raising of its color reprodubility, can expect the raising of its contrast based on absorbing reflected light, so be promising a kind of mode.

In addition, in the CCM mode of the combination organic EL of white (2) and the mode of colored filter and (3), owing to can only use a kind of with the organic EL of coloured light, therefore there is no need in the OLED display of aforesaid way (1), integrate the characteristic of organic EL of all kinds, can cut down operation quantity and material, also be the full color mode that gets most of the attention aspect manufacturing cost.

Using colored filter and with color conversion filter and organic luminorphor in the organic EL as the look mapping mode of inscape, reach desired thermotolerance in the color monitor manufacturing process for needs, the device of the weatherability when using as display and the image of high-fineness, the main flow way is to use the colored filter of making by the Pigments method, with redness, blue or green pigment is following little being scattered in the photoresist solution of particle diameter 1 μ m, after being coated on the thing of gained on the glass substrate, form the pixel of desirable pattern by photoetch method.

For colored filter, pursue the raising of its excitation, chroma, light transmission amount, past, to improve light transmission amount as purpose, adopt such method: reduce image form with in the material with respect to the content of the coloring pigment of photoresist, perhaps attenuate is formed the thickness that forms of the pixel that forms with material by image.Yet, these methods have reduced the chroma of colored filter self, the distinctness sense of required color in the demonstration has been sacrificed in the whole whiting of display, and is opposite, increase coloring pigment content if preferentially satisfy chroma, then display integral body is dimmed, at this moment, and in order to ensure brightness, have to heighten light quantity backlight, the problem that causes display consumes electric power to increase is arranged.

Relative therewith, to improve light transmission amount as purpose, known have the granules of pigments differential loose, make its particle diameter be the method below 1/2 (non-patent literature 1) of its colour developing wavelength, but because blue pigment compares with red, viridine green, the colour generation wavelength is shorter, and this moment, further differential was loose, and the stability after cost raising and the dispersion becomes problem.

On the other hand, use dyestuff also still advancing as the exploitation of the colored filter of colorant.For example record such colored filter in the patent documentation 1: it is provided with, and to contain C.I. acid blue 83(triallylamine be the look material) and C.I. solvent blue 67(copper phthalocyanine be the look material) blue color filter layer.

In addition, put down in writing the colored filter that uses the polymkeric substance that contains the polymerism kiton colors that following formula represents in the patent documentation 2.

[changing 1]

(the R of following formula ₁In, at least one is the specific polymerizable group that contains carbon-to-carbon double bond)

Further, the record that relates to the colored resin composition that contains the look material that ad hoc structure represents is also arranged in the patent documentation 3.

The prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2002-14222 communique

Patent documentation 2: Japanese Patent Laid-Open 2000-162429 communique

Patent documentation 3: Japanese Patent Laid-Open 2009-235392 communique

Non-patent literature

Non-patent literature 1: the bridge pawl is clear, " look material association will ", in Dec, 1967, P608

Summary of the invention

The problem that invention will solve

But, use the colored filter of the dyestuff of putting down in writing in the above-mentioned document, there is the particularly problem of transmitance (brightness) and thermotolerance deficiency.

The object of the invention is to, provide and satisfy desired stable on heating colored resin composition in the above-mentioned color monitor manufacturing process.In addition, purpose is, by using such colored resin composition, provides excitation and the excellent colored filter of transmitance (brightness) of blue pixel, and the OLED display of blue high color purity and liquid crystal indicator.

Solve the means of problem

People of the present invention find that the salt that has the compound formation of ad hoc structure by use is used dyestuff as the blue pixel formation of colored filter, can solve above-mentioned problem, thereby finish the present invention.

Be that the first main points of the present invention are the colored resin composition shown in following (1) ~ (3) (below, be sometimes referred to as " the 1st colored resin composition ").

(1) a kind of colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (I).

[changing 2]

(in the above-mentioned formula (I), (Z ₁) ^M1-The disulfonyl imines negative ion of expression m1 valency.

M1 represents 1 ~ 4 integer.

R ¹~ R ⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Adjacent R ¹~ R ⁶Between can connect into ring, this ring can also have substituting group.

R ⁷And R ⁸Expression hydrogen atom or substituting group arbitrarily.

R ⁷And R ⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (I) can further have any substituting group.

R ¹⁰¹And R ¹⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have substituent carbon number 2 ~ 6 thiazolinyl, can have substituent aromatic ring yl, or fluorine atom.

R ¹⁰¹And R ¹⁰²Can be connected to each other to ring, this ring can also have substituting group.

In addition, if contain a plurality of following formulas (I) in a part _CAShown kation, then they can be same structures, also can be different structures.）

[changing 3]

(2) colored resin composition described in (1) is characterized in that, the compound of above-mentioned formula (I) expression is the compound of following formula (I-1) expression.

[changing 4]

(in the above-mentioned formula (I-1), R ¹~ R ⁸, R ¹⁰¹And R ¹⁰²Identical with the definition in the above-mentioned formula (I).

Phenyl ring in the above-mentioned formula (I-1) can further have any substituting group.

R ²¹And R ²²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ²¹And R ²²Can be connected to each other to ring, this ring can also have substituting group.）

(3) colored resin composition described in above-mentioned (2) is characterized in that above-mentioned R ²¹And R ²²At least one be the contain fluorine atoms group.

The second main points of the present invention are the colored resin composition shown in following (4) ~ (6) (below, be sometimes referred to as " the 2nd colored resin composition ").

(4) a kind of colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (II).

[changing 5]

(in the above-mentioned formula (II), (Z ₂) ^M2-The disulfonyl imines negative ion of expression m2 valency.

M2 represents 1 ~ 4 integer.

R ¹¹~ R ¹⁶Represent independently of one another hydrogen atom, can have substituent alkyl, maybe can have substituent aromatic ring yl.

Adjacent R ¹¹~ R ¹⁶Between can connect into ring, this ring can also have substituting group.

R ¹⁷And R ¹⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ¹⁷And R ¹⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (II) and indole ring can further have any substituting group.

In addition, if contain a plurality of following formulas (II) in a part _CAShown kation, then they can be same structures, also can be different structures.）

[changing 6]

(5) colored resin composition described in above-mentioned (4) is characterized in that, the compound of above-mentioned formula (II) expression is the compound of following formula (II-1) expression.

[changing 7]

(in the above-mentioned formula (II-1), R ¹¹~ R ¹⁸Identical with the definition in the above-mentioned formula (II).

Phenyl ring in the above-mentioned formula (II-1) and indole ring can further have any substituting group.

R ³¹And R ³²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ³¹And R ³²Can be connected to each other to ring, this ring can also have substituting group.）

(6) colored resin composition described in above-mentioned (5) is characterized in that above-mentioned R ³¹And R ³²At least one be the contain fluorine atoms group.

The 3rd main points of the present invention are the colored resin composition shown in following (7) ~ (9) (below, be sometimes referred to as " the 3rd colored resin composition ").

(7) a kind of colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (III).

[changing 8]

(in the above-mentioned formula (III), (Z ₃) ^M3-The disulfonyl imines negative ion of expression m3 valency.

M3 represents 1 ~ 4 integer.

Q represents 1 ~ 5 integer.

R ⁵⁰¹And R ⁵⁰²Independently of one another expression can have the aliphatic alkyl of substituent carbon number 1 ~ 20.

R ⁵¹And R ⁵²Independently of one another expression-O-,-S-,-N-,-Se-or-CR ⁵⁰³R ⁵⁰⁴-.

R ⁵⁰³And R ⁵⁰⁴The aliphatic alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 6.

Wherein, if R ⁵¹And R ⁵²For-CR ⁵⁰³R ⁵⁰⁴-, R then ⁵⁰³Between can be connected to each other to ring, this ring can also have substituting group.

Ring Y ¹And Y ²Independently of one another expression can have substituting group phenyl ring or naphthalene nucleus.

Wherein, ring Y ¹And Y ²Phenyl ring and naphthalene nucleus do not have nitro and perfluoroalkyl as substituting group.）

(8) colored resin composition described in above-mentioned (7) is characterized in that, the compound of above-mentioned formula (III) expression is the compound of following formula (III-1) expression.

[changing 9]

(in the above-mentioned formula (III-1), q, R ⁵¹And R ⁵², R ⁵⁰¹And R ⁵⁰²And ring Y ¹And Y ²Identical with the definition in the above-mentioned formula (III).

R ⁴¹And R ⁴²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ⁴¹And R ⁴²Can be connected to each other to ring, this ring can also have substituting group.）

(9) colored resin composition described in above-mentioned (8) is characterized in that above-mentioned R ⁴¹And R ⁴²At least one be the contain fluorine atoms group.

The 4th main points of the present invention are the colored resin composition shown in following (10) ~ (12) (below, be sometimes referred to as " the 4th colored resin composition ").

(10) a kind of colored resin composition, contain (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that, (A) dyestuff contains the counter ion counterionsl gegenions of kation and negative ion formation, the molecular weight of this negative ion is more than 150, below 600, and these counter ion counterionsl gegenions satisfy the relation of following formula (1) ~ (3).

[several 1]

$|\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}-\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}|\≤2.2---\left(1\right)$

$3.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}\≤4.0---\left(2\right)$

$1.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}\≤3.4---\left(3\right)$

(in the above-mentioned formula,

IP _CationRepresent above-mentioned cationic ionization potential (hartree),

EA _CationRepresent above-mentioned cationic electron affinity (hartree),

IP _AnionThe ionization potential (hartree) that represents above-mentioned negative ion,

EA _AnionThe electron affinity (hartree) that represents above-mentioned negative ion.）

(11) colored resin composition described in above-mentioned (10) is characterized in that, above-mentioned kation is by following formula (I-2) _CAExpression.

[changing 10]

(above-mentioned formula (I-2) _CAIn, R ⁶¹~ R ⁶⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Adjacent R ⁶¹~ R ⁶⁶Between can connect into ring, this ring can also have substituting group.

R ⁶⁷And R ⁶⁸Expression hydrogen atom or substituting group arbitrarily.

R ⁶⁷And R ⁶⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, above-mentioned formula (I-2) _CAIn phenyl ring can further have any substituting group.

R ⁶⁰¹And R ⁶⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, can have substituent aromatic ring yl or fluorine atom.

R ⁶⁰¹And R ⁶⁰²Can be connected to each other to ring, this ring can also have substituting group.）

(12) colored resin composition described in above-mentioned (10) is characterized in that, above-mentioned kation is by following formula (II-2) _CAExpression.

[changing 11]

(above-mentioned formula (II-2) _CAIn, R ⁷¹~ R ⁷⁶Represent independently of one another hydrogen atom, can have substituent alkyl, maybe can have substituent aromatic ring yl.

Adjacent R ⁷¹~ R ⁷⁶Between can connect into ring, this ring can also have substituting group.

R ⁷⁷And R ⁷⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ⁷⁷And R ⁷⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, above-mentioned formula (II-2) _CAIn phenyl ring and indole ring can further have any substituting group.）

Colored resin composition shown in above-mentioned (1) ~ (12) can also further contain (D) polymerizable monomer, (E) photopolymerization to be caused composition and thermal polymerization and causes in the composition at least one, and (F) pigment.

The present invention also is, contains colored filter, liquid crystal indicator and the OLED display of the pixel of useful colored resin composition formation of the present invention.

In addition, " colored resin composition of the present invention " is the general name of above-mentioned " the 1st ~ 4 colored resin composition ".

The effect of invention

According to the present invention, can obtain having desired thermotolerance in the color monitor manufacturing process, the colored filter of the excitation of blue pixel and transmitance excellence.By using such colored filter, can more effectively obtain backlight luminous of luminous, the colored filter of OLED display, liquid crystal indicator and the OLED display of taking into account high color reprodubility and high brightness can be provided.In addition, also can improve the contrast of liquid crystal indicator.

Description of drawings

[Fig. 1] shows the schematic cross-section of an example of the organic EL with colored filter of the present invention.

10 transparent support substrates

50 transparent anodes

52 hole transporting layers

53 luminescent layers

55 negative electrodes

100 organic ELs

20 blue pixel

30 organic protection layers

40 inorganic oxide films

500 organic luminorphors

51 hole injection layers

54 electron injecting layers

Embodiment

Below, explain embodiments of the present invention, but following explanation being an example of embodiments of the present invention, the present invention is not limited by these contents.

Also have; in the present invention; " (methyl) acryloyl group ", " (methyl) acrylate " etc. refer to " acryloyl group and/or methacryl ", " acrylate and/or methacrylate " etc., and for example " (methyl) acrylic acid " refers to " acrylic acid and/or methacrylic acid ".

" total solids composition " refers to all the components of the colored resin composition of the present invention except the aftermentioned solvent composition in addition.

C.I. refer to color index (color index).

Colored resin composition of the present invention contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff is any one of following (a) ~ (d).

Any is compared with dye composition in the past, particularly excellent heat resistance.

(a) contain the compound shown in the following formula (I) (below be sometimes referred to as compound (I)).

[changing 12]

(in the above-mentioned formula (I), (Z ₁) ^M1-The disulfonyl imines negative ion of expression m1 valency.

M1 represents 1 ~ 4 integer.

R ¹~ R ⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Adjacent R ¹~ R ⁶Between can connect into ring, this ring can also have substituting group.

R ⁷And R ⁸Expression hydrogen atom or substituting group arbitrarily.

R ⁷And R ⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (I) can further have any substituting group.

R ¹⁰¹And R ¹⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, can have substituent aromatic ring yl or fluorine atom.

R ¹⁰¹And R ¹⁰²Can be connected to each other to ring, this ring can also have substituting group.

In addition, if contain a plurality of following formulas (I) in a part _CAShown kation,

[changing 13]

Then they can be same structures, also can be different structures.）

(b) contain the compound shown in the following formula (II) (below be sometimes referred to as compound (II)).

[changing 14]

(in the above-mentioned formula (II), (Z ₂) ^M2-The disulfonyl imines negative ion of expression m2 valency.

M2 represents 1 ~ 4 integer.

R ¹¹~ R ¹⁶Represent independently of one another hydrogen atom, can have substituent alkyl, maybe can have substituent aromatic ring yl.

Adjacent R ¹¹~ R ¹⁶Between can connect into ring, this ring can also have substituting group.

R ¹⁷And R ¹⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ¹⁷And R ¹⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (II) and indole ring can further have any substituting group.

In addition, if contain a plurality of following formulas (II) in a part _CAShown kation,

[changing 15]

Then they can be same structures, also can be different structures.）

(c) contain the compound shown in the following formula (III) (below be sometimes referred to as compound (III)).

[changing 16]

(in the above-mentioned formula (III), (Z ₃) ^M3-The disulfonyl imines negative ion of expression m3 valency.

M3 represents 1 ~ 4 integer.

Q represents 1 ~ 5 integer.

R ⁵⁰¹And R ⁵⁰²Independently of one another expression can have the aliphatic alkyl of substituent carbon number 1 ~ 20.

R ⁵¹And R ⁵²Independently of one another expression-O-,-S-,-N-,-Se-or-CR ⁵⁰³R ⁵⁰⁴-.

R ⁵⁰³And R ⁵⁰⁴The aliphatic alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 6.

Wherein, if R ⁵¹And R ⁵²For-CR ⁵⁰³R ⁵⁰⁴-, R then ⁵⁰³Between can be connected to each other to ring, this ring can also have substituting group.

Ring Y ¹And Y ²Independently of one another expression can have substituting group phenyl ring or naphthalene nucleus.

Wherein, ring Y ¹And Y ²Phenyl ring and naphthalene nucleus do not have nitro and perfluoroalkyl as substituting group.）

(d) dyestuff contains such compound: contain the counter ion counterionsl gegenions that kation and negative ion form, the molecular weight of this negative ion is more than 150, below 600, and these counter ion counterionsl gegenions satisfy the relation (below be sometimes referred to as compound (IV)) of following formula (1) ~ (3).

[several 2]

$|\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}-\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}|\≤2.2---\left(1\right)$

$3.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}\≤4.0---\left(2\right)$

$1.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}\≤3.4---\left(3\right)$

(in the above-mentioned formula,

IP _CationRepresent above-mentioned cationic ionization potential (hartree),

EA _CationRepresent above-mentioned cationic electron affinity (hartree),

IP _AnionThe ionization potential (hartree) that represents above-mentioned negative ion,

EA _AnionThe electron affinity (hartree) that represents above-mentioned negative ion.）

Colored resin composition of the present invention contains (A) dyestuff, (B) solvent and (C) adhesive resin, preferably further contain (D) polymerizable monomer, (E) photopolymerization initiation composition and/or thermal polymerization cause composition, (F) pigment, further contain other compositions that mix as required.

＜(A) dyestuff＞

At first, (A) dyestuff contained in the colored resin composition of the present invention is described.

［ structural feature ］

The structural feature of compound is as described below shown in the above-mentioned formula (I) ~ (III).

The compound shown in the contained above-mentioned formula (I) ~ (III) forms counter ion counterionsl gegenions in (A) dyestuff among the present invention.

Form the dyestuff of counter ion counterionsl gegenions, the property effect physical property, particularly thermotolerance of its kation and negative ion.This is owing to compare with neutral molecule, has the reactivity of the kation of electric charge deflection and negative ion higher respectively.

Therefore, infer by reducing the reactivity of kation and negative ion, can improve the thermotolerance of dyestuff.That is to say, think by making the electric charge non-localized in kation and the negative ion reduce its reactivity, interrelate with stable on heating raising.

Among the present invention, as negative ion, use disulfonyl imines negative ion.

Because the ionic species of disulfonyl imines negative ion is sulfoamido, therefore easy to manufacture.In addition because negative charge is non-localized, so negative ion is more stable.Have the fluoro substituents of containing in the further preferred disulfonic acid amide, at this moment, because negative ion is pulled to and contains fluoro substituents one side, be dispersed as the molecule total charge, think to form more stable structure.

In addition, the negative ion among the present invention does not all have to absorb at visible region.Thereby less on the impact of transmitance (brightness).

As from the foregoing, the colored resin composition of the application of the invention and the colored filter that obtains can be taken into account transmitance (brightness) and thermotolerance.

［ compound shown in the formula (I) ］

At first, the compound shown in the above-mentioned formula (I) is described.

The 1st colored resin composition of the present invention contains the compound of following formula (I) expression as (A) dyestuff.

The compound of following formula (I) expression, from excellent heat resistance, it is preferred that the aspect of especially blue purity and transmitance excellence is considered.

[changing 17]

(in the above-mentioned formula (I), (Z ₁) ^M1-The disulfonyl imines negative ion of expression m1 valency.

M1 represents 1 ~ 4 integer.

R ¹~ R ⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Adjacent R ¹~ R ⁶Between can connect into ring, this ring can also have substituting group.

R ⁷And R ⁸Expression hydrogen atom or substituting group arbitrarily.

R ⁷And R ⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (I) can further have any substituting group.

R ¹⁰¹And R ¹⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, can have substituent aromatic ring yl or fluorine atom.

R ¹⁰¹And R ¹⁰²Can be connected to each other to ring, this ring can also have substituting group.

In addition, if contain a plurality of following formulas (I) in a part _CAShown kation,

[changing 18]

Then they can be same structures, also can be different structures.）

(about R ¹~ R ⁶)

R ¹~ R ⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

R ¹~ R ⁶In alkyl, can enumerate the alkyl of straight chain shape, chain or ring-type, its carbon number is generally more than 1, in addition, usually below 8, the alkyl below 5 preferably.Object lesson can be enumerated methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, cyclohexyl etc.

R ¹~ R ⁶In aromatic ring yl can enumerate aromatic cyclic hydrocarbon group and aromatic heterocycle.

Aromatic cyclic hydrocarbon group can be that monocycle also can be condensed ring, as long as forming the carbon number of ring and be 5 ~ 18 just is not particularly limited, for example can enumerate, have 1 free valent phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene ring, benzopyrene ring, The groups such as ring (Chrysene), benzo phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring.

In addition, aromatic heterocycle can be that monocycle also can be condensed ring, as long as forming the carbon number of ring and be 3 ~ 10 just is not particularly limited, for example can enumerate, have 1 free valent furan nucleus, the coumarone ring, thiphene ring, the benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring oxadiazole rings, indole ring, the carbazole ring, the pyrrolo-imidazole ring, the pyrrolo-pyrazole ring, the pyrrolopyrrole ring, the Thienopyrroles ring, the thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran benzoxazole ring, the benzisothiazole ring, the benzimidazole ring, pyridine ring, the pyrazine ring, the pyridazine ring, pyrimidine ring, triazine ring, the quinoline ring, the isoquinoline ring, the cinnolines ring, quinoxaline ring, the phenanthridines ring, the perimidine ring, the quinazoline ring, the quinazolinone ring, the groups such as azulenes.

Adjacent R ¹~ R ⁶Between can connect into ring, further this ring can also have substituting group.

In addition, this ring also can be the ring by the heteroatoms bridging, as this object lesson, can enumerate for example following structure.

[changing 19]

Consider R from the aspect of chemical stability ¹~ R ⁶The alkyl that preferably represent independently of one another hydrogen atom, can have a substituent carbon number 1 ~ 8 maybe can have substituent phenyl, perhaps adjacent R ¹~ R ⁶Be connected to each other to ring.From improving the thermotolerance of dyestuff, the aspect of the excellent heat resistance of the colored filter that obtains considers that the alkyl that more preferably can have substituent carbon number 1 ~ 8 maybe can have substituent phenyl.

Work as R ¹~ R ⁶Be in the time of to have the alkyl of substituent carbon number 1 ~ 8, can infer that owing to hyperconjugation, the electric charge in the kation disperses, thereby so that kation obtain stabilization.

In addition, if R ¹~ R ⁶Be to have substituent phenyl, because conjugated system prolongs, the electric charge in the kation disperses, and kation obtains stabilization.Can think that the result of cationic stabilized is like this, the thermotolerance of the colored filter that obtains is more excellent.

As R ¹~ R ⁶The be connected to each other substituting group of the ring that forms of alkyl, aromatic ring yl and can having, can enumerate for example following (replacing basic group W) group.

(replacing basic group W)

Fluorine atom, the chlorine atom, the alkyl of carbon number 1 ~ 8, the thiazolinyl of carbon number 2 ~ 8, the alkoxy of carbon number 1 ~ 8, phenyl, isopropylidene, tolyl, naphthyl, cyano group, acetoxyl group, the alkanoyloxy of carbon number 2 ~ 9, sulfoamido, the sulfo group alkylamidoalkyl of carbon number 2 ~ 9, the alkyl-carbonyl of carbon number 2 ~ 9, phenethyl, hydroxyethyl, acetamido, the alkyl linked dialkyl amido ethyl that forms of carbon number 1 ~ 4, trifluoromethyl, the trialkyl silyl of carbon number 1 ~ 8, nitro, the alkyl sulfenyl of carbon number 1 ~ 8.

Wherein, as R ¹~ R ⁶The be connected to each other substituting group of the ring that forms of alkyl, aromatic ring yl and can having, sulfo group alkylamidoalkyl and the fluorine atom of the alkyl carboxyl of the alkyl of preferred carbon number 1 ~ 8, the alkoxy of carbon number 2 ~ 8, cyano group, acetoxyl group, carbon number 2 ~ 8, sulfoamido, carbon number 2 ~ 8.

(about R ⁷And R ⁸)

R ⁷And R ⁸Expression hydrogen atom or substituting group arbitrarily.As this any substituting group, can enumerate halogen atom for example, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl etc.

On the phenyl ring in formula (I), for the key that forms with the carbon atom that is positioned at triarylmethane structure central authorities, if at its ortho position bonding during bulky group, will hinder the planarity of molecule, may reduce the excitation of compound.Therefore, preferred ortho position does not have substituting group, or substituting group is the alkyl of halogen atom, carbon number 1 ~ 8.

In addition, the alkyl of this carbon number 1 ~ 8 is considered from sterically hindered little aspect, the alkyl of further preferred carbon number 1 ~ 4.

In addition, R ⁷And R ⁸Can be connected to each other to ring, this ring can also have substituting group.As this substituting group, can enumerate the group such as record in above-mentioned (replacing basic group W).

If R ⁷And R ⁸Between connect into ring, they can also be the rings by the heteroatoms bridging.

R ⁷And R ⁸The structure of coupling part can be listed below.The structure of these coupling parts can also have substituting group.

[changing 20]

The gained colored filter is considered preferred R if blue from the aspect of high brightness ⁷And R ⁸Between be not connected to each other to ring.

In addition, the gained colored filter is if purple, and considers from the aspect of high brightness, preferably is connected to each other to ring.

(about R ¹⁰¹And R ¹⁰²)

R ¹⁰¹And R ¹⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, can have substituent aromatic ring yl or fluorine atom.

As alkyl and aromatic ring yl, can enumerate above-mentioned (about R ¹~ R ⁶) in the record group.

Thiazolinyl can be enumerated carbon number and be generally group more than 2, below 6.Object lesson has been enumerated vinyl, allyl, 1-butenyl group etc.

In addition, pass through R ¹⁰¹And R ¹⁰²Couple together a part that consists of ring, since the plane that consists of with respect to the phenyl ring of the sp2 carbon atom of triarylmethane structure centre and adjacency, R ¹⁰¹And R ¹⁰²The phenyl ring of institute's bonding becomes the position relationship of distortion, becomes to have blue the absorption, therefore considers it is preferred from the colored filter that uses it with the aspect that dichroism improves, the contrast of blue display member is easy to improve of colored resin composition.

R ¹⁰¹And R ¹⁰²The structure of coupling part can be listed below.

[changing 21]

R ¹⁰¹And R ¹⁰²The structure of coupling part, can have substituting group.

As this substituting group, can enumerate the group such as record in above-mentioned (replacing basic group W) item.

In addition, the phenyl ring in the above-mentioned formula (I) can further have any substituting group.That is, in the scope of not damaging effect of the present invention, can have the substituting group in addition of writing exactly in the formula (I), but consider from the aspect of easy manufacturing, preferably not have the substituting group in addition of writing exactly in the formula (I).

As such substituting group, can enumerate the substituting group of record in above-mentioned (replacing basic group W) item.

［ about the compound of formula (I-1) expression ］

The compound of above-mentioned formula (I) expression, the compound of preferred following formula (I-1) expression.

[changing 22]

(in the above-mentioned formula (I-1), R ¹~ R ⁸, R ¹⁰¹And R ¹⁰²Identical with the definition in the above-mentioned formula (I).

Phenyl ring in the above-mentioned formula (I-1) can further have any substituting group.

R ²¹And R ²²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ²¹And R ²²Can be connected to each other to ring, this ring can also have substituting group.）

(about R ²¹And R ²²)

R ²¹And R ²²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ²¹And R ²²Can be connected to each other to ring, this ring can also further have substituting group.

As R ²¹And R ²²In alkyl, thiazolinyl, naphthenic base and can have the substituting group of the ring that is connected to each other and forms, can enumerate the group of record in for example above-mentioned (replacing basic group W).

Wherein, as R ²¹And R ²²In the substituting group that has of alkyl, thiazolinyl or naphthenic base, non-localized, the stable on heating aspect that improves dyestuff consider preferably have fluorine atom as substituting group more from the electric charge of negative ion.

Wherein, consider R from the electric charge dispersion of negative ion, the aspect of anionic stabilization ²¹And R ²²The group that preferably contains fluorine atom, the particularly preferably perfluoroalkyl of carbon number 1 ~ 8.

More specifically, the negative ion in the compound of above-mentioned formula (I-1) expression, i.e. following formula (I-1) _AThe negative ion of expression (below, be sometimes referred to as " negative ion in the compound of formula (I-1) expression "), further preferred following formula (I '-1) _AThe compound of expression.

[changing 23]

[changing 24]

(above-mentioned formula (I '-1) _AIn, n and n ' represent 1 ~ 8 integer independently of one another.）

N and n ' are 1 ~ 8 integer, preferred 1 ~ 4 integer.

N and n ' can be identical or different.

When n is identical with n ', as the object lesson of sulfimide negative ion, can enumerate two fluoroform sulfimides, two 3-pentafluorobutane sulfimides etc.

N and n ' as the object lesson of sulfimide negative ion, can enumerate pentafluoroethane sulphonyl fluoroform sulfimide, fluoroform sulphonyl heptafluoro-propane sulfimide, fluorine butane sulphonyl fluoroform sulfimide etc. not simultaneously.

Among above-mentioned, two pentafluoroethane sulfimides of n=n '=2 are because the stabilization of negative ion, so particularly preferably.

On the other hand, R ²¹And R ²²Also can be interconnected to ring.

If Cheng Huan, R ²¹And R ²²The group that connects and form is the fluoro alkylidene of carbon number 2 ~ 12 particularly preferably.That is, the negative ion in the compound of above-mentioned formula (I-1) expression, preferred following formula (I '-2) _AThe negative ion of expression.

[changing 25]

(above-mentioned formula (I '-2) _AIn, n " expression 2 ~ 12 integer.）

N " consider from the good aspect of thermotolerance, preferred 2 ~ 8, more preferably 3.

N " numeral less, the impact of the sterically hindered repulsion of molecule is less, can obtain stronger interaction.That is, " less, negative ion and cationic interaction are larger, and supposition can make the counter ion counterionsl gegenions stabilization, improve the thermotolerance of dyestuff for n.

In addition, the compound of above-mentioned formula (I) expression also can be from for example, R ¹~ R ⁶And R ¹⁰¹And R ¹⁰²Extension key forms dipolymer or trimer etc.

(molecular weight)

The molecular weight of the compound of above-mentioned formula (I) expression is generally more than 570 among the present invention, and is preferred more than 840, in addition usually below 2600.

If in the above-mentioned scope, the favorable solubility in solvent and easy to manufacture then is so preferred.

(synthetic method)

The compound of above-mentioned formula (I) expression can be according to for example J.Chem.Soc., PerkinTrans.1998,2,297., international disclose No. 2006/120205 and the international method of putting down in writing in No. 2009/107734 that disclose is synthesized.

The preferred concrete example of the compound of formula of the present invention (I) expression is as follows, but the present invention is not limited to these compounds.

［ concrete example of the compound of formula (I) expression ］

[changing 26]

[changing 27]

[changing 28]

(amount)

The ratio of the compound of contained formula (I) expression in the 1st colored resin composition of the present invention, in the total solids composition, more than preferred 1 % by weight, more preferably more than 3 % by weight, particularly preferably more than 5 % by weight, in addition below preferred 50 % by weight, more preferably below 40 % by weight, particularly preferably below 30 % by weight.

If below the above-mentioned upper limit, the curing of filming is difficult for descending, and enough film strengths are arranged, thereby preferred.In addition, if more than above-mentioned lower limit, because enough colouring powers are arranged, thus obtain easily the colourity of desirable concentration, and thickness is difficult for thickening, so preferred.

In the 1st colored resin composition of the present invention, as (A) dyestuff, can only contain a kind in the compound (I), also can contain more than 2 kinds.

And then, can also contain one kind or two or more other dyestuffs.In addition, the content of all (A) dyestuffs is in composition more than preferred 1 % by weight, or below preferred 30 % by weight in the 1st colored resin composition.

In addition, in the 1st colored resin composition of the present invention, the content of compound (I) is in the solid constituent of all (A) dyestuffs, more than preferred 30 % by weight.

［ about the compound of formula (II) expression ］

The compound that the 2nd colored resin composition of the present invention represents by containing following formula (II), the excellent heat resistance of the colored filter that obtains, and have high permeability, so preferred.

[changing 29]

(in the above-mentioned formula (II), (Z ₂) ^M2-The disulfonyl imines negative ion of expression m2 valency.

M2 represents 1 ~ 4 integer.

R ¹¹~ R ¹⁶Represent independently of one another hydrogen atom, can have substituent alkyl, maybe can have substituent aromatic ring yl.

Adjacent R ¹¹~ R ¹⁶Between can connect into ring, this ring can also have substituting group.

R ¹⁷And R ¹⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ¹⁷And R ¹⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, the phenyl ring in the above-mentioned formula (II) and indole ring can further have any substituting group.

In addition, if contain a plurality of following formulas (II) in a part _CAShown kation,

[changing 30]

Then they can be same structures, also can be different structures.）

(about R ¹¹~ R ¹⁶)

R ¹¹~ R ¹⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Alkyl and aromatic ring yl and above-mentioned (about R as carbon number 1 ~ 8 ¹~ R ⁶) in the phase of record same.Preferred configuration is also identical.

In addition, adjacent R ¹¹~ R ¹⁶Between, i.e. R ¹¹And R ¹², R ¹³And R ¹⁴And R ¹⁵And R ¹⁶Can be connected to each other to ring respectively, this ring can also have substituting group.

Adjacent R ¹¹~ R ¹⁶If between connect into ring, they also can be the rings that forms by the heteroatoms bridging.As the object lesson of this ring, with above-mentioned (about R ¹~ R ⁶) in the phase of record same.Preferred configuration is also identical.

(about R ¹⁷And R ¹⁸)

R ¹⁷And R ¹⁸Expression hydrogen atom or substituting group arbitrarily.As this substituting group arbitrarily, can enumerate above-mentioned (about R ⁷And R ⁸) in the thing of record.

On the phenyl ring in formula (II), for the key that forms with the carbon atom that is positioned at triarylmethane structure central authorities, if at its ortho position bonding during bulky group, will hinder the planarity of molecule, the excitation of compound can descend sometimes.Therefore, preferred ortho position does not have substituting group, or substituting group is the alkyl of halogen atom, carbon number 1 ~ 4.

In addition, R ¹⁷And R ¹⁸Can be connected to each other to ring, this ring can also have substituting group.As this substituting group, can enumerate in above-mentioned (replacing basic group W) item and put down in writing group.

R ¹⁷And R ¹⁸If between connect into ring, they also can be the rings that forms by the heteroatoms bridging, its object lesson, with above-mentioned (about R ⁷And R ⁸) in the record group identical.

The gained colored filter is if purple is considered preferred R from the aspect of high brightness ⁷And R ⁸Between be not connected to each other to ring.

In addition, the gained colored filter is if red, and considers from the aspect of high brightness, preferably is connected to each other to ring.

Among the present invention, from the angle of the excellent heat resistance of the colored filter that obtains, particularly preferably R ¹¹~ R ¹⁸In the alkyl of at least one carbon number 1 ~ 8 that is replaced by fluorine atom.

This supposition be because, by electrostatic interaction in fluorine atom and the intramolecular positive charge zone generation molecule, thus kation stabilization more.The fluorine atom that this and electronegativity are high attracts to make its localization with the electronics of the carbon of its bonding, thereby produces the carbon atom with a small amount of positive charge, thereby the prediction of kation destabilization is opposite.

In addition, the phenyl ring in the above-mentioned formula (II) and indole ring can further have any substituting group.That is, in the scope of not damaging effect of the present invention, can have the substituting group in addition of writing exactly in the formula (II), but consider from the aspect of easy manufacturing, preferably not have the substituting group in addition of writing exactly in the formula (II).

As such substituting group, can enumerate the substituting group of record in above-mentioned (replacing basic group W) item.

In addition, the compound of above-mentioned formula (II) expression also can be from for example, R ¹¹~ R ¹⁸Extension key forms dipolymer or trimer etc.

［ about the compound of formula (II-1) expression ］

In the compound of above-mentioned formula (II) expression, the compound of preferred following formula (II-1) expression.

[changing 31]

(in the above-mentioned formula (II-1), R ¹¹~ R ¹⁸Identical with the definition of above-mentioned formula (II).

Phenyl ring in the above-mentioned formula (II-1) and indole ring can further have any substituting group.

R ³¹And R ³²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ³¹And R ³²Can be connected to each other to ring, this ring can also have substituting group.）

(about R ³¹And R ³²)

R ³¹And R ³²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ³¹And R ³²Can be connected to each other to ring, this ring can also have substituting group.

R ³¹And R ³²With the R in the above-mentioned formula (I-1) ²¹And R ²²Identical, preferred configuration is also identical.

It is the further preferred above-mentioned formula (I '-1) of negative ion in the compound of above-mentioned formula (II-1) expression _AOr (I '-2) _AThe negative ion of expression.

(synthetic method)

The compound of above-mentioned formula (II) expression can be according to for example J.Chem.Soc., PerkinTrans.1998,2,297., international disclose No. 2006/120205 and the international method of putting down in writing in No. 2009/107734 that disclose is synthesized.

(molecular weight)

The molecular weight of the compound of above-mentioned formula (II) expression is generally more than 600 among the present invention, and is preferred more than 750, in addition usually below 2800.

If in the above-mentioned scope, the favorable solubility in solvent and easy to manufacture then is so preferred.

The preferred concrete example of the compound of formula of the present invention (II) expression is as follows, but the present invention is not limited to these compounds.

［ object lesson of the compound of formula (II) expression ］

[changing 32]

[changing 33]

(amount)

The ratio of the compound of contained formula (II) expression in the 2nd colored resin composition of the present invention, in the total solids composition, more than preferred 1 % by weight, more preferably more than 3 % by weight, particularly preferably more than 5 % by weight, in addition below preferred 50 % by weight, more preferably below 40 % by weight, particularly preferably below 30 % by weight.

If below the above-mentioned upper limit, the curing of filming is difficult for descending, and enough film strengths are arranged, thereby preferred.In addition, if more than above-mentioned lower limit, because enough colouring powers are arranged, thus obtain easily the colourity of desirable concentration, and thickness is difficult for thickening, so preferred.

In addition, in the 2nd colored resin composition of the present invention, as (A) dyestuff, can only contain a kind in the compound (II), also can contain more than 2 kinds.

Further, can contain one kind or two or more other dyestuffs, but in the 2nd colored resin composition content of all (A) dyestuffs in composition more than preferred 1 % by weight, or below preferred 30 % by weight.

In addition, in the 2nd colored resin composition of the present invention, the content of compound (II) is in the solid constituent of all (A) dyestuffs, more than preferred 30 % by weight.

＜about the compound of formula (III) expression＞

The 3rd colored resin composition of the present invention contains the compound of following formula (III) expression as (A) dyestuff.

The compound of following formula (III) expression considers it is preferred from the thermotolerance of the colored filter that obtains and the aspect of transmitance excellence.

[changing 34]

(in the above-mentioned formula (III), (Z ₃) ^M3-The disulfonyl imines negative ion of expression m3 valency.

M3 represents 1 ~ 4 integer.

Q represents 1 ~ 5 integer.

R ⁵⁰¹And R ⁵⁰²Independently of one another expression can have the aliphatic alkyl of substituent carbon number 1 ~ 20.

R ⁵¹And R ⁵²Independently of one another expression-O-,-S-,-N-,-Se-or-CR ⁵⁰³R ⁵⁰⁴-.

R ⁵⁰³And R ⁵⁰⁴The aliphatic alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 6.

Wherein, if R ⁵¹And R ⁵²For-CR ⁵⁰³R ⁵⁰⁴-, R then ⁵⁰³Between can be connected to each other to ring, this ring can also have substituting group.

Ring Y ¹And Y ²Independently of one another expression can have substituent phenyl ring or naphthalene nucleus.

Wherein, ring Y ¹And Y ²Phenyl ring and naphthalene nucleus do not have nitro and perfluoroalkyl as substituting group.）

(about q)

Q is 1 ~ 5 integer, considers particularly preferably 1 ~ 3 from the good viewpoint of the thermotolerance of dyestuff.

(about R ⁵⁰¹And R ⁵⁰²)

R ⁵⁰¹And R ⁵⁰²Independently of one another expression can have the aliphatic alkyl of substituent carbon number 1 ~ 20.

Aliphatic alkyl for example can be enumerated, methyl, ethyl, vinyl, ethinyl, propyl group, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, 2-propynyl, butyl, isobutyl, sec-butyl, the tert-butyl group, 2-butenyl group, 1,3-butadiene base, amyl group, isopentyl, neopentyl, tertiary pentyl, 1-methyl amyl, 2-methyl amyl, 2-amylene-4-alkynyl, hexyl, isohesyl, 5-methyl hexyl, heptyl, octyl group etc.

In addition, the substituting group that can have as aliphatic alkyl, for example just like phenyl, o-tolyl, a tolyl, p-methylphenyl, xylyl, isopropylidene, adjacent cumenyl, a cumenyl, to the aromatic hydrocarbyl of cumenyl etc.; The alkoxys such as methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, phenoxy group, benzyloxy; The halogens such as fluorine-based, chloro, bromo, iodo; Carboxyl, nitro, cyano group etc. are further arranged.

R ⁵⁰¹And R ⁵⁰²The alkyl of the preferred carbon number 1 ~ 8 of difference, the more preferably alkyl of carbon number 1 ~ 5.

As R ⁵⁰¹And R ⁵⁰²The substituting group that can have can be enumerated in above-mentioned (replacing basic group W) item and put down in writing group.

(about R ⁵¹And R ⁵²)

R ⁵¹And R ⁵²Independently of one another expression-O-,-S-,-N-,-Se-or-CR ⁵⁰³R ⁵⁰⁴-.

R ⁵⁰³And R ⁵⁰⁴The aliphatic alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 6.

Wherein, if R ⁵¹And R ⁵²For-CR ⁵⁰³R ⁵⁰⁴-, R then ⁵⁰³Between can be connected to each other to ring.

R ⁵¹And R ⁵²The structure of coupling part can be listed below, but the present invention is not limited thereto.

[changing 35]

In addition, as R ⁵⁰³And R ⁵⁰⁴In can have that aliphatic alkyl is connected to each other and the substituting group of the ring that forms, for example can enumerate in above-mentioned (replacing basic group W) and put down in writing group.

(about ring Y ¹And Y ²)

Ring Y ¹And Y ²Independently of one another expression can have substituent phenyl ring or naphthalene nucleus.

Wherein, as ring Y ¹And Y ²Phenyl ring and the naphthalene nucleus substituting group that can have, get rid of nitro and perfluoroalkyl.

This be because, if having nitro or perfluoroalkyl as substituting group, then the compound of above-mentioned formula (III) expression forms agglutination body easily in composition or film, the brightness of the colored filter that obtains like this descends easily.

In addition because, nitro and perfluoroalkyl be easy to from around molecule obtain electronics, therefore the compound as above-mentioned formula (III) expression causes decomposition easily, the thermotolerance of the colored filter that obtains like this becomes and descends easily.

The compound of above-mentioned formula (III) expression can also be from R ⁵¹, R ⁵², R ⁵⁰¹And R ⁵⁰²Extension key forms dipolymer or trimer etc.

In addition, in the compound of above-mentioned formula (III) expression, there is the cis-trans isomeride in cationic moiety, and any isomeride can.

［ compound of formula (III-1) expression ］

The compound of the preferred following formula of compound (III-1) expression of above-mentioned formula (III) expression.

[changing 36]

(in the above-mentioned formula (III-1), q, R ⁵¹And R ⁵², R ⁵⁰¹And R ⁵⁰²And ring Y ¹And Y ²Identical with the definition of above-mentioned formula (III).

R ⁴¹And R ⁴²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ⁴¹And R ⁴²Can be connected to each other to ring, this ring can also have substituting group.

(about R ⁴¹And R ⁴²)

R ⁴¹And R ⁴²Independently of one another expression can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, maybe can have the naphthenic base of substituent carbon number 3 ~ 8.

In addition, R ⁴¹And R ⁴²Can be connected to each other to ring, this ring can also have substituting group.

R ⁴¹And R ⁴²With the R in the above-mentioned formula (I-1) ²¹And R ²²Identical, preferred configuration is also identical.

That is, consider R from the electric charge dispersion of negative ion, the aspect of anionic stabilization ⁴¹And R ⁴²The group that preferably has fluorine atom, the particularly preferably perfluoroalkyl of carbon number 1 ~ 8.

That is, the negative ion in the compound of above-mentioned formula (III-1) expression, further preferred above-mentioned formula (I '-1) _AOr (I '-2) _AThe negative ion of expression.

(synthetic method)

The compound of above-mentioned formula (III) expression can be according to for example J.Chem.Soc., PerkinTrans.1998,2,297., international disclose No. 2006/120205 and the international method of putting down in writing in No. 2009/107734 that disclose is synthesized.

(molecular weight)

The molecular weight of the compound of above-mentioned formula (III) expression is generally more than 550 among the present invention, and is preferred more than 600, in addition usually below 2100.

If in above-mentioned scope, the favorable solubility in solvent and easy to manufacture then is so preferred.

The preferred concrete example of the compound of formula of the present invention (III) expression is as follows, but the present invention is not limited to these compounds.

［ object lesson of the compound of formula (III) expression ］

[changing 37]

(amount)

The compound of contained formula (III) expression in the 3rd colored resin composition of the present invention is in the total solids composition, more than preferred 1 % by weight, more preferably more than 3 % by weight, particularly preferably more than 5 % by weight, in addition below preferred 50 % by weight, more preferably below 40 % by weight, particularly preferably below 30 % by weight.

If below the above-mentioned upper limit, the curing of filming is difficult for descending, and enough film strengths are arranged, thereby preferred.In addition, if more than above-mentioned lower limit, because enough colouring powers are arranged, thus obtain easily the colourity of desirable concentration, and thickness is difficult for thickening, so preferred.

In the 3rd colored resin composition of the present invention, as (A) dyestuff, can only contain a kind in the compound (III), also can contain more than 2 kinds.

Further, can contain one kind or two or more other dyestuffs, but in the 3rd colored resin composition content of all (A) dyestuffs in composition more than preferred 1 % by weight, or below preferred 30 % by weight.

In addition, in the 3rd colored resin composition of the present invention, the content of compound (III) is in the solid constituent of all (A) dyestuffs, more than preferred 30 % by weight.

［ (A) dyestuff of the 4th form ］

Contained (A) dyestuff contains the counter ion counterionsl gegenions that are made of kation and negative ion in the 4th colored resin composition of the present invention, the molecular weight of this negative ion is more than 150, below 600, and these counter ion counterionsl gegenions are the compound (IV) that satisfies the relation of formula (1) ~ (3).

[several 3]

$|\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}-\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}|\≤2.2---\left(1\right)$

$3.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}\≤4.0---\left(2\right)$

$1.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}\≤3.4---\left(3\right)$

(in the above-mentioned formula,

IP _CationRepresent above-mentioned cationic ionization potential (hartree),

EA _CationRepresent above-mentioned cationic electron affinity (hartree),

IP _AnionThe ionization potential (hartree) that represents above-mentioned negative ion,

EA _AnionThe electron affinity (hartree) that represents above-mentioned negative ion.）

Based on said structure, especially the reason of excellent heat resistance is presumed as follows.

Cationic electronics localization degree in formula (2) the expression counter ion counterionsl gegenions, in addition the electronics localization degree of the negative ion in formula (3) the expression counter ion counterionsl gegenions.

If counter ion counterionsl gegenions then have negative ion and cationic electronics localization degree more approaching, negative ion and the stronger tendency of cationic interaction.Be that formula (1) shows the poor of negative ion and cationic localization degree, expression be the more close negative ion of localization degree and cationic combination.

Further, even negative ion and the close thing of cationic localization degree if negative ion is larger, just is difficult to form only key with kation, thereby is difficult to bring stable on heating raising.So the molecular weight of negative ion is more than 150, below 600.

As compound of the present invention (IV), the molecular weight that make negative ion is more than 150, below 600, and satisfies above-mentioned (1) ~ (3), suitably selects to get final product from known material.

Among the present invention, ionization potential and electron affinity are, at HF/6-31G(D) calculated level carry out the optimization of molecular structure, with the energy of the HOMO that obtains and LUMO respectively as ionization potential (hartree) and electron affinity (hartree).

In addition, when calculating ionization potential and electron affinity, kation and negative ion will calculate respectively.

As kation, can from the dyestuff of records such as for example " Industrial Dyes-Chemistry, Properties, Applications-(Wiley-VCH,, Klaus Hunger Knitting collection in 2003) ", select to satisfy the material of above-mentioned formula (3).

More specifically, can enumerate the compound of chromophories (Chromophore) such as having triarylmethane class, phthalocyanines, phenylethylene, azines, can suitably select according to desirable color.

As alternative negative ion, can be from satisfying above-mentioned formula (2), and molecular weight selects in the material more than 150, below 600, guarantees that further itself and cationic relation satisfy formula (1).

The molecular weight of negative ion is usually more than 150, and is preferred more than 200, further preferred more than 250, and usually below 600, preferred below 500.

If in above-mentioned scope, then can be fine reach effect of the present invention, so preferred.

In addition, the molecular weight of compound among the present invention (IV), preferred more than 570, further preferred more than 600, in addition usually below 3000.

If in above-mentioned scope, the favorable solubility in solvent and easy to manufacture then is so preferred.

This compound (IV), further preferred its kation is following formula (I-2) _CAOr (II-2) _CAThe compound of expression.

[changing 38]

(above-mentioned formula (I-2) _CAIn, R ⁶¹~ R ⁶⁶Represent independently of one another hydrogen atom, can have the alkyl of substituent carbon number 1 ~ 8, maybe can have substituent aromatic ring yl.

Adjacent R ⁶¹~ R ⁶⁶Between can connect into ring, this ring can also have substituting group.

R ⁶⁷And R ⁶⁸Expression hydrogen atom or substituting group arbitrarily.

R ⁶⁷And R ⁶⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, above-mentioned formula (I-2) _CAIn phenyl ring can further have any substituting group.

R ⁶⁰¹And R ⁶⁰²The expression hydrogen atom, can have substituent carbon number 1 ~ 8 alkyl, can have the thiazolinyl of substituent carbon number 2 ~ 6, can have substituent aromatic ring yl or fluorine atom.

R ⁶⁰¹And R ⁶⁰²Can be connected to each other to ring, this ring can also have substituting group.）

[changing 39]

(above-mentioned formula (II-2) _CAIn, R ⁷¹~ R ⁷⁶Represent independently of one another hydrogen atom, can have substituent alkyl, maybe can have substituent aromatic ring yl.

Adjacent R ⁷¹~ R ⁷⁶Between can connect into ring, this ring can also have substituting group.

R ⁷⁷And R ⁷⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ⁷⁷And R ⁸⁸Can be connected to each other to ring, this ring can also have substituting group.

In addition, above-mentioned formula (II-2) _CAIn phenyl ring and indole ring can further have any substituting group.

Above-mentioned formula (I-2) _CA(II-2) _CAThe form of the compound of expression respectively with [formula (I) expression compound] in kation and the cationic homomorphosis in [compound of formula (II) expression].Preferred form is also identical.

That is, above-mentioned formula (I-2) _CAR in the compound of expression ⁶¹~ R ⁶⁶With the kation R in [compound of formula (I) expression] ¹~ R ⁶, R ⁶⁷And R ⁶⁸With R ⁷And R ⁸, R ⁶⁰¹And R ⁶⁰²With R ¹⁰¹And R ¹⁰²Form respectively identical.

In addition, above-mentioned formula (II-2) _CAR in the compound of expression ⁷¹~ R ⁷⁶With the kation R in [compound of formula (II) expression] ¹¹~ R ¹⁶, R ⁷⁷And R ⁸⁸With R ¹⁷And R ¹⁸Form respectively identical.

Among the present invention, the compound of the compound of above-mentioned formula (I) expression and above-mentioned formula (II) expression further preferably can satisfy the relation of above-mentioned formula (1) ~ (3).

(amount)

Contained compound (IV) in the 4th colored resin composition of the present invention is in the total solids composition, preferably more than 1 % by weight, more preferably more than 3 % by weight, particularly preferably more than 5 % by weight, in addition below preferred 50 % by weight, more preferably below 40 % by weight, particularly preferably below 30 % by weight.

If below the above-mentioned upper limit, the curing of filming is difficult for descending, and enough film strengths are arranged, thereby preferred.In addition, if more than above-mentioned lower limit, because enough colouring powers are arranged, thus obtain easily the colourity of desirable concentration, and thickness is difficult for thickening, so preferred.

In the 4th colored resin composition of the present invention, as (A) dyestuff, can only contain a kind in the compound (IV), also can contain more than 2 kinds.

Further, can contain one kind or two or more other dyestuffs, but in the 1st colored resin composition content of all (A) dyestuffs in composition more than preferred 1 % by weight, or below preferred 30 % by weight.

In addition, in the 4th colored resin composition of the present invention, the content of compound (IV) is in the solid constituent of all (A) dyestuffs, more than preferred 30 % by weight.

(C) adhesive resin

Preferably (C) adhesive resin is different and different with the curing of pigmentary resin composition.

If colored resin composition of the present invention is the optical polymerism resin combination, then for example can use as (C) adhesive resin, Japanese patent laid-open 7-207211 communique, Japanese patent laid-open 8-259876 communique, Japanese patent laid-open 10-300922 communique, Japanese patent laid-open 11-140144 communique, Japanese patent laid-open 11-174224 communique, Japanese Patent Laid-Open 2000-56118 communique, the macromolecular compound of each communique such as Japanese Patent Laid-Open 2003-233179 communique etc. records, but following (C-1) ~ (C-5) resin preferably wherein.

(C-1): to the multipolymer of (methyl) acrylate of containing epoxy radicals and other free radical polymerization monomers, the resin that the unsaturated monoacid of addition forms at least a portion epoxy radicals that this multipolymer has, or the alkali soluble resin that obtains at addition polyprotonic acid acid anhydrides at least a portion hydroxyl that generates through this addition reaction (below be also referred to as " resin (C-1) ").

(C-2): carboxylic straight chain shape alkali soluble resin (C-2) (following sometimes be also referred to as " resin (C-2) ").

(C-3): addition contains the resin (following sometimes be also referred to as " resin (C-3) ") that the unsaturated compound of epoxy radicals forms on the carboxy moiety of above-mentioned resin (C-2).

(C-4): (methyl) acrylic resin (following sometimes be also referred to as " resin (C-4) ").

(C-5): the Epocryl (following sometimes be also referred to as " resin (C-5) ") with carboxyl.

The particularly preferred resin (C-1) of enumerating wherein below describes this resin.

In addition, resin (C-2) ~ (C-5) is so long as be dissolvable in water in the alkaline-based developer, have can implementation goal development treatment degree deliquescent material get final product, identical with the record of the same project of Japanese Patent Laid-Open 2009-025813 communique respectively.Preferred form is also identical.

(C-1): to the multipolymer of (methyl) acrylate of containing epoxy radicals and other free radical polymerization monomers, the resin that the unsaturated monoacid of addition forms at least a portion epoxy radicals that this multipolymer has, or at least a portion hydroxyl that generates through this addition reaction addition polyprotonic acid acid anhydrides and the alkali soluble resin that obtains.

As particularly preferably one of the resin in the resin (C-1), can enumerate, multipolymer to 10 ~ 95 % by mole of 5 ~ 90 % by mole of (methyl) acrylate of containing epoxy radicals and other free radical polymerization monomers, the resin that the unsaturated monoacid of addition forms on 10 ~ 100 % by mole the epoxy radicals that this multipolymer has, or on 10 ~ 100 % by mole the hydroxyl that generates through this addition reaction addition polyprotonic acid acid anhydrides and the alkali soluble resin that obtains.

Contain (methyl) acrylate of epoxy radicals as this, but illustration as, (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxy butyl ester, (methyl) acrylic acid (3,4-epoxycyclohexyl) methyl esters, (methyl) acrylic acid-4-hydroxyl butyl ester glycidol ether etc.Wherein, preferred (methyl) glycidyl acrylate.These contain epoxy radicals (methyl) acrylate and can be used alone, and also can more than 2 kinds and use.

As with above-mentioned other free radical polymerization monomers that contain (methyl) acrylic ester copolymer of epoxy radicals, only otherwise damage effect of the present invention, just be not particularly limited, can enumerate such as the vinyl aromatic same clan, dienes, (methyl) esters of acrylic acid, (methyl) acrylic amide, vinyl compound class, unsaturated dicarboxylic acid diester class, single maleimide etc., list (methyl) acrylate that particularly preferably has structure shown in the following formula (7).

Derive from the repetitive of list (methyl) acrylate with structure shown in the following formula (7), in the repetitive that derives from " other free radical polymerization monomers ", preferably contain 5 ~ 90 % by mole, further preferably contain 10 ~ 70 % by mole, particularly preferably contain 15 ~ 50 % by mole.

[changing 40]

In the above-mentioned formula (7), R ⁸⁹Expression hydrogen atom or methyl, R ⁹⁰The structure that represents following formula (8) expression.

[changing 41]

In the above-mentioned formula (8), R ⁹¹~ R ⁹⁸The alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 3.In addition, R ⁹⁶And R ⁹⁸Can also be connected to each other to ring.

R ⁹⁶And R ⁹⁸Connect formed ring preferred fat ring, saturated or unsaturated can, further preferred carbon number is 5 ~ 6.

Wherein, in the structure of formula (8) expression, particularly preferably following structural formula (8a), (8b) or (8c) thing of expression.

[changing 42]

In addition, list (methyl) acrylate with above-mentioned formula (8) expression structure can be used alone, and also can more than 2 kinds and use.

Except list (methyl) acrylate with above-mentioned formula (8) expression structure, as " other free radical polymerization monomers ", from the thermotolerance that can improve the colored resin composition excellence and the angle of intensity, can enumerate styrene, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) benzyl acrylate, (methyl) acrylic acid-2-hydroxyl ethyl ester, N-phenylmaleimide, N-N-cyclohexylmaleimide.

Derive from preferred 1 ~ 70 % by mole of the content of at least a kind the repetitive that is selected from above-mentioned haplometrotic colony, further preferred 3 ~ 50 % by mole.

In addition, above-mentioned (methyl) acrylate of epoxy radicals and the applicable known solution polymerization process of copolyreaction of above-mentioned other free radical polymerization monomers of containing.

Among the present invention, as above-mentioned (methyl) acrylate of epoxy radicals and the multipolymer of above-mentioned other free radical polymerization monomers of containing, preferably derive from 5 ~ 90 % by mole of the repetitives of (methyl) acrylate that contains epoxy radicals, material with 10 ~ 95 % by mole of formation of repetitive that derive from other free radical polymerization monomers, further preferred the former 20 ~ 80 % by mole of materials with 80 ~ 20 % by mole of formation of the latter, particularly preferably the former 30 ~ 70 % by mole of materials with 70 ~ 30 % by mole of formation of the latter.

If in above-mentioned scope, then the addition amount of polymerism composition described later and alkali-soluble composition is enough, and thermotolerance and film strength are enough, and is therefore preferred.

With the synthetic as mentioned above epoxy radicals part that contains the epoxy radicals multipolymer, with unsaturated monoacid (polymerism composition), further react with polyprotonic acid acid anhydrides (alkali-soluble composition).

Herein, as with the unsaturated monoacid of epoxy radicals addition, can use known material, can give an example as have the unsaturated carboxylic acid of ethene unsaturated double-bond.

As object lesson, can enumerate (methyl) acrylic acid, butenoic acid, neighbour,, to the vinyl benzoic acid, monocarboxylic acids such as (methyl) acrylic acid that alpha-halogen alkyl, alkoxy, halogen atom, nitro or cyano group etc. replace etc. are arranged.Preferred (methyl) acrylic acid wherein.These can be used alone, also can two or more and usefulness.

By the such composition of addition, can give adhesive resin polymerism used in the present invention.

10 ~ 100 % by mole of additions of the epoxy radicals that these unsaturated monoacid usually have with above-mentioned multipolymer are preferably with 30 ~ 100 % by mole of additions, more preferably with 50 ~ 100 % by mole of additions.If in above-mentioned scope, then the ageing stability of colored resin composition is excellent, and is therefore preferred.In addition, as with the epoxy radicals of multipolymer and the method for unsaturated monoacid addition, can adopt known method.

And then the polyprotonic acid acid anhydrides of the hydroxyl addition that generates as with the epoxy radicals of multipolymer and unsaturated monoacid addition the time can use known material.

For example can enumerate the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, acid phthalic anhydride, tetrahydrochysene acid phthalic anhydride, six hydrogen acid phthalic anhydrides, chlorendic anhydride; The acid anhydrides of the above acid of the ternarys such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Wherein preferred succinic anhydride and tetrahydrochysene acid phthalic anhydride.These polyprotonic acid acid anhydrides can be used alone, also can two or more and usefulness.

By the such composition of addition, can give adhesive resin alkali-soluble used in the present invention.

These polyprotonic acid acid anhydrides, the epoxy radicals that usually has with 10 ~ 100 % by mole above-mentioned multipolymers and unsaturated monoacid addition and the hydroxyl that generates carries out addition are preferably with 20 ~ 90 % by mole of additions, more preferably with 30 ~ 80 % by mole of additions.

If in above-mentioned scope, residual film ratio and dissolubility when then developing are enough, so preferred.

In addition, the method as with polyprotonic acid acid anhydrides and this hydroxyl addition can adopt known method.

Further, in order to improve light sensitivity, can be behind the above-mentioned polyprotonic acid acid anhydrides of addition, with the part of the carboxyl that generates and (methyl) glycidyl acrylate or have the glycidyl ether compound addition of polymerism unsaturated group.About the structure of such resin, for example to some extent record in Japanese patent laid-open 8-297366 communique and the Japanese Patent Laid-Open 2001-89533 communique.

Above-mentioned adhesive resin (C-1) use the GPC(gel permeation chromatography) weight-average molecular weight that is scaled polystyrene (Mw) measured is preferred 3000 ~ 100000, particularly preferably 5000 ~ 50000.If in above-mentioned scope, then from thermotolerance and film strength, further also have the aspect of the favorable solubility of developer solution is considered it is preferred.

In addition, as the target of molecular weight distribution, the ratio preferred 2.0 ~ 5.0 of weight-average molecular weight (Mw)/number-average molecular weight (Mn).

Moreover the acid number of adhesive resin (C-1) is 10 ~ 200mg-KOH/g normally, preferred 15 ~ 150mg-KOH/g, further preferred 25 ~ 100mg-KOH/g.If acid number is excessively low, the relative decreased solubility of developer solution sometimes then.On the contrary, if too high, the coarse of film occurs sometimes then.

The content of (C) adhesive resin in the colored resin composition in the total solids composition, is generally 0.1 ~ 80 % by weight, preferred 1 ~ 60 % by weight.

If in above-mentioned scope, then from good with the adaptation of substrate, and developer solution is appropriate to the perviousness of exposure section, and the good aspect of the surface smoothness of pixel and sensitivity considers it is preferred.

(B) solvent

In the colored resin composition of the present invention, (B) solvent is essential composition.Solvent has each contained in colored resin composition composition dissolving or disperses the function of adjusting viscosity.

Be somebody's turn to do (B) solvent so long as can get final product consisting of each composition dissolving of colored resin composition or the thing of dispersion, preferably select boiling point at the material of 100 ~ 200 ℃ of scopes.The material that more preferably has 120 ~ 170 ℃ boiling point.

Such solvent can be listed below states material.

Glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol list tertbutyl ether, diethylene glycol monomethyl ether, TC, methoxy amylalcohol, propylene glycol list ethylether, dipropylene glycol list ethylether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, the such glycol monoalkyl ethers of tripropylene glycol monomethyl ether;

Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, the such glycol dialkyl ether of dibutyl ethylene glycol ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, methoxy butyl acetate, acetic acid-3-methoxyl butyl ester, acetic acid methoxyl pentyl ester, TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetate, the acetic acid-such glycol alkyl ether acetate esters of 3-methyl-3-methoxyl butyl ester;

Diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, the such ethers of two hexyl ethers;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisobutyl acetone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, the such ketone of methyl nonyl ketone;

Ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, such monobasic or the polyalcohols of glycerine;

N-pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene, the such aliphatic hydrocarbon of dodecane;

Cyclohexane, methylcyclohexane, methylcyclohexene, the such ester ring type hydro carbons of bis cyclohexane;

Such aromatic hydrocarbon based of benzene,toluene,xylene, isopropyl benzene;

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, the ethylene glycol ethyl ethers acid esters, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, ethyl caprilate, butyl stearate, ethyl benzoate, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the chain that gamma-butyrolacton is such or cyclic ester class;

3-methoxypropionic acid, the such alkoxy carboxylic acids of 3-ethoxy-propionic acid;

Butyl chloride, the such halogenated hydrocarbon of amyl chloride;

The ether ketone that the methoxy pentanone is such;

Acetonitrile, the such nitrile of benzonitrile.

Meet above-mentioned commercially available solvent and can enumerate mineral spirits, バ Le ソ Le #2, ア プ コ #18 solvent, ア プ コ thinning agent, ソ ー カ Le solvent No.1 and No.2, ソ Le ベ ッ ソ #150, シ ェ Le TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methylcellosolve acetate, diethylene glycol dimethyl ether (Diglyme) (being all trade name) etc.

These solvents can be used alone, also can two or more and usefulness.

In the above-mentioned solvent, consider preferred diol monoalkyl ethers from the deliquescent aspect of (A) dyestuff of the invention described above.Wherein, the especially deliquescent angle of various constituents, particularly preferably propylene glycol monomethyl ether from composition.

In addition, when for example containing aftermentioned (F) pigment as any composition, good from the balance of coating, surface tension etc., the angle that the solubleness of the constituent in the composition is higher is set out, and further more preferably mixes and uses the glycol alkyl ether acetate esters as solvent.In addition, contain in the composition of pigment, the polarity of glycol monoalkyl ethers is high, and the tendency that makes the pigment aggegation is arranged, and the situation of the storage stabilities such as the viscosity raising reduction of colored resin composition occurs sometimes.Therefore, the use amount of preferred diol monoalkyl ethers can not be too much, and (B) ratio of glycol monoalkyl ethers is preferably 5 ~ 50 % by weight in the solvent, more preferably 5 ~ 30 % by weight.

In addition, from considering with the adaptive viewpoint of the slot coated mode of the nearest large substrate of reply etc., also preferred and with the solvent with the boiling point more than 150 ℃.At this moment, the content of this high boiling solvent is whole with respect to (B) solvent, preferred 3 ~ 50 % by weight, more preferably 5 ~ 40 % by weight, particularly preferably 5 ~ 30 % by weight.If the amount of high boiling solvent is very few, then having the dyestuff at gap nozzle tip for example to become to grade separates out, solidifies, cause the possibility of foreign matter defective, if too much in addition, then rate of drying is slack-off, in the aftermentioned colored filter manufacturing process, may cause that the beat of drying under reduced pressure operation is bad, the residual (ピ of the pin trace ン Trace of preliminary drying) etc. problem.

Moreover the solvent of boiling point more than 150 ℃ can be the glycol alkyl ether acetate esters, also can be the glycol alkyl ether class in addition, and at this moment, also it doesn't matter not contain in addition the solvent of boiling point more than 150 ℃.

Colored resin composition of the present invention can be supplied with the colored filter manufacturing based on ink-jet method, but in making based on the colored filter of ink-jet method, because very small from the printing ink of nozzle ejection, only have several ~ tens pL, therefore have around reaching jet hole or before in pixel storehouse (picture element バ Application Network), the solvent evaporation, the tendency that printing ink is concentrated, dry.In order to avoid this problem, the boiling point of preferred solvent is high, and concrete preferred (B) solvent contains the solvent of boiling point more than 180 ℃.Particularly preferably containing boiling point is more than 200 ℃, especially preferably contains boiling point and be the solvent more than 220 ℃.In addition, the preferred high boiling solvent of boiling point more than 180 ℃ is more than 50 % by weight in (B) solvent.If ratio less than 50 % by weight of such high boiling solvent then may not give full play to preventing that solvent is from the effect of droplet of ink evaporation.

In the colored resin composition of the present invention, (B) content of solvent is not particularly limited, and its upper limit is generally 99 % by weight.If the content of (B) solvent surpasses 99 % by weight in the composition, then the concentration of each composition except (B) solvent is too small, may be not suitable for forming coated film.On the other hand, (B) lower limit of the content of solvent, the viscosity that consideration is suitable for being coated with etc. are generally 75 % by weight, preferred 80 % by weight, further preferred 82 % by weight.

(D) polymerizable monomer

Colored resin composition of the present invention preferably contains (D) polymerizable monomer.

(D) polymerizable monomer so long as polymerisable low molecular compound just be not particularly limited, but preferably have at least the compound (below, be sometimes referred to as " ethene compound ") of the addition polymerization of the two keys of an ethene.

The ethene compound is such compound with the two keys of ethene: when colored resin composition of the present invention is subject to the active ray irradiation, cause the effect of composition based on the aftermentioned photopolymerization, addition polymerization occurs and solidify.In addition, (D) polymerizable monomer among the present invention is the concept relative with so-called polymer substance, except the monomer of narrow sense, also comprises dipolymer, trimer, oligomer.

As the ethene compound in (D) polymerizable monomer, for example can enumerate the unsaturated carboxylic acids such as (methyl) acrylic acid; The ester of monohydroxy compound and unsaturated carboxylic acid; The ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid; The ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid; The ester that obtains based on the esterification of the multi-hydroxy compounds such as unsaturated carboxylic acid and polybasic carboxylic acid and above-mentioned aliphatic polyhydroxy compound, aromatic polyhydroxy compounds; The ethene compound with urethanes skeleton that polyisocyanate compounds is got with the hydroxyl compound reaction that contains (methyl) acryloyl group; Deng.

As the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, can enumerate ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, (methyl) acrylate such as glycerine (methyl) acrylate.In addition, can enumerate (methyl) acrylate moiety with these (methyl) acrylate replaces with itaconate that itaconic acid partly forms, replaces with the butenoate that butenoic acid partly forms or replaces with maleate that maleic acid partly forms etc.

As the ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid, can enumerate quinhydrones two (methyl) acrylate, resorcinol two (methyl) acrylate, pyrogallol three (methyl) acrylate etc.

Based on the ester that the esterification of unsaturated carboxylic acid and polybasic carboxylic acid and multi-hydroxy compound obtains, can be one matter, also can be potpourri.As representation example, can enumerate the condensation product of (methyl) acrylic acid, phthalic acid and ethylene glycol; The condensation product of (methyl) acrylic acid, maleic acid and diethylene glycol; The condensation product of (methyl) acrylic acid, terephthalic acid (TPA) and pentaerythrite; The condensation product of (methyl) acrylic acid, hexane diacid, butylene glycol and glycerine etc.

As making polyisocyanate compounds and the ethene compound with urethanes skeleton that the hydroxyl compound reaction that contains (methyl) acryloyl group forms, can enumerate the aliphatic isocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate; The ester ring type diisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate; The aromatic diisocyanates such as toluylene group diisocyanate, '-diphenylmethane diisocyanate; with 2-hydroxyethyl (methyl) acrylate, 3-hydroxyl [1; 1,1-three (methyl) acryloyl-oxy ylmethyl] propane etc. contains the reactant of the hydroxyl compound of (methyl) acryloyl group.

As the example of the ethene compound that uses among other the present invention, can enumerate (methyl) acrylic amides such as ethylenebis (methyl) acrylamide; The allyl ester classes such as diallyl phthalate; Divinyl phthalate ester etc. contains the compound of vinyl etc.

The wherein ester of preferred aliphat polyol and unsaturated carboxylic acid, more preferably (methyl) acrylate of pentaerythrite or dipentaerythritol, particularly preferably dipentaerythritol six (methyl) acrylate.

In addition, the ethene compound also can be the monomer with acid number.As the monomer with acid number, preference is as unreacted hydroxyl reaction ester, that make non-aromatic carboxylic acid anhydrides and aliphatic polyhydroxy compound of aliphatic polyhydroxy compound and unsaturated carboxylic acid and the polyfunctional monomer with acid group that obtains, particularly preferably in this ester, aliphatic polyhydroxy compound is pentaerythrite and/or dipentaerythritol.

These monomers can be used alone, but owing to be difficult to obtain single compound on making, so also can use the potpourri more than 2 kinds.

In addition, can as required, will not have the polyfunctional monomer of acid group and have polyfunctional monomer and the usefulness of acid group, as (D) polymerizable monomer yet.

The preferred acid number of polyfunctional monomer with acid group is 0.1 ~ 40mg-KOH/g, particularly preferably 5 ~ 30mg-KOH/g.

If in above-mentioned scope, the dissolution characteristics that then develops is difficult for descending, and makes and process easily.And then, because curing property such as surface smoothness of the difficult decline of photopolymerization performance, pixel are good, therefore preferred.

Among the present invention, preferred polyfunctional monomer with acid group for example is, the potpourri take the succinate of dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol five acrylate as major component.This polyfunctional monomer and other polyfunctional monomers can also be used in combination.

In the colored resin composition of the present invention, the content of these (D) polymerizable monomers is in the total solids composition, usually more than 1 % by weight, more than preferred 5 % by weight, more than further preferred 10 % by weight, and usually below 80 % by weight, below preferred 70 % by weight, further below preferred 50 % by weight, particularly preferably below 40 % by weight.

In addition, (D) polymerizable monomer with respect to the ratio of above-mentioned (A) dyestuff usually more than 1 % by weight, more than preferred 5 % by weight, further more than preferred 10 % by weight, particularly preferably more than 20 % by weight, and usually below 200 % by weight, below preferred 100 % by weight, further below preferred 80 % by weight.

If in above-mentioned scope, because photocuring appropriateness, it is bad to be difficult for driving fit during development, and the cross section after developing is difficult for becoming back taper, so be difficult for because of decreased solubility cause peeling, come off bad, so preferred.

［ (E) photopolymerization causes composition and/or thermal polymerization initiation composition ］

Colored resin composition of the present invention preferably contains (E) photopolymerization and causes composition and/or thermal polymerization initiation composition based on the purpose that makes the sclerosis of filming.But the method for curing also can not rely on these initiating agents.

Particularly preferably be, when colored resin composition of the present invention contains the resin with the two keys of ethene as (C) composition, when containing the ethene compound as (D) composition, contain and possess direct absorption optical or by photoactivate decomposition reaction or dehydrogenation reaction are occured, the photopolymerization that produces the function of polymerization activity free radical causes composition and/or causes composition by the thermal polymerization that heat produces the polymerization activity free radical.In addition, (E) composition that causes composition as photopolymerization among the present invention refers to, in Photoepolymerizationinitiater initiater (following also at random be called " (E1) composition ") and with the potpourri of the adjuvants such as polymerization accelerant (following also at random be called " (E2) composition "), sensitization pigment (following also at random be called " (E3) composition ").

(photopolymerization initiation composition)

The photopolymerization that can contain in the colored resin composition of the present invention causes composition, normally as (E1) Photoepolymerizationinitiater initiater and (E2) polymerization accelerant that adds as required and (E3) potpourri of the adjuvant such as sensitization pigment use, to have direct absorption optical or by photoactivate, decomposition reaction or dehydrogenation reaction occur, and produce the composition of the function of polymerization activity free radical.

As (E1) Photoepolymerizationinitiater initiater that consists of photopolymerization and cause composition, can enumerate such as the clear 59-152396 of Japanese Patent Laid-Open number, two luxuriant titanium derivative classes of the records such as each communique of the clear 61-151197 communique of Japanese Patent Laid-Open; Six aryl united imidazole derivative classes of the record such as each communique of Japanese patent laid-open 10-300922 communique, Japanese patent laid-open 11-174224 communique, Japanese Patent Laid-Open 2000-56118 communique; The Lu of the record such as Japanese patent laid-open 10-39503 communique is for Jia oxadiazole derivatives class, halogenated methyl-s-pyrrolotriazine derivatives class, N-aryl-a-amino acid salt, N-aryl-free radical activity agent, α-amine alkyl phenones derivant class such as α-aminoacidesters class; The oxime ester of the records such as Japanese Patent Laid-Open 2000-80068 communique is the derivant class.

Can enumerate particularly such as the world and disclose the Photoepolymerizationinitiater initiater that waits record for No. 2009/107734 etc.

More preferably α-amine alkyl phenones derivant class, oxime ester are derivant class, united imidazole derivative class, acetophenone derivs class and thioxanthone derivates class in these (E1) Photoepolymerizationinitiater initiaters.

In addition, be the derivant class as the oxime ester, can enumerate 1-(4-thiophenyl phenyl)-2-(o-benzoyl oxime)-1,2-acetyl caproyl, 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-the adjacent acetyl group oxime of 1-() ethyl ketone etc.

In addition can enumerate styrax alkyl ether, anthraquinone derivative class; 2-methyl-(4'-methyl mercapto phenyl)-2-morpholino-acetophenone derivs class, 2-ethyl thioxanthones, 2 such as 1-acetone, the thioxanthone derivates classes such as 4-diethyl thioxanthone, benzoic acid ester derivant class, acridine derivatives class, azophenlyene derivant class, anthracyclinone derivatives class etc.

In these Photoepolymerizationinitiater initiaters, more preferably α-amine alkyl phenones derivant class, thioxanthone derivates class, oxime ester are the derivant class.Particularly preferably the oxime ester is the derivant class.

As (E2) polymerization accelerant that uses as required, for example can enumerate N, the N such as N-methylamino ethyl benzoate, N-alkyl amino benzoic acid alkyl esters; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle; The sulfhydryl compound classes such as the multifunctional sulfhydryl compound of aliphatics etc.

These (E1) Photoepolymerizationinitiater initiaters and (E2) polymerization accelerant can be used alone respectively, also can be more than 2 kinds and use.

In addition, to improve induction sensitivity as purpose, can use as required (E3) sensitization pigment.The sensitization pigment can use suitable material according to the wavelength of pattern exposure light source, and the xanthene (Xanthene) that can enumerate such as the records such as each communique of Japanese patent laid-open 4-221958 communique, Japanese patent laid-open 4-219756 communique is pigment; The coumarin series pigment with heterocycle of the records such as each communique of Japanese patent laid-open 3-239703 communique, Japanese patent laid-open 5-289335 communique; The 3-ketone group coumarin series pigment of the record such as each communique of Japanese patent laid-open 3-239703 communique, Japanese patent laid-open 5-289335 communique; Pyrroles's methine (Pyrromethene) of the records such as Japanese patent laid-open 6-19240 communique is pigment; The clear 47-2528 communique of Japanese Patent Laid-Open, the clear 54-155292 communique of Japanese Patent Laid-Open, the examined patent publication 45-37377 of Japan communique, the clear 48-84183 communique of Japanese Patent Laid-Open, the clear 52-112681 communique of Japanese Patent Laid-Open, the clear 58-15503 communique of Japanese Patent Laid-Open, the clear 60-88005 communique of Japanese Patent Laid-Open, the clear 59-56403 communique of Japanese Patent Laid-Open, Japanese patent laid-open 2-69 communique, the clear 57-168088 communique of Japanese Patent Laid-Open, Japanese patent laid-open 5-107761 communique, Japanese patent laid-open 5-210240 communique, the pigment with dialkyl amido benzene skeleton of the records such as each communique of Japanese patent laid-open 4-288818 communique etc.

(E3) the sensitization pigment also is to be used alone, and also can more than 2 kinds and use.

In the colored resin composition of the present invention, these (E) photopolymerization cause the content of composition in the total solids composition, usually more than 0.1 % by weight, more than preferred 0.2 % by weight, further more than preferred 0.5 % by weight, and usually below 40 % by weight, below preferred 30 % by weight, further below preferred 20 % by weight.

If in above-mentioned scope, then good to exposure light sensitivity, and to the favorable solubility of the development of unexposed portion, therefore preferred.

(thermal polymerization initiation composition)

The thermal polymerization that can contain as colored resin composition of the present invention causes the object lesson of composition, can enumerate azo based compound, organic peroxide and hydrogen peroxide etc.Among these, preferably use the azo based compound.More specifically, can use and disclose the thermal polymerization of putting down in writing in No. 2009/107734 grade such as the world and cause composition.

These thermal polymerizations cause composition and can be used alone, also can two or more and usefulness.

［ other any compositions ］

Colored resin composition of the present invention can also contain surfactant, organic carboxyl acid and/or organic carboxyl acid acid anhydride, Thermocurable compound, plastifier, thermal polymerization inhibitor, preserving stabilizer, surface protectant, driving fit improving agent, development modifying agent etc. except above-mentioned each composition.When containing in addition (F) described later pigment, can also contain spreading agent and dispersing aid.As these any compositions, can use for example various compounds of Japanese Patent Laid-Open 2007-113000 communique record.

＜(F) pigment＞

Colored resin composition of the present invention, the purposes such as thermotolerance based on improving resulting colored filter in the scope of not damaging effect of the present invention, can also contain (F) pigment.

As (F) pigment, during such as the pixel that forms colored filter etc., can use the versicolor pigment such as blueness, purple.In addition, as its chemical constitution, can enumerate such as phthalocyanine system, quinacridone, benzimidazolone be that, dioxazine (Dioxazine) is, indanthrone (Indanthrene) is, the organic pigment of perylene system etc.Also may utilize other various inorganic pigments etc.The pigment numbering that below shows the object lesson of operable pigment.

As blue pigment, can enumerate such as, C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79 etc.

Wherein, preferred blue copper phthalocyanine as this copper phthalocyanine, is preferably enumerated C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6 etc., more preferably the C.I. pigment blue 15: 6.

Therefore, colored resin composition of the present invention is when containing blue pigment, and with respect to the total content of blue pigment, more than preferred 80 % by weight, particularly preferably more than 90 % by weight, especially preferred 95 ~ 100 % by weight are the C.I. pigment blue 15: 6.

As violet pigment, can enumerate such as, C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50 etc.

Wherein, preferred purple De triazine dioxin pigment as this copper phthalocyanine, is preferably enumerated C.I. pigment violet 19,23 etc., more preferably the C.I. pigment Violet 23.

Therefore, colored resin composition of the present invention is when containing violet pigment, and with respect to the total content of violet pigment, more than preferred 80 % by weight, particularly preferably more than 90 % by weight, especially preferred 95 ~ 100 % by weight are the C.I. pigment Violet 23.

These can be used alone, also can be so that combination and ratio use mixing more than 2 kinds arbitrarily.

(F) pigment that uses in the colored resin composition of the present invention is from the angle of the pixel that can form high-contrast, the preferred little pigment of average primary particle diameter, and specifically, preferred average primary particle diameter is below 40nm, more preferably below 35nm.

Especially, also be the same for the copper phthalocyanine of blueness, preferred average primary particle diameter below 40nm, more preferably below 35nm, 20 ~ 30nm more preferably.

In addition, for triazine dioxin pigment, preferred average primary particle diameter below 40nm, 25 ~ 35nm more preferably.The not agglutinophilic angle of pigment from colored resin composition, preferred average primary particle diameter is within reason little.

In addition, herein, (F) average primary particle diameter of pigment is the value of measuring, calculating according to following method.

At first, (F) pigment ultrasound wave in chloroform is disperseed, drop to and post the online of collodion membrane, make it dry, by observing with transmission electron microscope (TEM), obtain the primary particle picture of pigment.Looking like to obtain from this and be converted into the diameter of a circle identical with each granules of pigments area---the area circle is the footpath quite, as the particle diameter of each granules of pigments, a plurality of (common about 200 ~ 300) granules of pigments is obtained respectively particle diameter.

The value of the primary particle size that use obtains is calculated number mean value according to following calculating formula, obtains mean grain size.

The particle diameter of each granules of pigments: X ₁, X ₂, X ₃, X ₄,, X _i, X _m

[several 4]

{ combined amount }

Among the present invention, when containing (F) pigment, in the colored resin composition content of pigment in the total solids composition, usually below 80 % by weight preferably below 50 % by weight.

In addition, with respect to the content of above-mentioned (A) dyestuff 100 weight portions, usually below 2000 weight portions, preferably below 1000 weight portions.

By in above-mentioned scope, the transmitance of compound (I) ~ (IV) there is not considerable influence, thermotolerance becomes better easily, so preferred.

［ spreading agent ］

Colored resin composition of the present invention preferably further contains spreading agent when containing (F) pigment.

As long as the spreading agent among the present invention can dispersed color, it is stable to keep, just do not take notice of especially kind.

For example, can use the spreading agents such as kation system, negative ion system, nonionic system or both sexes, but the preferred polymers spreading agent.Can enumerate particularly alkylammonium salt or phosphate ester salt, the kation sex comb type graft polymer etc. of segmented copolymer, polyurethane, polyester, high-molecular copolymer.In these spreading agents, preferred block copolymer, polyurethane, kation sex comb type graft polymer.Particularly preferably segmented copolymer wherein preferably has the A block of solvophilic and the segmented copolymer of the B block formation with nitrogen atom functional group.

Particularly, can enumerate side chain as the B block with nitrogen atom functional group and have quaternary ammonium salt base and/or amino cellular construction, on the other hand, can enumerate the cellular construction that does not have quaternary ammonium salt base and amino as the A block with solvophilic.

The B block that consists of this acrylic acid series segmented copolymer is to have quaternary ammonium salt base and/or have amino cellular construction, possesses the position of pigment adsorption function.

In addition, as this B block, if having quaternary ammonium salt base, then this quaternary ammonium salt base can be directly and the main chain bonding, also can be situated between by divalent linking group and main chain bonding.

As such segmented copolymer, can enumerate the thing of being put down in writing such as Japanese Patent Laid-Open 2009-025813 communique.

In addition, colored resin composition of the present invention can also contain above-mentioned spreading agent in addition.As other spreading agents, can enumerate the thing of being put down in writing such as Japanese Patent Laid-Open 2006-343648 communique.

Colored resin composition of the present invention, if contain (F) pigment as (A) dyestuff, then the content of spreading agent in the total solids composition preferably uses 2 ~ 1000 % by weight of the total content of (F) pigment, 5 ~ 500 % by weight particularly preferably, especially preferred 10 ~ 250 % by weight.

By in above-mentioned scope, on the not impact of thermotolerance of compound (I) ~ (IV), can guarantee good pigment-dispersing, and the dispersion stabilization of pigment is better, so preferred.

［ preparation method of colored resin composition ］

Among the present invention, colored resin composition can be by suitable method preparation, for example, can by with above-mentioned (A) dyestuff and (C) adhesive resin and (B) solvent and as required the composition of use together mix and prepare.

In addition, preparation method when containing (F) pigment as (A) dyestuff is, to contain (A) dyestuff of (F) pigment in solvent, in the presence of spreading agent and the dispersing aid that adds as required, according to circumstances with a part (C) adhesive resin, use for example coating vibrator (paint shaker), sand milling (sand grinder), bowl mill (ballmill), tumbling mill (roll mill), stone mill (stone mill), aeropulverizer (jet mill), homogenizer (homogenizer) etc., mix when pulverizing and disperse, prepare painted dispersion liquid.Can enumerate add in this painted dispersion liquid mix (A) dyestuff, (C) adhesive resin, (D) polymerizable monomer as required, (E) photopolymerization causes composition and/or thermal polymerization causes into the method for grading and preparing.

［ application of colored resin composition ］

Colored resin composition of the present invention is generally the state that all constituents dissolve or disperse in solvent.Such colored resin composition is supplied on the substrate, forms the component parts of colored filter, liquid crystal indicator or OLED display etc.

Below, as the application examples of colored resin composition of the present invention, to as the application of the pixel of colored filter and use its liquid crystal indicator (panel) and OLED display to describe.

＜colored filter＞

Colored filter of the present invention has the pixel that is formed by colored resin composition of the present invention.

Below the formation method of colored filter of the present invention is described.

The pixel of colored filter can form by this method.Herein so that be that example describes with the optical polymerism colored resin composition by the situation that photoetch method forms, but manufacture method is not limited thereto.

Can at first form as required black matrix" and distinguish the part that forms pixel on the surface of substrate, after this substrate coating colored resin composition of the present invention, carry out preliminary drying and make the solvent evaporation, formation is filmed.Then, to this film be situated between exposed by photomask after, use alkaline developer to develop, the unexposed section of filming is removed in dissolving, then by rear baking, forms each red, green, blue pixel, the making colored filter.

The substrate that uses when forming pixel can be enumerated such as polyester based resin, polyolefin-based resins, polycarbonate-based resin, acrylic resin, thermoplastic resin thin slice processed, epoxy resin, thermoset resin, various glass etc. so long as transparent and have suitable intensity just to be not particularly limited.

The film that can apply based on silane coupling agent or polyurethane series resin etc. at these substrates as required in addition, forms the suitable pre-treatments such as surface treatment such as processing, Corona discharge Treatment or ozone treatment.

When being applied to colored resin composition on the substrate, can enumerate spin-coating method, steel wire bar (wire bar) method, flow coat method (flowcoat), Xia Feng ﹠amp; Rotation (slit and spin) method, die coating (die coat) method, roller coat (roll coat) method, spraying (spray coat) method etc.Wherein, preferred Xia Feng ﹠amp; Rotary process and die rubbing method.

The thickness of coated film as dried thickness, is generally 0.2 ~ 20 μ m, preferred 0.5 ~ 10 μ m, more preferably 0.8 ~ 5.0 μ m.

If in above-mentioned scope, in pattern development and liquid crystal cell chemical industry order the thick adjustment of box easy, and embody easily desired color, so preferred.

Employed radioactive ray can use such as visible light, ultraviolet ray, far ultraviolet, electron beam, X-ray etc. during exposure, but the radioactive ray of optimal wavelength in 190 ~ 450nm scope.

The light source of the radioactive ray of the generation wavelength 190 ~ 450nm that uses in the pixel exposure is not particularly limited, and can enumerate the lamp source such as xenon lamp, halogen lamp, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, fluorescent light; The LASER Light Source such as Argon ion laser, YAG laser instrument, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser etc.If the light of specific wavelength is used in irradiation, then also can utilize optical filter.

The exposure of radioactive ray is preferred 10 ~ 10,000J/m ²

In addition, above-mentioned alkaline developer preference is such as, inorganic alkaline compounds such as NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium silicate, potassium silicate, sodium methyl silicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; Single/pair or/triethanolamine, list/pair or/trimethylamine, list/pair or/triethylamine, list/pair or/tri-isopropyl amine, n-butylamine, list/pair or/aqueous solution of organic basic compounds such as triisopropanolamine, Ethylenimine, ethylene diimine, Tetramethylammonium hydroxide (TMAH), choline etc.

In the above-mentioned alkaline developer, can also add in right amount water-miscible organic solvents such as isopropyl alcohol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol, diacetone alcohol or surfactant etc.In addition, alkali is washed after developing usually.

The development treatment method can be according to any method in dip-type developing method, spray development method, brush (brush) development method, the ultrasound wave development method etc.Lower 5 ~ 300 seconds of the preferred room temperature of development conditions (23 ℃).

The condition of developing is not particularly limited, but development temperature is wherein preferred more than 15 ℃ usually more than 10 ℃, and is more preferably more than 20 ℃, wherein preferred below 45 ℃ usually below 50 ℃ in addition, more preferably below 40 ℃.

Developing method can be according to any method in dip-type developing method, spray development method, brush development method, the ultrasound wave development method etc.

When the colored filter of making like this is used for liquid crystal indicator, can under this state, directly form the transparency electrodes such as ITO at picture, part as the parts of color monitor, liquid crystal indicator etc. is used, but in order to improve surface smoothness and permanance, as required, the surface coatings such as polyamide, polyimide can be set at picture.In addition, a part does not form transparency electrode sometimes yet in the purposes such as plane orthotype type of drive (IPS pattern).In addition, in vertical orientation type of drive (MVA pattern), sometimes also form arch rib (rib).In addition, sometimes also form rod structure (light spacer block, photo spacer) by photoetch method and replace pearl dispersal type spacer block.

＜liquid crystal indicator＞

Liquid crystal indicator of the present invention uses the colored filter of the invention described above.Pattern and the structure of liquid crystal indicator of the present invention have no particular limits, and can use colored filter of the present invention to assemble according to conventional method.

For example can be according to " method of record forms liquid crystal indicator of the present invention in the liquid crystal device handbook (daily magazine industry newspaper office, distribution on September 29th, 1989, JSPS the 142nd council work).

＜OLED display＞

When making comprises the OLED display of colored filter of the present invention; for example as shown in Figure 1; on transparent support substrate 10; form blue pixel 20 with colored resin composition of the present invention at blue color filter; be situated between by organic protection layer 30 and inorganic oxide film 40 stacked organic luminorphors 500 at this blue color filter, thereby make multicolor organic element 100.

Laminating method as organic luminorphor 500, the method that forms successively transparent anode 50, hole injection layer 51, hole transporting layer 52, luminescent layer 53, electron injecting layer 54 and negative electrode 55 at the colored filter upper surface can be enumerated, and the method on the inorganic oxide film 40 will be fitted at the organic luminorphor 500 that another substrate forms.The organic EL 100 of making like this goes for the OLED display of passive matrix mode, also goes for the OLED display of active drive mode.

Real is executed example

Then, be described more specifically the present invention for synthesis example, embodiment and comparative example, but the present invention only otherwise break away from its purport, just do not limited by following examples.

［ 1 ］ (C) adhesive resin synthetic

(with reference to synthesis example 1: adhesive resin a's is synthetic)

Propylene glycol methyl ether acetate 145 weight portions are stirred when being replaced into nitrogen, be warming up to 120 ℃.Change into society's system to styrene 20 weight portions that wherein drip, 57 parts of glycidyl methacrylate and mono acrylic ester FA-513M(Hitachi with tricyclodecane skeleton) 82 weight portions, and then stirred 2 hours 120 ℃ of lower continuation.Then will be replaced into air in the reaction vessel, drop into acrylic acid 27 weight portions, three (dimethylamino methyl) phenol 0.7 weight portion and quinhydrones 0.12 weight portion, reacted 6 hours 120 ℃ of lower continuation.Then, add tetrahydrochysene acid phthalic anhydride (THPA) 52 weight portions, triethylamine 0.7 weight portion, 120 ℃ of lower reactions 3.5 hours.The adhesive resin a that obtains like this is about 15000 with the weight-average molecular weight Mw that GPC records by polystyrene conversion, and acid number is 78mgKOH/g.The structure of adhesive resin a (macromolecular compound that contains following 4 kinds of repetitives) as follows.

[changing 43]

［ 2 ］ (A) dyestuff synthetic

(synthesis example 1)

[changing 44]

With compound 1(6.0g, 25mmol: press the international method that disclose record in No. 2008/003604 and synthesize), compound 2(6.4ml, 50mmol: change into from Tokyo and to buy), the potpourri of sal tartari (6.9g, 50mmol), METHYLPYRROLIDONE (25ml) adds thermal agitation 4 hours under 110 ~ 125 ℃.Add water after being cooled to room temperature, with the toluene extraction, with watery hydrochloric acid and saturated common salt water washing toluene layer, use anhydrous sodium sulfate drying.Reduced pressure concentration obtains 9.2g Sandy oil.It is dissolved in ethanol (40ml), adds water (25ml) solution of NaOH (2g, 52.3mmol), 85 ℃ of lower stirrings 1 hour.Let cool, with the toluene extraction, with saturated common salt water washing toluene layer, use anhydrous sodium sulfate drying.Reduced pressure concentration is purified with silica gel column chromatography (n-hexane/ethyl acetate=3/1), obtains compound 3(5.95g, yield 94%) white powder.

[changing 45]

With compound 4(1.47g, 4.34mmol: the method that discloses No. 2009/107734 record according to the world is synthetic), compound 3(1.1g, 4.34mmol), the potpourri of toluene (30ml), phosphorus oxychloride (0.6ml) adds hot reflux after 4 hours, be cooled to room temperature, add water, use chloroform extraction.With the chloroform layer reduced pressure concentration, with silica gel column chromatography (developing solvent: chloroform/methanol=15/1 ~ 10/1) purify, the solid that obtains is washed with normal hexane, obtain compound 5(1.32g, yield 50%).

[changing 46]

With compound 5(8.9g, 14.6mmol), compound 6(4.2g, 14.6mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (50ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/2, obtain Compound D 1(11.5g, yield 92.3%).

(synthesis example 2)

[changing 47]

With compound 5(4.27g, 7.0mmol), compound 7(2.32g, 7.0mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (200ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/2, obtain Compound D 2(5.42g, yield 89%).

(synthesis example 3)

[changing 48]

With compound 5(427mg, 0.7mmol), compound 8(161mg, 0.7mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (30ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration washes the solid that obtains with water, obtains compound d3 (480mg, yield 87.7%).

(synthesis example 4)

[changing 49]

Reaction 6: with compound 9(2.56g, 23.9mmol), compound 10(1,1,1-three fluoro-4-iodine) potpourri of butane (TCI, 12.5g, 52.5mmol), sal tartari (7.25g, 52.5mmol) and METHYLPYRROLIDONE (50ml) adds thermal agitation 5 hours under 100 ℃, after being cooled to room temperature, dilute with ethyl acetate, suction filtration washs with ethyl acetate.After mother liquor washes 2 times with water, reduced pressure concentration.Oil is dissolved in toluene, washes with water 3 times, use the saturated common salt water washing.Use anhydrous sodium sulfate drying, reduced pressure concentration is with silica gel column chromatography (Northeast chemistry 60N processed of society, 200g, n-hexane/ethyl acetate=20/1-15/1) purify obtain compound 10(6.91g, yield 88%).

Reaction 7: to compound 11(25g) and in the potpourri of toluene (100ml) add thionyl chloride (14ml), after 1 hour, reduced pressure concentration obtains acyl chlorides 80 ℃ of lower stirrings.The potpourri of ice bath cooling anhydrous Aluminum chloride (20.4g) and 1,2-ethylene dichloride (100ml) in another container, 1 of the acyl chlorides that drips, 2-ethylene dichloride (50ml) solution.Stir after 15 minutes, compound 10(21.1g drips), reach room temperature after, inject frozen water.Be adjusted to pH more than 10 with the 4N sodium hydrate aqueous solution, use chloroform extraction.Wash chloroform layer with the 1N aqueous sodium hydroxide washes, remove insolubles with diatomite filtration.It is used the saturated common salt water washing, use anhydrous sodium sulfate drying, reduced pressure concentration.Purify with silica gel column chromatography (silica gel 800g, n-hexane/ethyl acetate=4/1), the crystal with the normal hexane washing obtains obtains compd A (14.6g).

[changing 50]

Reaction 8: to compd A (3.38g), compound 12(1.71g) and in the potpourri of toluene (15ml) add phosphorus oxychloride (1.4ml), 120 ℃ of lower stirrings 2 hours.After being cooled to room temperature, add 1N hydrochloric acid, stirred 15 minutes, use chloroform extraction.Water and saturated common salt water washing chloroform layer are used anhydrous sodium sulfate drying.Reduced pressure concentration is with silica gel column chromatography (chloroform/methanol=15/1-10/1-7/1) purify, the solid with the normal hexane washing obtains obtains compound 13(3.21g).

The reaction 9: with compound 13(1.06g) and acid blue 80(0.70g) be dissolved in methyl alcohol after, reduced pressure concentration.Use the admixture solvent of methanol/water (1/2) to wash the solid that obtains, obtain Compound D 4(1.34g).

(synthesis example 5)

[changing 51]

With compound 14(397mg, 0.6mmol: the method that discloses No. 2009/107734 record according to the world is synthetic), compound 6(172mg, 0.6mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (30ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/2, obtain Compound D 5(410mg, yield 75.3%).

(synthesis example 6)

[changing 52]

With compound 14(397mg, 0.6mmol: it is synthetic to press the international method that disclose No. 2009/107734 record), compound 7(200mg, 0.6mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (30ml) is 50 ℃ of lower stirrings after 1.5 hours, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/2, obtain Compound D 6(450mg, yield 81.6%).

(synthesis example 7)

[changing 53]

Reaction 10: with compound 17(10g) DMF (100ml) solution cools off with ice bath, adds sodium hydride (60%, 4.3g), stir a little while after, add bit by bit compound 18(6.5g).After at room temperature stirring 5 hours, add water, carry out dichloromethane extraction, purifying with silica gel column chromatography obtains compd B (3.1g).

[changing 54]

Reaction 11: to compd B (5.61g), compound 19(2.65g), add phosphorus oxychloride (1.8ml) in the potpourri of toluene (15ml), 115 ℃ of lower stirrings 2 hours.After getting back to room temperature, add saturated aqueous common salt (30ml), use chloroform extraction 2 times.With silica gel column chromatography (silica gel 300g, chloroform/methanol=1/0-10/1/7/1) purify, the solid with the normal hexane washing obtains obtains compound 20(9.23g).

Reaction 12: with compound 20(5.00g), acid blue 80(2.56g), the potpourri of methyl alcohol (50ml) 40 ℃ lower stir 1 hour after, reduced pressure concentration adds water and filters to get solid.Solid with methanol/water=1/3(200ml) washing, is used methanol/water=1/3(200ml) washing again, obtain Compound D 7(5.90g).

(synthesis example 8)

[changing 55]

With compound 14(397mg, 0.6mmol: it is synthetic to press the international method that disclose No. 2009/107734 record), acid blue 80(200mg, 0.6mmol: Tokyo changes into society's system), the potpourri of methyl alcohol (30ml) is 50 ℃ of lower stirrings after 1.5 hours, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/2, obtain Compound D 8(450mg, yield 81.6%).

［ synthesis example and the embodiment of the compound of formula (IV) expression ］

(synthesis example 9)

[changing 56]

Woods protobiochemistry institute system), compound 8(2.13g, 9.25mmol with compound 20(5g, 9.25mmol:: Tokyo changes into society's system), the potpourri of methyl alcohol (40ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains is washed with methanol/water=1/3, obtain Compound D 9(4.98g, yield 86.7%).

(synthesis example 10)

[changing 57]

Woods protobiochemistry institute system), compound 6(1.70g, 5.9mmol with compound 20(3.21g, 5.9mmol:: Tokyo changes into society's system), the potpourri of methyl alcohol (200ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains obtains Compound D 10(3.91g, yield 95% with methanol/water=1/2 washing).

(synthesis example 11)

[changing 58]

With compound 20(5.41g, 10mmol: woods protobiochemistry institute system), compound 7(3.31g, 10mmol, Tokyo changes into society's system), the potpourri of methyl alcohol (200ml) 50 ℃ lower stir 1.5 hours after, reduced pressure concentration, the solid that obtains obtains Compound D 11(6.65g, yield 94% with methanol/water=1/2 washing).

［ 3 ］ mensuration of ionization potential and electron affinity

To above-mentioned synthetic compound, carry out the optimization of molecular structure with the calculated level of HF/6-31G (D), with the HOMO that obtains and LUMO energy as each ionization potential and electron affinity.

Measurement result is summarized in table 1.

[table 1]

※ 1: in the above-mentioned table 1, and the expression of zero in formula (1) ~ (3) hurdle " meeting " various scope, * expression " not meeting " various scope.

※ 2: in the above-mentioned table 1, and the scope of the expression of zero in the molecular weight hurdle " meeting " molecular weight 150 ~ 600, the scope of * expression " not meeting " molecular weight 150 ~ 600.

［ 4 ］ preparation of colored resin composition (embodiment 1 ~ 6 and comparative example 1 ~ 3)

(A) dyestuff that uses in embodiment 1 ~ 6 and the comparative example 1 ~ 3 is shown in table 2.

[table 2]

?	(A) dyestuff	?
			Embodiment 1	The compound that obtains in the D1(synthesis example 1)	Meet formula (I)
Embodiment 2	The compound that obtains in the D2(synthesis example 2)	Meet formula (I)
			Embodiment 3	The compound that obtains in the D5(synthesis example 5)	Meet formula (II)
Embodiment 4	The compound that obtains in the D6(synthesis example 6)	Meet formula (II)
			Embodiment 5	D10 (compound that obtains in the synthesis example 10)	Meet formula (III)
Embodiment 6	D11 (compound that obtains in the synthesis example 11)	Meet formula (III)
			Comparative example 1	The compound that obtains in the D3(synthesis example 3)	-
Comparative example 2	The compound that obtains in the D7(synthesis example 7)	-
			Comparative example 3	The compound that obtains in the D9(synthesis example 9)	-

The ratio of pressing record in the table 3 mixes above-mentioned each dyestuff and other compositions, the preparation colored resin composition.During mixing, stir more than 1 hour, until dyestuff fully dissolves, the frame type filter with 5 μ m filters at last, removes foreign matter.

[table 3]

The preparation of dye composite

［ 5 ］ dichroism and Evaluation of Heat Tolerance

Be cut on the square glass substrate of 5cm, with above-mentioned each colored resin composition of spin-coating method coating, making dry film thickness is 1.8 μ m, behind the drying under reduced pressure, carries out 80 ℃ of preliminary dryings of 3 minutes at hot plate.Then, with 60mJ/cm ²The exposure blanket exposure after, with spectrophotometric Meter U-3310(Hitachi system) measure spectrophotometric transmittance, calculate colourity (illuminant-C) and brightness in the xyz color specification system.The result is shown in table 4 in the lump.

Then, in dustless baking oven (clean oven), aforesaid substrate is carried out 230 ℃ of sintering of 30 minutes, afterwards in the same manner as described above, measure spectrophotometric transmittance, with the aberration (Δ E*ab) of colourity before the sintering, i.e. thermotolerance, measurement result is shown in the following table 4.

[table 4]

As shown in table 4, with the pixel that colored resin composition of the present invention forms, brightness does not significantly reduce, and thermotolerance improves tremendously.

Although understand in detail the present invention with reference to specific embodiment, only it will be apparent to those skilled in the art that otherwise break away from the spirit and scope of the present invention, can add various changes and correction.The present invention is based on the Japanese patent application (Patent 2010-142748) of application on June 23rd, 2010, quote its content as reference herein.

Claims (18)

1. colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (I),

[changing 1]

In the described formula (I), (Z ₁) ^M1-The disulfonyl imines negative ion of expression m1 valency,

M1 represents 1 ~ 4 integer,

R ¹~ R ⁶Represent independently of one another hydrogen atom, have or do not have the alkyl of substituent carbon number 1 ~ 8, or have or do not have substituent aromatic ring yl, adjacent R ¹~ R ⁶Between connect into the ring or do not connect into ring, this ring has or does not have substituting group,

R ⁷And R ⁸Expression hydrogen atom or substituting group arbitrarily,

R ⁷And R ⁸Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group,

In addition, the phenyl ring in the described formula (I) further has any substituting group or does not have substituting group,

R ¹⁰¹And R ¹⁰²The expression hydrogen atom, have or do not have substituent carbon number 1 ~ 8 alkyl, have or do not have substituent carbon number 2 ~ 6 thiazolinyl, have or do not have substituent aromatic ring yl or fluorine atom,

R ¹⁰¹And R ¹⁰²Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group,

In addition, in a part, contain a plurality of following formulas (I) _CADuring shown kation,

[changing 2]

Then they are same structure or different structure.

2. colored resin composition as claimed in claim 1 is characterized in that, the compound of described formula (I) expression is the compound of following formula (I-1) expression.

[changing 3]

In the described formula (I-1), R ¹~ R ⁸, R ¹⁰¹And R ¹⁰²It is identical with the definition in the described formula (I),

Phenyl ring in the described formula (I-1) further has any substituting group or does not have substituting group,

R ²¹And R ²²Represent independently of one another hydrogen atom, have or do not have substituent carbon number 1 ~ 8 alkyl, have or do not have the thiazolinyl of substituent carbon number 2 ~ 6, or have or do not have the naphthenic base of substituent carbon number 3 ~ 8,

In addition, R ²¹And R ²²Be connected to each other to ring or do not connect into ring, this ring has substituting group or does not have substituting group.

3. colored resin composition as claimed in claim 2 is characterized in that, described R ²¹And R ²²At least one be the contain fluorine atoms group.

4. colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (II),

[changing 4]

In the described formula (II), (Z ₂) ^M2-The disulfonyl imines negative ion of expression m2 valency,

M2 represents 1 ~ 4 integer,

R ¹¹~ R ¹⁶Represent independently of one another hydrogen atom, have or do not have substituent alkyl, or have or do not have substituent aromatic ring yl,

Adjacent R ¹¹~ R ¹⁶Between connect into the ring or do not connect into ring, this ring has substituting group or does not have substituting group,

R ¹⁷And R ¹⁸Represent independently of one another hydrogen atom or substituting group arbitrarily,

R ¹⁷And R ¹⁸Be connected to each other to ring or do not connect into ring, this ring has substituting group or does not have substituting group,

In addition, the phenyl ring in the described formula (II) and indole ring further have any substituting group or do not have substituting group,

In addition, in a part, contain a plurality of following formulas (II) _CADuring shown kation,

[changing 6]

Then they are same structure or different structure.

5. colored resin composition as claimed in claim 4 is characterized in that, the compound of described formula (II) expression is the compound of following formula (II-1) expression,

[changing 6]

In the described formula (II-1), R ¹¹~ R ¹⁸It is identical with the definition in the described formula (II),

Phenyl ring in the described formula (II-1) and indole ring further have any substituting group or do not have substituting group,

R ³¹And R ³²Independently of one another expression have or do not have substituent carbon number 1 ~ 8 alkyl, have or do not have the thiazolinyl of substituent carbon number 2 ~ 6, or have or do not have the naphthenic base of substituent carbon number 3 ~ 8,

In addition, R ³¹And R ³²Be connected to each other to ring or do not connect into ring, this ring has substituting group or does not have substituting group.

6. colored resin composition as claimed in claim 5 is characterized in that, described R ³¹And R ³²At least one be the contain fluorine atoms group.

7. colored resin composition contains (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that (A) dyestuff contains the compound shown in the following formula (III),

[changing 7]

In the described formula (III), (Z ₃) ^M3-The disulfonyl imines negative ion of expression m3 valency,

M3 represents 1 ~ 4 integer,

Q represents 1 ~ 5 integer,

R ⁵⁰¹And R ⁵⁰²Independently of one another expression has or does not have the aliphatic alkyl of substituent carbon number 1 ~ 20,

R ⁵¹And R ⁵²Independently of one another expression-O-,-S-,-N-,-Se-or-CR ⁵⁰³R ⁵⁰⁴-,

R ⁵⁰³And R ⁵⁰⁴The aliphatic alkyl that represents independently of one another hydrogen atom or carbon number 1 ~ 6,

Wherein, work as R ⁵¹And R ⁵²For-CR ⁵⁰³R ⁵⁰⁴-time, then R ⁵⁰³Between be connected to each other to the ring or do not connect into ring, this ring has or does not have substituting group,

Ring Y ¹And Y ²Independently of one another expression has or does not have substituent phenyl ring or naphthalene nucleus,

Wherein, ring Y ¹And Y ²Phenyl ring and the substituting group of naphthalene nucleus do not have nitro and perfluoroalkyl.

8. colored resin composition as claimed in claim 7 is characterized in that, the compound of described formula (III) expression is the compound of following formula (III-1) expression,

[changing 8]

In the described formula (III-1), q, R ⁵¹And R ⁵², R ⁵⁰¹And R ⁵⁰²And ring Y ¹And Y ²It is identical with the definition in the described formula (III),

R ⁴¹And R ⁴²Independently of one another expression have or do not have substituent carbon number 1 ~ 8 alkyl, have or do not have the thiazolinyl of substituent carbon number 2 ~ 6, or have or do not have the naphthenic base of substituent carbon number 3 ~ 8,

In addition, R ⁴¹And R ⁴²Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group.

9. colored resin composition as claimed in claim 8 is characterized in that, described R ⁴¹And R ⁴²At least one be the contain fluorine atoms group.

10. colored resin composition, contain (A) dyestuff, (B) solvent and (C) adhesive resin, it is characterized in that, (A) dyestuff contains the counter ion counterionsl gegenions of kation and negative ion formation, the molecular weight of this negative ion is more than 150, below 600, and these counter ion counterionsl gegenions satisfy the relation of following formula (1) ~ (3)

[several 1]

$|\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}-\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}|\≤2.2---\left(1\right)$

$3.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{cation}}-{\mathrm{EA}}_{\mathrm{cation}}}\≤4.0---\left(2\right)$

$1.4\≤\frac{1}{{\mathrm{IP}}_{\mathrm{anion}}-{\mathrm{EA}}_{\mathrm{anion}}}\≤3.4---\left(3\right)$

In the described formula,

IP _CationRepresent described cationic ionization potential, its unit is hartree,

EA _CationRepresent described cationic electron affinity, its unit is hartree,

IP _AnionThe ionization potential that represents described negative ion, its unit is hartree,

EA _AnionThe electron affinity that represents described negative ion, its unit is hartree.

11. colored resin composition as claimed in claim 10 is characterized in that, described kation is by following formula (I-2) _CAExpression,

[changing 9]

Described formula (I-2) _CAIn, R ⁶¹~ R ⁶⁶Represent independently of one another hydrogen atom, have or do not have the alkyl of substituent carbon number 1 ~ 8, or have or do not have substituent aromatic ring yl,

Adjacent R ⁶¹~ R ⁶⁶Between connect into the ring or do not connect into ring, this ring has or does not have substituting group,

R ⁶⁷And R ⁶⁸Expression hydrogen atom or substituting group arbitrarily,

R ⁶⁷And R ⁶⁸Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group,

In addition, described formula (I-2) _CAIn phenyl ring further have any substituting group or do not have substituting group,

R ⁶⁰¹And R ⁶⁰²The expression hydrogen atom, have or do not have substituent carbon number 1 ~ 8 alkyl, have or do not have substituent carbon number 2 ~ 6 thiazolinyl, have or do not have substituent aromatic ring yl, or fluorine atom,

R ⁶⁰¹And R ⁶⁰²Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group.

12. colored resin composition as claimed in claim 10 is characterized in that, described kation is by following formula (II-2) _CAExpression,

[changing 10]

Described formula (II-2) _CAIn, R ⁷¹~ R ⁷⁶Represent independently of one another hydrogen atom, have or do not have substituent alkyl, or have or do not have substituent aromatic ring yl,

Adjacent R ⁷¹~ R ⁷⁶Between connect into the ring or do not connect into ring, this ring has or does not have substituting group.

R ⁷⁷And R ⁷⁸Represent independently of one another hydrogen atom or substituting group arbitrarily.

R ⁷⁷And R ⁷⁸Be connected to each other to ring or do not connect into ring, this ring has or does not have substituting group.

In addition, described formula (II-2) _CAIn phenyl ring and indole ring further have any substituting group or do not have substituting group.

13. each the described colored resin composition as in the claim 1 ~ 12 is characterized in that, further contains (D) polymerizable monomer.

14. each the described colored resin composition as in the claim 1 ~ 13 is characterized in that, further contains in (E) photopolymerization initiation composition and the thermal polymerization initiation composition at least one.

15. each the described colored resin composition as in the claim 1 ~ 14 is characterized in that, further contains (F) pigment.

16. a colored filter has the pixel that right to use requires each the described colored resin composition in 1 ~ 15 to form.

17. a liquid crystal indicator has the described colored filter of claim 16.

18. an OLED display has the described colored filter of claim 16.

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